Science.gov

Sample records for air mass dilution

  1. 40 CFR 1065.667 - Dilution air background emission correction.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calculations and Data Requirements § 1065.667 Dilution air background emission correction. (a) To determine the mass of background emissions to subtract... 40 Protection of Environment 34 2012-07-01 2012-07-01 false Dilution air background...

  2. 40 CFR 1065.667 - Dilution air background emission correction.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calculations and Data Requirements § 1065.667 Dilution air background emission correction. (a) To determine the mass of background emissions to subtract... 40 Protection of Environment 34 2013-07-01 2013-07-01 false Dilution air background...

  3. 40 CFR 1065.667 - Dilution air background emission correction.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calculations and Data Requirements § 1065.667 Dilution air background emission correction. (a) To determine the mass of background emissions to subtract... 40 Protection of Environment 33 2011-07-01 2011-07-01 false Dilution air background...

  4. 40 CFR 1065.667 - Dilution air background emission correction.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calculations and Data Requirements § 1065.667 Dilution air background emission correction. (a) To determine the mass of background emissions to subtract... 40 Protection of Environment 33 2014-07-01 2014-07-01 false Dilution air background...

  5. 40 CFR 1065.667 - Dilution air background emission correction.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calculations and Data Requirements § 1065.667 Dilution air background emission correction. (a) To determine the mass of background emissions to subtract... 40 Protection of Environment 32 2010-07-01 2010-07-01 false Dilution air background...

  6. Characteristics of particle number and mass emissions during heavy-duty diesel truck parked active DPF regeneration in an ambient air dilution tunnel

    NASA Astrophysics Data System (ADS)

    Yoon, Seungju; Quiros, David C.; Dwyer, Harry A.; Collins, John F.; Burnitzki, Mark; Chernich, Donald; Herner, Jorn D.

    2015-12-01

    Diesel particle number and mass emissions were measured during parked active regeneration of diesel particulate filters (DPF) in two heavy-duty diesel trucks: one equipped with a DPF and one equipped with a DPF + SCR (selective catalytic reduction), and compliant with the 2007 and 2010 emission standards, respectively. The emission measurements were conducted using an ambient air dilution tunnel. During parked active regeneration, particulate matter (PM) mass emissions measured from a 2007 technology truck were significantly higher than the emissions from a 2010 technology truck. Particle number emissions from both trucks were dominated by nucleation mode particles having a diameter less than 50 nm; nucleation mode particles were orders of magnitude higher than accumulation mode particles having a diameter greater than 50 nm. Accumulation mode particles contributed 77.8 %-95.8 % of the 2007 truck PM mass, but only 7.3 %-28.2 % of the 2010 truck PM mass.

  7. Engineering correlations of variable-property effects on laminar forced convection mass transfer for dilute vapor species and small particles in air

    NASA Technical Reports Server (NTRS)

    Gokoglu, S. A.; Rosner, D. E.

    1984-01-01

    A simple engineering correlation scheme is developed to predict the variable property effects on dilute species laminar forced convection mass transfer applicable to all vapor molecules or Brownian diffusing small particle, covering the surface to mainstream temperature ratio of 0.25 T sub W/T sub e 4. The accuracy of the correlation is checked against rigorous numerical forced convection laminar boundary layer calculations of flat plate and stagnation point flows of air containing trace species of Na, NaCl, NaOH, Na2SO4, K, KCl, KOH, or K2SO4 vapor species or their clusters. For the cases reported here the correlation had an average absolute error of only 1 percent (maximum 13 percent) as compared to an average absolute error of 18 percent (maximum 54 percent) one would have made by using the constant-property results.

  8. 40 CFR 1065.240 - Dilution air and diluted exhaust flow meters.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... dilution system, you may use a laminar flow element, an ultrasonic flow meter, a subsonic venturi, a... § 1065.240 Dilution air and diluted exhaust flow meters. (a) Application. Use a diluted exhaust flow meter to determine instantaneous diluted exhaust flow rates or total diluted exhaust flow over a...

  9. Quantification of VX vapor in ambient air by liquid chromatography isotope dilution tandem mass spectrometric analysis of glass bead filled sampling tubes.

    PubMed

    Evans, Ronald A; Smith, Wendy L; Nguyen, Nam-Phuong; Crouse, Kathy L; Crouse, Charles L; Norman, Steven D; Jakubowski, E Michael

    2011-02-15

    An analysis method has been developed for determining low parts-per-quadrillion by volume (ppqv) concentrations of nerve agent VX vapor actively sampled from ambient air. The method utilizes glass bead filled depot area air monitoring system (DAAMS) sampling tubes with isopropyl alcohol extraction and isotope dilution using liquid chromatography coupled with a triple-quadrupole mass spectrometer (LC/MS/MS) with positive ion electrospray ionization for quantitation. The dynamic range was from one-tenth of the worker population limit (WPL) to the short-term exposure limit (STEL) for a 24 L air sample taken over a 1 h period. The precision and accuracy of the method were evaluated using liquid-spiked tubes, and the collection characteristics of the DAAMS tubes were assessed by collecting trace level vapor generated in a 1000 L continuous flow chamber. The method described here has significant improvements over currently employed thermal desorption techniques that utilize a silver fluoride pad during sampling to convert VX to a higher volatility G-analogue for gas chromatographic analysis. The benefits of this method are the ability to directly analyze VX with improved selectivity and sensitivity, the injection of a fraction of the extract, quantitation using an isotopically labeled internal standard, and a short instrument cycle time.

  10. 40 CFR 1065.240 - Dilution air and diluted exhaust flow meters.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... interval. You may use the difference between a diluted exhaust flow meter and a dilution air meter to.... We recommend that you use a diluted exhaust flow meter that meets the specifications in Table 1 of... verification in § 1065.307 and the calibration and verifications in § 1065.340 and § 1065.341. You may use...

  11. 40 CFR 1065.240 - Dilution air and diluted exhaust flow meters.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... interval. You may use the difference between a diluted exhaust flow meter and a dilution air meter to.... We recommend that you use a diluted exhaust flow meter that meets the specifications in Table 1 of... verification in § 1065.307 and the calibration and verifications in § 1065.340 and § 1065.341. You may use...

  12. 40 CFR 1065.240 - Dilution air and diluted exhaust flow meters.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... interval. You may use the difference between a diluted exhaust flow meter and a dilution air meter to.... We recommend that you use a diluted exhaust flow meter that meets the specifications in Table 1 of... verification in § 1065.307 and the calibration and verifications in § 1065.340 and § 1065.341. You may use...

  13. 40 CFR 1065.240 - Dilution air and diluted exhaust flow meters.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... interval. You may use the difference between a diluted exhaust flow meter and a dilution air meter to.... We recommend that you use a diluted exhaust flow meter that meets the specifications in Table 1 of... verification in § 1065.307 and the calibration and verifications in § 1065.340 and § 1065.341. You may use...

  14. Automated high-speed analysis of selected organic compounds in urban air by on-line isotopic dilution cryofocusing gas chromatography/mass spectrometry.

    PubMed

    Davoli, E; Cappellini, L; Maggi, M; Fanelli, R

    1994-11-01

    An automated environmental air monitor has been developed to measure selected organic compounds in urban air. The instrument is based on a cryofocusing-thermal desorption gas chromatographic mass spectrometry technique where the mass spectrometer is a slightly modified residual gas analyzer (RGA). The RGA was chosen as a detector because the whole system must be robust for long periods, with 24-h continuous air monitoring. RCA are extremely simple and seemed the most reliable mass spectrometers for this purpose. Moreover, because they have no physically limited ion source, contamination is considerably reduced, so maintenance intervals are longer.The gas chromatograph is equipped with a computer-controlled six-way sampling valve, with a 100-mL sampling loop and thermal desorption cold trap injector. Environmental air is enriched with an isotopically labeled internal standard in the sampling line. This internal standard is added with a validated, custom-made, permeation tube device. The "on-line" internal standard provides for high quality quantitative data because all variations in instrument sensitivity in cryofocusing or in thermal desorption efficiency are taken into account. High repetition rates (down to 5 min for a full analytical cycle) are obtained with the use of an isothermal gas chromatography program, microbore capillary column, and environmental air sampling during the gas chromatography run.

  15. Calibration graphs in isotope dilution mass spectrometry.

    PubMed

    Pagliano, Enea; Mester, Zoltán; Meija, Juris

    2015-10-01

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

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

    PubMed Central

    Tretyakova, Natalia; Goggin, Melissa; Janis, Gregory

    2012-01-01

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

  17. Dispersal and air entrainment in unconfined dilute pyroclastic density currents

    NASA Astrophysics Data System (ADS)

    Andrews, Benjamin J.

    2014-09-01

    Unconfined scaled laboratory experiments show that 3D structures control the behavior of dilute pyroclastic density currents (PDCs) during and after liftoff. Experiments comprise heated and ambient temperature 20 μm talc powder turbulently suspended in air to form density currents within an unobstructed 8.5 × 6 × 2.6-m chamber. Comparisons of Richardson, thermal Richardson, Froude, Stokes, and settling numbers and buoyant thermal to kinetic energy densities show good agreement between experimental currents and dilute PDCs. The experimental Reynolds numbers are lower than those of PDCs, but the experiments are fully turbulent; thus, the large-scale dynamics are similar between the two systems. High-frequency, simultaneous observation in three orthogonal planes shows that the currents behave very differently than previous 2D (i.e., confined) currents. Specifically, whereas ambient temperature currents show radial dispersal patterns, buoyancy reversal, and liftoff of heated currents focuses dispersal along narrow axes beneath the rising plumes. The aspect ratios, defined as the current length divided by a characteristic width, are typically 2.5-3.5 in heated currents and 1.5-2.5 in ambient temperature currents, reflecting differences in dispersal between the two types of currents. Mechanisms of air entrainment differ greatly between the two currents: entrainment occurs primarily behind the heads and through the upper margins of ambient temperature currents, but heated currents entrain air through their lateral margins. That lateral entrainment is much more efficient than the vertical entrainment, >0.5 compared to ˜0.1, where entrainment is defined as the ratio of cross-stream to streamwise velocity. These experiments suggest that generation of coignimbrite plumes should focus PDCs along narrow transport axes, resulting in elongate rather than radial deposits.

  18. Critical masses of highly enriched uranium diluted with matrix material

    SciTech Connect

    Sanchez, R.; Kimpland, R.; Jaegers, P.; Butterfield, K.; Casson, W.; Bounds, J.; Myers, W.; Densmore, J. Rendon, G.

    2000-07-01

    Radioactive waste containing fissile material is frequently encountered in decontamination and decommissioning activities. Most of this waste is placed in containers or drums and stored in storage facilities. The amount of fissile material in each drum is generally small because criticality safety limits have been calculated with computer transport codes utilizing cross-section sections with large uncertainties. To the best of their knowledge, no experimental critical mass data are available to ensure the correctness of these calculations or any calculations for systems containing fissile material ({sup 235}U, {sup 239}Pu, or {sup 233}U) in contact with matrix material such as Al{sub 2}O{sub 3}, CaO, SiO{sub 2}, Al, MgO, etc. The experiments discussed in this paper establish the critical masses of highly enriched uranium foils diluted in various X/{sup 235}U ratios with polyethylene and SiO{sub 2}, polyethylene and aluminum, and polyethylene and MgO. In addition, these critical mass experimental data will be used to validate computer transport codes and cross-section data.

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

    SciTech Connect

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

    1990-12-31

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

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

    SciTech Connect

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

    1990-01-01

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

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

    ERIC Educational Resources Information Center

    Hill, Devon W.; And Others

    1988-01-01

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

  2. Total body water and lean body mass estimated by ethanol dilution

    NASA Technical Reports Server (NTRS)

    Loeppky, J. A.; Myhre, L. G.; Venters, M. D.; Luft, U. C.

    1977-01-01

    A method for estimating total body water (TBW) using breath analyses of blood ethanol content is described. Regression analysis of ethanol concentration curves permits determination of a theoretical concentration that would have existed if complete equilibration had taken place immediately upon ingestion of the ethanol; the water fraction of normal blood may then be used to calculate TBW. The ethanol dilution method is applied to 35 subjects, and comparison with a tritium dilution method of determining TBW indicates that the correlation between the two procedures is highly significant. Lean body mass and fat fraction were determined by hydrostatic weighing, and these data also prove compatible with results obtained from the ethanol dilution method. In contrast to the radioactive tritium dilution method, the ethanol dilution method can be repeated daily with its applicability ranging from diseased individuals to individuals subjected to thermal stress, strenuous exercise, water immersion, or the weightless conditions of space flights.

  3. Effects of Coaxial Air on Nitrogen-Diluted Hydrogen Jet Diffusion Flame Length and NOx Emission

    SciTech Connect

    Weiland, N.T.; Chen, R.-H.; Strakey, P.A.

    2007-10-01

    Turbulent nitrogen-diluted hydrogen jet diffusion flames with high velocity coaxial air flows are investigated for their NOx emission levels. This study is motivated by the DOE turbine program’s goal of achieving 2 ppm dry low NOx from turbine combustors running on nitrogen-diluted high-hydrogen fuels. In this study, effects of coaxial air velocity and momentum are varied while maintaining low overall equivalence ratios to eliminate the effects of recirculation of combustion products on flame lengths, flame temperatures, and resulting NOx emission levels. The nature of flame length and NOx emission scaling relationships are found to vary, depending on whether the combined fuel and coaxial air jet is fuel-rich or fuel-lean. In the absence of differential diffusion effects, flame lengths agree well with predicted trends, and NOx emissions levels are shown to decrease with increasing coaxial air velocity, as expected. Normalizing the NOx emission index with a flame residence time reveals some interesting trends, and indicates that a global flame strain based on the difference between the fuel and coaxial air velocities, as is traditionally used, is not a viable parameter for scaling the normalized NOx emissions of coaxial air jet diffusion flames.

  4. Microbial removal of alkanes from dilute gaseous waste streams: kinetics and mass transfer considerations.

    PubMed

    Barton, J W; Klasson, K T; Koran, L J; Davison, B H

    1997-01-01

    Treatment of dilute gaseous hydrocarbon waste streams remains a current need for many industries, particularly as increasingly stringent environmental regulations and oversight force emission reduction. Biofiltration systems hold promise for providing low-cost alternatives to more traditional, energy-intensive treatment methods such as incineration and adsorption. Elucidation of engineering principles governing the behavior of such systems, including mass transfer limitations, will broaden their applicability. Our processes exploit a microbial consortium to treat a mixture of 0.5% n-pentane and 0.5% isobutane in air. Since hydrocarbon gases are sparingly soluble in water, good mixing and high surface area between the gas and liquid phases are essential for biodegradation to be effective. One liquid-continuous columnar bioreactor was operated for more than 30 months with continued degradation of n-pentane and isobutane as sole carbon and energy sources. The maximum degradation rate observed in this gas-recycle system was 2 g of volatile organic compounds (VOC)/(m3.h). A trickle-bed bioreactor was operated continuously for over 24 months to provide a higher surface area (using a structured packing) with increased rates. Degradation rates consistently achieved were approximately 50 g of VOC/(m3.h) via single pass in this gas-continuous columnar system. Effective mass transfer coefficients comparable to literature values were also measured for this reactor; these values were substantially higher than those found in the gas-recycle reactor. Control of biomass levels was implemented by limiting the level of available nitrogen in the recirculating aqueous media, enabling long-term stability of reactor performance. PMID:9413140

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

    USGS Publications Warehouse

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

    1987-01-01

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

  6. Analysis of mass transfer performance in an air stripping tower

    SciTech Connect

    Chung, T.W.; Lai, C.H.; Wu, H.

    1999-10-01

    The carryover of working solution in a traditional stripping tower is of serious concern in real applications. A U-shaped spray tower to prevent carryover has been designed to study the stripping of water vapor from aqueous desiccant solutions of 91.8 to 95.8 wt% triethylene glycol. In this study, water vapor was removed from the diluted desiccant solution by heating the solution and stripping it with the ambient air. Therefore, the solution was concentrated to a desired concentration. This spray tower was capable of handling air flow rates from 3.2 to 5.13 kg/min and liquid flow rates from 1.6 to 2.76 kg/min. Since the literature data on air stripping towers are limited, studies on the mass transfer coefficient and other mass transfer parameters were carried out in this study. Under the operating conditions, the overall mass transfer coefficient calculated from the experimental data varied from 0.053 to 0.169 mol/m{sup 3}{center{underscore}dot}s. These corresponded to heights of a transfer unit of 2.3 to 0.71 m, respectively. The rates of stripping in this spray tower were typically varied from 2.28 to 12.15 kg H{sub 2}O/h. A correlation of the mass transfer coefficient for the air stripping process was also developed in this study.

  7. Hydrogen chloride partitioning in a Titan III exhaust cloud diluted with ambient air

    NASA Technical Reports Server (NTRS)

    Sebacher, D. I.; Wornom, D. E.; Bendura, R. J.

    1979-01-01

    Measurements and analysis are presented of the partitioning of HCl between hydrochloric acid aerosol and gaseous HCl in a Titan III exhaust cloud, as the cloud is diluted with humid ambient air. Partitioning was determined by measuring the gaseous HCl concentration with a recently developed airborne Gas Filter Correlation detector and simultaneously with a chemiluminescence detector which measures total HCl. Although equilibrium predictions for HCl aerosol formation indicated that no HCl aerosol should exist in the exhaust cloud for the meteorological conditions of this launch, the measurements indicated significant HCl aerosol formation. These measurements will provide verification for advanced modeling programs now under development.

  8. Total body skeletal muscle mass: estimation by creatine (methyl-d3) dilution in humans.

    PubMed

    Clark, Richard V; Walker, Ann C; O'Connor-Semmes, Robin L; Leonard, Michael S; Miller, Ram R; Stimpson, Stephen A; Turner, Scott M; Ravussin, Eric; Cefalu, William T; Hellerstein, Marc K; Evans, William J

    2014-06-15

    Current methods for clinical estimation of total body skeletal muscle mass have significant limitations. We tested the hypothesis that creatine (methyl-d3) dilution (D3-creatine) measured by enrichment of urine D3-creatinine reveals total body creatine pool size, providing an accurate estimate of total body skeletal muscle mass. Healthy subjects with different muscle masses [n = 35: 20 men (19-30 yr, 70-84 yr), 15 postmenopausal women (51-62 yr, 70-84 yr)] were housed for 5 days. Optimal tracer dose was explored with single oral doses of 30, 60, or 100 mg D3-creatine given on day 1. Serial plasma samples were collected for D3-creatine pharmacokinetics. All urine was collected through day 5. Creatine and creatinine (deuterated and unlabeled) were measured by liquid chromatography mass spectrometry. Total body creatine pool size and muscle mass were calculated from D3-creatinine enrichment in urine. Muscle mass was also measured by magnetic resonance imaging (MRI), dual-energy x-ray absorptiometry (DXA), and traditional 24-h urine creatinine. D3-creatine was rapidly absorbed and cleared with variable urinary excretion. Isotopic steady-state of D3-creatinine enrichment in the urine was achieved by 30.7 ± 11.2 h. Mean steady-state enrichment in urine provided muscle mass estimates that correlated well with MRI estimates for all subjects (r = 0.868, P < 0.0001), with less bias compared with lean body mass assessment by DXA, which overestimated muscle mass compared with MRI. The dilution of an oral D3-creatine dose determined by urine D3-creatinine enrichment provides an estimate of total body muscle mass strongly correlated with estimates from serial MRI with less bias than total lean body mass assessment by DXA.

  9. Expansion of mass-flowering crops leads to transient pollinator dilution and reduced wild plant pollination.

    PubMed

    Holzschuh, Andrea; Dormann, Carsten F; Tscharntke, Teja; Steffan-Dewenter, Ingolf

    2011-11-22

    Agricultural land use results in direct biodiversity decline through loss of natural habitat, but may also cause indirect cross-habitat effects on conservation areas. We conducted three landscape-scale field studies on 67 sites to test the hypothesis that mass flowering of oilseed rape (Brassica napus) results in a transient dilution of bees in crop fields, and in increased competition between crop plants and grassland plants for pollinators. Abundances of bumble-bees, which are the main pollinators of the grassland plant Primula veris, but also pollinate oilseed rape (OSR), decreased with increasing amount of OSR. This landscape-scale dilution affected bumble-bee abundances strongly in OSR fields and marginally in grasslands, where bumble-bee abundances were generally low at the time of Primula flowering. Seed set of Primula veris, which flowers during OSR bloom, was reduced by 20 per cent when the amount of OSR within 1 km radius increased from 0 to 15 per cent. Hence, the current expansion of bee-attractive biofuel crops results in transient dilution of crop pollinators, which means an increased competition for pollinators between crops and wild plants. In conclusion, mass-flowering crops potentially threaten fitness of concurrently flowering wild plants in conservation areas, despite the fact that, in the long run, mass-flowering crops can enhance abundances of generalist pollinators and their pollination service.

  10. Expansion of mass-flowering crops leads to transient pollinator dilution and reduced wild plant pollination

    PubMed Central

    Holzschuh, Andrea; Dormann, Carsten F.; Tscharntke, Teja; Steffan-Dewenter, Ingolf

    2011-01-01

    Agricultural land use results in direct biodiversity decline through loss of natural habitat, but may also cause indirect cross-habitat effects on conservation areas. We conducted three landscape-scale field studies on 67 sites to test the hypothesis that mass flowering of oilseed rape (Brassica napus) results in a transient dilution of bees in crop fields, and in increased competition between crop plants and grassland plants for pollinators. Abundances of bumble-bees, which are the main pollinators of the grassland plant Primula veris, but also pollinate oilseed rape (OSR), decreased with increasing amount of OSR. This landscape-scale dilution affected bumble-bee abundances strongly in OSR fields and marginally in grasslands, where bumble-bee abundances were generally low at the time of Primula flowering. Seed set of Primula veris, which flowers during OSR bloom, was reduced by 20 per cent when the amount of OSR within 1 km radius increased from 0 to 15 per cent. Hence, the current expansion of bee-attractive biofuel crops results in transient dilution of crop pollinators, which means an increased competition for pollinators between crops and wild plants. In conclusion, mass-flowering crops potentially threaten fitness of concurrently flowering wild plants in conservation areas, despite the fact that, in the long run, mass-flowering crops can enhance abundances of generalist pollinators and their pollination service. PMID:21471115

  11. Expansion of mass-flowering crops leads to transient pollinator dilution and reduced wild plant pollination.

    PubMed

    Holzschuh, Andrea; Dormann, Carsten F; Tscharntke, Teja; Steffan-Dewenter, Ingolf

    2011-11-22

    Agricultural land use results in direct biodiversity decline through loss of natural habitat, but may also cause indirect cross-habitat effects on conservation areas. We conducted three landscape-scale field studies on 67 sites to test the hypothesis that mass flowering of oilseed rape (Brassica napus) results in a transient dilution of bees in crop fields, and in increased competition between crop plants and grassland plants for pollinators. Abundances of bumble-bees, which are the main pollinators of the grassland plant Primula veris, but also pollinate oilseed rape (OSR), decreased with increasing amount of OSR. This landscape-scale dilution affected bumble-bee abundances strongly in OSR fields and marginally in grasslands, where bumble-bee abundances were generally low at the time of Primula flowering. Seed set of Primula veris, which flowers during OSR bloom, was reduced by 20 per cent when the amount of OSR within 1 km radius increased from 0 to 15 per cent. Hence, the current expansion of bee-attractive biofuel crops results in transient dilution of crop pollinators, which means an increased competition for pollinators between crops and wild plants. In conclusion, mass-flowering crops potentially threaten fitness of concurrently flowering wild plants in conservation areas, despite the fact that, in the long run, mass-flowering crops can enhance abundances of generalist pollinators and their pollination service. PMID:21471115

  12. Automated isotope dilution liquid chromatography-tandem mass spectrometry with on-line dilution and solid phase extraction for the measurement of cortisol in human serum sample.

    PubMed

    Kawaguchi, Migaku; Eyama, Sakae; Takatsu, Akiko

    2014-08-01

    A candidate reference measurement procedure involving automated isotope dilution coupled with liquid chromatography-tandem mass spectrometry (ID-LC-MS/MS) with on-line dilution and solid phase extraction (SPE) has been developed and critically evaluated. We constructed the LC-MS/MS with on-line dilution and SPE system. An isotopically labelled internal standard, cortisol-d4, was added to serum sample. After equilibration, the methanol was added to the sample, and deproteination was performed. Then, the sample was applied to the LC-MS/MS system. The limit of detection (LOD) and limit of quantification (LOQ) were 0.2 and 1ngg(-1), respectively. Excellent precision was obtained with within-day variation (RSD) of 1.9% for ID-LC-MS/MS analysis (n=6). This method, which demonstrates simple, easy, good accuracy, high precision, and is free from interferences from structural analogues, qualifies as a reference measurement procedure.

  13. Determination of perchlorate in infant formula by isotope dilution ion chromatography/tandem mass spectrometry

    PubMed Central

    Wang, Z.; Lau, B.P.-Y.; Tague, B.; Sparling, M.; Forsyth, D.

    2011-01-01

    A sensitive and selective isotope dilution ion chromatography/tandem mass spectrometry (ID IC-MS/MS) method was developed and validated for the determination of perchlorate in infant formula. The perchlorate was extracted from infant formula by using 20 ml of methanol and 5 ml of 1% acetic acid. All samples were spiked with 18O4 isotope-labelled perchlorate internal standard prior to extraction. After purification on a graphitised carbon solid-phase extraction column, the extracts were injected into an ion chromatography system equipped with an Ionpac AS20 column for separation of perchlorate from other anions. The presence of perchlorate in samples was quantified by isotope dilution mass spectrometry. Analysis of both perchlorate and its isotope-labelled internal standard was carried out on a Waters Quattro Ultima triple quadrupole mass spectrometer operating in a multiple reaction monitoring (MRM) negative ionisation mode. The method was validated for linearity and range, accuracy, precision, sensitivity, and matrix effects. The limit of quantification (LOQ) was 0.4 μg 1−1 for liquid infant formula and 0.95 μg kg−1 for powdered infant formula. The recovery ranged from 94% to 110% with an average of 98%. This method was used to analyse 39 infant formula, and perchlorate concentrations ranging from

  14. Simplified preparation of TO14 and Title III air toxic standards using a Windows software package and dynamic dilution schemes

    SciTech Connect

    Cardin, D.B.; Galoustian, E.A.

    1994-12-31

    The preparation of Air Toxic standards in the laboratory can be performed using several methods. These include injection of purge and trap standards, static dilution from pure compounds, and dynamic dilution from NIST traceable standards. A software package running under Windows has been developed that makes calculating dilution parameters for even complex mixtures fast and simple. Compound parameters such are name, molecular weight, boiling point, and density are saved in a data base for later access. Gas and liquid mixtures can be easily defined and saved as an inventory item, with preparation screens that calculate appropriate transfer volumes of each analyte. These mixtures can be utilized by both the static and dynamic dilution analysis windows to calculate proper flow rates and injection volumes for obtaining requested concentrations. A particularly useful approach for making accurate polar VOC standards will be presented.

  15. Investigating Mass Transport Limitations on Xylan Hydrolysis During Dilute Acid Pretreatment of Poplar

    SciTech Connect

    Mittal, Ashutosh; Pilath, Heid M.; Parent, Yves; Chatterjee, Siddharth G.; Donohoe, Bryon S.; Yarbrough, John M.; Himmel, Michael E.; Nimlos, Mark R.; Johnson, David K.

    2014-04-28

    Mass transport limitations could be an impediment to achieving high sugar yields during biomass pretreatment and thus be a critical factor in the economics of biofuels production. The objective of this work was to study the mass transfer restrictions imposed by the structure of biomass on the hydrolysis of xylan during dilute acid pretreatment of biomass. Mass transfer effects were studied by pretreating poplar wood at particle sizes ranging from 10 micrometers to 10 mm. This work showed a significant reduction in the rate of xylan hydrolysis in poplar when compared to the intrinsic rate of hydrolysis for isolated xylan that is possible in the absence of mass transfer. In poplar samples we observed no significant difference in the rates of xylan hydrolysis over more than two orders of magnitude in particle size. It appears that no additional mass transport restrictions are introduced by increasing particle size from 10 micrometers to 10 mm. This work suggests that the rates of xylan hydrolysis in biomass particles are limited primarily by the diffusion of hydrolysis products out of plant cell walls. A mathematical description is presented to describe the kinetics of xylan hydrolysis that includes transport of the hydrolysis products through biomass into the bulk solution. The modeling results show that the effective diffusion coefficient of the hydrolysis products in the cell wall is several orders of magnitude smaller than typical values in other applications signifying the role of plant cell walls in offering resistance to diffusion of the hydrolysis products.

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  17. Iodine determination in food samples using inductively coupled plasma isotope dilution mass spectrometry.

    PubMed

    Rädlinger, G; Heumann, K G

    1998-06-01

    Two different sample treatment methods are used in connection with inductively coupled plasma isotope dilution mass spectrometry for accurate and precise determinations of iodine traces in food samples. 129I-enriched iodate is applied as a spike compound for the isotope dilution step. Extraction of iodine by tetramethylammonium hydroxide (TMAH) solution at high temperatures in a closed vessel is one of the sample treatment methods. The other one is a complete decomposition of the sample with a mixture of perchloric acid and nitric acid using microwave assistance. By analyzing different certified reference materials (three milk powders with different iodine levels, BCR CRM 63, 150, and 151; bovine liver BCR CRM 185), the accuracy of ICP-IDMS with both sample treatment methods could be demonstrated. The relative standard deviation was typically in the range of 0.6-2.8% for iodine concentrations between 0.1 microgram g-1 and 5 micrograms g-1. The detection limit was 8 ng g-1 using sample weights of 0.8 g. In a round robin test, using two different types of infant food samples, the results of the two ICP-IDMS methods and of an ICP-MS method without the isotope dilution technique, but applying the TMAH extraction procedure, agree very well with the mean of results of all participating laboratories also using ICP-MS/TMAH. However, the ICP-IDMS method is faster, more precise, widely independent of matrix effects, and, therefore, relatively accurate, which makes this method especially attractive for use as a routine method.

  18. Quantitative Fourier transform ion cyclotron resonance mass spectrometry--the determination of creatinine by isotope dilution mass spectrometry.

    PubMed

    Bristow, Tony; Stokes, Peter; O'Connor, Gavin

    2005-01-01

    Accurate quantitation has been demonstrated on many different types of mass spectrometer. However, quantitative applications of Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) have been limited. In this study, the quantitative potential of FTICRMS has been investigated using an exact matching isotope dilution method for the determination of creatinine in serum. Creatinine is an important clinical biomarker and its measurement is used as an assessment of renal function. The quantitation of creatinine was selected because a high-accuracy high-performance liquid chromatography/mass spectrometry (HPLC/MS) determination using a triple quadrupole mass spectrometer has already been successfully developed in-house. Therefore, a direct comparison of the quantitative capability of FTICRMS could be made against an established method. The accuracy of the quantitation of creatinine was found to be equivalent to that obtained using LC/MS. However, the expanded measurement uncertainty (k = 2) was larger, at 6%, when using FTICRMS compared with 1% when using HPLC/MS with the triple quadrupole mass spectrometer.

  19. Evaluation of online carbon isotope dilution mass spectrometry for the purity assessment of synthetic peptide standards.

    PubMed

    Cueto Díaz, Sergio; Ruiz Encinar, Jorge; García Alonso, J Ignacio

    2014-09-24

    We present a novel method for the purity assessment of peptide standards which is applicable to any water soluble peptide. The method is based on the online (13)C isotope dilution approach in which the peptide is separated from its related impurities by liquid chromatography (LC) and the eluent is mixed post-column with a continuous flow of (13)C-enriched sodium bicarbonate. An online oxidation step using sodium persulfate in acidic media at 99°C provides quantitative oxidation to (12)CO2 and (13)CO2 respectively which is extracted to a gaseous phase with the help of a gas permeable membrane. The measurement of the isotope ratio 44/45 in the mass spectrometer allows the construction of the mass flow chromatogram. As the only species that is finally measured in the mass spectrometer is CO2, the peptide content in the standard can be quantified, on the base of its carbon content, using a generic primary standard such as potassium hydrogen phthalate. The approach was validated by the analysis of a reference material (NIST 8327), and applied to the quantification of two commercial synthetic peptide standards. In that case, the results obtained were compared with those obtained using alternative methods, such as amino acid analysis and ICP-MS. The results obtained proved the value of the method for the fast, accurate and precise mass purity assignment of synthetic peptide standards. PMID:25172815

  20. Evaluation of online carbon isotope dilution mass spectrometry for the purity assessment of synthetic peptide standards.

    PubMed

    Cueto Díaz, Sergio; Ruiz Encinar, Jorge; García Alonso, J Ignacio

    2014-09-24

    We present a novel method for the purity assessment of peptide standards which is applicable to any water soluble peptide. The method is based on the online (13)C isotope dilution approach in which the peptide is separated from its related impurities by liquid chromatography (LC) and the eluent is mixed post-column with a continuous flow of (13)C-enriched sodium bicarbonate. An online oxidation step using sodium persulfate in acidic media at 99°C provides quantitative oxidation to (12)CO2 and (13)CO2 respectively which is extracted to a gaseous phase with the help of a gas permeable membrane. The measurement of the isotope ratio 44/45 in the mass spectrometer allows the construction of the mass flow chromatogram. As the only species that is finally measured in the mass spectrometer is CO2, the peptide content in the standard can be quantified, on the base of its carbon content, using a generic primary standard such as potassium hydrogen phthalate. The approach was validated by the analysis of a reference material (NIST 8327), and applied to the quantification of two commercial synthetic peptide standards. In that case, the results obtained were compared with those obtained using alternative methods, such as amino acid analysis and ICP-MS. The results obtained proved the value of the method for the fast, accurate and precise mass purity assignment of synthetic peptide standards.

  1. Mass-flowering crops dilute pollinator abundance in agricultural landscapes across Europe.

    PubMed

    Holzschuh, Andrea; Dainese, Matteo; González-Varo, Juan P; Mudri-Stojnić, Sonja; Riedinger, Verena; Rundlöf, Maj; Scheper, Jeroen; Wickens, Jennifer B; Wickens, Victoria J; Bommarco, Riccardo; Kleijn, David; Potts, Simon G; Roberts, Stuart P M; Smith, Henrik G; Vilà, Montserrat; Vujić, Ante; Steffan-Dewenter, Ingolf

    2016-10-01

    Mass-flowering crops (MFCs) are increasingly cultivated and might influence pollinator communities in MFC fields and nearby semi-natural habitats (SNHs). Across six European regions and 2 years, we assessed how landscape-scale cover of MFCs affected pollinator densities in 408 MFC fields and adjacent SNHs. In MFC fields, densities of bumblebees, solitary bees, managed honeybees and hoverflies were negatively related to the cover of MFCs in the landscape. In SNHs, densities of bumblebees declined with increasing cover of MFCs but densities of honeybees increased. The densities of all pollinators were generally unrelated to the cover of SNHs in the landscape. Although MFC fields apparently attracted pollinators from SNHs, in landscapes with large areas of MFCs they became diluted. The resulting lower densities might negatively affect yields of pollinator-dependent crops and the reproductive success of wild plants. An expansion of MFCs needs to be accompanied by pollinator-supporting practices in agricultural landscapes.

  2. Mass-flowering crops dilute pollinator abundance in agricultural landscapes across Europe.

    PubMed

    Holzschuh, Andrea; Dainese, Matteo; González-Varo, Juan P; Mudri-Stojnić, Sonja; Riedinger, Verena; Rundlöf, Maj; Scheper, Jeroen; Wickens, Jennifer B; Wickens, Victoria J; Bommarco, Riccardo; Kleijn, David; Potts, Simon G; Roberts, Stuart P M; Smith, Henrik G; Vilà, Montserrat; Vujić, Ante; Steffan-Dewenter, Ingolf

    2016-10-01

    Mass-flowering crops (MFCs) are increasingly cultivated and might influence pollinator communities in MFC fields and nearby semi-natural habitats (SNHs). Across six European regions and 2 years, we assessed how landscape-scale cover of MFCs affected pollinator densities in 408 MFC fields and adjacent SNHs. In MFC fields, densities of bumblebees, solitary bees, managed honeybees and hoverflies were negatively related to the cover of MFCs in the landscape. In SNHs, densities of bumblebees declined with increasing cover of MFCs but densities of honeybees increased. The densities of all pollinators were generally unrelated to the cover of SNHs in the landscape. Although MFC fields apparently attracted pollinators from SNHs, in landscapes with large areas of MFCs they became diluted. The resulting lower densities might negatively affect yields of pollinator-dependent crops and the reproductive success of wild plants. An expansion of MFCs needs to be accompanied by pollinator-supporting practices in agricultural landscapes. PMID:27531385

  3. Indicator dilution measurements of lung volumes and alveolar air exchange during breathing.

    PubMed

    Hechtman, H B; Reid, M H; Dorn, B C; Weisel, R D

    1973-05-01

    A new triple tracer indicator dilution technique has been used to measure alveolar ventilation as well as air and tissue volumes in the lungs of experimental animals and man. The tracers indocyanine green, [(121)I]antipyrine and xenon-133 were rapidly injected into the right atrium, while sampling was carried out from a peripheral artery. Blood flow and tissue volumes were obtained by classical analysis of the indocyanine green and antipyrine concentration-time curves. A double exit-port, constant air flow model was used to analyze the xenon curves, because ventilatory loss led to incomplete recovery of the gas tracer in effluent blood. Uniform ventilation and perfusion were assumed. This analysis permitted calculation of alveolar ventilation (VA(Xe)) and functional residual capacity (FRC(Xe)) during normal breathing. In control studies, VA(Xe) was similar to VA(co2), obtained with the steady-state CO(2) method (r = 0.87), while in critically ill patients the xenon measurement was significantly lower, averaging 54% of VA(co2). In theory, underestimates in VA(Xe) and decrease in the ratio VA(Xe)/VA(co2) relate to nonuniformity in regional ventilation and perfusion. The effect is greatest for the slightly soluble gas, xenon. The significant inverse correlation between VA(Xe)/VA(co2) and the physiologic shunt is consistent with this postulate.FRC(Xe) was similar to the predicted FRC in animals but was 76% of the helium measured FRC in patients. FRC(Xe) was significantly lower than the xenon measured air volumes during breath-holding when nonuniformity of ventilation was not operative. Lung tissue volumes in animals were 83% of gravimetric lung weights, while in patients the volumes were much lower than predicted. Nonhomogeneous lung function, including failure to perfuse the entire capillary bed, with resultant incomplete penetration of tracers into all segments of lung air and tissue, may explain these findings. The resultant errors can be significant in sick

  4. Validation of New Instrumentation for Isotope Dilution Mass Spectrometric Determination of Organic Serum Analytes

    PubMed Central

    Ellerbe, P.; Phinney, C. S.; Sniegoski, L. T.; Welch, M. J.

    1999-01-01

    A major activity in the 20 year collaboration between the Analytical Chemistry Division at NIST and the College of American Pathologists (CAP) has been the development of highly accurate and precise “definitive” methods for important clinical analytes in human serum. Definitive methods for organic analytes use isotope dilution/gas chromatography/mass spectrometry and require a mass spectrometer capable of making highly precise measurements of the ratio between the ion intensities of a characteristic ion from the analyte of interest and its stable-isotope-labeled analog. Recently, the mass spectrometer used for 20 years for definitive method development and measurements was replaced with a modern instrument capable of automated operation, with accompanying gains in convenience and sample throughput. Switching to the new instrument required modifications of measurement protocols, acceptance criteria, and ratio calculations with background corrections to go along with automated instrument operation. Results demonstrated that the two instruments gave comparable results for measurements of both urea and cholesterol in samples from various serum-based Standard Reference Materials [SRMs] and College of American Pathologists materials.

  5. Detection and quantification of ricin in beverages using isotope dilution tandem mass spectrometry.

    PubMed

    McGrath, Sara C; Schieltz, David M; McWilliams, Lisa G; Pirkle, James L; Barr, John R

    2011-04-15

    The toxic plant protein ricin has gained notoriety due to wide availability and potential use as a bioterrorism agent, with particular concern for food supply contamination. We have developed a sensitive and selective mass spectrometry-based method to detect ricin in tap water, 2% milk, apple juice, and orange juice. Ricin added to beverage matrices was extracted using antibody-bound magnetic beads and digested with trypsin. Absolute quantification was performed using isotope dilution mass spectrometry with a linear ion trap operating in product-ion-monitoring mode. The method allows for identification of ricin A chain and B chain and for distinction of ricin from ricin agglutinin within a single analytical run. Ricin-bound beads were also tested for deadenylase activity by incubation with a synthetic ssDNA oligomer. Depurination of the substrate by ricin was confirmed by matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOFMS). This method was used successfully to extract ricin from each beverage matrix. The activity of recovered ricin was assessed, and quantification was achieved, with a limit of detection of 10 fmol/mL (0.64 ng/mL). PMID:21428278

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

    SciTech Connect

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

    1990-02-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    SciTech Connect

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

    1991-01-01

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

  9. Sooting Limits Of Diffusion Flames With Oxygen-Enriched Air And Diluted Fuel

    NASA Technical Reports Server (NTRS)

    Sunderland, P. B.; Urban, D. L.; Stocker, D. P.; Chao, B. H.; Axelbaum, R. L.

    2003-01-01

    Oxygen-enhanced combustion permits certain benefits and flexibility that are not otherwise available in the design of practical combustors, as discussed by Baukal. The cost of pure and enriched oxygen has declined to the point that oxygen-enhanced combustion is preferable to combustion in air for many applications. Carbon sequestration is greatly facilitated by oxygen enrichment because nitrogen can be eliminated from the product stream. For example, when natural gas (or natural gas diluted with CO2) is burned in pure oxygen, the only significant products are water and CO2. Oxygen-enhanced combustion also has important implications for soot formation, as explored in this work. We propose that soot inception in nonpremixed flames requires a region where C/O ratio, temperature, and residence time are above certain critical values. Soot does not form at low temperatures, with the threshold in nonpremixed flames ranging from about 1250-1650 K, a temperature referred to here as the critical temperature for soot inception, Tc. Soot inception also can be suppressed when residence time is short (equivalently, when the strain rate in counterflow flames is high). Soot induction times of 0.8-15 ms were reported by Tesner and Shurupov for acetylene/nitrogen mixtures at 1473 K. Burner stabilized spherical microgravity flames are employed in this work for two main reasons. First, this configuration offers unrestricted control over convection direction. Second, in steady state these flames are strain-free and thus can yield intrinsic sooting limits in diffusion flames, similar to the way past work in premixed flames has provided intrinsic values of C/O ratio associated with soot inception limits.

  10. The Effective Mass of a Ball in the Air

    ERIC Educational Resources Information Center

    Messer, J.; Pantaleone, J.

    2010-01-01

    The air surrounding a projectile affects the projectile's motion in three very different ways: the drag force, the buoyant force, and the added mass. The added mass is an increase in the projectile's inertia from the motion of the air around it. Here we experimentally measure the added mass of a spherical projectile in air. The results agree well…

  11. A Computational and Experimental Study of Coflow Laminar Methane/Air Diffusion Flames: Effects of Fuel Dilution, Inlet Velocity, and Gravity

    NASA Technical Reports Server (NTRS)

    Cao, S.; Ma, B.; Bennett, B. A. V.; Giassi, D.; Stocker, D. P.; Takahashi, F.; Long, M. B.; Smooke, M. D.

    2014-01-01

    The influences of fuel dilution, inlet velocity, and gravity on the shape and structure of laminar coflow CH4-air diffusion flames were investigated computationally and experimentally. A series of nitrogen-diluted flames measured in the Structure and Liftoff in Combustion Experiment (SLICE) on board the International Space Station was assessed numerically under microgravity (mu g) and normal gravity (1g) conditions with CH4 mole fraction ranging from 0.4 to 1.0 and average inlet velocity ranging from 23 to 90 cm/s. Computationally, the MC-Smooth vorticity-velocity formulation was employed to describe the reactive gaseous mixture, and soot evolution was modeled by sectional aerosol equations. The governing equations and boundary conditions were discretized on a two-dimensional computational domain by finite differences, and the resulting set of fully coupled, strongly nonlinear equations was solved simultaneously at all points using a damped, modified Newton's method. Experimentally, flame shape and soot temperature were determined by flame emission images recorded by a digital color camera. Very good agreement between computation and measurement was obtained, and the conclusions were as follows. (1) Buoyant and nonbuoyant luminous flame lengths are proportional to the mass flow rate of the fuel mixture; computed and measured nonbuoyant flames are noticeably longer than their 1g counterparts; the effect of fuel dilution on flame shape (i.e., flame length and flame radius) is negligible when the flame shape is normalized by the methane flow rate. (2) Buoyancy-induced reduction of the flame radius through radially inward convection near the flame front is demonstrated. (3) Buoyant and nonbuoyant flame structure is mainly controlled by the fuel mass flow rate, and the effects from fuel dilution and inlet velocity are secondary.

  12. Serum/plasma methylmercury determination by isotope dilution gas chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Baxter, Douglas C; Faarinen, Mikko; Österlund, Heléne; Rodushkin, Ilia; Christensen, Morten

    2011-09-01

    A method for the determination of methylmercury in plasma and serum samples was developed. The method uses isotope dilution with (198)Hg-labeled methylmercury, extraction into dichloromethane, back-extraction into water, aqueous-phase ethylation, purge and trap collection, thermal desorption, separation by gas chromatography, and mercury isotope specific detection by inductively coupled plasma mass spectrometry. By spiking 2 mL sample with 1.2 ng tracer, measurements in a concentration interval of (0.007-2.9) μg L(-1) could be performed with uncertainty amplification factors <2. A limit of quantification of 0.03 μg L(-1) was estimated at 10 times the standard deviation of concentrations measured in preparation blanks. Within- and between-run relative standard deviations were <10% at added concentration levels of 0.14 μg L(-1), 0.35 μg L(-1) and 2.8 μg L(-1), with recoveries in the range 82-110%. Application of the method to 50 plasma/serum samples yielded a median (mean; range) concentration of methylmercury of 0.081 (0.091; <0.03-0.19) μg L(-1). This is the first time methylmercury has been directly measured in this kind of specimen, and is therefore the first estimate of a reference range.

  13. Quantitation of Thioprolines in Grape Wine by Isotope Dilution-Liquid Chromatography-Tandem Mass Spectrometry.

    PubMed

    Liu, Jingjing; Meng, Xiangpeng; Chan, Wan

    2016-02-17

    Cysteine reacts with reactive carbonyls to form thioprolines, which have been demonstrated to possess various pharmaceutical properties. Therefore, thioproline formation is considered as a major detoxification pathway for carcinogenic reactive carbonyls. In this study, we report the initial identification of thiazolidine-4-carboxylic acid (1) and 2-methylthiazolidine-4-carboxylic acid (2), two very common thioprolines, formed by reacting formaldehyde and acetaldehyde with cysteine in grape wine samples. We have developed an isotope dilution-liquid chromatography-tandem mass spectrometry method featuring high sensitivity (limit of detection of ≤1.5 ng/mL) and selectivity to quantitate compounds 1 and 2. The method after validated to be highly accurate (recovery of ≥92%) and precise [intraday relative standard deviation (RSD) of ≤4.1% and interday RSD of ≤9.7%] was applied to determine the varying compound 1 and 2 contents in grape wine samples. Results revealed the grape type and storage duration-dependent formation of thioprolines in grape wines. Overall, the results are expected to facilitate compound-dependent investigations of the health benefits of grape wine, and our findings could be adopted to predict the age of grape wine.

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

    PubMed

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

    2006-08-01

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

  15. Quantification of influenza virus hemagglutinins in complex mixtures using isotope dilution tandem mass spectrometry.

    PubMed

    Williams, Tracie L; Luna, Leah; Guo, Zhu; Cox, Nancy J; Pirkle, James L; Donis, Ruben O; Barr, John R

    2008-05-12

    Influenza vaccination is the primary method for preventing influenza and its severe complications. Licensed inactivated vaccines for seasonal or pandemic influenza are formulated to contain a preset amount of hemagglutinin (HA), the critical antigen to elicit protection. Current methods to establish the HA concentration of vaccines rely on indirect measurements that are subject to considerable experimental variability. We present a liquid chromatography-tandem mass spectrometry (LC/MS/MS) method for the absolute quantification of viral proteins in a complex mixture. Through use of an isotope dilution approach, HA from viral subtypes H1, H3, H5, and B was determined both directly and rapidly. This method can be applied to purified virus preparations, to monovalent bulk concentrates, or to trivalent inactivated influenza vaccines with improved speed, sensitivity, precision, and accuracy. This LC/MS/MS approach may substantially increase the reliability of methods used to quantitate the amount of antigen in seasonal and pandemic influenza vaccines and reduce the time and effort to deliver influenza vaccines for public health use during the next influenza pandemic.

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

    PubMed

    Ren, Yao; Walczyk, Thomas

    2014-09-01

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

  17. A generalized mass transfer law unifying various particle transport mechanisms in dilute dispersions

    NASA Astrophysics Data System (ADS)

    Guha, Abhijit

    2008-09-01

    A generalized mass transfer law for dilute dispersion of particles (or droplets) of any sizes suspended in a fluid has been described, which can be applied to turbulent or laminar flow. The generalized law reduces to the Fick’s law of diffusion in the limit of very small particles. Thus the study shows how the well-known and much-used Fick’s law of diffusion fits into the broader context of particle transport. The general expression for particle flux comprises a diffusive flux due to Brownian motion and turbulent fluctuation, a diffusive flux due to temperature gradient (thermophoresis plus stressphoresis) and a convective flux that arises primarily due to the interaction of particle inertia and the inhomogeneity of the fluid turbulence field (turbophoresis). Shear-induced lift force, electrical force, gravity, etc. also contribute to the convective flux. The present study includes the effects of surface roughness, and the calculations show that the presence of small surface roughness even in the hydraulically smooth regime significantly enhances deposition especially of small particles. Thermophoresis can have equally strong effects, even with a modest temperature difference between the wall and the bulk fluid. For particles of the intermediate size range, turbophoresis, thermophoresis and roughness are all important contributors to the overall deposition rate. The paper includes a parametric study of the effects of electrostatic forces due to mirror charging. The present work provides a unified framework to determine the combined effect of various particle transport mechanisms on mass transfer rate and the inclusion of other mechanisms not considered in this paper is possible.

  18. Simultaneous quantification of hemagglutinin and neuraminidase of influenza virus using isotope dilution mass spectrometry.

    PubMed

    Williams, Tracie L; Pirkle, James L; Barr, John R

    2012-03-23

    Influenza vaccination is the primary method for preventing influenza and its severe complications. Licensed inactivated vaccines for seasonal or pandemic influenza are formulated to contain a preset amount of hemagglutinin (HA), the critical antigen to elicit protection. There is currently no regulatory method that quantifies neuraminidase (NA), the other major membrane-bound protein thought to have protective capability. This is primarily due to the limitations both in sensitivity and in selectivity of current means to quantify these antigens. Current methods to establish the HA concentration of vaccines rely on indirect measurements that are subject to considerable experimental variability. We present a liquid chromatography-tandem mass spectrometry (LC/MS/MS) method for the absolute quantification of viral proteins in a complex mixture. Through use of an isotope dilution approach, HA and NA from viral subtypes H1N1, H3N2, and B were determined both directly and rapidly. Three peptides of each subtype were used in the analysis of HA to ensure complete digestion of the protein and accuracy of the measurement. This method has been applied to purified virus preparations, to monovalent bulk concentrates, to trivalent inactivated influenza vaccines, and even crude allantoic fluid with improved speed, sensitivity, precision, and accuracy. Detection of 1 μg/mL of protein is easily obtained using this method. The sensitivity of the method covers the range expected in vaccine preparations, including adjuvant-based vaccine. This LC/MS/MS approach substantially increases the selectivity, accuracy and precision used to quantify the amount of viral proteins in seasonal and pandemic influenza vaccines and reduce the time and effort to deliver influenza vaccines for public health use during the next influenza pandemic.

  19. Determination of trace iron in zirconium by isotope dilution-thermal ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Elliot, N. L.; Campbell, M. A.; Green, L. W.

    1995-08-01

    An isotope dilution-thermal ionization mass spectrometry method for the determination of parts-per-million levels of iron in zirconium is required for precise, accurate analyses in studies of the effects of iron on the irradiation deformation of nuclear alloys. A two-stage purification procedure was developed to avoid the signal suppression and interference caused by the zirconium matrix. After sample dissolution and spiking with 54Fe, the bulk of the zirconium is removed by ion exchange chromatography, and the eluted Fe(III) is further purified by micro-solvent extraction into tributyl phosphate-impregnated resin beads. The iron is back-extracted, submicrogram amounts are loaded onto previously outgassed zone-refined Re filaments, and 54/56 ratios are measured at 1170°C. A silica gel/boric acid ionization enhancer is used to obtain stable Fe+ currents as strong as 2 × 10-14. A from nanogram loadings of pure iron. The procedural blank of 20 ± 6 ng is sufficiently low to allow determination of ppm levels of iron in 0.1 g zirconium samples. The analyses of solution standards showed agreement within 2% between measured and expected values, and a good fit, r2 = 0.99997, to a linear regression. The analyses of metal standards exhibited a similar good fit to a linear regression of measured against expected values, and showed good agreement with other methods. The method meets the requirements for zirconium metallurgical studies, and may be extended to other applications.

  20. Symptomatic Effects of Exposure to Diluted Air Sampled from a Swine Confinement Atmosphere on Healthy Human Subjects

    PubMed Central

    Schiffman, Susan S.; Studwell, Clare E.; Landerman, Lawrence R.; Berman, Katherine; Sundy, John S.

    2005-01-01

    Aerial emissions from a swine house at North Carolina State University’s field laboratory were diluted to a level that could occur at varying distances downwind from a confined animal feeding operation (CAFO) both within and beyond the property line, and these emissions were delivered to an environmental exposure chamber. The study design consisted of two 1-hr sessions, one in which 48 healthy human adult volunteers were exposed to diluted swine air and another in which they were exposed to clean air (control). Objective measures of blood pressure, temperature, heart rate, respiratory rate, lung function, nasal inflammation, secretory immunity, mood, attention, and memory were correlated with objective measures of air quality. Ratings of perceived (self-reported) health symptoms were also obtained. The mean levels of airborne constituents in the swine air condition were hydrogen sulfide (24 ppb), ammonia (817 ppb), total suspended particulates (0.0241 mg/m3), endotoxin (7.40 endotoxin units/m3), and odor (57 times above odor threshold). No statistical differences on objective measures of physical symptoms, mood, or attention resulted from the 1-hr exposure to swine emissions in the environmental chamber when compared with clean air for healthy human volunteers. However, subjects were 4.1 (p = 0.001) times more likely to report headaches, 6.1 (p = 0.004) times more likely to report eye irritation, and 7.8 (p = 0.014) times more likely to report nausea in the swine air (experimental) condition than in the control condition. These results indicate that short-term exposure in an environmental chamber to malodorous emissions from a swine house at levels expected downwind can induce clinically important symptoms in healthy human volunteers. PMID:15866765

  1. Symptomatic effects of exposure to diluted air sampled from a swine confinement atmosphere on healthy human subjects.

    PubMed

    Schiffman, Susan S; Studwell, Clare E; Landerman, Lawrence R; Berman, Katherine; Sundy, John S

    2005-05-01

    Aerial emissions from a swine house at North Carolina State University's field laboratory were diluted to a level that could occur at varying distances downwind from a confined animal feeding operation (CAFO) both within and beyond the property line, and these emissions were delivered to an environmental exposure chamber. The study design consisted of two 1-hr sessions, one in which 48 healthy human adult volunteers were exposed to diluted swine air and another in which they were exposed to clean air (control). Objective measures of blood pressure, temperature, heart rate, respiratory rate, lung function, nasal inflammation, secretory immunity, mood, attention, and memory were correlated with objective measures of air quality. Ratings of perceived (self-reported) health symptoms were also obtained. The mean levels of airborne constituents in the swine air condition were hydrogen sulfide (24 ppb), ammonia (817 ppb), total suspended particulates (0.0241 mg/m3), endotoxin (7.40 endotoxin units/m3), and odor (57 times above odor threshold). No statistical differences on objective measures of physical symptoms, mood, or attention resulted from the 1-hr exposure to swine emissions in the environmental chamber when compared with clean air for healthy human volunteers. However, subjects were 4.1 (p = 0.001) times more likely to report headaches, 6.1 (p = 0.004) times more likely to report eye irritation, and 7.8 (p = 0.014) times more likely to report nausea in the swine air (experimental) condition than in the control condition. These results indicate that short-term exposure in an environmental chamber to malodorous emissions from a swine house at levels expected downwind can induce clinically important symptoms in healthy human volunteers. PMID:15866765

  2. Traceable values for nitrate in water samples by isotope dilution analysis using a small thermionic quadrupole mass spectrometer.

    PubMed

    Wolff, J C; Taylor, D P; De Bièvre, P

    1996-09-15

    An isotope dilution mass spectrometric procedure was developed for the determination of nitrate in water samples. The isotope dilution experiments were carried out using the Institute for Reference Materials and Measurements's 15N-enriched nitrate spike reference material IRMM-627. Nitrate was isolated from the matrix by precipitating it as nitron nitrate, from which emission of negative thermal NO2-ions was found to be best. The ions were produced in the ion source of a small, low-cost, easy-to-handle thermionic quadrupole mass spectrometer equipped with a secondary electron multiplier coupled to an ion counter. The procedure developed was applied to the measurement of nitrate in a certified reference material (stimulated rainwater, CRM 409 from Community Bureau of Reference), in sparkling mineral water, and in tap water. Results were compared with those obtained using ion chromatography. Good agreement (within 1%) was found between the concentration determined by isotope dilution mass spectrometry, the values from ion chromatography, and the certified value. The procedure developed allowed accurate and traceable determinations of nitrate in water samples, with an expanded uncertainty (coverage factor k = 2) of 2-5%, and the detection limit was found to be 2 mumol kg-1.

  3. Estimating lean mass over a wide range of body composition: a calibration of deuterium dilution in the arctic ground squirrel.

    PubMed

    Lee, Trixie N; Fridinger, Robert W; Barnes, Brian M; Loren Buck, C; O'Brien, Diane M

    2011-12-15

    Calculating body water through isotope dilution has become a useful way to nondestructively estimate body composition in many species. The most accurate estimates using this method require calibration against proximate chemical analysis of body composition for individual species, but no studies to our knowledge have calibrated this method on a hibernating mammal that seasonally undergoes dramatic changes in body composition. We use deuterium oxide to estimate total body water in captive arctic ground squirrels, Urocitellus parryii, and compare two approaches of calculating lean mass from total body water, both calibrated against lean mass based on proximate analysis. The first method uses a single tissue hydration constant to calculate lean mass from total body water; the second method uses a predictive equation to calculate lean mass from total body water and body mass. We found that the predictive equation performs better over the large range of body composition common to this species. Distillation of blood samples did not affect lean mass estimates from either calculation method. These findings indicate that isotope dilution using a predictive equation should work well as an alternative to destructive methods in other small mammals that undergo radical changes in body composition across their annual cycle.

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

    USGS Publications Warehouse

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

    1973-01-01

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

  5. Influence of Baseline Air Masses and Wildland Fires on Air Quality in the Western United States

    NASA Astrophysics Data System (ADS)

    Wigder, Nicole L.

    This dissertation focuses on several key uncertainties related to particulate matter (PM) and O3 concentrations in the western U.S. Each analysis conducted for this dissertation centers on data collected at the Mount Bachelor Observatory (MBO, 2.8 km a.s.l., 43.98° N, 121.69° W), a mountaintop research site in central Oregon, U.S. The first component of this dissertation is an analysis of the contribution of baseline O3 to observed O3 concentrations in two western U.S. urban areas, Enumclaw, Washington (WA) and Boise, Idaho, during 2004 -- 2010. I compared O3 data from two baseline sites (MBO and Cheeka Peak, WA) to O3 concentrations in the two urban areas on days when backward air mass trajectories showed transport between the baseline and urban sites. I found that the urban areas studied had relatively low O3 on the days with a strong influence from baseline air masses (28.3 -- 48.3 ppbv). These data suggested that there was low production of O3 from urban emissions on these days, which allowed me to quantify the impact of baseline O3 on urban O3 concentrations. A regression of the Boise and MBO O3 observations showed that free tropospheric air masses were diluted by 50% as they were entrained into the boundary layer at Boise. These air masses can contain high O3 concentrations (>70 ppbv) from Asian pollution sources or stratospheric intrusions, indicating that these sources can greatly contribute to urban surface O 3 concentrations. In addition, I found that the elevation and surface temperature of the urban areas studied impacted baseline O3 concentrations in these areas, with higher elevation and greater surface temperatures leading to greater O3 concentrations. The second and third components of this dissertation are analyses of the impact of wildland fires on PM and O3 concentrations in the western U.S. For both of these analyses, I calculated pollutant enhancement ratios for PM, O3, and other species in wildland fire plumes observed at MBO during 2004

  6. An application of nitrogen microwave-induced plasma mass spectrometry to isotope dilution analysis of selenium in marine organisms.

    PubMed

    Shirasaki, T; Yoshinaga, J; Morita, M; Okumoto, T; Oishi, K

    1996-01-01

    Nitrogen microwave-induced plasma mass spectrometry was studied for its applicability to the isotope dilution analysis of selenium in biological samples. Spectroscopic interference by calcium, which is present in high concentrations in biological samples, was investigated. No detectable background spectrum was observed for the major selenium isotopes of 78Se and 80Se. No detectable interferences by sodium, potassium, calcium and phosphorus on the isotope ratio 80Se/78Se were observed up to concentration of 200 mg/ml. The method was applied to the analysis of selenium in biological reference materials of marine organisms. The results showed good agreement between the certified and found values. PMID:8848792

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

    PubMed

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

    2014-06-18

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

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

    PubMed

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

    2010-10-01

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

  9. Improved measurement of iodine in food samples using inductively coupled plasma isotope dilution mass spectrometry.

    PubMed

    Haldimann, M; Eastgate, A; Zimmerli, B

    2000-11-01

    A new ICP-MS method for the determination of iodine in food samples is presented. The method makes use of a new miniature cyclonic spray chamber and a concentric glass nebulizer that is designed for low sample uptakes and is operated in a self-aspirating mode. As a consequence the wash-out was accelerated over conventional systems. This configuration allows the direct determination of iodine in mineralized solutions following digestion with nitric acid only. No strong oxidizing reagents such as perchloric acid or lengthy sample preparation were necessary to alter the chemical form of potentially volatile species. The isotope dilution technique using the long-lived isotope 129I was applied to obtain freedom from matrix effects. The present study reports on results for total iodine in selected nutritional and biological reference materials and makes a comparison with instrumental neutron activation analysis.

  10. Treatment of a dilute waste oil emulsion by chemical addition (CA)-dissolved air flotation (DAF)

    SciTech Connect

    Reed, B.E.; Carriere, P.; Zhu, X.; Lorkowski, T.

    1995-12-31

    Treatment of wastewater from aluminum rolling mill operations is an inherent problem in the aluminum fabrication industry. In this study, wastewater from the manufacturer`s processes was transferred to two holding ponds having a total capacity of about 5 million gallons and a detention time of about 10 days. In the holding ponds, free oil was allowed to rise to the surface where it was periodically removed. Wastewater from the holding ponds was withdrawn from about a depth of 9 ft. and used as influent to a variety of technologies. In this paper, results from the chemical addition (CA)-dissolved air flotation (DAF) portion of the treatability study are presented.

  11. Headspace stir bar sorptive extraction-gas chromatography/mass spectrometry characterization of the diluted vapor phase of cigarette smoke delivered to an in vitro cell exposure chamber.

    PubMed

    Kaur, Navneet; Cabral, Jean-Louis; Morin, André; Waldron, Karen C

    2011-01-14

    Advanced smoke generation systems, such as the Borgwaldt RM20S(®) smoking machine used in combination with the BAT exposure chamber, allow for the generation, dilution and delivery of fresh cigarette smoke to cell or tissue cultures for in vitro cell culture analyses. Recently, our group confirmed that the Borgwaldt RM20S(®) is a reliable tool to generate and deliver repeatable and reproducible exposure concentrations of whole smoke to in vitro cultures. However, the relationship between dose and diluted smoke components found within the exposure chamber has not been characterized. The current study focused on the development of a headspace stir bar sorptive extraction (HSSE) method to chemically characterize some of the vapor phase components of cigarette smoke generated by the Borgwaldt RM20S(®) and collected within a cell culture exposure chamber. The method was based on passive sampling within the chamber by HSSE using a Twister™ stir bar. Following exposure, sorbed analytes were recovered using a thermal desorption unit and a cooled injection system coupled to gas chromatograph/mass spectrometry for identification and quantification. Using the HSSE method, sixteen compounds were identified. The desorption parameters were assessed using ten reference compounds and the following conditions led to the maximal response: desorption temperature of 200°C for 2 min with cryofocussing temperature of -75°C. During transfer of the stir bars to the thermal desorption system, significant losses of analytes were observed as a function of time; therefore, the exposure-to-desorption time interval was kept at the minimum of 10±0.5 min. Repeatability of the HSSE method was assessed by monitoring five reference compounds present in the vapor phase (10.1-12.9% RSD) and n-butyl acetate, the internal standard (18.5% RSD). The smoke dilution precision was found to be 17.2, 6.2 and 11.7% RSD for exposure concentrations of 1, 2 and 5% (v/v) cigarette vapor phase in air

  12. Air sparging effectiveness: laboratory characterization of air-channel mass transfer zone for VOC volatilization.

    PubMed

    Braida, W J; Ong, S K

    2001-10-12

    Air sparging in conjunction with soil vapor extraction is one of many technologies currently being applied for the remediation of groundwater contaminated with volatile organic compounds (VOCs). Mass transfer at the air-water interface during air sparging is affected by various soil and VOC properties. In this study with a single air-channel apparatus, mass transfer of VOCs was shown to occur within a thin layer of saturated porous media next to the air channel. In this zone, the VOCs were found to rapidly deplete during air sparging resulting in a steep concentration gradient while the VOC concentration outside the zone remained fairly constant. The sizes of the mass transfer zone were found to range from 17 to 41 mm or 70d(50) and 215d(50) (d(50)=mean particle size) for low organic carbon content media (<0.01% OC). The size of the mass transfer zone was found to be proportional to the square root of the aqueous diffusivity of the VOC, and was affected by the mean particle size, and the uniformity coefficient. Effects of the volatility of the VOCs as represented by the Henry's law constants and the airflow rates on the mass transfer zone were found to be negligible but VOC mass transfer from air-water interface to bulk air phase seems to play a role. A general correlation for predicting the size of the mass transfer zone was developed. The model was developed using data from nine different VOCs and verified by two other VOCs. The existence of the mass transfer zone provides an explanation for the tailing effect of the air phase concentration under prolonged air sparging and the rebound in the VOC air phase concentration after the sparging system is turned off.

  13. Opposed jet diffusion flames of nitrogen-diluted hydrogen vs air - Axial LDA and CARS surveys; fuel/air rates at extinction

    SciTech Connect

    Pellett, G.L.; Northam, G.B.; Wilson, L.G.; Jarrett, O. Jr.; Antcliff, R.R.

    1989-01-01

    An experimental study of H-air counterflow diffusion flames (CFDFs) is reported. Coaxial tubular opposed jet burners were used to form dish-shaped CFDFs centered by opposing laminar jets of H2/N2 and air in an argon bath at 1 atm. Jet velocities for extinction and flame restoration limits are shown versus input H2 concentration. LDA velocity data and CARS temperature and absolute N2, O2 density data give detailed flame structure on the air side of the stagnation point. The results show that air jet velocity is a more fundamental and appropriate measure of H2-air CFDF extinction than input H2 mass flux or fuel jet velocity. It is proposed that the observed constancy of air jet velocity for fuel mixtures containing 80 to 100 percent H2 measure a maximum, kinetically controlled rate at which the CFDF can consume oxygen in air. Fuel velocity mainly measures the input jet momentum required to center an H2/N2 versus air CFDF. 42 refs.

  14. Opposed jet diffusion flames of nitrogen-diluted hydrogen vs air - Axial LDA and CARS surveys; fuel/air rates at extinction

    NASA Technical Reports Server (NTRS)

    Pellett, G. L.; Northam, G. B.; Wilson, L. G.; Jarrett, Olin, Jr.; Antcliff, R. R.

    1989-01-01

    An experimental study of H-air counterflow diffusion flames (CFDFs) is reported. Coaxial tubular opposed jet burners were used to form dish-shaped CFDFs centered by opposing laminar jets of H2/N2 and air in an argon bath at 1 atm. Jet velocities for extinction and flame restoration limits are shown versus input H2 concentration. LDA velocity data and CARS temperature and absolute N2, O2 density data give detailed flame structure on the air side of the stagnation point. The results show that air jet velocity is a more fundamental and appropriate measure of H2-air CFDF extinction than input H2 mass flux or fuel jet velocity. It is proposed that the observed constancy of air jet velocity for fuel mixtures containing 80 to 100 percent H2 measure a maximum, kinetically controlled rate at which the CFDF can consume oxygen in air. Fuel velocity mainly measures the input jet momentum required to center an H2/N2 versus air CFDF.

  15. Enthalpy and mass flowrate measurements for two-phase geothermal production by Tracer dilution techniques

    SciTech Connect

    Hirtz, Paul; Lovekin, Jim; Copp, John; Buck, Cliff; Adams, Mike

    1993-01-28

    A new technique has been developed for the measurement of steam mass flowrate, water mass flowrate and total enthalpy of two-phase fluids produced from geothermal wells. The method involves precisely metered injection of liquid and vapor phase tracers into the two-phase production pipeline and concurrent sampling of each phase downstream of the injection point. Subsequent chemical analysis of the steam and water samples for tracer content enables the calculation of mass flowrate for each phase given the known mass injection rates of tracer. This technique has now been used extensively at the Coso geothermal project, owned and operated by California Energy Company. Initial validation of the method was performed at the Roosevelt Hot Springs geothermal project on wells producing to individual production separators equipped with orificeplate flowmeters for each phase.

  16. Determination of phentermine, N-hydroxyphentermine and mephentermine in urine using dilute and shoot liquid chromatography-tandem mass spectrometry.

    PubMed

    Choi, Yun Jeong; Sim, Arum; Kim, Min Kyung; Suh, Sunglll; In, Moon Kyo; Kim, Jin Young

    2016-09-01

    Nonmedical use of prescription stimulants such as phentermine (PT) has been regulated by law enforcement authorities due to its euphorigenic and relaxing effects. Due to high potential for its abuse, reliable analytical methods were required to detect and identify PT and its metabolite in biological samples. Thus a dilute and shoot liquid chromatography-tandem mass spectrometric (LC-MS/MS) method was developed and validated for simultaneous determination of PT, N-hydroxyphentermine (NHOPT) and mephentermine (MPT) in urine. A 5μL aliquot of diluted urine was injected into the LC-MS/MS system. Chromatographic separation was performed by reversed-phase C18 column with gradient elution for all analytes within 5min. Identification and quantification were based on multiple reaction monitoring (MRM) detection. Linear least-squares regression with a 1/x(2) weighting factor was used to generate a calibration curve and the assay was linear from 50 to 15000ng/mL (PT and MPT) and 5 to 750ng/mL (NHOPT). The intra- and inter-day precisions were within 8.9% while the intra- and inter-day accuracies ranged from -6.2% to 11.2%. The limits of quantification were 3.5ng/mL (PT), 1.5ng/mL (NHOPT) and 1.0ng/mL (MPT). Method validation requirements for selectivity, dilution integrity, matrix effect and stability were satisfied. The applicability of the developed method was examined by analyzing urine samples from drug abusers. PMID:27398632

  17. Dilution-Free Analysis from Picoliter Droplets by Nano-Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kelly, Ryan T.; Page, Jason S.; Marginean, Ioan; Tang, Keqi; Smith, Richard D.

    2009-09-01

    The expanding role of microfluidics for chemical and biochemical analysis is due to factors including the favorable scaling of separation performance with reduced channel dimensions,[1] flexibility afforded by computer-aided device design, and the ability to integrate multiple sample handling and analysis steps into a single platform.[2] Such devices enable smaller liquid volumes and sample sizes to be handled than can be achieved on the benchtop, where sub-microliter volumes are difficult to work with and where sample losses to the surfaces of multiple reaction vessels become prohibitive. A particularly attractive microfluidic platform for sample-limited analyses employs aqueous droplets or plugs encapsulated by an immiscible oil.[3,4] Each droplet serves as a discrete compartment or reaction chamber enabling, e.g., high throughput screening[5,6] and kinetic studies[7-9] of femto- to nanoliter samples, as well as the encapsulation[10-12] and lysis[10] of individual cells with limited dilution of the cellular contents

  18. Total-body creatine pool size and skeletal muscle mass determination by creatine-(methyl-D3) dilution in rats.

    PubMed

    Stimpson, Stephen A; Turner, Scott M; Clifton, Lisa G; Poole, James C; Mohammed, Hussein A; Shearer, Todd W; Waitt, Greg M; Hagerty, Laura L; Remlinger, Katja S; Hellerstein, Marc K; Evans, William J

    2012-06-01

    There is currently no direct, facile method to determine total-body skeletal muscle mass for the diagnosis and treatment of skeletal muscle wasting conditions such as sarcopenia, cachexia, and disuse. We tested in rats the hypothesis that the enrichment of creatinine-(methyl-d(3)) (D(3)-creatinine) in urine after a defined oral tracer dose of D(3)-creatine can be used to determine creatine pool size and skeletal muscle mass. We determined 1) an oral tracer dose of D(3)-creatine that was completely bioavailable with minimal urinary spillage and sufficient enrichment in the body creatine pool for detection of D(3)-creatine in muscle and D(3)-creatinine in urine, and 2) the time to isotopic steady state. We used cross-sectional studies to compare total creatine pool size determined by the D(3)-creatine dilution method to lean body mass determined by independent methods. The tracer dose of D(3)-creatine (<1 mg/rat) was >99% bioavailable with 0.2-1.2% urinary spillage. Isotopic steady state was achieved within 24-48 h. Creatine pool size calculated from urinary D(3)-creatinine enrichment at 72 h significantly increased with muscle accrual in rat growth, significantly decreased with dexamethasone-induced skeletal muscle atrophy, was correlated with lean body mass (r = 0.9590; P < 0.0001), and corresponded to predicted total muscle mass. Total-body creatine pool size and skeletal muscle mass can thus be accurately and precisely determined by an orally delivered dose of D(3)-creatine followed by the measurement of D(3)-creatinine enrichment in a single urine sample and is promising as a noninvasive tool for the clinical determination of skeletal muscle mass. PMID:22422801

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

    PubMed

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

    2012-11-20

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

  20. Trace analysis of acidic pharmaceutical residues in waters with isotope dilution gas chromatography-mass spectrometry via methylation derivatization.

    PubMed

    Hu, Ruikang; Yang, Zhaoguang; Zhang, Lifeng

    2011-09-30

    Acidic pharmaceutical residues are pollutants of emerging concern and are generally monitored by HPLC-MS/MS. However, due to the limited separation efficiency of HPLC column and lack of suitable mass transition for confirmation analysis, some interference may not be separated completely and differentiated from ibuprofen, which may cause the results with interference, especially in sample with complex matrix. The objective of this study is to develop a sensitive and reliable method for the determination of acidic pharmaceutical residues in water samples by GC-MS with better resolution by using methylation derivatization and isotope dilution techniques. TMSDM, a mild reagent, was used as the derivatization reagent coupling with the isotope dilution technique, for the first time, to improve the precision and accuracy of the analytical method to determine the pharmaceutical residues in water. The MDLs for the five acidic organic compounds: ibuprofen, gemfibrozil, naproxen, ketoprofen and diclofenac were from 0.7 to 1.1 ng/L, with recoveries ranging from 93 to 110%. Alternative to the HPLC-MS/MS method, the developed GC-MS protocols provides an additional option for the analysis of acidic pharmaceutical residues in water, with better separation efficiency in reducing interferences from complicated sample matrix, for determination of ibuprofen residues.

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

    PubMed

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

    2009-05-01

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

  2. Combining Experiments and Simulation of Gas Absorption for Teaching Mass Transfer Fundamentals: Removing CO2 from Air Using Water and NaOH

    ERIC Educational Resources Information Center

    Clark, William M.; Jackson, Yaminah Z.; Morin, Michael T.; Ferraro, Giacomo P.

    2011-01-01

    Laboratory experiments and computer models for studying the mass transfer process of removing CO2 from air using water or dilute NaOH solution as absorbent are presented. Models tie experiment to theory and give a visual representation of concentration profiles and also illustrate the two-film theory and the relative importance of various…

  3. High accuracy determination of malachite green and leucomalachite green in salmon tissue by exact matching isotope dilution mass spectrometry.

    PubMed

    Hall, Zoe; Hopley, Chris; O'Connor, Gavin

    2008-10-15

    A high accuracy method for the quantification of malachite green (MG) and leucomalachite green (LMG) in salmon is described. Analytical challenges including the effects of analyte instability and matrix suppression were minimised by the use of exact matching isotope dilution mass spectrometry. The developed method included overnight extraction in acidified acetonitrile/ammonium acetate buffer and analysis by LC-MS/MS utilising isotopic internal standards. This method was used to determine the level of MG and LMG in a sample of salmon used in an international inter-comparison organised by the Comité Consultatif pour la Quantité de Matière (CCQM). The sum of MG and LMG was found to be 9.32+/-0.98ngg(-1) at the 95% confidence interval (relative expanded uncertainty 10.5% (k=2)). This encompassed the mean and median of the CCQM inter-comparison.

  4. Application of speciated isotope dilution mass spectrometry to evaluate extraction methods for determining mercury speciation in soils and sediments.

    PubMed

    Rahman, G M Mizanur; Kingston, H M Skip

    2004-07-01

    Extraction techniques commonly used to extract methylmercury or mercury species from various matrixes have been evaluated regarding their potential to transform inorganic mercury to methylmercury, or vice versa, during sample preparation steps by applying speciated isotope dilution mass spectrometry. Two of the five tested methods were highly prone to form inorganic mercury from methylmercury. Some published methods converted methylmercury to inorganic mercury approximately 100% (including the spiked CH(3)(201)Hg(+)). In other methods, as much as 45% of methylmercury was converted to inorganic mercury during extraction. The methods evaluated included cold acid extraction and sonication. Other methods, such as the proposed EPA RCRA Draft Method 3200, microwave-assisted extraction, and another sonication-based methods induced very little or no methylmercury transformation to inorganic mercury. Among these three methods, the proposed Draft EPA Method 3200 was found to be the most efficient.

  5. Measurement of salicylic acid in human serum using stable isotope dilution and gas chromatography-mass spectrometry.

    PubMed

    Battezzati, A; Fiorillo, G; Spadafranca, A; Bertoli, S; Testolin, G

    2006-07-15

    A simple, highly selective, and sensitive method using stable isotope dilution and gas chromatography-mass spectrometry has been developed to quantify salicylic acid (SA) at concentrations naturally occurring in biological fluids, such as in the serum of subjects not taking aspirin. After extraction of liquid-liquid with diethyl ether and ethyl acetate and preparation of the tert-butyldimethylsilyl derivative, SA content was detected using deuterated SA as internal standard. The mean recovery of SA from serum was 85 +/- 6%. Intra- and interday precision and % relative error were <15% in all cases. With a detection limit of 0.6 ng and a quantification limit of 2 ng, the method is therefore also adequate for population studies because of the small amount of blood necessary to perform the analyses.

  6. Simultaneous determination of alachlor, metolachlor, atrazine, and simazine in water and soil by isotope dilution gas chromatography/mass spectrometry

    SciTech Connect

    Huang, L.Q.

    1989-03-01

    A multiresidue method was developed for the simultaneous determination of low parts per billion (ppb) concentrations of the herbicides alachlor, metolachlor, atrazine, and simazine in water and soil using isotope dilution gas chromatography/mass spectrometry (GC/MS). Known amounts of /sup 15/N,/sup 13/C-alachlor and /sup 2/H/sub 5/-atrazine were added to each sample as internal standards. The samples were then prepared by a solid phase extraction with no further cleanup. A high resolution GC/low resolution MS system with data acquisition in selected ion monitoring mode was used to quantitate herbicides in the extract. The limit of detection was 0.05 ppb for water and 0.5 ppb for soil. Accuracy greater than 80% and precision better than 4% was demonstrated with spiked samples.

  7. "Dilute-and-shoot" triple parallel mass spectrometry method for analysis of vitamin D and triacylglycerols in dietary supplements.

    PubMed

    Byrdwell, William Craig

    2011-12-01

    A method is demonstrated for analysis of vitamin D fortified dietary supplements that eliminates virtually all chemical pretreatment prior to analysis, which is referred to as a "dilute-and-shoot" method. Three mass spectrometers, in parallel, plus a UV detector, an evaporative light-scattering detector (ELSD), and a corona charged aerosol detector (CAD) were used to allow a comparison of six detectors simultaneously. Ultraviolet data were analyzed using internal standard, external standard, and response factor approaches. The contents of gelcaps that contained 2,000 IU (50 μg) vitamin D(3) in rice bran oil, diluted to 100 mL, were analyzed without the need for lengthy saponification and extraction. Vitamin D(3) was analyzed using UV detection, extracted ion chromatograms, selected ion monitoring (SIM) atmospheric pressure chemical ionization mass spectrometry (APCI-MS), and two transitions of multiple reaction monitoring (MRM) APCI-MS. The internal standard, external standard, and response factor methods gave values of 0.5870 ± 0.0045, 0.5893 ± 0.0041, and 0.5889 ± 0.0045 μg/mL, respectively, by UV detection. The values obtained by MS were 0.6117 ± 0.0140, 0.6018 ± 0.0244, and 0.5848 ± 0.0146 μg/mL by SIM and two transitions of MRM, respectively. The triacylglycerols in the oils were analyzed using full-scan APCI-MS, electrospray ionization (ESI) MS, up to MS(4), an ELSD, and a CAD. The method proved to be very sensitive for vitamin D(3), as well as triacylglycerols (TAGs), allowing identification of intact TAGs containing fatty acids up to 28 carbons in length. LC-ESI-MS of glycerin polymers is also demonstrated. PMID:21964772

  8. Contribution of Liquid/Gas Mass-Transfer Limitations to Dissolved Methane Oversaturation in Anaerobic Treatment of Dilute Wastewater.

    PubMed

    Yeo, Hyeongu; An, Junyeong; Reid, Robertson; Rittmann, Bruce E; Lee, Hyung-Sool

    2015-09-01

    The mechanisms controlling the accumulation of dissolved methane in anaerobic membrane bioreactors (AnMBRs) treating a synthetic dilute wastewater (a glucose medium) were assessed experimentally and theoretically. The AnMBR was maintained at a temperature of 24-26 °C as the organic loading rate increased from 0.39 to 1.1 kg COD/m(3)-d. The measured concentration of dissolved methane was consistently 2.2- to 2.5-fold larger than the concentration of dissolved methane at thermodynamic equilibrium with the measured CH4 partial pressure, and the fraction of dissolved methane was as high as 76% of the total methane produced. The low gas production rate in the AnMBR significantly slowed the mass transport of dissolved methane to the gas phase. Although the production rate of total methane increased linearly with the COD loading rate, the concentration of dissolved methane only slightly increased with an increasing organic loading rate, because the mass-transfer rate increased by almost 5-fold as the COD loading increased from 0.39 to 1.1 kg COD/m(3)-d. Thus, slow mass transport kinetics exacerbated the situation in which dissolved methane accounted for a substantial fraction of the total methane generated from the AnMBR. PMID:26238158

  9. Contribution of Liquid/Gas Mass-Transfer Limitations to Dissolved Methane Oversaturation in Anaerobic Treatment of Dilute Wastewater.

    PubMed

    Yeo, Hyeongu; An, Junyeong; Reid, Robertson; Rittmann, Bruce E; Lee, Hyung-Sool

    2015-09-01

    The mechanisms controlling the accumulation of dissolved methane in anaerobic membrane bioreactors (AnMBRs) treating a synthetic dilute wastewater (a glucose medium) were assessed experimentally and theoretically. The AnMBR was maintained at a temperature of 24-26 °C as the organic loading rate increased from 0.39 to 1.1 kg COD/m(3)-d. The measured concentration of dissolved methane was consistently 2.2- to 2.5-fold larger than the concentration of dissolved methane at thermodynamic equilibrium with the measured CH4 partial pressure, and the fraction of dissolved methane was as high as 76% of the total methane produced. The low gas production rate in the AnMBR significantly slowed the mass transport of dissolved methane to the gas phase. Although the production rate of total methane increased linearly with the COD loading rate, the concentration of dissolved methane only slightly increased with an increasing organic loading rate, because the mass-transfer rate increased by almost 5-fold as the COD loading increased from 0.39 to 1.1 kg COD/m(3)-d. Thus, slow mass transport kinetics exacerbated the situation in which dissolved methane accounted for a substantial fraction of the total methane generated from the AnMBR.

  10. Quantification of ferritin-bound iron in plant samples by isotope tagging and species-specific isotope dilution mass spectrometry.

    PubMed

    Hoppler, Matthias; Zeder, Christophe; Walczyk, Thomas

    2009-09-01

    Ferritin is nature's predominant iron storage protein. The molecule consists of a hollow protein shell composed of 24 subunits which is capable of storing up to 4500 iron atoms per molecule. Recently, this protein has been identified as a target molecule for increasing iron content in plant staple foods in order to combat dietary iron deficiency, a major public health problem in developing countries. Here, we present a novel technique for quantification of ferritin-bound iron in edible plant seeds using species-specific isotope dilution mass spectrometry (IDMS) by means of a biosynthetically produced (57)Fe-labeled ferritin spike and negative thermal ionization mass spectrometry (NTIMS). Native plant ferritin and added spike ferritin were extracted in 20 mM Tris buffer (pH 7.4) and separated by anion exchange chromatography (DEAE Sepharose), followed by isotopic analysis by thermal ionization mass spectrometry. The chosen IDMS approach was critically evaluated by assessing the (i) efficiency of analyte extraction, (ii) identical behavior of spike and analyte, and (iii) potential iron isotope exchange with natural iron. Repeatabilities that can be achieved are on the order of <5% RSD for quintuplicate analyses at an absolute detection limit of 60 ng of ferritin-bound iron for plant seeds. Studies in six different legumes revealed ferritin-iron contents ranging from 15% of total iron in red kidney beans up to 69% in lentils. PMID:19653660

  11. Urinary detection of conjugated and unconjugated anabolic steroids by dilute-and-shoot liquid chromatography-high resolution mass spectrometry.

    PubMed

    Tudela, Eva; Deventer, Koen; Geldof, Lore; Van Eenoo, Peter

    2015-02-01

    Anabolic androgenic steroids (AAS) are an important class of doping agents. The metabolism of these substances is generally very extensive and includes phase-I and phase-II pathways. In this work, a comprehensive detection of these metabolites is described using a 2-fold dilution of urine and subsequent analysis by liquid chromatography-high resolution mass spectrometry (LC-HRMS). The method was applied to study 32 different metabolites, excreted free or conjugated (glucuronide or sulfate), which permit the detection of misuse of at least 21 anabolic steroids. The method has been fully validated for 21 target compounds (8 glucuronide, 1 sulfate and 12 free steroids) and 18 out of 21 compounds had detection limits in the range of 1-10 ng mL(-1) in urine. For the conjugated compounds, for which no reference standards are available, metabolites were synthesized in vitro or excretion studies were investigated. The detection limits for these compounds ranged between 0.5 and 18 ng mL(-1) in urine. The simple and straightforward methodology complements the traditional methods based on hydrolysis, liquid-liquid extraction, derivatization and analysis by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS).

  12. Body composition in Mexican adults by air displacement plethysmography (ADP) with the BOD-POD and deuterium oxide dilution using infrared spectroscopy (IRS-DOD).

    PubMed

    Macías, Nayeli; Calderón de la Barca, Ana María; Bolaños, Adriana V; Alemán, Heliodoro; Esparza, Julián; Valencia, Mauro E

    2002-09-01

    Thirty four subjects (13 men and 21 women), 24 to 70 years old from northern Mexico, were measured for body density by air displacement plethysmography (ADP) with the BOD-POD, and for total body water by deuterium oxide dilution and infrared spectroscopy (IRS-DOD). Subjects were given a 30 g dose of deuterium oxide. Saliva samples were filtered, sublimated, and deuterium was measured using a Miran 1 FF, IRS. Linear regression of the fat mass (FM) derived from both methods showed that the intercept (0.071) was not different from zero (p = .96) and the slope was 0.96 (p < .0001) demonstrating the techniques to be equivalent. Further, mean FM was 26.7 +/- 12.4 and 25.6 +/- 12.4 kg, for IRS-DOD and ADP techniques, respectively (p = .08). Precision analysis by the model R2 showed that 92.3% of the variability was explained (SEM = 3.4 kg). Bland-Altman analysis showed no significant bias (r = 0.017; p = .93). Mean difference between methods was -1.08 (CI: -2.3 to + 0.13) kg FM.

  13. An experimental study of the fuel dilution effect on the propagation of methane-air tribrachial flames

    SciTech Connect

    Seo, Jeong Il; Shin, Hyun Dong; Kim, Nam Il

    2008-05-15

    The effects of fuel dilution with nitrogen on the propagation of tribrachial flames were studied experimentally using a multislot burner, which can stabilize lifted flames at low concentration gradients. Three fuel dilutions with nitrogen (N{sub 2} 0%, 25%, and 50% dilution) were employed. The lift-off height and OH-radical content of the flames were measured using an intensified CCD camera and an OH-PLIF scheme. Regardless of the fuel dilution mole fractions, the lift-off height of the tribrachial flames exhibited U-shaped trends with a minimal value during the increase of the concentration gradients. This implies that the propagation velocity is maximized at a specific concentration gradient regardless of the fuel dilution. Overall, the propagation velocity of the tribrachial flame was reduced by the fuel dilution, and the fuel dilution weakly affected the generation of the diffusion flame. The OH radicals in the diffusion branch became prominently active at the critical concentration gradient and these phenomena were more clearly detected at higher fuel dilution mole fractions. The decrease of the three modes of the OH radicals in a streamwise direction is discussed regarding the relation of the diffusion branch to the propagation velocity of the tribrachial flames. It is suggested that the effect of the diffusion branch on the propagation velocity of tribrachial flames needs to be reconsidered, especially when the concentration gradient is small. (author)

  14. Human aflatoxin albumin adducts quantitatively compared by ELISA, HPLC with fluorescence detection, and HPLC with isotope dilution mass spectrometry.

    PubMed

    McCoy, Leslie F; Scholl, Peter F; Sutcliffe, Anne E; Kieszak, Stephanie M; Powers, Carissa D; Rogers, Helen S; Gong, Yun Yun; Groopman, John D; Wild, Christopher P; Schleicher, Rosemary L

    2008-07-01

    Essential to the conduct of epidemiologic studies examining aflatoxin exposure and the risk of heptocellular carcinoma, impaired growth, and acute toxicity has been the development of quantitative biomarkers of exposure to aflatoxins, particularly aflatoxin B(1). In this study, identical serum sample sets were analyzed for aflatoxin-albumin adducts by ELISA, high-performance liquid chromatography (HPLC) with fluorescence detection (HPLC-f), and HPLC with isotope dilution mass spectrometry (IDMS). The human samples analyzed were from an acute aflatoxicosis outbreak in Kenya in 2004 (n = 102) and the measured values ranged from 0.018 to 67.0, nondetectable to 13.6, and 0.002 to 17.7 ng/mg albumin for the respective methods. The Deming regression slopes for the HPLC-f and ELISA concentrations as a function of the IDMS concentrations were 0.71 (r(2) = 0.95) and 3.3 (r(2) = 0.96), respectively. When the samples were classified as cases or controls, based on clinical diagnosis, all methods were predictive of outcome (P < 0.01). Further, to evaluate assay precision, duplicate samples were prepared at three levels by dilution of an exposed human sample and were analyzed on three separate days. Excluding one assay value by ELISA and one assay by HPLC-f, the overall relative SD were 8.7%, 10.5%, and 9.4% for IDMS, HPLC-f, and ELISA, respectively. IDMS was the most sensitive technique and HPLC-f was the least sensitive method. Overall, this study shows an excellent correlation between three independent methodologies conducted in different laboratories and supports the validation of these technologies for assessment of human exposure to this environmental toxin and carcinogen.

  15. On-line double isotope dilution laser ablation inductively coupled plasma mass spectrometry for the quantitative analysis of solid materials.

    PubMed

    Fernández, Beatriz; Rodríguez-González, Pablo; García Alonso, J Ignacio; Malherbe, Julien; García-Fonseca, Sergio; Pereiro, Rosario; Sanz-Medel, Alfredo

    2014-12-01

    We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6-21% for pressed pellets and 3-21% for fused solids were obtained from n=3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches.

  16. Quantification of glycosaminoglycans in urine by isotope-dilution liquid chromatography-electrospray ionization tandem mass spectrometry.

    PubMed

    Zhang, Haoyue; Young, Sarah P; Millington, David S

    2013-01-01

    Mucopolysaccharidoses (MPSs) are complex lysosomal storage disorders that result in the accumulation of glycosaminoglycans (GAGs) in urine, blood, and tissues. Lysosomal enzymes responsible for GAG degradation are defective in MPSs. GAGs including chondroitin sulfate (CS), dermatan sulfate (DS), heparan sulfate (HS), and keratan sulfate (KS) are disease-specific biomarkers for MPSs. This unit describes a stable isotope dilution-tandem mass spectrometric method for quantifying CS, DS, and HS in urine samples. The GAGs are methanolyzed to uronic or iduronic acid-N-acetylhexosamine or iduronic acid-N-sulfo-glucosamine dimers and mixed with internal standards derived from deuteriomethanolysis of GAG standards. Specific dimers derived from HS, DS, and CS are separated by ultra-performance liquid chromatography (UPLC) and analyzed by electrospray ionization tandem mass spectrometry (MS/MS) using selected reaction monitoring for each targeted GAG product and its corresponding internal standard. This new GAG assay is useful for identifying patients with MPS types I, II, III, VI, and VII.

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

    PubMed

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

    2011-06-01

    Analytical methods are generally developed and optimized for specific commodities. Total Diet Studies, representing typical food products 'as consumed', pose an analytical challenge since every food product is different. In order to address this technical challenge, a selective and sensitive analytical method was developed suitable for the quantitation of ochratoxin A (OTA) in Canadian Total Diet Study composites. The method uses an acidified solvent extraction, an immunoaffinity column (IAC) for clean-up, liquid chromatography-tandem mass spectrometry (LC-MS/MS) for identification and quantification, and a uniformly stable isotope-labelled OTA (U-[(13)C(20)]-OTA) as an internal recovery standard. Results are corrected for this standard. The method is accurate (101% average recovery) and precise (5.5% relative standard deviation (RSD)) based on 17 duplicate analysis of various food products over 2 years. A total of 140 diet composites were analysed for OTA as part of the Canadian Total Diet Study. Samples were collected at retail level from two Canadian cities, Quebec City and Calgary, in 2008 and 2009, respectively. The results indicate that 73% (102/140) of the samples had detectable levels of OTA, with some of the highest levels of OTA contamination found in the Canadian bread supply.

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

    PubMed Central

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

    2011-01-01

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

  19. Warm-air advection, air mass transformation and fog causes rapid ice melt

    NASA Astrophysics Data System (ADS)

    Tjernström, Michael; Shupe, Matthew D.; Brooks, Ian M.; Persson, P. Ola G.; Prytherch, John; Salisbury, Dominic J.; Sedlar, Joseph; Achtert, Peggy; Brooks, Barbara J.; Johnston, Paul E.; Sotiropoulou, Georgia; Wolfe, Dan

    2015-07-01

    Direct observations during intense warm-air advection over the East Siberian Sea reveal a period of rapid sea-ice melt. A semistationary, high-pressure system north of the Bering Strait forced northward advection of warm, moist air from the continent. Air-mass transformation over melting sea ice formed a strong, surface-based temperature inversion in which dense fog formed. This induced a positive net longwave radiation at the surface while reducing net solar radiation only marginally; the inversion also resulted in downward turbulent heat flux. The sum of these processes enhanced the surface energy flux by an average of ~15 W m-2 for a week. Satellite images before and after the episode show sea-ice concentrations decreasing from > 90% to ~50% over a large area affected by the air-mass transformation. We argue that this rapid melt was triggered by the increased heat flux from the atmosphere due to the warm-air advection.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    SciTech Connect

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

    2015-03-17

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

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

    PubMed

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

    2016-01-01

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

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

    SciTech Connect

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

    2015-03-01

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

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

    PubMed

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

    2014-09-10

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

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

    PubMed

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

    2015-11-01

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

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

    PubMed

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

    2014-09-10

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

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

    DOE PAGES

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

    2015-03-17

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

  8. Analysis of organophosphate flame retardants and plasticisers in water by isotope dilution gas chromatography-electron ionisation tandem mass spectrometry.

    PubMed

    Teo, Tiffany L L; McDonald, James A; Coleman, Heather M; Khan, Stuart J

    2015-10-01

    The widespread use of organophosphate flame retardants (PFRs) in commercial products have led to their increased presence in the environment. In this study, a rapid and reliable analytical method was developed for the analysis of five PFRs in water using gas chromatography tandem mass spectrometry (GC-MS/MS) with electron ionisation (EI) and a run time of 13 min. The PFRs investigated were tributyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCP) and triphenyl phosphate (TPP). Solid phase extraction (SPE) was undertaken to extract and concentrate target analytes from aqueous matrices. All water samples were extracted from a volume of 500 mL. Isotopically labelled compounds were used to account for analytical variability and for accurate quantification by isotope dilution. Method recoveries for all compounds were above 80% in all tested water samples. Method detection limits for all target analytes ranged from 0.3 to 24 ng/L in ultrapure water, tap water, seawater, surface water, secondary effluent and swimming pool water. Validation of this method confirmed satisfactory method stability with less than 1% coefficients of variation, verifying that this approach produced good reproducibility. PMID:26078137

  9. Determination of atrazine, lindane, pentachlorophenol, and diazinon in water and soil by isotope dilution gas chromatography/mass spectrometry

    SciTech Connect

    Lopez-Avila, V.; Hirata, P.; Kraska, S.; Flanagan, M.; Taylor, J.H. Jr.; Hern, S.C.

    1985-12-01

    This paper describes an isotope dilution GC/MS technique for the analysis of low-parts-per-billion concentrations of atrazine, lindane, pentachlorophenol, and diazinon in water and soil. Known amounts of stable-labeled isotopes such as atrazine-d/sub 5/, lindane-d/sub 6/, pentachlorophenol-/sup 13/C/sub 6/, and diazinon-d/sub 10/ are spiked into each sample prior to extraction. Water samples are extracted with methylene chloride; soil samples are extracted with acetone/hexane. Analysis is performed by high-resolution GC/MS with the mass spectrometer operated in the selected ion monitoring mode. Accuracy greater than 86% and precision better than 8% were demonstrated by use of spiked samples. This technique has been used successfully in the analysis of over 300 water and 300 soil samples. Detection limits of 0.1-1.0 ppb were achieved for the test compounds by selected ion monitoring GC/MS. 8 references, 2 figures, 4 tables.

  10. Liquid chromatography, chemical oxidation, and online carbon isotope dilution mass spectrometry as a universal quantification system for nonvolatile organic compounds.

    PubMed

    Díaz, Sergio Cueto; Encinar, Jorge Ruiz; Sanz-Medel, Alfredo; Alonso, J Ignacio García

    2013-02-01

    A procedure for the universal detection and quantification of polar organic compounds separated by liquid chromatography (LC) based on postcolumn carbon isotope dilution mass spectrometry (IDMS) was developed. The eluent from the LC column is mixed online with a continuous flow of (13)C-enriched sodium bicarbonate, and the sodium persulfate oxidation reaction in acidic media is employed to achieve isotope equilibration. All carbon-containing compounds eluting from the column are oxidized to (12)CO(2) and (13)CO(2), respectively, and the carbon dioxide is separated from the aqueous phase using a gas-permeable membrane. The gaseous carbon dioxide is then carried to the mass spectrometer for isotope ratio measurements. Different water-soluble organic compounds were evaluated using a flow injection configuration to assess the efficiency of the oxidation process. Most water-soluble organic compounds tested showed quantitative oxidation. However, chemical structures involving conjugated C═N double bounds and guanidinium-like structures were found to be resistant to the oxidation and were further studied. For this purpose, (13)C(1)-labeled creatine (with the isotopic label in the guanidinium group) was employed as model compound. Specific conditions for the quantitative oxidation of these compounds required lower flow rates and the addition of metallic catalysts. This novel approach was tested as a universal detection and quantification system for LC. A simple standard mixture of four amino acids was separated under 100% aqueous conditions and quantified without the need for specific standards with good accuracy and precision using potassium hydrogen phthalate as internal standard. The main field of application of the developed method is for the purity assessment of organic standards with direct traceability to the International System of Units (SI). PMID:23252800

  11. [International comparison APMP. QM-S6: determination of clenbuterol in porcine meat by isotopic dilution mass spectrometry].

    PubMed

    Xu, Sen; Li, Xiuqin; Luo, Ximing; Zhang, Qinghe

    2014-10-01

    A method was developed for the determination of clenbuterol in porcine meat by iso- topic dilution mass spectrometry (IDMS). National Institute of Metrology of China (NIM) par- ticipated in the international comparison activity organized by Asia Pacific Metrology (APMP) and got an international mutual recognition result using this method. The important factors of the method, such as the spray voltage, mobile phase, chromatographic column, extraction, purification and filtration conditions were investigated to acquire optimum conditions. The opti- mization results showed that the composition and pH value of the mobile phase had effects on the response of the mass spectrum of clenbuterol and the optimal value of the spray voltage. The solvent of sample had influences on the chromatographic retention behavior of clenbuterol. It was found that methanol caused a serious solvent effect, even made chromatographic peak split. Since clenbuterol was easily adsorbed on hydrophilic filter membranes and solid phase extraction columns, there were interference suppressions for the quantification of clenbuterol because of the eluate of the solid phase extraction columns. The homogenate method with extraction solvent of 0.1% (v/v) formic acid in acetonitrile had the highest extraction efficiency. The limit of the detection (LOD, S/N > 3) of the method was 0.2 μg/kg. The determination results of clenbuterol in the porcine meat by this method were 5.18 μg/kg ± 0.50 μg/kg (k = 2). This method is accurate, reliable, reproducible, and suitable for the determination of clenbuterol with trace quantity in porcine meat.

  12. Determination of serum glucose by isotope dilution liquid chromatography-tandem mass spectrometry: a candidate reference measurement procedure.

    PubMed

    Zhang, Tianjiao; Zhang, Chuanbao; Zhao, Haijian; Zeng, Jie; Zhang, Jiangtao; Zhou, Weiyan; Yan, Ying; Wang, Yufei; Wang, Mo; Chen, Wenxiang

    2016-10-01

    Accurate and precise glucose measurements are requisite for ensuring appropriate diagnosis and management of diseases related to hyperglycemia or hypoglycemia. It is necessary to have a higher order method to provide an accuracy base to which routine methods can be compared. We developed and evaluated a highly reliable measurement procedure based on isotope dilution liquid chromatography-tandem mass spectrometry (ID LC-MS/MS) with a simple one-step derivatization. An appropriate amount of serum was accurately weighed and spiked with an isotope-labeled internal standard. After protein precipitation, the supernatant was reacted with 1-phenyl-3-methyl-5-pyrazolone for chemical structural transformation. The glucose derivatives were analyzed with LC-MS/MS in positive electrospray ionization mode. The within-run and total CVs ranged from 0.28 to 0.42 % and from 0.42 to 0.76 %, respectively, for a concentration range of 1.691 to 15.676 mmol/L. A regression comparison of the presented method to an existing RMP based on ID GC-MS showed agreement with no statistical difference (Y = 0.9985X-0.008; 95 % CI for the slope, 0.9966 to 1.001; 95 % CI for the intercept, -0.012 to 0.019). The structural analogs of glucose with a molecular mass of 180 were tested, and no significant interference effect was found. The limit of quantification was estimated to 0.8 ng glucose in absolute amount. This method is accurate, simple, and can serve as a candidate reference measurement procedure (RMP) in the establishment of a serum glucose reference system. PMID:27481169

  13. Simultaneous detection of five one-carbon metabolites in plasma using stable isotope dilution liquid chromatography tandem mass spectrometry.

    PubMed

    Adaikalakoteswari, Antonysunil; Webster, Craig; Goljan, Ilona; Saravanan, Ponnusamy

    2016-02-15

    Disturbance in one-carbon (1-C) cycle occurs due to nutritional deficiencies (vitamin B12/folate) or specific genetic polymorphisms. This leads to altered levels of key 1-C metabolites such as SAM (s-adenosyl methionine), SAH (s-adenosyl homocysteine), methionine, homocysteine and MMA (methyl malonic acid). These 1-C metabolites are determinants of cellular methylation potential and epigenetic modifications of DNA which impairs metabolic pathways in several pathological diseases and developmental programming. Though methods were able to measure these analytes only independently, none of the methods detect simultaneously. Therefore we developed a method to measure these five 1-C metabolites in a single run using liquid chromatography tandem mass spectrometry (LC-MS/MS). We used stable isotopes dilution LC-MS/MS to measure the 1-C metabolites in human plasma. Blood samples were collected from pregnant women (n=30) at early gestation in the ongoing, multicentre, prospective PRiDE study. Linearity exhibited across the calibration range for all the analytes with the limit of detection (LOD) of 1.005nmol/l for SAM, 0.081nmol/l for SAH, 0.002μmol/l for methionine, 0.046μmol/l for homocysteine and 3.920nmol/l for MMA. The average recovery for SAM was 108%, SAH-110%, methionine-97%, homocysteine-91% and MMA-102%. The inter-assay CV for SAM was 7.3, SAH-5.6%, methionine-3.5%, homocysteine-7.0% and MMA-4.0%. The intra-assay CV for SAM was 8.7%, SAH-4.7%, methionine-5.4%, homocysteine-8.1% and MMA-6.1%. Pregnant women at early gestation with low B12 levels had significantly higher homocysteine, MMA, lower levels of methionine, SAM and SAM:SAH ratio and higher triglycerides. We developed a simple and rapid method to simultaneously quantify 1-C metabolites such as SAM, SAH, methionine, homocysteine and MMA in plasma by stable isotope dilution LC-MS/MS which would be useful to elucidate the epigenetic mechanisms related in the gene-nutrient interactions.

  14. A universal SI-traceable isotope dilution mass spectrometry method for protein quantitation in a matrix by tandem mass tag technology.

    PubMed

    Li, Jiale; Wu, Liqing; Jin, Youxun; Su, Ping; Yang, Bin; Yang, Yi

    2016-05-01

    Isotope dilution mass spectrometry (IDMS), an important metrological method, is widely used for absolute quantification of peptides and proteins. IDMS employs an isotope-labeled peptide or protein as an internal standard although the use of a protein provides improved accuracy. Generally, the isotope-labeled protein is obtained by stable isotope labeling by amino acids in cell culture (SILAC) technology. However, SILAC is expensive, laborious, and time-consuming. To overcome these drawbacks, a novel universal SI-traceable IDMS method for absolute quantification of proteins in a matrix is described with human transferrin (hTRF). The hTRF and a human serum sample were labeled with different tandem mass tags (TMTs). After mixing the TMT-labeled hTRF and serum sample together followed by digestion, the peptides were separated by nano-liquid chromatography and analyzed by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Using the signature peptides, we calculated the ratios of reporter ions from the TMT-labeled peptides which, in turn, allowed determination of the mass fraction of hTRF. The recovery ranged from 97% to 105% with a CV of 3.9%. The LOD and LOQ were 1.71 × 10(-5) g/g and 5.69 × 10(-5) g/g of hTRF in human serum, respectively, and the relative expanded uncertainty was 4.7% with a mass fraction of 2.08 mg/g. For comparison, an enzyme-linked immunosorbent assay (ELISA) method for hTRF yielded a mass fraction of 2.03 mg/g. This method provides a starting point for establishing IDMS technology to accurately determine the mass fractions of protein biomarkers in a matrix with traceability to SI units. This technology should support the development of a metrological method useful for quantification of a wide variety of proteins. PMID:26942737

  15. Analytical model for contaminant mass removal by air sparging

    SciTech Connect

    Rabideau, A.J.; Blayden, J.M.

    1998-12-31

    An analytical model was developed to predict the removal of volatile organic compounds (VOCs) from ground water by air sparging (AS). The model treats the air sparging zone as a completely mixed reactor subject to the removal of dissolved contaminants by volatilization, advection, and first-order decay. Nonequilibrium desorption is approximated as a first-order mass transfer process. The model reproduces the tailing and rebound behavior often observed at AS sites, and would normally require the estimation of three site-specific parameters. Dimensional analysis demonstrates that predicting tailing can be interpreted in terms of kinetic desorption or diffusion of aqueous phase contaminants into discrete air channels. Related work is ongoing to test the model against field data.

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

    PubMed

    Vassileva, Emilia; Hoenig, Michel

    2011-09-01

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

  17. The mass and speed dependence of meteor air plasma temperatures.

    PubMed

    Jenniskens, Peter; Laux, Christophe O; Wilson, Michael A; Schaller, Emily L

    2004-01-01

    The speed and mass dependence of meteor air plasma temperatures is perhaps the most important data needed to understand how small meteoroids chemically change the ambient atmosphere in their path and enrich the ablated meteoric organic matter with oxygen. Such chemistry can play an important role in creating prebiotic compounds. The excitation conditions in various air plasma emissions were measured from high-resolution optical spectra of Leonid storm meteors during NASA's Leonid Multi-Instrument Aircraft Campaign. This was the first time a sufficient number and range of temperature measurements were obtained to search for meteoroid mass and speed dependencies. We found slight increases in temperature with decreasing altitude, but otherwise nearly constant values for meteoroids with speeds between 35 and 72 km/s and masses between 10(-5) g and 1 g. We conclude that faster and more massive meteoroids produce a larger emission volume, but not a higher air plasma temperature. We speculate that the meteoric plasma may be in multiphase equilibrium with the ambient atmosphere, which could mean lower plasma temperatures in a CO(2)-rich early Earth atmosphere.

  18. The mass and speed dependence of meteor air plasma temperatures

    NASA Technical Reports Server (NTRS)

    Jenniskens, Peter; Laux, Christophe O.; Wilson, Michael A.; Schaller, Emily L.

    2004-01-01

    The speed and mass dependence of meteor air plasma temperatures is perhaps the most important data needed to understand how small meteoroids chemically change the ambient atmosphere in their path and enrich the ablated meteoric organic matter with oxygen. Such chemistry can play an important role in creating prebiotic compounds. The excitation conditions in various air plasma emissions were measured from high-resolution optical spectra of Leonid storm meteors during NASA's Leonid Multi-Instrument Aircraft Campaign. This was the first time a sufficient number and range of temperature measurements were obtained to search for meteoroid mass and speed dependencies. We found slight increases in temperature with decreasing altitude, but otherwise nearly constant values for meteoroids with speeds between 35 and 72 km/s and masses between 10(-5) g and 1 g. We conclude that faster and more massive meteoroids produce a larger emission volume, but not a higher air plasma temperature. We speculate that the meteoric plasma may be in multiphase equilibrium with the ambient atmosphere, which could mean lower plasma temperatures in a CO(2)-rich early Earth atmosphere.

  19. Isotope dilution mass spectrometry for quantitative elemental analysis of powdered samples by radiofrequency pulsed glow discharge time of flight mass spectrometry.

    PubMed

    Alvarez-Toral, Aitor; Fernandez, Beatriz; Malherbe, Julien; Claverie, Fanny; Molloy, John L; Pereiro, Rosario; Sanz-Medel, Alfredo

    2013-10-15

    In recent years particular effort is being devoted to the development of pulsed glow discharges (PGDs) for mass spectrometry because this powering operation mode could offer important ionization analytical advantages. However, the capabilities of radiofrequency (RF) PGD coupled to a time of flight mass spectrometry (ToFMS) for accurate isotope ratio measurements have not been demonstrated yet. This work is focused on investigating different time positions along the pulse profile for the accurate measurement of isotope ratios. As a result, a method has been developed for the direct and simultaneous multielement determination of trace elements in powdered geological samples by RF-PGD-ToFMS in combination with isotope dilution mass spectrometry (IDMS) as an absolute measurement method directly traceable to the International System of Units. Optimized operating conditions were 70 W of applied radiofrequency power, 250 Pa of pressure, 2 ms of pulse width and 4 ms of pulse period, being argon the plasma gas used. To homogeneously distribute the added isotopically-enriched standards, lithium borate fusion of powdered solid samples was used as sample preparation approach. In this way, Cu, Zn, Ba and Pb were successfully determined by RF-PGD-ToF(IDMS) in two NIST Standard Reference Materials (SRM 2586 and SRM 2780) representing two different matrices of geological interest (soil and rock samples). Cu, Zn, Ba and Pb concentrations determined by RF-PGD-ToF(IDMS) were well in agreement with the certified values at 95% confidence interval and precisions below 12% relative standard deviation were observed for three independent analyses. Elemental concentrations investigated were in the range of 81-5770 mg/kg, demonstrating the potential of RF-PGD-ToF(IDMS) for a sensitive, accurate and robust analysis of powdered samples.

  20. Isotope dilution mass spectrometry for quantitative elemental analysis of powdered samples by radiofrequency pulsed glow discharge time of flight mass spectrometry.

    PubMed

    Alvarez-Toral, Aitor; Fernandez, Beatriz; Malherbe, Julien; Claverie, Fanny; Molloy, John L; Pereiro, Rosario; Sanz-Medel, Alfredo

    2013-10-15

    In recent years particular effort is being devoted to the development of pulsed glow discharges (PGDs) for mass spectrometry because this powering operation mode could offer important ionization analytical advantages. However, the capabilities of radiofrequency (RF) PGD coupled to a time of flight mass spectrometry (ToFMS) for accurate isotope ratio measurements have not been demonstrated yet. This work is focused on investigating different time positions along the pulse profile for the accurate measurement of isotope ratios. As a result, a method has been developed for the direct and simultaneous multielement determination of trace elements in powdered geological samples by RF-PGD-ToFMS in combination with isotope dilution mass spectrometry (IDMS) as an absolute measurement method directly traceable to the International System of Units. Optimized operating conditions were 70 W of applied radiofrequency power, 250 Pa of pressure, 2 ms of pulse width and 4 ms of pulse period, being argon the plasma gas used. To homogeneously distribute the added isotopically-enriched standards, lithium borate fusion of powdered solid samples was used as sample preparation approach. In this way, Cu, Zn, Ba and Pb were successfully determined by RF-PGD-ToF(IDMS) in two NIST Standard Reference Materials (SRM 2586 and SRM 2780) representing two different matrices of geological interest (soil and rock samples). Cu, Zn, Ba and Pb concentrations determined by RF-PGD-ToF(IDMS) were well in agreement with the certified values at 95% confidence interval and precisions below 12% relative standard deviation were observed for three independent analyses. Elemental concentrations investigated were in the range of 81-5770 mg/kg, demonstrating the potential of RF-PGD-ToF(IDMS) for a sensitive, accurate and robust analysis of powdered samples. PMID:24054645

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

    SciTech Connect

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

    1988-03-01

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

  2. Quantification of Polybrominated and Polychlorinated Biphenyls in Human Matrices by Isotope-Dilution Gas Chromatography-Tandem Mass Spectrometry.

    PubMed

    Marder, M Elizabeth; Panuwet, Parinya; Hunter, Ronald E; Ryan, P Barry; Marcus, Michele; Barr, Dana Boyd

    2016-09-01

    We have developed a highly sensitive and selective analytical method capable of quantifying a total of 15 polybrominated and polychlorinated biphenyls (11 PBBs and 4 PCBs) in human serum. Samples were subjected to liquid-liquid extraction followed by solid-phase extraction prior to measurement using gas chromatography-tandem mass spectrometry in multiple reaction monitoring mode. Quantification was performed using isotope-dilution calibration covering a concentration range of 0.005-12.5 ng/mL. Limits of detection for all target compounds were in the low range (0.7-6.5 pg/mL). The method was validated using in-house pooled human serum fortified at two concentrations (0.5 ng/mL and 1.0 ng/mL), whole semen fortified at one concentration (0.25 ng/mL), and NIST Standard Reference Material (SRM) 1958, which includes five of the target compounds. Method accuracies for all target compounds ranged from 84 to 119% with relative standard deviations (RSDs) of <19%. The measured values for the five target compounds present in the SRM agreed with the certified reference values (89-119% accuracy with RSDs <9%). As this method was developed to support ongoing epidemiologic investigations, we evaluated its suitability by analyzing subsets of serum and whole semen samples from the Michigan PBB Registry cohort. PBB-153, PCB-118, PCB-138, PCB-153 and PCB-180 were detected in all serum samples analyzed, with PBB-77 and PBB-101 detected less frequently in serum. PBB-153, PCB-118, PCB-138, PCB-153 and PCB-180 were detected in at least one whole semen sample. PMID:27445313

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

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

  4. Certification of methylmercury in cod fish tissue certified reference material by species-specific isotope dilution mass spectrometric analysis.

    PubMed

    Inagaki, Kazumi; Kuroiwa, Takayoshi; Narukawa, Tomohiro; Yarita, Takashi; Takatsu, Akiko; Okamoto, Kensaku; Chiba, Koichi

    2008-07-01

    A new cod fish tissue certified reference material, NMIJ CRM 7402-a, for methylmercury analysis was certified by the National Metrological Institute of Japan in the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Cod fish was collected from the sea close to Japan. The cod muscle was powdered by freeze-pulverization and was placed into 600 glass bottles (10 g each), which were sterilized with gamma-ray irradiation. The certification was carried out using species-specific isotope dilution gas chromatography inductively coupled plasma mass spectrometry (SSID-GC-ICPMS), where (202)Hg-enriched methylmercury (MeHg) was used as the spike compound. In order to avoid any possible analytical biases caused by nonquantitative extraction, degradation and/or formation of MeHg in sample preparations, two different extraction methods (KOH/methanol and HCl/methanol extractions) were performed, and one of these extraction methods utilized two different derivatization methods (ethylation and phenylation). A double ID method was adopted to minimize the uncertainty arising from the analyses. In order to ensure not only the reliability of the analytical results but also traceability to SI units, the standard solution of MeHg used for the reverse-ID was prepared from high-purity MeHg chloride and was carefully assayed as follows: the total mercury was determined by ID-ICPMS following aqua regia digestion, and the ratio of Hg as MeHg to the total Hg content was estimated by GC-ICPMS. The certified value given for MeHg is 0.58 +/- 0.02 mg kg(-1) as Hg.

  5. Simultaneous analysis of urinary phthalate metabolites of residents in Korea using isotope dilution gas chromatography-mass spectrometry.

    PubMed

    Kim, Miok; Song, Na Rae; Choi, Jong-Ho; Lee, Jeongae; Pyo, Heesoo

    2014-02-01

    Phthalates are used in industry products, household items, and medical tools as plasticizers. Human exposure to phthalates has raised concern about its toxicity. In the present study, optimization was conducted for the simultaneous analysis of eight kinds of phthalate metabolites using gas chromatography-mass spectrometry (GC-MS): MEP, MiBP, MnBP, MBzP, MiNP, MEHP, MEOHP, and MEHHP. In order to minimize the matrix effect and to do quantitative analysis, isotope dilution and LLE-GC-MS methods were performed. Urine samples were enzymatically hydrolyzed, extracted with a mixture of n-hexane and ethyl ether (8:2; v:v), and subsequently derivatized with trimethylsilylation. All eight kinds of analytes showed clear resolution and high reproducibility in GC-MS results. The method detection limit ranged from 0.05 ng/mL to 0.2 ng/mL. Calibration curves were found to be linear from 0.2 to 100 ng/mL with -(2)>0.992. The relative standard deviation of the intraday precision using water and urine ranged from 2.1% to 16.3%. The analysis was performed with urine samples that were collected from adults residing in the Republic of Korea. The analyzed concentration results were compared according to gender and region. As a result, DEHP metabolites showed the highest detected concentration (75.92 μg/g creatinine, 100%), and MiNP, a metabolite of DiNP, showed the lowest detected concentration (0.42 μg/g creatinine, 22.5%). On average, female urine (200.76 μg/g creatinine) had a higher detected concentration of ∑8 phthalate metabolites than male urine. Samples from rural regions (211.96 μg/g creatinine) had higher levels than samples from urban regions. PMID:23928369

  6. Aerial observations of air masses transported from East Asia to the Western Pacific: Vertical structure of polluted air masses

    NASA Astrophysics Data System (ADS)

    Hatakeyama, Shiro; Ikeda, Keisuke; Hanaoka, Sayuri; Watanabe, Izumi; Arakaki, Takemitsu; Bandow, Hiroshi; Sadanaga, Yasuhiro; Kato, Shungo; Kajii, Yoshizumi; Zhang, Daizhou; Okuyama, Kikuo; Ogi, Takashi; Fujimoto, Toshiyuki; Seto, Takafumi; Shimizu, Atsushi; Sugimoto, Nobuo; Takami, Akinori

    2014-11-01

    There has been only limited information about the vertical chemical structure of the atmosphere, so far. We conducted aerial observations on 11, 12, and 14 December 2010 over the northern part of the East China Sea to analyze the spatial distribution of atmospheric pollutants from East Asia and to elucidate transformation processes of air pollutants during the long-range transport. On 11 December, a day on which Asian dust created hazy conditions, the average PM10 concentration was 40.69 μg m-3, and we observed high concentrations of chemical components such as Ca2+, NO3-, SO42-, Al, Ca, Fe, and Zn. The height of the boundary layer was about 1200 m, and most species of pollutants (except for dust particles and SO2) had accumulated within the boundary layer. In contrast, concentrations of pollutants were low in the boundary layer (up to 1000 m) on 12 December because clean Pacific air from the southeast had diluted the haze. However, we observed natural chemical components (Na+, Cl-, Al, Ca, and Fe) at 3000 m, the indication being that dust particles, including halite, were present in the lower free troposphere. On 14 December, peak concentrations of SO2 and black carbon were measured within the boundary layer (up to 700 m) and at 2300 m. The concentrations of anthropogenic chemical components such as NO3-, NH4+, and Zn were highest at 500 m, and concentrations of both anthropogenic and natural chemical components (SO42-, Pb, Ca2+, Ca, Al, and Fe) were highest at 2000 m. Thus, it was clearly indicated that the air above the East China Sea had a well-defined, layered structure below 3000 m.

  7. Determination of thyroid hormones in mouse tissues by isotope-dilution microflow liquid chromatography-mass spectrometry method.

    PubMed

    De Angelis, Meri; Giesert, Florian; Finan, Brian; Clemmensen, Christoffer; Müller, Timo D; Vogt-Weisenhorn, Daniela; Tschöp, Matthias H; Schramm, Karl-Werner

    2016-10-15

    Thyroid hormones (THs) play a critical role in the regulation of many biological processes such as growth, metabolism and development both in humans and wildlife. In general, TH levels are measured by immunoassay (IA) methods but the specificity of the antibodies used in these assays limits selectivity. In the last decade, several analytical methods using liquid chromatography-mass spectrometry (LC-MS) and tandem mass spectrometry (LC-MS/MS) have been developed to measure THs. These new techniques proved to be more accurate than the IA analysis and they were widely used for the determination of TH level in different human and animal tissues. A large part of LC-MS/MS methods described in literature employed between 200 and 500mg of sample, however this quantity can be considered too high especially when preclinical studies are conducted using mice as test subjects. Thus an analytical method that reduces the amount of tissue is essential. In this study, we developed a procedure for the analysis of six THs; L-thyroxine (T4), 3,3',5-triiodo-l-thyronine (T3), 3,3',5'-triiodo-l-thyronine (rT3), 3,5-diiodo-l-thyronine (rT2), 3,3'-diiodo-l-thyronine (T2), 3-iodo-l-thyronine (T1) using isotope ((13)C6-T4, (13)C6-T3, (13)C6-rT3, (13)C6-T2) dilution liquid chromatography-mass spectrometry. The major difference with previously described methods lies in the utilization of a nano-UPLC (Ultra Performance Liquid Chromatography) system in micro configuration. This approach leads to a reduction compared to the published methods, of column internal diameter, flow rate, and injected volume. The result of all these improvements is a decrease in the amount of sample necessary for the analysis. The method was tested on six different mouse tissues: liver, heart, kidney, muscle, lung and brown adipose tissue (BAT). The nano-UPLC system was interfaced with a quadrupole time-of-flight mass spectrometer (Q-TOF2-MS) using the positive ion mode electrospray ionization. In our analytical method

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

    PubMed

    Surugaya, Naoki; Hiyama, Toshiaki; Watahiki, Masaru

    2008-06-01

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

  9. Validation of a gas chromatography-mass spectrometry isotope dilution method for the determination of 2-butoxyethanol and other common glycol ethers in consumer products.

    PubMed

    Tokarczyk, Ryszard; Jiang, Ying; Poole, Gary; Turle, Richard

    2010-10-29

    A gas chromatography-mass spectrometry isotope dilution (GC-MS ID) method was developed and tested for the determination of 14 common glycol ethers in consumer products. Stable isotope labelled standards, 2-methoxyethanol-D(7) and 2-butoxyethanol-(13)C(2) (CDN isotopes) were employed to enhance the accuracy and precision of the glycol ethers determination. A 1000-fold sample dilution with methanol was applied to avoid column overload and contamination. At this dilution matrix effects were in most cases negligible and did not interfere with the analysis. The instrument detection limit (IDL) for analysed compounds varied from 0.01 to 1 μg/mL; while the estimated limit of quantification (LoQ) varied between different glycol ethers from 0.02 to 3.4 μg/mL. Calibration was tested in the range of 0.1-200 μg/mL and showed that the linear fit is upheld from 0.1 to 10 μg/mL, and extends beyond this range for some of the analytes. Recoveries of glycol ethers from products with different matrices were similar. The recoveries varied from 87% to 116% between the analysed compounds, while measurements precision varied between 2% and 14%. The method is applicable to products with glycol ether concentrations above 0.002-0.2% (w/w). The concentration range can be extended below the specified limits by decreasing the dilution factor; however, with lower dilution the sample matrix effect is expected to be stronger. Products with very high concentrations of glycol ether (>20%) may need to be further diluted prior to injection to avoid column overload. The method can be used for testing liquid and aerosol products designed for household use, such as cleaners, paints, solvents and paint stripers, for compliance and enforcement of regulations which limit glycol ethers content.

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

    PubMed

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

    2015-07-16

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

  11. 40 CFR 1066.615 - NOX intake-air humidity correction.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... vapor pressure at the ambient dry bulb temperature. RH = relative humidity of ambient air M air = molar mass of air. p atmos = atmospheric pressure. ER28AP14.106 Where: x NOXdexh = measured dilute...

  12. [Analysis of polycyclic aromatic hydrocarbons in air samples by gas chromatography-triple quadrupole mass spectrometry].

    PubMed

    Zhao, Bo; Li, Yuqing; Zhang, Sukun; Han, Jinglei; Xu, Zhencheng; Fang, Jiande

    2014-09-01

    A method of gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-MS/MS) has been optimized for the determination of polycyclic aromatic hydrocarbons (PAHs) in air samples. In the analysis step, isotope dilution was introduced to the quantification of PAHs. The GC-MS/MS method was applied to the analysis of the real air samples around a big petrochemical power plant in South China. The results were compared with those obtained by gas chromatography coupled to mass spectrometry (GC-MS). The results showed that better selectivity and sensitivity were obtained by GC-MS/MS. It was found that the external standard of deuterated-PAHs and internal standard of hexamethyl benzene were disturbed seriously with GC-MS, and the problems were both solved effectively by GC-MS/MS. Therefore more accurate quantification results of PAHs were obtained with GC-MS/MS. For the analysis of real samples, the RSDs of relative response factors ranged from 2.60% to 15.6% in standard curves; the recoveries of deuterated-PAHs ranged from 55.2% to 82.3%; the recoveries of spiked samples ranged from 98.9% to 111%; the RSDs of parallel specimens ranged from 6.50% to 18.4%; the concentrations of field blank samples ranged from not detected to 44.3 pg/m3; and the concentrations of library blank samples ranged from not detected to 36.5 pg/m3. The study indicated that the application of GC-MS/MS on the analysis of PAHs in air samples was recommended. PMID:25752088

  13. Functional forms for approximating the relative optical air mass

    NASA Astrophysics Data System (ADS)

    Rapp-Arrarás, Ígor; Domingo-Santos, Juan M.

    2011-12-01

    This article constitutes a review and systematic comparison of functional forms for approximating the air mass from the zenith to the horizon. Among them, we find the most meaningful forms in atmospheric optics, geophysics, meteorology, and solar energy science, as well as several forms arising from the study of the atmospheric delay of electromagnetic signals, whose relationship with the air mass was recently proved by the authors. In total, we have compared 26 functional forms, and the fits have been done for three atmospheric profiles, an observer at sea level, and the median wavelength of the Sun's spectral irradiance (0.7274 μm). As a result, the best of the uniparametric forms has more than three centuries of history; the best of the biparametric forms was recently introduced by one of the authors; the best of the tri- and tetraparametric forms were originally proposed for modeling the atmospheric delay of radio signals; and the best of the forms with more than four parameters is used here for the first time. On the basis of these, for the 1976 U.S. Standard Atmosphere (USSA-76), we provide one-, two-, three-, four-, and five-parameter formulas whose maximum deviations are 1.70, 2.91 × 10-1, 3.28 × 10-2, 2.49 × 10-3, and 3.24 × 10-4, respectively.

  14. Determination of benzene, toluene, ethylbenzene and xylenes in air by solid phase micro-extraction/gas chromatography/mass spectrometry.

    PubMed

    Tumbiolo, Simonetta; Gal, Jean-François; Maria, Pierre-Charles; Zerbinati, Orfeo

    2004-11-01

    The aim of the study was to analyse BTEX compounds (benzene, toluene, ethylbenzene, xylenes) in air by solid phase micro-extraction/gas chromatography/mass spectrometry (SPME/GC/MS), and this article presents the features of the calibration method proposed. Examples of real-world air analysis are given. Standard gaseous mixtures of BTEX in air were generated by dynamic dilution. SPME sampling was carried out under non-equilibrium conditions using a Carboxen/PDMS fibre exposed for 30 min to standard gas mixtures or to ambient air. The behaviour of the analytical response was studied from 0 to 65 microg/m3 by adding increasing amounts of BTEX to the air matrix. Detection limits range from 0.05 to 0.1 microg/m3 for benzene, depending on the fibre. Inter-fibre relative standard deviations (reproducibility) are larger than 18%, although the repeatability for an individual fibre is better than 10%. Therefore, each fibre should be considered to be a particular sampling device, and characterised individually depending on the required accuracy. Sampling indoor and outdoor air by SPME appears to be a suitable short-delay diagnostic method for volatile organic compounds, taking advantage of short sampling time and simplicity.

  15. Isotope dilution for quantitation of steroid estrogens and nonylphenols by gas chromatography with tandem mass spectrometry in septic, soil, and groundwater matrices.

    PubMed

    Stanford, Benjamin D; Weinberg, Howard S

    2007-12-28

    A simplified, in-line solid-phase extraction and clean-up process is presented for rapid extraction and analysis of steroid estrogens and nonylphenols by gas chromatography with tandem mass spectrometry. Isotope dilution with multiple deuterated standards has been developed, evaluated, and verified using this method against standard addition for the analysis of estrone, estradiol, estriol, ethinylestradiol, and 4-nonylphenols in septic, soil, and groundwater matrices. The accuracy and precision of isotope dilution was comparable to standard addition yet was able to quantify analytes with the use of fewer samples by including [(2)H(4)]estradiol, [(2)H(4)]ethinylestradiol, [(2)H(4)]nonylphenol, and estradiol-17-acetate as internal standards. Specific details and validation of the method are presented as are data showing the occurrence of estrogens and nonylphenols in an on-site wastewater treatment (septic) system with advanced stages of pretreatment and recirculation to an office building for non-potable reuse.

  16. High-Altitude Air Mass Zero Calibration of Solar Cells

    NASA Technical Reports Server (NTRS)

    Woodyard, James R.; Snyder, David B.

    2005-01-01

    Air mass zero calibration of solar cells has been carried out for several years by NASA Glenn Research Center using a Lear-25 aircraft and Langley plots. The calibration flights are carried out during early fall and late winter when the tropopause is at the lowest altitude. Measurements are made starting at about 50,000 feet and continue down to the tropopause. A joint NASA/Wayne State University program called Suntracker is underway to explore the use of weather balloon and communication technologies to characterize solar cells at elevations up to about 100 kft. The balloon flights are low-cost and can be carried out any time of the year. AMO solar cell characterization employing the mountaintop, aircraft and balloon methods are reviewed. Results of cell characterization with the Suntracker are reported and compared with the NASA Glenn Research Center aircraft method.

  17. Monitoring Trace Contaminants in Air Via Ion Trap Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Palmer, Peter T.; Karr, Dane; Pearson, Richard; Valero, Gustavo; Wong, Carla

    1995-01-01

    Recent passage of the Clean Air Act with its stricter regulation of toxic gas emissions, and the ever-growing number of applications which require faster turnaround times between sampling and analysis are two major factors which are helping to drive the development of new instrument technologies for in-situ, on-line, real-time monitoring. The ion trap, with its small size, excellent sensitivity, and tandem mass spectrometry capability is a rapidly evolving technology which is well-suited for these applications. In this paper, we describe the use of a commercial ion trap instrument for monitoring trace levels of chlorofluorocarbons (CFCs) and volatile organic compounds (VOCs) in air. A number of sample introduction devices including a direct transfer line interface, short column GC, and a cryotrapping interface are employed to achieve increasing levels of sensitivity. MS, MS/MS, and MS/MS/MS methods are compared to illustrate trade-offs between sensitivity and selectivity. Filtered Noise Field (FNF) technology is found to be an excellent means for achieving lower detection limits through selective storage of the ion(s) of interest during ionization. Figures of merit including typical sample sizes, detection limits, and response times are provided. The results indicate the potential of these techniques for atmospheric assessments, the High Speed Research Program, and advanced life support monitoring applications for NASA.

  18. Reference measurements for total mercury and methyl mercury content in marine biota samples using direct or species-specific isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Krata, Agnieszka; Vassileva, Emilia; Bulska, Ewa

    2016-11-01

    The analytical procedures for reference measurements of the total Hg and methyl mercury (MeHg) mass fractions at various concentration levels in marine biota samples, candidates for certified reference materials (oyster and clam Gafrarium tumidum), were evaluated. Two modes of application of isotope dilution inductively coupled plasma mass spectrometry method (ID ICP-MS), namely direct isotope dilution and species-specific isotope dilution analysis with the use of two different quantification mass spectrometry techniques were compared. The entire ID ICP-MS measurement procedure was described by mathematical modelling and the combined uncertainty of measurement results was estimated. All factors influencing the final results as well as isotopic equilibrium were systematically investigated. This included the procedural blank, the moisture content in the biota samples and all factors affecting the blend ratio measurements (instrumental background, spectral interferences, dead time and mass discrimination effects as well as the repeatability of measured isotopic ratios). Modelling of the entire measurement procedures and the use of appropriate certified reference materials enable to assure the traceability of obtained values to the International System of Units (SI): the mole or the kilogram. The total mass fraction of mercury in oyster and clam biota samples, after correction for moisture contents, was found to be: 21.1 (1.1) 10(-9) kg kg(-1) (U =5.1% relative, k=2) and 390.0 (9.4) 10(-9) kg kg(-1) (U=2.4% relative, k=2), respectively. For the determination of mercury being present as methyl mercury, the non-chromatographic separation on anion-exchange resin AG1-X8 of the blended samples was applied. The content of MeHg (as Hg) in oyster sample was found: 4.81 (24) 10(-9)kgkg(-1) (U=5.0%, k=2) and 4.84 (21) 10(-9)kgkg(-1) (U=4.3%, k=2) with the use of quadrupole (ICP QMS) or sector field (ICP SFMS) inductively coupled plasma mass spectrometers, respectively. In the

  19. Reference measurements for total mercury and methyl mercury content in marine biota samples using direct or species-specific isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Krata, Agnieszka; Vassileva, Emilia; Bulska, Ewa

    2016-11-01

    The analytical procedures for reference measurements of the total Hg and methyl mercury (MeHg) mass fractions at various concentration levels in marine biota samples, candidates for certified reference materials (oyster and clam Gafrarium tumidum), were evaluated. Two modes of application of isotope dilution inductively coupled plasma mass spectrometry method (ID ICP-MS), namely direct isotope dilution and species-specific isotope dilution analysis with the use of two different quantification mass spectrometry techniques were compared. The entire ID ICP-MS measurement procedure was described by mathematical modelling and the combined uncertainty of measurement results was estimated. All factors influencing the final results as well as isotopic equilibrium were systematically investigated. This included the procedural blank, the moisture content in the biota samples and all factors affecting the blend ratio measurements (instrumental background, spectral interferences, dead time and mass discrimination effects as well as the repeatability of measured isotopic ratios). Modelling of the entire measurement procedures and the use of appropriate certified reference materials enable to assure the traceability of obtained values to the International System of Units (SI): the mole or the kilogram. The total mass fraction of mercury in oyster and clam biota samples, after correction for moisture contents, was found to be: 21.1 (1.1) 10(-9) kg kg(-1) (U =5.1% relative, k=2) and 390.0 (9.4) 10(-9) kg kg(-1) (U=2.4% relative, k=2), respectively. For the determination of mercury being present as methyl mercury, the non-chromatographic separation on anion-exchange resin AG1-X8 of the blended samples was applied. The content of MeHg (as Hg) in oyster sample was found: 4.81 (24) 10(-9)kgkg(-1) (U=5.0%, k=2) and 4.84 (21) 10(-9)kgkg(-1) (U=4.3%, k=2) with the use of quadrupole (ICP QMS) or sector field (ICP SFMS) inductively coupled plasma mass spectrometers, respectively. In the

  20. Simultaneous determination of creatinine and creatine in human serum by double-spike isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry (GC-MS).

    PubMed

    Fernández-Fernández, Mario; Rodríguez-González, Pablo; Añón Álvarez, M Elena; Rodríguez, Felix; Menéndez, Francisco V Álvarez; García Alonso, J Ignacio

    2015-04-01

    This work describes the first multiple spiking isotope dilution procedure for organic compounds using (13)C labeling. A double-spiking isotope dilution method capable of correcting and quantifying the creatine-creatinine interconversion occurring during the analytical determination of both compounds in human serum is presented. The determination of serum creatinine may be affected by the interconversion between creatine and creatinine during sample preparation or by inefficient chemical separation of those compounds by solid phase extraction (SPE). The methodology is based on the use differently labeled (13)C analogues ((13)C1-creatinine and (13)C2-creatine), the measurement of the isotopic distribution of creatine and creatinine by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and the application of multiple linear regression. Five different lyophilized serum-based controls and two certified human serum reference materials (ERM-DA252a and ERM-DA253a) were analyzed to evaluate the accuracy and precision of the proposed double-spike LC-MS/MS method. The methodology was applied to study the creatine-creatinine interconversion during LC-MS/MS and gas chromatography-mass spectrometry (GC-MS) analyses and the separation efficiency of the SPE step required in the traditional gas chromatography-isotope dilution mass spectrometry (GC-IDMS) reference methods employed for the determination of serum creatinine. The analysis of real serum samples by GC-MS showed that creatine-creatinine separation by SPE can be a nonquantitative step that may induce creatinine overestimations up to 28% in samples containing high amounts of creatine. Also, a detectable conversion of creatine into creatinine was observed during sample preparation for LC-MS/MS. The developed double-spike LC-MS/MS improves the current state of the art for the determination of creatinine in human serum by isotope dilution mass spectrometry (IDMS), because corrections are made for all the possible errors

  1. Mass transfer of VOCs in laboratory-scale air sparging tank.

    PubMed

    Chao, Keh-Ping; Ong, Say Kee; Huang, Mei-Chuan

    2008-04-15

    Volatilization of VOCs was investigated using a 55-gal laboratory-scale model in which air sparging experiments were conducted with a vertical air injection well. In addition, X-ray imaging of an air sparging sand box showed air flows were in the form of air bubbles or channels depending on the size of the porous media. Air-water mass transfer was quantified using the air-water mass transfer coefficient which was determined by fitting the experimental data to a two-zone model. The two-zone model is a one-dimensional lumped model that accounts for the effects of air flow type and diffusion of VOCs in the aqueous phase. The experimental air-water mass transfer coefficients, KGa, obtained from this study ranged from 10(-2) to 10(-3)1/min. From a correlation analysis, the air-water mass transfer coefficient was found to be directly proportional to the air flow rate and the mean particle size of soil but inversely proportional to Henry's constant. The correlation results implied that the air-water mass transfer coefficient was strongly affected by the size of porous media and the air flow rates. PMID:17804158

  2. Changing air mass frequencies in Canada: potential links and implications for human health.

    PubMed

    Vanos, J K; Cakmak, S

    2014-03-01

    Many individual variables have been studied to understand climate change, yet an overall weather situation involves the consideration of many meteorological variables simultaneously at various times diurnally, seasonally, and yearly. The current study identifies a full weather situation as an air mass type using synoptic scale classification, in 30 population centres throughout Canada. Investigative analysis of long-term air mass frequency trends was completed, drawing comparisons between seasons and climate zones. We find that the changing air mass trends are highly dependent on the season and climate zone being studied, with an overall increase of moderate ('warm') air masses and decrease of polar ('cold') air masses. In the summertime, general increased moisture content is present throughout Canada, consistent with the warming air masses. The moist tropical air mass, containing the most hot and humid air, is found to increase in a statistically significant fashion in the summertime in 46% of the areas studied, which encompass six of Canada's ten largest population centres. This emphasises the need for heat adaptation and acclimatisation for a large proportion of the Canadian population. In addition, strong and significant decreases of transition/frontal passage days were found throughout Canada. This result is one of the most remarkable transition frequency results published to date due to its consistency in identifying declining trends, coinciding with research completed in the United States (US). We discuss relative results and implications to similar US air mass trend analyses, and draw upon research studies involving large-scale upper-level air flow and vortex connections to air mass changes, to small-scale meteorological and air pollution interactions. Further research is warranted to better understand such connections, and how these air masses relate to the overall and city-specific health of Canadians.

  3. Microbial air quality in mass transport buses and work-related illness among bus drivers of Bangkok Mass Transit Authority.

    PubMed

    Luksamijarulkul, Pipat; Sundhiyodhin, Viboonsri; Luksamijarulkul, Soavalug; Kaewboonchoo, Orawan

    2004-06-01

    The air quality in mass transport buses, especially air-conditioned buses may affect bus drivers who work full time. Bus numbers 16, 63, 67 and 166 of the Seventh Bus Zone of Bangkok Mass Transit Authority were randomly selected to investigate for microbial air quality. Nine air-conditioned buses and 2-4 open-air buses for each number of the bus (36 air-conditioned buses and 12 open-air buses) were included. Five points of in-bus air samples in each studied bus were collected by using the Millipore A ir Tester Totally, 180 and 60 air samples collected from air-conditioned buses and open-air buses were cultured for bacterial and fungal counts. The bus drivers who drove the studied buses were interviewed towards histories of work-related illness while working. The results revealed that the mean +/- SD of bacterial counts in the studied open-air buses ranged from 358.50 +/- 146.66 CFU/m3 to 506 +/- 137.62 CFU/m3; bus number 16 had the highest level. As well as the mean +/- SD of fungal counts which ranged from 93.33 +/- 44.83 CFU/m3 to 302 +/- 294.65 CFU/m3; bus number 166 had the highest level. Whereas, the mean +/- SD of bacterial counts in the studied air-conditioned buses ranged from 115.24 +/- 136.01 CFU/m3 to 244.69 +/- 234.85 CFU/m3; bus numbers 16 and 67 had the highest level. As well as the mean +/- SD of fungal counts which rangedfrom 18.84 +/- 39.42 CFU/m3 to 96.13 +/- 234.76 CFU/m3; bus number 166 had the highest level. When 180 and 60 studied air samples were analyzed in detail, it was found that 33.33% of the air samples from open-air buses and 6.11% of air samples from air-conditioned buses had a high level of bacterial counts (> 500 CFU/m3) while 6.67% of air samples from open-air buses and 2.78% of air samples from air-conditioned buses had a high level of fungal counts (> 500 CFU/m3). Data from the history of work-related illnesses among the studied bus drivers showed that 91.67% of open-air bus drivers and 57.28% of air-conditioned bus drivers had

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

    USGS Publications Warehouse

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

    2009-01-01

    The U.S. Geological Survey method (0-2141-09) presented is approved for the determination of glyphosate, its degradation product aminomethylphosphonic acid (AMPA), and glufosinate in water. It was was validated to demonstrate the method detection levels (MDL), compare isotope dilution to standard addition, and evaluate method and compound stability. The original method USGS analytical method 0-2136-01 was developed using liquid chromatography/mass spectrometry and quantitation by standard addition. Lower method detection levels and increased specificity were achieved in the modified method, 0-2141-09, by using liquid chromatography/tandem mass spectrometry (LC/MS/MS). The use of isotope dilution for glyphosate and AMPA and pseudo isotope dilution of glufosinate in place of standard addition was evaluated. Stable-isotope labeled AMPA and glyphosate were used as the isotope dilution standards. In addition, the stability of glyphosate and AMPA was studied in raw filtered and derivatized water samples. The stable-isotope labeled glyphosate and AMPA standards were added to each water sample and the samples then derivatized with 9-fluorenylmethylchloroformate. After derivatization, samples were concentrated using automated online solid-phase extraction (SPE) followed by elution in-line with the LC mobile phase; the compounds separated and then were analyzed by LC/MS/MS using electrospray ionization in negative-ion mode with multiple-reaction monitoring. The deprotonated derivatized parent molecule and two daughter-ion transition pairs were identified and optimized for glyphosate, AMPA, glufosinate, and the glyphosate and AMPA stable-isotope labeled internal standards. Quantitative comparison between standard addition and isotope dilution was conducted using 473 samples analyzed between April 2004 and June 2006. The mean percent difference and relative standard deviation between the two quantitation methods was 7.6 plus or minus 6.30 (n = 179), AMPA 9.6 plus or minus 8

  5. Pre-column dilution large volume injection ultra-high performance liquid chromatography-tandem mass spectrometry for the analysis of multi-class pesticides in cabbages.

    PubMed

    Zhong, Qisheng; Shen, Lingling; Liu, Jiaqi; Yu, Dianbao; Li, Siming; Yao, Jinting; Zhan, Song; Huang, Taohong; Hashi, Yuki; Kawano, Shin-ichi; Liu, Zhaofeng; Zhou, Ting

    2016-04-15

    Pre-column dilution large volume injection (PD-LVI), a novel sample injection technique for reverse phase ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), was developed in this study. The PD-LVI UHPLC-MS/MS system was designed by slightly modifying the commercial UHPLC-MS/MS equipment with a mixer chamber. During the procedure of PD-LVI, sample solution of 200μL was directly carried by the organic mobile phase to the mixer and diluted with the aqueous mobile phase. After the mixture was introduced to the UHPLC column in a mobile phase of acetonitrile-water (15/85, v/v), the target analytes were stacked on the head of the column until following separation. Using QuEChERS extraction, no additional steps such as solvent evaporation or residue redissolution were needed before injection. The features of PD-LVI UHPLC-MS/MS system were systematically investigated, including the injection volume, the mixer volume, the precondition time and the gradient elution. The efficiency of this approach was demonstrated by direct analysis of 24 pesticides in cabbages. Under the optimized conditions, low limits of detection (0.00074-0.8 ng/kg) were obtained. The recoveries were in the range of 63.3-109% with relative standard deviations less than 8.1%. Compared with common UHPLC-MS/MS technique, PD-LVI UHPLC-MS/MS showed significant advantages such as excellent sensitivity and reliability. The mechanism of PD-LVI was demonstrated to be based on the column-head stacking effect with pre-column dilution. Based on the results, PD-LVI as a simple and effective sample injection technique of reverse phase UHPLC-MS/MS for the analysis of trace analytes in complex samples showed a great promising prospect. PMID:26979268

  6. Pre-column dilution large volume injection ultra-high performance liquid chromatography-tandem mass spectrometry for the analysis of multi-class pesticides in cabbages.

    PubMed

    Zhong, Qisheng; Shen, Lingling; Liu, Jiaqi; Yu, Dianbao; Li, Siming; Yao, Jinting; Zhan, Song; Huang, Taohong; Hashi, Yuki; Kawano, Shin-ichi; Liu, Zhaofeng; Zhou, Ting

    2016-04-15

    Pre-column dilution large volume injection (PD-LVI), a novel sample injection technique for reverse phase ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), was developed in this study. The PD-LVI UHPLC-MS/MS system was designed by slightly modifying the commercial UHPLC-MS/MS equipment with a mixer chamber. During the procedure of PD-LVI, sample solution of 200μL was directly carried by the organic mobile phase to the mixer and diluted with the aqueous mobile phase. After the mixture was introduced to the UHPLC column in a mobile phase of acetonitrile-water (15/85, v/v), the target analytes were stacked on the head of the column until following separation. Using QuEChERS extraction, no additional steps such as solvent evaporation or residue redissolution were needed before injection. The features of PD-LVI UHPLC-MS/MS system were systematically investigated, including the injection volume, the mixer volume, the precondition time and the gradient elution. The efficiency of this approach was demonstrated by direct analysis of 24 pesticides in cabbages. Under the optimized conditions, low limits of detection (0.00074-0.8 ng/kg) were obtained. The recoveries were in the range of 63.3-109% with relative standard deviations less than 8.1%. Compared with common UHPLC-MS/MS technique, PD-LVI UHPLC-MS/MS showed significant advantages such as excellent sensitivity and reliability. The mechanism of PD-LVI was demonstrated to be based on the column-head stacking effect with pre-column dilution. Based on the results, PD-LVI as a simple and effective sample injection technique of reverse phase UHPLC-MS/MS for the analysis of trace analytes in complex samples showed a great promising prospect.

  7. Dilution Confusion: Conventions for Defining a Dilution

    ERIC Educational Resources Information Center

    Fishel, Laurence A.

    2010-01-01

    Two conventions for preparing dilutions are used in clinical laboratories. The first convention defines an "a:b" dilution as "a" volumes of solution A plus "b" volumes of solution B. The second convention defines an "a:b" dilution as "a" volumes of solution A diluted into a final volume of "b". Use of the incorrect dilution convention could affect…

  8. Multiple spiking species-specific isotope dilution analysis by molecular mass spectrometry: simultaneous determination of inorganic mercury and methylmercury in fish tissues.

    PubMed

    Castillo, Angel; Rodríguez-González, Pablo; Centineo, Giuseppe; Roig-Navarro, Antoni Francesc; García Alonso, J Ignacio

    2010-04-01

    This work demonstrates, for the first time, the applicability of multiple spiking isotope dilution analysis to molecular mass spectrometry exemplified by the speciation analysis of mercury using GC(EI)MS instrumentation. A double spike isotope dilution approach using isotopically enriched mercury isotopes has been applied for the determination of inorganic mercury Hg(II) and methylmercury (MeHg) in fish reference materials. The method is based on the application of isotope pattern deconvolution for the simultaneous determination of degradation-corrected concentrations of methylmercury and inorganic mercury. Mass isotopomer distributions are employed instead of isotope ratios to calculate the corrected concentrations of the Hg species as well as the extent of species degradation reactions. The isotope pattern deconvolution equations developed here allow the calculation of the different molar fractions directly from the GC(EI)MS mass isotopomer distribution pattern and take into account possible impurities present in the spike solutions employed. The procedure has been successfully validated with the analysis of two different certified reference materials (BCR-464 and DOLT-4) and with the comparison of the results obtained by GC(ICP)MS. For the tuna fish matrix (BCR-464), no interconversion reactions were observed at the optimized conditions of open focused microwave extraction at 70 degrees C during 8 min. However, significant demethylation was found under the same conditions in the case of the certified dogfish liver DOLT-4. Methylation and demethylation factors were confirmed by GC(ICP)MS. Transformation reactions have been found to depend on the sample matrix and on the derivatization reagent employed. Thus, it is not possible to recommend optimum extraction conditions suitable for all types of matrices demonstrating the need to apply multiple spiking methodologies for the determination of MeHg and Hg(II) in biological samples. Double spike isotope dilution

  9. Multiple spiking species-specific isotope dilution analysis by molecular mass spectrometry: simultaneous determination of inorganic mercury and methylmercury in fish tissues.

    PubMed

    Castillo, Angel; Rodríguez-González, Pablo; Centineo, Giuseppe; Roig-Navarro, Antoni Francesc; García Alonso, J Ignacio

    2010-04-01

    This work demonstrates, for the first time, the applicability of multiple spiking isotope dilution analysis to molecular mass spectrometry exemplified by the speciation analysis of mercury using GC(EI)MS instrumentation. A double spike isotope dilution approach using isotopically enriched mercury isotopes has been applied for the determination of inorganic mercury Hg(II) and methylmercury (MeHg) in fish reference materials. The method is based on the application of isotope pattern deconvolution for the simultaneous determination of degradation-corrected concentrations of methylmercury and inorganic mercury. Mass isotopomer distributions are employed instead of isotope ratios to calculate the corrected concentrations of the Hg species as well as the extent of species degradation reactions. The isotope pattern deconvolution equations developed here allow the calculation of the different molar fractions directly from the GC(EI)MS mass isotopomer distribution pattern and take into account possible impurities present in the spike solutions employed. The procedure has been successfully validated with the analysis of two different certified reference materials (BCR-464 and DOLT-4) and with the comparison of the results obtained by GC(ICP)MS. For the tuna fish matrix (BCR-464), no interconversion reactions were observed at the optimized conditions of open focused microwave extraction at 70 degrees C during 8 min. However, significant demethylation was found under the same conditions in the case of the certified dogfish liver DOLT-4. Methylation and demethylation factors were confirmed by GC(ICP)MS. Transformation reactions have been found to depend on the sample matrix and on the derivatization reagent employed. Thus, it is not possible to recommend optimum extraction conditions suitable for all types of matrices demonstrating the need to apply multiple spiking methodologies for the determination of MeHg and Hg(II) in biological samples. Double spike isotope dilution

  10. Modification of a commercial gas chromatography isotope ratio mass spectrometer for on-line carbon isotope dilution: Evaluation of its analytical characteristics for the quantification of organic compounds.

    PubMed

    Alonso Sobrado, Laura; Robledo Fernández, Mario; Cueto Díaz, Sergio; Ruiz Encinar, Jorge; García Alonso, J Ignacio

    2015-11-01

    We describe the instrumental modification of a commercial gas chromatography isotope ratio mass spectrometer (GC-IRMS) and its application for on-line carbon isotope dilution. The main modification consisted in the addition of a constant flow of enriched (13)CO2 diluted in helium after the chromatographic column through the splitter holder located inside the chromatographic oven of the instrument. In addition, and in contrast to the conventional mode of operation of GC-IRMS instruments where the signal at m/z 45 is amplified 100-fold with respect to the signal at m/z 44, the same signal amplification was used in both Faraday cups at m/z 44 and 45. Under these conditions isotope ratio precision for the ratio 44/45 was around 0.05% RSD (n=50). The evaluation of the instrument was performed with mixtures of organic compounds including 11 n-alkanes, 16 PAHs, 12 PCBs and 3 benzothiophenes. It was observed that compounds of very different boiling points could be analysed without discrimination in the injector when a Programmable Temperature Vaporizer (PTV) injector was employed. Moreover, the presence of heteroatoms (Cl or S) in the structure of the organic compounds did not affect their combustion efficiency and therefore the trueness of the results. Quantitative results obtained for all the analytes assayed were excellent in terms of precision (<3% RSD) and accuracy (average relative error≤4%) and what is more important using a single and simple generic internal standard for quantification. PMID:26435309

  11. Determination of the alkylpyrazine composition of coffee using stable isotope dilution-gas chromatography-mass spectrometry (SIDA-GC-MS).

    PubMed

    Pickard, Stephanie; Becker, Irina; Merz, Karl-Heinz; Richling, Elke

    2013-07-01

    A stable isotope dilution analysis based on gas chromatography-mass spectrometry analysis (SIDA-GC-MS) was developed for the quantitative analysis of 12 alkylpyrazines found in commercially available coffee samples. These compounds contribute to coffee flavor. The accuracy of this method was tested by analyzing model mixtures of alkylpyrazines. Comparisons of alkylpyrazine-concentrations suggested that water as extraction solvent was superior to dichloromethane. The distribution patterns of alkylpyrazines in different roasted coffees were quite similar. The most abundant alkylpyrazine in each coffee sample was 2-methylpyrazine, followed by 2,6-dimethylpyrazine, 2,5-dimethylpyrazine, 2-ethylpyrazine, 2-ethyl-6-methylpyrazine, 2-ethyl-5-methylpyrazine, and 2,3,5-trimethylpyrazine, respectively. Among the alkylpyrazines tested, 2,3-dimethylpyrazine, 2-ethyl-3-methylpyrazine, 2-ethyl-3,6-dimethylpyrazine, and 2-ethyl-3,5-dimethylpyrazine revealed the lowest concentrations in roasted coffee. By the use of isotope dilution analysis, the total concentrations of alkylpyrazines in commercially available ground coffee ranged between 82.1 and 211.6 mg/kg, respectively. Decaffeinated coffee samples were found to contain lower amounts of alkylpyrazines than regular coffee samples by a factor of 0.3-0.7, which might be a result of the decaffeination procedure. PMID:23745606

  12. Determination of the alkylpyrazine composition of coffee using stable isotope dilution-gas chromatography-mass spectrometry (SIDA-GC-MS).

    PubMed

    Pickard, Stephanie; Becker, Irina; Merz, Karl-Heinz; Richling, Elke

    2013-07-01

    A stable isotope dilution analysis based on gas chromatography-mass spectrometry analysis (SIDA-GC-MS) was developed for the quantitative analysis of 12 alkylpyrazines found in commercially available coffee samples. These compounds contribute to coffee flavor. The accuracy of this method was tested by analyzing model mixtures of alkylpyrazines. Comparisons of alkylpyrazine-concentrations suggested that water as extraction solvent was superior to dichloromethane. The distribution patterns of alkylpyrazines in different roasted coffees were quite similar. The most abundant alkylpyrazine in each coffee sample was 2-methylpyrazine, followed by 2,6-dimethylpyrazine, 2,5-dimethylpyrazine, 2-ethylpyrazine, 2-ethyl-6-methylpyrazine, 2-ethyl-5-methylpyrazine, and 2,3,5-trimethylpyrazine, respectively. Among the alkylpyrazines tested, 2,3-dimethylpyrazine, 2-ethyl-3-methylpyrazine, 2-ethyl-3,6-dimethylpyrazine, and 2-ethyl-3,5-dimethylpyrazine revealed the lowest concentrations in roasted coffee. By the use of isotope dilution analysis, the total concentrations of alkylpyrazines in commercially available ground coffee ranged between 82.1 and 211.6 mg/kg, respectively. Decaffeinated coffee samples were found to contain lower amounts of alkylpyrazines than regular coffee samples by a factor of 0.3-0.7, which might be a result of the decaffeination procedure.

  13. Mathematical modeling of heat exchange between mine air and rock mass during fire

    SciTech Connect

    A.E. Krasnoshtein; B.P. Kazakov; A.V. Shalimov

    2006-05-15

    Solution of problems on heat exchange between ventilating air and rock mass and on gas admixture propagation in mine workings serve as a base for considering changes in heat-gas-air state at a mine after inflammation. The presented mathematical relations allow calculation of a varied velocity and movement direction of air flows, their temperatures and smoking conditions during fire.

  14. An objective definition of air mass types affecting Athens, Greece; the corresponding atmospheric pressure patterns and air pollution levels.

    PubMed

    Sindosi, O A; Katsoulis, B D; Bartzokas, A

    2003-08-01

    This work aims at defining characteristic air mass types that dominate in the region of Athens, Greece during the cold (November-March) and the warm (May-September) period of the year and also at evaluating the corresponding concentration levels of the main air pollutants. For each air mass type, the mean atmospheric pressure distribution (composite maps) over Europe and the Mediterranean is estimated in order to reveal the association of atmospheric circulation with air pollution levels in Athens. The data basis for this work consists of daily values of thirteen meteorological and six pollutant parameters covering the period 1993-97. The definition of the characteristic air mass types is attempted objectively by using the methods of Factor Analysis and Cluster Analysis. The results show that during the cold period of the year there are six prevailing air mass types (at least 3% of the total number of days) and six infrequent ones. The examination of the corresponding air pollution concentration levels shows that the primary air pollutants appear with increased concentrations when light or southerly winds prevail. This is usually the case when a high pressure system is located over the central Mediterranean or a low pressure system lays over south Italy, respectively. Low levels of the primary pollutants are recorded under northeasterly winds, mainly caused by a high pressure system over Ukraine. During the warm period of the year, the southwestern Asia thermal low and the subtropical anticyclone of the Atlantic Ocean affect Greece. Though these synoptic systems cause almost stagnant conditions, four main air mass types are dominant and ten others, associated with extreme weather, are infrequent. Despite the large amounts of total solar radiation characterizing this period, ozone concentrations remain at low levels in central Athens because of its destruction by nitric oxide.

  15. Quantitative determination of free and total bisphenol A in human urine using labeled BPA glucuronide and isotope dilution mass spectrometry.

    PubMed

    Kubwabo, Cariton; Kosarac, Ivana; Lalonde, Kaela; Foster, Warren G

    2014-07-01

    Bisphenol A (BPA) is a widely used industrial chemical in the manufacturing of polycarbonate plastic bottles, food and beverage can linings, thermal receipts, and dental sealants. Animal and human studies suggest that BPA may disrupt normal hormonal function and hence, potentially, have negative effects on the human health. While total BPA is frequently reported, it is recognized that free BPA is the biologically active form and is rarely reported in the literature. The objective of this study was to develop a sensitive and improved method for the measurement of free and total BPA in human urine. Use of a labeled conjugated BPA (bisphenol A-d6 β-D-glucuronide) allowed for the optimization of the enzymatic reaction and permitted an accurate determination of the conjugated BPA concentration in urine samples. In addition, a (13)C12-BPA internal standard was used to account for the analytical recoveries and performance of the isotope dilution method. Solid-phase extraction (SPE) combined with derivatization and analysis using a triple quadrupole GC-EI/MS/MS system achieved very low method detection limit of 0.027 ng/mL. BPA concentrations were measured in urine samples collected during the second and third trimesters of pregnancy in 36 Canadian women. Total maternal BPA concentrations in urine samples ranged from not detected to 9.40 ng/mL (median, 1.21 ng/mL), and free BPA concentrations ranged from not detected to 0.950 ng/mL (median, 0.185 ng/mL). Eighty-six percent of the women had detectable levels of conjugated BPA, whereas only 22 % had detectable levels of free BPA in their urine. BPA levels measured in this study agreed well with data reported internationally.

  16. Air Mass Origin as a Diagnostic of Seasonally-Varying Transport into the Arctic

    NASA Astrophysics Data System (ADS)

    Orbe, C.; Waugh, D. W.; Holzer, M. B.; Newman, P. A.; Polvani, L. M.; Oman, L.; Li, F.

    2013-12-01

    While the signatures of the seasonal cycle on basic state variables such as temperature, winds and on chemical composition have been explored in depth, its signature on air mass composition has received relatively little attention. To this end, we present the first analysis of the seasonally varying transport from the northern hemisphere (NH) midlatitudes into the Arctic using rigorously defined air masses. The fractional contribution from each air mass partitions Arctic air according to where it was last in the planetary boundary layer (PBL) at midlatitudes over the Pacific and Atlantic oceans, North America, Europe, and Asia. Air mass fractions are computed using the coupled climate-chemistry model GEOSCCM subject to fixed present-day climate forcings. We find that during DJF 48% of the air in the free troposphere poleward of 60N was last at midlatitudes primarily at the Pacific and Atlantic oceans, at 20% and 10% respectively. During JJA, however, the largest contributions to Arctic air come from Asian and North American source regions, revealing that transport from the industrialized midlatitude regions dominates during boreal summer. Preliminary calculations of future air masses for a model integration subject to A1B greenhouse gases also reveal the model's climate change response in arctic air mass composition. In concert with weakened tropospheric eddy kinetic energy and a weakened Hadley cell, we find that changes in annual mean arctic air mass fractions are of the order 10%, with increased contributions from air that was last in contact with the PBL over North America and over the Atlantic and Pacific oceans. Air-mass fractions, and their changes, thus help to isolate the role of transport to changes in composition, which are not only driven by changes in chemistry and emissions but also crucially by changes in atmospheric flow.

  17. Ultrasonication extraction and gel permeation chromatography clean-up for the determination of polycyclic aromatic hydrocarbons in edible oil by an isotope dilution gas chromatography–mass spectrometry.

    PubMed

    Wang, Jian-Hua; Guo, Cui

    2010-07-01

    An analytical method for the determination of US EPA priority pollutant 16 polycyclic aromatic hydrocarbons (PAHs) in edible oil was developed by an isotope dilution gas chromatography-mass spectrometry (GC-MS). Extraction was performed with ultrasonication mode using acetonitrile as solvent, and subsequent clean-up was applied using narrow gel permeation chromatographic column. Three deuterated PAHs surrogate standards were used as internal standards for quantification and analytical quality control. The limits of quantification (LOQs) were globally below 0.5 ng/g, the recoveries were in the range of 81-96%, and the relative standard deviations (RSDs) were lower than 20%. Further trueness assessment of the method was also verified through participation in international cocoa butter proficiency test (T0638) organised by the FAPAS with excellent results in 2008. The results obtained with the described method were satisfying (z ≤ 2). The method has been applied to determine PAH in real edible oil samples. PMID:20627308

  18. Simultaneous determination of the quantity and isotopic ratios of uranium in individual micro-particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS).

    PubMed

    Park, Jong-Ho; Choi, Eun-Ju

    2016-11-01

    A method to determine the quantity and isotopic ratios of uranium in individual micro-particles simultaneously by isotope dilution thermal ionization mass spectrometry (ID-TIMS) has been developed. This method consists of sequential sample and spike loading, ID-TIMS for isotopic measurement, and application of a series of mathematical procedures to remove the contribution of uranium in the spike. The homogeneity of evaporation and ionization of uranium content was confirmed by the consistent ratio of n((233)U)/n((238)U) determined by TIMS measurements. Verification of the method was performed using U030 solution droplets and U030 particles. Good agreements of resulting uranium quantity, n((235)U)/n((238)U), and n((236)U)/n((238)U) with the estimated or certified values showed the validity of this newly developed method for particle analysis when simultaneous determination of the quantity and isotopic ratios of uranium is required.

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

  20. The measurement of theophylline in human serum or plasma using gas chromatography and isotope dilution-mass spectrometry (GC-IDMS) taking other substituted xanthines into consideration.

    PubMed

    Kress, Michael; Meissner, Dieane; Kaiser, Patricia; Hanke, Rainer; Wood, William Graham

    2002-01-01

    A method is described which uses a combination of gas chromatography and isotope dilution-mass spectrometry (GC-IDMS) to determine the concentration of theophylline (1,3-dimethyl xanthine) in human plasma or serum samples. The effects of similar substituted xanthines - namely theobromine (3,7-dimethyl xanthine), paraxanthine (1,7-dimethyl xanthine) 1,3-dimethyl-7-(2-hydroxyethyl) xanthine (internal standard HPLC) and caffeine (1,3,7-trimethyl xanthine) were tested to confirm the specificity of the method. The derivatisation of all xanthines was performed with N-methyl-N-trimethylsilyl trifluroacetamide (MSTFA). The internal standard used was 2-(13)C ,1,3-(15)N2-theophylline. The extraction and derivatisation procedures were examined in detail and optimised stepwise during the development of the method. High-performance liquid chromatography (HPLC) was used for comparison.

  1. Simultaneous determination of the quantity and isotopic ratios of uranium in individual micro-particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS).

    PubMed

    Park, Jong-Ho; Choi, Eun-Ju

    2016-11-01

    A method to determine the quantity and isotopic ratios of uranium in individual micro-particles simultaneously by isotope dilution thermal ionization mass spectrometry (ID-TIMS) has been developed. This method consists of sequential sample and spike loading, ID-TIMS for isotopic measurement, and application of a series of mathematical procedures to remove the contribution of uranium in the spike. The homogeneity of evaporation and ionization of uranium content was confirmed by the consistent ratio of n((233)U)/n((238)U) determined by TIMS measurements. Verification of the method was performed using U030 solution droplets and U030 particles. Good agreements of resulting uranium quantity, n((235)U)/n((238)U), and n((236)U)/n((238)U) with the estimated or certified values showed the validity of this newly developed method for particle analysis when simultaneous determination of the quantity and isotopic ratios of uranium is required. PMID:27591656

  2. Development and co-validation of porcine insulin certified reference material by high-performance liquid chromatography-isotope dilution mass spectrometry.

    PubMed

    Wu, Liqing; Takatsu, Akiko; Park, Sang-Ryoul; Yang, Bin; Yang, Huaxin; Kinumi, Tomoya; Wang, Jing; Bi, Jiaming; Wang, Yang

    2015-04-01

    This article concerns the development and co-validation of a porcine insulin (pINS) certified reference material (CRM) produced by the National Institute of Metrology, People's Republic of China. Each CRM unit contained about 15 mg of purified solid pINS. The moisture content, amount of ignition residue, molecular mass, and purity of the pINS were measured. Both high-performance liquid chromatography-isotope dilution mass spectrometry and a purity deduction method were used to determine the mass fraction of the pINS. Fifteen units were selected to study the between-bottle homogeneity, and no inhomogeneity was observed. A stability study concluded that the CRM was stable for at least 12 months at -20 °C. The certified value of the CRM was (0.892 ± 0.036) g/g. A co-validation of the CRM was performed among Chinese, Japanese, and Korean laboratories under the framework of the Asian Collaboration on Reference Materials. The co-validation results agreed well with the certified value of the CRM. Consequently, the pINS CRM may be used as a calibration material or as a validation standard for pharmaceutical purposes to improve the quality of pharmaceutical products.

  3. Mass spectrometric profiling of Bacillus cereus strains and quantitation of the emetic toxin cereulide by means of stable isotope dilution analysis and HEp-2 bioassay.

    PubMed

    Stark, Timo; Marxen, Sandra; Rütschle, Andrea; Lücking, Genia; Scherer, Siegfried; Ehling-Schulz, Monika; Hofmann, Thomas

    2013-01-01

    A fast and robust high-throughput ultra-performance liquid chromatography/time-of-flight mass spectrometry (UPLC-TOF MS) profiling method was developed and successfully applied to discriminate a total of 78 Bacillus cereus strains into no/low, medium and high producers of the emetic toxin cereulide. The data obtained by UPLC-TOF MS profiling were confirmed by absolute quantitation of cereulide in selected samples by means of high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS) and stable isotope dilution assay (SIDA). Interestingly, the B. cereus strains isolated from four vomit samples and five faeces samples from patients showing symptoms of intoxication were among the group of medium or high producers. Comparison of HEp-2 bioassay data with those determined by means of mass spectrometry showed differences, most likely because the HEp-2 bioassay is based on the toxic action of cereulide towards mitochondria of eukaryotic cells rather than on a direct measurement of the toxin. In conclusion, the UPLC-electrospray ionization (ESI)-TOF MS and the HPLC-ESI-MS/MS-SIDA analyses seem to be promising tools for the robust high-throughput analysis of cereulide in B. cereus cultures, foods and other biological samples.

  4. A Comparison of the Red Green Blue Air Mass Imagery and Hyperspectral Infrared Retrieved Profiles

    NASA Technical Reports Server (NTRS)

    Berndt, E. B.; Folmer, Michael; Dunion, Jason

    2014-01-01

    The Red Green Blue (RGB) Air Mass imagery is derived from multiple channels or paired channel differences. Multiple channel products typically provide additional information than a single channel can provide alone. The RGB Air Mass imagery simplifies the interpretation of temperature and moisture characteristics of air masses surrounding synoptic and mesoscale features. Despite the ease of interpretation of multiple channel products, the combination of channels and channel differences means the resulting product does not represent a quantity or physical parameter such as brightness temperature in conventional single channel satellite imagery. Without a specific quantity to reference, forecasters are often confused as to what RGB products represent. Hyperspectral infrared retrieved profiles of temperature, moisture, and ozone can provide insight about the air mass represented on the RGB Air Mass product and provide confidence in the product and representation of air masses despite the lack of a quantity to reference for interpretation. This study focuses on RGB Air Mass analysis of Hurricane Sandy as it moved north along the U.S. East Coast, while transitioning to a hybrid extratropical storm. Soundings and total column ozone retrievals were analyzed using data from the Cross-track Infrared and Advanced Technology Microwave Sounder Suite (CrIMSS) on the Suomi National Polar Orbiting Partnership satellite and the Atmospheric Infrared Sounder (AIRS) on the National Aeronautics and Space Administration Aqua satellite along with dropsondes that were collected from National Oceanic and Atmospheric Administration and Air Force research aircraft. By comparing these datasets to the RGB Air Mass, it is possible to capture quantitative information that could help in analyzing the synoptic environment enough to diagnose the onset of extratropical transition. This was done by identifying any stratospheric air intrusions (SAIs) that existed in the vicinity of Sandy as the wind

  5. Air Mass Origin in the Arctic and its Response to Future Warming

    NASA Technical Reports Server (NTRS)

    Orbe, Clara; Newman, Paul A.; Waugh, Darryn W.; Holzer, Mark; Oman, Luke; Polvani, Lorenzo M.; Li, Feng

    2014-01-01

    We present the first climatology of air mass origin in the Arctic in terms of rigorously defined air mass fractions that partition air according to where it last contacted the planetary boundary layer (PBL). Results from a present-day climate integration of the GEOSCCM general circulation model reveal that the Arctic lower troposphere below 700 mb is dominated year round by air whose last PBL contact occurred poleward of 60degN, (Arctic air, or air of Arctic origin). By comparison, approx. 63% of the Arctic troposphere above 700 mb originates in the NH midlatitude PBL, (midlatitude air). Although seasonal changes in the total fraction of midlatitude air are small, there are dramatic changes in where that air last contacted the PBL, especially above 700 mb. Specifically, during winter air in the Arctic originates preferentially over the oceans, approx. 26% in the East Pacific, and approx. 20% in the Atlantic PBL. By comparison, during summer air in the Arctic last contacted the midlatitude PBL primarily over land, overwhelmingly so in Asia (approx. 40 %) and, to a lesser extent, in North America (approx. 24%). Seasonal changes in air-mass origin are interpreted in terms of seasonal variations in the large-scale ventilation of the midlatitude boundary layer and lower troposphere, namely changes in the midlatitude tropospheric jet and associated transient eddies during winter and large scale convective motions over midlatitudes during summer.

  6. Quantitative measurement of odor detection thresholds using an air dilution olfactometer, and association with genetic variants in a sample of diverse ancestry

    PubMed Central

    Cook, Gillian R.; Krithika, S; Edwards, Melissa; Kavanagh, Paula

    2014-01-01

    Genetic association studies require a quantitative and reliable method for odor threshold assessment in order to examine the contribution of genetic variants to complex olfactory phenotypes. Our main goal was to assess the feasibility of a portable Scentroid air dilution olfactometer for use in such studies. Using the Scentroid SM110C and the SK5 n-butanol Sensitivity Kit (IDES Canada Inc.), n-butanol odor thresholds were determined for 182 individuals of diverse ancestry (mean age: 20.4 ± 2.5 years; n = 128 female; n = 54 male). Threshold scores from repeat participants were used to calculate a test–retest reliability coefficient, which was statistically significant (r = 0.754, p < 0.001, n = 29), indicating that the Scentroid provides reliable estimates of odor thresholds. In addition, we performed a preliminary genetic analysis evaluating the potential association of n-butanol odor thresholds to six single-nucleotide polymorphisms (SNPs) putatively involved in general olfactory sensitivity (GOS). The results of multiple linear regression analysis revealed no significant association between the SNPs tested and threshold scores. However, our sample size was relatively small, and our study was only powered to identify genetic markers with strong effects on olfactory sensitivity. Overall, we find that the Scentroid provides reliable quantitative measures of odor detection threshold and is well suited for genetic studies of olfactory sensitivity. PMID:25392755

  7. Extinction measurements for optical band gap determination of soot in a series of nitrogen-diluted ethylene/air non-premixed flames.

    PubMed

    Adkins, Erin M; Miller, J Houston

    2015-01-28

    Visible light extinction was measured in a series of nitrogen-diluted, ethylene/air, non-premixed flames and this data was used to determine the optical band gap, OBG, as a function of flame position. Collimated light from a supercontinuum source is telescopically expanded and refocused to match the f- number of a dispersing monochromator. The dispersed light is split into a power metering channel and a channel that is periscoped and focused into the flame. The transmitted light is then recollimated and focussed onto a silicon photodiode detector. After tomographic reconstruction of the radial extinction field, the OBG was derived from the near-edge absorption feature using Tauc/Davis-Mott analysis. A slight evolution in OBG was observed throughout all flame systems with a consistent range of OBG observed between approximately 1.85 eV and 2.35 eV. Averaging over all positions the mean OBG was approximately 2.09 eV for all flame systems. Comparing these results to previously published computational results relating calculated HOMO-LUMO gaps for a variety of D2h PAH molecules to the number of aromatic rings in the structure, showed that the observed optical band gap is consistent with a PAH of about 14 rings or a conjugation length of 0.97 nm. This work provides experimental support to the model of soot formation where the transition from chemical to physical growth starts at a modest molecular size; about the size of circumpyrene.

  8. Reduction of measurement uncertainty by experimental design in high-order (double, triple, and quadruple) isotope dilution mass spectrometry: application to GC-MS measurement of bromide.

    PubMed

    Pagliano, Enea; Mester, Zoltán; Meija, Juris

    2013-03-01

    Since its introduction a century ago, isotope dilution analysis has played a central role in developments of analytical chemistry. This method has witnessed many elaborations and developments over the years. To date, we have single, double, and even triple isotope dilution methods. In this manuscript, we summarize the conceptual aspects of isotope dilution methods and introduce the quadruple dilution and the concept of exact matching triple and quadruple dilutions. The comparison of isotope dilution methods is performed by determination of bromide ions in groundwater using novel ethyl-derivatization chemistry in conjunction with GC/MS. We show that the benefits of higher-order isotope dilution methods are countered with a greater need for careful experimental design of the isotopic blends. Just as for ID(2)MS, ID(3)MS and ID(4)MS perform best when the isotope ratio of one sample/spike blend is matched with that of a standard/spike blend (exact matching).

  9. Reduction of measurement uncertainty by experimental design in high-order (double, triple, and quadruple) isotope dilution mass spectrometry: application to GC-MS measurement of bromide.

    PubMed

    Pagliano, Enea; Mester, Zoltán; Meija, Juris

    2013-03-01

    Since its introduction a century ago, isotope dilution analysis has played a central role in developments of analytical chemistry. This method has witnessed many elaborations and developments over the years. To date, we have single, double, and even triple isotope dilution methods. In this manuscript, we summarize the conceptual aspects of isotope dilution methods and introduce the quadruple dilution and the concept of exact matching triple and quadruple dilutions. The comparison of isotope dilution methods is performed by determination of bromide ions in groundwater using novel ethyl-derivatization chemistry in conjunction with GC/MS. We show that the benefits of higher-order isotope dilution methods are countered with a greater need for careful experimental design of the isotopic blends. Just as for ID(2)MS, ID(3)MS and ID(4)MS perform best when the isotope ratio of one sample/spike blend is matched with that of a standard/spike blend (exact matching). PMID:23371530

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

    PubMed

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

    2015-05-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  12. Stable isotope dilution analysis of salicylic acid and hydroquinone in human skin samples by gas chromatography with mass spectrometric detection.

    PubMed

    Judefeind, Anja; van Rensburg, Peet Jansen; Langelaar, Stephan; du Plessis, Jeanetta

    2007-06-01

    A sensitive and accurate gas chromatographic-mass spectrometric (GC-MS) method has been developed for the quantitative determination of salicylic acid (SA) and hydroquinone (HQ) from human skin samples and cosmetic emulsions. Deuterium labeled SA-d(6) and HQ-d(6) were used as internal standards (IS). The samples were extracted with methanol, dried under nitrogen and derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA)+1% trimethylchlorosilane (TMCS). Quantification was performed in SIM mode with a limit of quantification (LOQ) of 50 ng ml(-1) for SA and 10 ng ml(-1) for HQ. The inter-day variation (R.S.D.) was less than 5% and the accuracy was better than 13.3% for both compounds. The recoveries from the different matrices ranged between 93.1 and 103.3% for SA, and 97.3 and 100.8% for HQ.

  13. Simultaneous analysis of polychlorinated biphenyls and polychlorinated naphthalenes by isotope dilution comprehensive two-dimensional gas chromatography high-resolution time-of-flight mass spectrometry.

    PubMed

    Xia, Dan; Gao, Lirong; Zheng, Minghui; Wang, Shasha; Liu, Guorui

    2016-09-21

    Polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) are listed as persistent organic pollutants (POPs) under the Stockholm Convention. Because they have similar physical and chemical properties, they are coeluted and are usually analyzed separately by different gas chromatography high-resolution mass spectrometry (GC-HRMS) methods. In this study, a novel method was developed for simultaneous analysis of six indicator PCBs, 12 dioxin-like PCBs, and 16 PCNs using isotope dilution comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry (GC × GC-HRTOF-MS). The method parameters, including the type of GC column, oven temperature program, and modulation period, were systematically optimized. Complete separation of all target analytes and the matrix was achieved with a DB-XLB column in the first dimension and a BPX-70 column in the second dimension. The isotope dilution method was used for quantification of the PCBs and PCNs by GC × GC-HRTOF-MS. The method showed good linearity from 5 to 500 pg μL(-1) for all the target compounds. The instrumental limit of detection ranged from 0.03 to 0.3 pg μL(-1) for the 18 PCB congeners and from 0.09 to 0.6 pg μL(-1) for the 16 PCN congeners. Repeatability for triplicate injections was always lower than 20%. The method was successfully applied to the determination of 18 PCBs present at 0.9-2054 pg g(-1) and 16 PCNs present at 0.2-15.7 pg g(-1) in three species of fish. The GC × GC-HRTOF-MS results agreed with those obtained by GC-HRMS. The GC × GC-HRTOF-MS method proved to be a sensitive and accurate technique for simultaneous analysis of the selected PCBs and PCNs. With the excellent chromatographic separation offered by GC × GC and accurate mass measurements offered by HRTOF-MS, this method allowed identification of non-target contaminants in the fish samples, including organochlorine pesticides and polycyclic aromatic hydrocarbons. PMID

  14. Simultaneous analysis of polychlorinated biphenyls and polychlorinated naphthalenes by isotope dilution comprehensive two-dimensional gas chromatography high-resolution time-of-flight mass spectrometry.

    PubMed

    Xia, Dan; Gao, Lirong; Zheng, Minghui; Wang, Shasha; Liu, Guorui

    2016-09-21

    Polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) are listed as persistent organic pollutants (POPs) under the Stockholm Convention. Because they have similar physical and chemical properties, they are coeluted and are usually analyzed separately by different gas chromatography high-resolution mass spectrometry (GC-HRMS) methods. In this study, a novel method was developed for simultaneous analysis of six indicator PCBs, 12 dioxin-like PCBs, and 16 PCNs using isotope dilution comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry (GC × GC-HRTOF-MS). The method parameters, including the type of GC column, oven temperature program, and modulation period, were systematically optimized. Complete separation of all target analytes and the matrix was achieved with a DB-XLB column in the first dimension and a BPX-70 column in the second dimension. The isotope dilution method was used for quantification of the PCBs and PCNs by GC × GC-HRTOF-MS. The method showed good linearity from 5 to 500 pg μL(-1) for all the target compounds. The instrumental limit of detection ranged from 0.03 to 0.3 pg μL(-1) for the 18 PCB congeners and from 0.09 to 0.6 pg μL(-1) for the 16 PCN congeners. Repeatability for triplicate injections was always lower than 20%. The method was successfully applied to the determination of 18 PCBs present at 0.9-2054 pg g(-1) and 16 PCNs present at 0.2-15.7 pg g(-1) in three species of fish. The GC × GC-HRTOF-MS results agreed with those obtained by GC-HRMS. The GC × GC-HRTOF-MS method proved to be a sensitive and accurate technique for simultaneous analysis of the selected PCBs and PCNs. With the excellent chromatographic separation offered by GC × GC and accurate mass measurements offered by HRTOF-MS, this method allowed identification of non-target contaminants in the fish samples, including organochlorine pesticides and polycyclic aromatic hydrocarbons.

  15. Exploiting dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) for sequential determination of trace elements in blood using a dilute-and-shoot procedure.

    PubMed

    Batista, Bruno Lemos; Rodrigues, Jairo Lisboa; Nunes, Juliana Andrade; Souza, Vanessa Cristina de Oliveira; Barbosa, Fernando

    2009-04-20

    Inductively coupled plasma mass spectrometry with quadrupole (q-ICP-MS) and dynamic reaction cell (DRC-ICP-MS) were evaluated for sequential determination of As, Cd, Co, Cr, Cu, Mn, Pb, Se, Tl, V and Zn in blood. The method requires as little as 100 microL of blood. Prior to analysis, samples (100 microL) were diluted 1:50 in a solution containing 0.01% (v/v) Triton X-100 and 0.5% (v/v) nitric acid. The use of the DRC was only mandatory for Cr, Cu, V and Zn. For the other elements the equipment may be operated in a standard mode (q-ICP-MS). Ammonia was used as reaction gas. Selection of best flow rate of ammonium gas and optimization of the quadrupole dynamic band-pass tuning parameter (RPq) were carried out, using a ovine base blood for Cr and V and a synthetic matrix solution (SMS) for Zn and Cu diluted 1:50 and spiked to contain 1 microg L(-1) of each element. Method detection limits (3 s) for (75)As, (114)Cd, (59)Co, (51)Cr, (63)Cu (55)Mn, (208)Pb, (82)Se, (205)Tl, (51)V, and (64)Zn were 14.0, 3.0, 11.0, 7.0, 280, 9.0, 3.0, 264, 0.7, 6.0 and 800 ng L(-1), respectively. Method validation was accomplished by the analysis of blood Reference Materials produced by the L'Institut National de Santé Publique du Quebec (Canada).

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

    PubMed

    Schött, Hans-Frieder; Lütjohann, Dieter

    2015-07-01

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

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

    PubMed

    Schött, Hans-Frieder; Lütjohann, Dieter

    2015-07-01

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

  18. 40 CFR 1065.140 - Dilution for gaseous and PM constituents.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Equipment Specifications § 1065.140 Dilution for gaseous and PM constituents. (a) General. You may dilute exhaust with ambient air, synthetic air, or... diluting exhaust at a location as close as possible to the location where ambient air dilution would...

  19. Application of Microwave-Induced Combustion and Isotope Dilution Strategies for Quantification of Sulfur in Coals via Sector-Field Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Christopher, Steven J; Vetter, Thomas W

    2016-05-01

    In recent years, microwave-induced combustion (MIC) has proved to be a robust sample preparation technique for difficult-to-digest samples containing high carbon content, especially for determination of halogens and sulfur. National Institute of Standards and Technology (NIST) has applied the MIC methodology in combination with isotope dilution analysis for sulfur determinations, representing the first-reported combination of this robust sample preparation methodology and high-accuracy quantification approach. Medium-resolution mode sector-field inductively coupled plasma mass spectrometry was invoked to avoid spectral interferences on the sulfur isotopes. The sample preparation and instrumental analysis scheme was used for the value assignment of total sulfur in Standard Reference Material (SRM) 2682c Subbituminous Coal (nominal mass fraction 0.5% sulfur). A description of the analytical procedures required is provided, along with metrological results, including an estimation of the overall method uncertainty (<1.5% relative expanded uncertainty) calculated using the IDMS measurement function and a Kragten spreadsheet approach. PMID:27032706

  20. Effects of conventional heating on the stability of major olive oil phenolic compounds by tandem mass spectrometry and isotope dilution assay.

    PubMed

    Attya, Mohamed; Benabdelkamel, Hicham; Perri, Enzo; Russo, Anna; Sindona, Giovanni

    2010-01-01

    The quality of olive oils is sensorially tested by accurate and well established methods. It enables the classification of the pressed oils into the classes of extra virgin oil, virgin oil and lampant oil. Nonetheless, it would be convenient to have analytical methods for screening oils or supporting sensorial analysis using a reliable independent approach based on exploitation of mass spectrometric methodologies. A number of methods have been proposed to evaluate deficiencies of extra virgin olive oils resulting from inappropriate technological treatments, such as high or low temperature deodoration, and home cooking processes. The quality and nutraceutical value of extra virgin olive oil (EVOO) can be related to the antioxidant property of its phenolic compounds. Olive oil is a source of at least 30 phenolic compounds, such as oleuropein, oleocanthal, hydroxytyrosol, and tyrosol, all acting as strong antioxidants, radical scavengers and NSAI-like drugs. We now report the efficacy of MRM tandem mass spectrometry, assisted by the isotope dilution assay, in the evaluation of the thermal stability of selected active principles of extra virgin olive oil. PMID:21124271

  1. Application of Microwave-Induced Combustion and Isotope Dilution Strategies for Quantification of Sulfur in Coals via Sector-Field Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Christopher, Steven J; Vetter, Thomas W

    2016-05-01

    In recent years, microwave-induced combustion (MIC) has proved to be a robust sample preparation technique for difficult-to-digest samples containing high carbon content, especially for determination of halogens and sulfur. National Institute of Standards and Technology (NIST) has applied the MIC methodology in combination with isotope dilution analysis for sulfur determinations, representing the first-reported combination of this robust sample preparation methodology and high-accuracy quantification approach. Medium-resolution mode sector-field inductively coupled plasma mass spectrometry was invoked to avoid spectral interferences on the sulfur isotopes. The sample preparation and instrumental analysis scheme was used for the value assignment of total sulfur in Standard Reference Material (SRM) 2682c Subbituminous Coal (nominal mass fraction 0.5% sulfur). A description of the analytical procedures required is provided, along with metrological results, including an estimation of the overall method uncertainty (<1.5% relative expanded uncertainty) calculated using the IDMS measurement function and a Kragten spreadsheet approach.

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

    PubMed

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

    2015-09-01

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

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

    PubMed

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

    2015-09-01

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

  4. Investigation of technology for the monitoring of UF/sub 6/ mass flow in UF/sub 6/ streams diluted with H/sub 2/

    SciTech Connect

    Baker, O.J.; Cooley, J.N.; Hewgley, W.A.; Moran, B.W.; Swindle, D.W. Jr.

    1986-12-01

    The applicability, availability, and effectiveness of gas flow meters are assessed as a means for verifying the mass flows of pure UF/sub 6/ streams diluted with a carrier gas. The initial survey identified the orifice, pitot tube, thermal, vortex shedding, and vortex precession (swirl) meters as promising for the intended use. Subsequent assessments of these flow meters revealed that two - the orifice meter and the pitot tube meter - are the best choices for the proposed applications: the first is recommended for low velocity gas, small diameter piping; the latter, for high velocity gas, large diameter piping. Final selection of the gas flow meters should be based on test loop evaluations in which the proposed meters are subjected to gas flows, temperatures, and pressures representative of those expected in service. Known instruments are evaluated that may be applicable to the measurement of uranium or UF/sub 6/ concentration in a UF/sub 6/ - H/sub 2/ process stream at an aerodynamic enrichment plant. Of the six procedures evaluated, four have been used for process monitoring in a UF/sub 6/ environment: gas mass spectrometry, infrared-ultraviolet-visible spectrophotometry, gas chromatography, and acoustic gas analysis. The remaining two procedures, laser fluorimetry and atomic absorption spectroscopy, would require significant development work before they could be used for process monitoring. Infrared-ultravioloet-visible spectrophotometry is judged to be the best procedure currently available to perform the required measurement.

  5. Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Malherbe, Julien; Claverie, Fanny; Alvarez, Aitor; Fernandez, Beatriz; Pereiro, Rosario; Molloy, John L

    2013-09-01

    Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n=3, 1σ). A good agreement between experimental results and the certified values was also observed.

  6. Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Malherbe, Julien; Claverie, Fanny; Alvarez, Aitor; Fernandez, Beatriz; Pereiro, Rosario; Molloy, John L

    2013-09-01

    Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n=3, 1σ). A good agreement between experimental results and the certified values was also observed. PMID:23953208

  7. Capture of the volatile carbonyl metabolite of flecainide on 2,4-dinitrophenylhydrazine cartridge for quantitation by stable-isotope dilution mass spectrometry coupled with chromatography.

    PubMed

    Prokai, Laszlo; Szarka, Szabolcs; Wang, Xiaoli; Prokai-Tatrai, Katalin

    2012-04-01

    Carbonyl compounds are common byproducts of many metabolic processes. These volatile chemicals are usually derivatized before mass spectrometric analysis to enhance the sensitivity of their detections. The classically used reagent for this purpose is 2,4-dinitrophenylhydrazine (DNPH) that forms the corresponding hydrazones. When DNPH is immobilized on specific cartridges it permits solvent-free collection and simultaneous derivatization of aldehydes and ketones from gaseous samples. The utility of this approach was tested by assembling a simple apparatus for the in vitro generation of trifluoroacetaldehyde (TFAA) and its subsequent capture on the attached DNPH cartridge. TFAA was generated via cytochrome P450-catalyzed dealkylation of flecainide, an antiarrhythmic agent, in pooled human liver microsomes. Stable-isotope dilution mass spectrometry coupled with GC and LC using negative chemical ionization (NCI) and electrospray ionization (ESI) was evaluated for quantitative analyses. To eliminate isotope effects observed with the use of deuterium-labeled DNPH, we selected its (15)N(4)-labeled analog to synthesize the appropriate TFAA adduct, as internal standard. Quantitation by GC-NCI-MS using selected-ion monitoring outperformed LC-ESI-MS methods considering limits of detection and linearity of the assays. The microsomal metabolism of 1.5 μmol of flecainide for 1.5h resulted in 2.6 ± 0.5 μg TFAA-DNPH, corresponding to 9.3 ± 1.7 nmol TFAA, captured by the cartridge. PMID:22342210

  8. Capture of the volatile carbonyl metabolite of flecainide on 2,4-dinitrophenylhydrazine cartridge for quantitation by stable-isotope dilution mass spectrometry coupled with chromatography

    PubMed Central

    Prokai, Laszlo; Szarka, Szabolcs; Wang, Xiaoli; Prokai-Tatrai, Katalin

    2012-01-01

    Carbonyl compounds are common byproducts of many metabolic processes. These volatile chemical entities are usually derivatized before mass spectrometric analysis to enhance the sensitivity of their detections. The classically used reagent for this purpose is 2,4-dinitrophenylhydrazine (DNPH) that forms the corresponding hydrazones. When DNPH is immobilized on specific cartridges it permits solvent-free collection and simultaneous derivatization of aldehydes and ketones from gaseous samples. The utility of this approach was tested by assembling a simple apparatus for the in vitro generation of trifluoroacetaldehyde (TFAA) and its subsequent capture on the attached DNPH cartridge. TFAA was generated via cytochrome P450-catalyzed dealkylation of flecainide, an antiarrhythmic agent, in pooled human liver microsomes. Stable-isotope dilution mass spectrometry coupled with GC and LC using negative chemical ionization (NCI) and electrospray ionization (ESI) was evaluated for quantitative analyses. To eliminate isotope effects observed with the use of deuterium-labeled DNPH, we selected its 15N4-labeled analog to synthesize the appropriate TFAA adduct, as internal standard. Quantitation by GC–NCI-MS using selected-ion monitoring outperformed LC–ESI-MS methods considering limits of detection and linearity of the assays. The microsomal metabolism of 1.5 μmol of flecainide for 1.5 h resulted in 2.6 ± 0.5 μg TFAA-DNPH, corresponding to 9.3 ± 1.7 nmol TFAA, captured by the cartridge. PMID:22342210

  9. Quantification of ricin, RCA and comparison of enzymatic activity in 18 Ricinus communis cultivars by isotope dilution mass spectrometry.

    PubMed

    Schieltz, David M; McWilliams, Lisa G; Kuklenyik, Zsuzsanna; Prezioso, Samantha M; Carter, Andrew J; Williamson, Yulanda M; McGrath, Sara C; Morse, Stephen A; Barr, John R

    2015-03-01

    The seeds of the Ricinus communis (Castor bean) plant are the source of the economically important commodity castor oil. Castor seeds also contain the proteins ricin and R. communis agglutinin (RCA), two toxic lectins that are hazardous to human health. Radial immunodiffusion (RID) and the enzyme linked immunosorbent assay (ELISA) are two antibody-based methods commonly used to quantify ricin and RCA; however, antibodies currently used in these methods cannot distinguish between ricin and RCA due to the high sequence homology of the respective proteins. In this study, a technique combining antibody-based affinity capture with liquid chromatography and multiple reaction monitoring (MRM) mass spectrometry (MS) was used to quantify the amounts of ricin and RCA independently in extracts prepared from the seeds of eighteen representative cultivars of R. communis which were propagated under identical conditions. Additionally, liquid chromatography and MRM-MS was used to determine rRNA N-glycosidase activity for each cultivar and the overall activity in these cultivars was compared to a purified ricin standard. Of the cultivars studied, the average ricin content was 9.3 mg/g seed, the average RCA content was 9.9 mg/g seed, and the enzymatic activity agreed with the activity of a purified ricin reference within 35% relative activity.

  10. Liquid chromatography with isotope-dilution mass spectrometry for determination of water-soluble vitamins in foods.

    PubMed

    Phillips, Melissa M

    2015-04-01

    Vitamins are essential for improving and maintaining human health, and the main source of vitamins is the diet. Measurement of the quantities of water-soluble vitamins in common food materials is important to understand the impact of vitamin intake on human health, and also to provide necessary information for regulators to determine adequate intakes. Liquid chromatography (LC) and mass spectrometry (MS) based methods for water-soluble vitamin analysis are abundant in the literature, but most focus on only fortified foods or dietary supplements or allow determination of only a single vitamin. In this work, a method based on LC/MS and LC/MS/MS has been developed to allow simultaneous quantitation of eight water-soluble vitamins, including multiple forms of vitamins B3 and B6, in a variety of fortified and unfortified food-matrix Standard Reference Materials (SRMs). Optimization of extraction of unbound vitamin forms and confirmation using data from external laboratories ensured accuracy in the assigned values, and addition of stable isotope labeled internal standards for each of the vitamins allowed for increased precision.

  11. The Analysis of PPM Levels of Gases in Air by Photoionization Mass Spectrometry

    ERIC Educational Resources Information Center

    Driscoll, John N.; Warneck, Peter

    1973-01-01

    Discusses analysis of trace gases in air by photoionization mass spectrometer. It is shown that the necessary sensitivity can be obtained by eliminating the UV monochromator and using direct ionization with a hydrogen light source. (JP)

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

    PubMed

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

    2012-07-01

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

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

    PubMed

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

    2005-07-01

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

  14. Lewisite Metabolites in Urine by Solid Phase Extraction-Dual Column Reversed-Phase Liquid Chromatography-Isotope Dilution Tandem Mass Spectrometry.

    PubMed

    Palcic, Jason D; Donovan, Stephen F; Jones, Janet S; Flagg, E Lindsay; Salonga, Redentor A; Mock, Walter E; Asirvatham, Victor S

    2016-07-01

    Lewisite (2-chlorovinyldichloroarsine) is a chemical warfare agent developed during World War I. A quantitative method using solid phase extraction (SPE) followed by dual column liquid chromatography (LC)-isotope dilution tandem mass spectrometry (MS-MS) was developed for the determination of (2-chlorovinyl)arsonic acid (CVAOA), a metabolite of Lewisite, in human urine. The sample was treated with hydrogen peroxide to oxidize any (2-chlorovinyl)arsonous acid (CVAA) that remained in the trivalent arsenic oxidation state. There was 1.19% (arsenic purity) of bis-(2-chlorovinyl)arsinic acid (BCVAOA), a minor Lewisite metabolite, in the stock CVAA material. The high-throughput method qualitatively assessed BCVAOA simultaneously utilizing normal-phase silica SPE followed by reversed-phase C18 LC for an orthogonal separation. The chromatographic method results in a 5.8-min cycle time with adequate retention (k' = 2.4) of CVAOA. The mass spectrometer was operated in positive electrospray ionization mode with quantitative m/z 186.9→61.0 and confirmation 186.9→91.0 mass transitions. This selective method demonstrated linearity, accuracy and reproducibility for the clinically relevant calibration range (25-3,200 µg/L as CVAA). The method detection limit was 3.3 µg/L as CVAA from a 10 µL injection. This LC-MS-MS emergency response method has a throughput of >240 samples (2.5 extracted 96-well plates) per day. PMID:27339483

  15. DNAPL REMOVAL MECHANISMS AND MASS TRANSFER CHARACTERISTICS DURING COSOLVENT-AIR FLOODING

    EPA Science Inventory

    The concurrent injection of cosolvent and air, a cosolvent-air (CA) flood was recently suggested for a dense nonaqueous phase liquid (DNAPL) remediation technology. The objectives of this study were to elucidate the DNAPL removal mechanisms of the CA flood and to quantify mass t...

  16. Experimental Determination of the Mass of Air Molecules from the Law of Atmospheres.

    ERIC Educational Resources Information Center

    Hayn, Carl H.; Galvin, Vincent, Jr.

    1979-01-01

    A gas pressure gauge has been constructed for use in a student experiment involving the law of atmospheres. From pressure data obtained at selected elevations the average mass of air molecules is determined and compared to that calculated from the molecular weights and percentages of constituents to the air. (Author/BB)

  17. Improving microbial air quality in air-conditioned mass transport buses by opening the bus exhaust ventilation fans.

    PubMed

    Luksamijarulkul, Pipat; Arunchai, Nongphon; Luksamijarulkul, Soavalug; Kaewboonchoo, Orawan

    2005-07-01

    The air quality in air-conditioned mass transport buses may affect bus drivers' health. In-bus air quality improvement with the voluntary participation of bus drivers by opening the exhaust ventilation fans in the bus was implemented in the Seventh Bus Zone of Bangkok Mass Transit Authority. Four bus numbers, including bus numbers 16, 63, 67 and 166, were randomly selected to investigate microbial air quality and to observe the effect of opening the exhaust ventilation fans in the bus. With each bus number, 9 to 10 air-conditioned buses (total, 39 air-conditioned buses) were included. In-bus air samples were collected at 5 points in each studied bus using the Millipore Air Tester. A total of 195 air samples were cultured for bacterial and fungal counts. The results reveal that the exhaust ventilation fans of 17 air-conditioned buses (43.6%) were opened to ventilate in-bus air during the cycle of the bus route. The means +/- SD of bacterial counts and fungal counts in the studied buses with opened exhaust ventilation fans (83.8 +/- 70.7 and 38.0 +/- 42.8 cfu/m3) were significantly lower than those in the studied buses without opened exhaust ventilation fans (199.6 +/- 138.8 and 294.1 +/- 178.7 cfu/m3), p < 0.0005. All the air samples collected from the studied buses with opened exhaust ventilation fans were at acceptable levels (< 500 cfu/m3) compared with 4.6% of the air samples collected from the studied buses without opened exhaust ventilation fans, which had high levels (> 500 cfu/m3). Of the studied buses with opened exhaust ventilation fans (17 buses), the bacterial and fungal counts after opening the exhaust ventilation fans (68.3 +/- 33.8 and 28.3 +/- 19.3 cfu/m3) were significantly lower than those before opening the exhaust ventilation fans (158.3 +/- 116.9 and 85.3 +/- 71.2 cfu/m3), p < 0.005.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    A method was developed for the determination of trace Os in geological samples by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) with the combination of chemical separation and preconcentration. Samples are digested using aqua regia in Carius tubes, and the Os analyte is converted into volatile OsO4, which is distilled and absorbed with HBr. The HBr solution is concentrated for further Os purification using the microdistillation technique. The purified Os is dissolved in 10 μl of 0.02% sucrose-0.005% H3PO4 solution and then evaporated on pieces of perfluoroalkoxy (PFA) film, resulting in the formation of a tiny object (< 3 × 104 μm2 superficial area). Using LA-ICP-MS measurements, the object can give Os signals at least 100 times higher than those provided by routine solution-ICP-MS while successfully avoiding the memory effect. The procedural blank and detection limit in the developed technique are 3.0 pg and 1.8 pg for Os, respectively when 1 g of samples is taken. Reference materials (RM) are analyzed, and their Os concentrations obtained by isotope dilution are comparable to reference or literature values. Based on the individual RM results, the precision is estimated within the range of 0.6 to 9.4% relative standard deviation (RSD), revealing that this method is applicable to the determination of trace Os in geological samples.

  19. Regional water-quality analysis of 2,4-D and dicamba in river water using gas chromatography-isotope dilution mass spectrometry

    USGS Publications Warehouse

    Thurman, E.M.; Zimmerman, L.R.; Aga, D.S.; Gilliom, R.J.

    2001-01-01

    Gas chromatography with isotope dilution mass spectrometry (GC-MS) and enzyme-linked immunosorbent assay (ELISA) were used in regional National Water Quality Assessment studies of the herbicides, 2,4-D and dicamba, in river water across the United States. The GC-MS method involved solid-phase extraction, derivatized with deutemted 2,4-D, and analysis by selected ion monitoring. The ELISA method was applied after preconcentration with solid-phase extraction. The ELISA method was unreliable because of interference from humic substances that were also isolated by solid-phase extraction. Therefore, GC-MS was used to analyzed 80 samples from river water from 14 basins. The frequency of detection of dicamba (28%) was higher than that for 2,4-D (16%). Concentrations were higher for dicamba than for 2,4-D, ranging from less than the detection limit (<0.05 ??g/L) to 3.77 ??g/L, in spite of 5 times more annual use of 2,4-D as compared to dicamba. These results suggest that 2,4-D degrades more rapidly in the environment than dicamba.

  20. Ultra-trace level speciated isotope dilution measurement of Cr(VI) using ion chromatography tandem mass spectrometry in environmental waters.

    PubMed

    Mädler, Stefanie; Todd, Aaron; Skip Kingston, H M; Pamuku, Matt; Sun, Fengrong; Tat, Cindy; Tooley, Robert J; Switzer, Teresa A; Furdui, Vasile I

    2016-08-15

    The reliable analysis of highly toxic hexavalent chromium, Cr(VI), at ultra-trace levels remains challenging, given its easy conversion to non-toxic trivalent chromium. This work demonstrates a novel analytical method to quantify Cr(VI) at low ngL(-1) concentration levels in environmental water samples by using speciated isotope dilution (SID) analysis and double-spiking with Cr(III) and Cr(VI) enriched for different isotopes. Ion chromatography tandem mass spectrometry (IC-MS/MS) was used for the analysis of Cr(VI) as HCrO4(-) → CrO3(-). Whereas the classical linear multipoint calibration (MPC) curve approach obtained a method detection limit (MDL) of 7ngL(-1) Cr(VI), the modified SID-MS method adapted from U. S. EPA 6800 allowed for the quantification of Cr(VI) with an MDL of 2ngL(-1) and provided results corrected for Cr(VI) loss occurred after sample collection. The adapted SID-MS approach proved to yield more accurate and precise results than the MPC method, allowed for compensation of Cr(VI) reduction during sample transportation and storage while eliminating the need for frequent external calibration. The developed method is a complementary tool to routinely used inductively-coupled plasma (ICP) MS and circumvents typically experienced interferences.

  1. Identification of odorants in frankincense (Boswellia sacra Flueck.) by aroma extract dilution analysis and two-dimensional gas chromatography-mass spectrometry/olfactometry.

    PubMed

    Niebler, Johannes; Buettner, Andrea

    2015-01-01

    Frankincense has been known, traded and used throughout the ages for its exceptional aroma properties, and is still commonly used in both secular and religious settings to convey a pleasant odor. Surprisingly, the odoriferous principle(s) underlying its unique odor profile have never been published. In this study, resin samples of Boswellia sacra Flueck. from both Somalia and Oman were investigated by aroma extract dilution analysis. In a comprehensive, odor-activity guided approach both chemo-analytical and human-sensory parameters were used to identify odor active constituents of the volatile fraction of B. sacra. Among the key odorants found were α-pinene, β-myrcene, linalool, p-cresol and two unidentified sesquiterpenoids. Overall, a total of 23 odorants were detected and analyzed by gas chromatography-olfactometry and heart-cut two-dimensional gas chromatography-mass spectrometry/olfactometry. The majority of the identified odorant compounds were oxygenated monoterpenes, along with some relevant mono- and sesquiterpenes and only one diterpenoid substance. Several of these compounds were reported here for the first time as odorous constituents in B. sacra. Identifying bioactive compounds might support a better understanding with regard to the potential benefits of frankincense, for example in aromatherapy or ecclesial settings. PMID:25468535

  2. Isotope dilution gas chromatography with mass spectrometry for the analysis of 4-octyl phenol, 4-nonylphenol, and bisphenol A in vegetable oils.

    PubMed

    Wu, Pinggu; Zhang, Liqun; Yang, Dajin; Zhang, Jing; Hu, Zhengyan; Wang, Liyuan; Ma, Bingjie

    2016-03-01

    By the combination of solid-phase extraction as well as isotope dilution gas chromatography with mass spectrometry, a sensitive and reliable method for the determination of endocrine-disrupting chemicals including bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils was established. The application of a silica/N-(n-propyl)ethylenediamine mixed solid-phase extraction cartridge achieved relatively low matrix effects for bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils. Experiments were designed to evaluate the effects of derivatization, and the extraction parameters were optimized. The estimated limits of detection and quantification for bisphenol A, 4-octylphenol, and 4-nonylphenol were 0.83 and 2.5 μg/kg, respectively. In a spiked experiment in vegetable oils, the recovery of the added bisphenol A was 97.5-110.3%, recovery of the added 4-octylphenol was 64.4-87.4%, and that of 4-nonylphenol was 68.2-89.3%. This sensitive method was then applied to real vegetable oil samples from Zhejiang Province of China, and none of the target compounds were detected.

  3. Identification of odorants in frankincense (Boswellia sacra Flueck.) by aroma extract dilution analysis and two-dimensional gas chromatography-mass spectrometry/olfactometry.

    PubMed

    Niebler, Johannes; Buettner, Andrea

    2015-01-01

    Frankincense has been known, traded and used throughout the ages for its exceptional aroma properties, and is still commonly used in both secular and religious settings to convey a pleasant odor. Surprisingly, the odoriferous principle(s) underlying its unique odor profile have never been published. In this study, resin samples of Boswellia sacra Flueck. from both Somalia and Oman were investigated by aroma extract dilution analysis. In a comprehensive, odor-activity guided approach both chemo-analytical and human-sensory parameters were used to identify odor active constituents of the volatile fraction of B. sacra. Among the key odorants found were α-pinene, β-myrcene, linalool, p-cresol and two unidentified sesquiterpenoids. Overall, a total of 23 odorants were detected and analyzed by gas chromatography-olfactometry and heart-cut two-dimensional gas chromatography-mass spectrometry/olfactometry. The majority of the identified odorant compounds were oxygenated monoterpenes, along with some relevant mono- and sesquiterpenes and only one diterpenoid substance. Several of these compounds were reported here for the first time as odorous constituents in B. sacra. Identifying bioactive compounds might support a better understanding with regard to the potential benefits of frankincense, for example in aromatherapy or ecclesial settings.

  4. Rapid and Precise Measurement of Serum Branched-Chain and Aromatic Amino Acids by Isotope Dilution Liquid Chromatography Tandem Mass Spectrometry

    PubMed Central

    Yang, Ruiyue; Dong, Jun; Guo, Hanbang; Li, Hongxia; Wang, Shu; Zhao, Haijian; Zhou, Weiyan; Yu, Songlin; Wang, Mo; Chen, Wenxiang

    2013-01-01

    Background Serum branched-chain and aromatic amino acids (BCAAs and AAAs) have emerged as predictors for the future development of diabetes and may aid in diabetes risk assessment. However, the current methods for the analysis of such amino acids in biological samples are time consuming. Methods An isotope dilution liquid chromatography tandem mass spectrometry (ID-LC/MS/MS) method for serum BCAAs and AAAs was developed. The serum was mixed with isotope-labeled BCAA and AAA internal standards and the amino acids were extracted with acetonitrile, followed by analysis using LC/MS/MS. The LC separation was performed on a reversed-phase C18 column, and the MS/MS detection was performed via the positive electronic spray ionization in multiple reaction monitoring mode. Results Specific analysis of the amino acids was achieved within 2 min. Intra-run and total CVs for the amino acids were less than 2% and 4%, respectively, and the analytical recoveries ranged from 99.6 to 103.6%. Conclusion A rapid and precise method for the measurement of serum BCAAs and AAAs was developed and may serve as a quick tool for screening serum BCAAs and AAAs in studies assessing diabetes risk. PMID:24339906

  5. Isotope dilution gas chromatography with mass spectrometry for the analysis of 4-octyl phenol, 4-nonylphenol, and bisphenol A in vegetable oils.

    PubMed

    Wu, Pinggu; Zhang, Liqun; Yang, Dajin; Zhang, Jing; Hu, Zhengyan; Wang, Liyuan; Ma, Bingjie

    2016-03-01

    By the combination of solid-phase extraction as well as isotope dilution gas chromatography with mass spectrometry, a sensitive and reliable method for the determination of endocrine-disrupting chemicals including bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils was established. The application of a silica/N-(n-propyl)ethylenediamine mixed solid-phase extraction cartridge achieved relatively low matrix effects for bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils. Experiments were designed to evaluate the effects of derivatization, and the extraction parameters were optimized. The estimated limits of detection and quantification for bisphenol A, 4-octylphenol, and 4-nonylphenol were 0.83 and 2.5 μg/kg, respectively. In a spiked experiment in vegetable oils, the recovery of the added bisphenol A was 97.5-110.3%, recovery of the added 4-octylphenol was 64.4-87.4%, and that of 4-nonylphenol was 68.2-89.3%. This sensitive method was then applied to real vegetable oil samples from Zhejiang Province of China, and none of the target compounds were detected. PMID:26698324

  6. Comparison of digestion procedures and methods for quantification of trace lead in breast milk by isotope dilution inductively coupled plasma mass spectrometry

    PubMed Central

    Amarasiriwardena, Chitra J.; Jayawardene, Innocent; Lupoli, Nicola; Barnes, Ramon M.; Hernandez-Avila, Mauricio; Hu, Howard

    2014-01-01

    Measurement of lead in breast milk is an important public health consideration and can be technically quite challenging. The reliable and accurate determination of trace lead in human breast milk is difficult for several reasons including: potential for contamination during sample collection, storage, and analysis; complexities related to the high fat content of human milk; and poor analytic sensitivity at low concentrations. Breast milk lead levels from previous published studies should therefore be reviewed with caution. Due to the difficulty in identifying a method that would successfully digest samples with 100% efficiency, we evaluated three different digestion procedures including: (1) dry ashing in a muffle furnace, (2) microwave oven digestion, and (3) digestion in high pressure asher. High temperature, high pressure asher digestion was selected as the procedure of choice for the breast milk samples. Trace lead analysis was performed using isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS). Measured lead concentrations in breast milk samples (n = 200) from Mexico ranged from 0.2 to 6.7 ng ml−1. The precision for these measurements ranged from 0.27–7.8% RSD. Use of strict contamination control techniques and of a very powerful digestion procedure, along with an ID-ICP-MS method for lead determination, enables us to measure trace lead levels as low as 0.2 ng ml−1 in milk (instrument detection limit = 0.01 ng ml−1). PMID:24808927

  7. [Determination of urinary cotinine of children exposed to passive smoking by stable isotope dilution gas chromatography-triple quadrupole mass spectrometry].

    PubMed

    Wang, Yun; Huang, Zhiqiang; Ye, Ying; Zhang, Ying; Xiao, Shuiyuan

    2014-06-01

    An analytical method for the determination of urinary cotinine of children exposed to passive smoking was established based on stable isotope dilution by gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS). The samples were extracted and purified with chloroform. The extracts were determined by GC-MS/MS in multiple reaction monitoring (MRM) mode. The cotinine-d3 as an isotope internal standard was applied to quantify and confirm the urinary cotinine of children exposed to passive smoking. The method had a good linearity from 0.1 microg/L to 10 microg/L with the correlation coefficient (r) > 0.998. The recoveries of the cotinine in blank urine were from 79.2% to 112.8% at spiked levels of 0.1, 1.0 and 10 microg/ L, with relative standard deviations (RSDs) from 2.1% to 5. 8%. The limit of quantification ( LOQ) of the method was 0.1 microg/L. The developed method is accurate, sensitive, rapid and can be applied to detect urinary cotinine of children exposed to passive smoking at home. PMID:25269267

  8. Simultaneous analysis of phthalates, adipate and polycyclic aromatic hydrocarbons in edible oils using isotope dilution-gas chromatography-mass spectrometry.

    PubMed

    Oh, Min-Seok; Lee, Seon-Hwa; Moon, Myeong Hee; Lee, Dong Soo; Park, Hyun-Mee

    2014-01-01

    A method for simultaneous determination of 12 priority phthalates, adipate and polycyclic aromatic hydrocarbons (PAHs) in edible oils by isotope dilution-gas chromatography-mass spectrometry (ID-GC-MS) was developed for fast, accurate and trace analysis. The extraction and clean-up procedures were optimised, and using stable isotope-labelled internal standards for each analyte, relative standard deviations (RSDs) of 0.92-10.6% and spiked sample recoveries of 80.6-97.8% were obtained. Limits of detection for PAHs were in the range of 0.15-0.77 µg/kg and those for phthalates were in the range of 4.6-10.0 µg/kg. The calibration curves exhibited good linearities with regression coefficients of R(2) ≥ 0.99. Twelve edible oils were examined to evaluate the efficiency of this method. Among the 12 analytes, dibutyl phthalates (DBP), diethylhexyl phthalates (DEHP), diethylhexyl adipate (DEHA), benzo[a]anthracene (B[a]A), chrysene (Chry) and benzo[b]fluoranthene (B[b]F) were detected in the range of 1.17-806 µg/kg.

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

    SciTech Connect

    Jaruga, Pawel; Xiao, Yan; Nelson, Bryant C.; Dizdaroglu, Miral

    2009-09-04

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

  10. Development and validation of a liquid chromatography isotope dilution mass spectrometry method for the reliable quantification of alkylphenols in environmental water samples by isotope pattern deconvolution.

    PubMed

    Fabregat-Cabello, Neus; Sancho, Juan V; Vidal, Andreu; González, Florenci V; Roig-Navarro, Antoni Francesc

    2014-02-01

    We present here a new measurement method for the rapid extraction and accurate quantification of technical nonylphenol (NP) and 4-t-octylphenol (OP) in complex matrix water samples by UHPLC-ESI-MS/MS. The extraction of both compounds is achieved in 30min by means of hollow fiber liquid phase microextraction (HF-LPME) using 1-octanol as acceptor phase, which provides an enrichment (preconcentration) factor of 800. On the other hand we have developed a quantification method based on isotope dilution mass spectrometry (IDMS) and singly (13)C1-labeled compounds. To this end the minimal labeled (13)C1-4-(3,6-dimethyl-3-heptyl)-phenol and (13)C1-t-octylphenol isomers were synthesized, which coelute with the natural compounds and allows the compensation of the matrix effect. The quantification was carried out by using isotope pattern deconvolution (IPD), which permits to obtain the concentration of both compounds without the need to build any calibration graph, reducing the total analysis time. The combination of both extraction and determination techniques have allowed to validate for the first time a HF-LPME methodology at the required levels by legislation achieving limits of quantification of 0.1ngmL(-1) and recoveries within 97-109%. Due to the low cost of HF-LPME and total time consumption, this methodology is ready for implementation in routine analytical laboratories. PMID:24423386

  11. A Simplified Method for Quantifying Sulfur Mustard Adducts to Blood Proteins by Ultra-High Pressure Liquid Chromatography-Isotope Dilution Tandem Mass Spectrometry

    PubMed Central

    Pantazides, Brooke G.; Crow, Brian S.; Garton, Joshua W.; Quiñones-González, Jennifer A.; Blake, Thomas A.; Thomas, Jerry D.; Johnson, Rudolph C.

    2016-01-01

    Sulfur mustard binds to reactive cysteine residues, forming a stable sulfur-hydroxyethylthioethyl [S-HETE] adduct that can be used as a long-term biomarker of sulfur mustard exposure in humans. The digestion of sulfur mustard-exposed blood samples with proteinase K following total protein precipitation with acetone produces the tripeptide biomarker [S-HETE]-Cys-Pro-Phe. The adducted tripeptide is purified by solid phase extraction, separated by ultra-high pressure liquid chromatography, and detected by isotope dilution tandem mass spectrometry. This approach was thoroughly validated and characterized in our laboratory. The average interday relative standard deviation was ≤ 9.49%, and the range of accuracy was between 96.1-109% over a concentration range of 3.00 to 250. ng/mL with a calculated limit of detection of 1.74 ng/mL. A full 96-well plate can be processed and analyzed in 8 h which is five times faster than our previous 96-well plate method and only requires 50 µL of serum, plasma, or whole blood. Extensive ruggedness and stability studies and matrix comparisons were conducted to create a robust, easily transferrable method. As a result, a simple and high-throughput method has been developed and validated for the quantitation of sulfur mustard blood protein adducts in low volume blood specimens which should be readily adaptable for quantifying human exposures to other alkylating agents. PMID:25622494

  12. Comparison of digestion procedures and methods for quantification of trace lead in breast milk by isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Amarasiriwardena, Chitra J; Jayawardene, Innocent; Lupoli, Nicola; Barnes, Ramon M; Hernandez-Avila, Mauricio; Hu, Howard; Ettinger, Adrienne S

    2013-01-01

    Measurement of lead in breast milk is an important public health consideration and can be technically quite challenging. The reliable and accurate determination of trace lead in human breast milk is difficult for several reasons including: potential for contamination during sample collection, storage, and analysis; complexities related to the high fat content of human milk; and poor analytic sensitivity at low concentrations. Breast milk lead levels from previous published studies should therefore be reviewed with caution. Due to the difficulty in identifying a method that would successfully digest samples with 100% efficiency, we evaluated three different digestion procedures including: (1) dry ashing in a muffle furnace, (2) microwave oven digestion, and (3) digestion in high pressure asher. High temperature, high pressure asher digestion was selected as the procedure of choice for the breast milk samples. Trace lead analysis was performed using isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS). Measured lead concentrations in breast milk samples (n = 200) from Mexico ranged from 0.2 to 6.7 ng ml(-1). The precision for these measurements ranged from 0.27-7.8% RSD. Use of strict contamination control techniques and of a very powerful digestion procedure, along with an ID-ICP-MS method for lead determination, enables us to measure trace lead levels as low as 0.2 ng ml(-1) in milk (instrument detection limit = 0.01 ng ml(-1)). PMID:24808927

  13. Stable isotope dilution ultra-high performance liquid chromatography-tandem mass spectrometry quantitative profiling of tryptophan-related neuroactive substances in human serum and cerebrospinal fluid.

    PubMed

    Hényková, Eva; Vránová, Hana Přikrylová; Amakorová, Petra; Pospíšil, Tomáš; Žukauskaitė, Asta; Vlčková, Magdaléna; Urbánek, Lubor; Novák, Ondřej; Mareš, Jan; Kaňovský, Petr; Strnad, Miroslav

    2016-03-11

    Many compounds related to L-tryptophan (L-TRP) have interesting biological or pharmacological activity, and their abnormal neurotransmission seems to be linked to a wide range of neurodegenerative and psychiatric diseases. A high-throughput method based on ultra-high performance liquid chromatography connected to electrospray tandem mass spectrometry (UHPLC-ESI-MS/MS) was developed for the quantitative analysis of L-TRP and 16 of its metabolites in human serum and cerebrospinal fluid (CSF), representing both major and minor routes of L-TRP catabolism. The combination of a fast LC gradient with selective tandem mass spectrometry enabled accurate analysis of almost 100 samples in 24h. The standard isotope dilution method was used for quantitative determination. The method's lower limits of quantification for serum and cerebrospinal fluid ranged from 0.05 to 15nmol/L and 0.3 to 45nmol/L, respectively. Analytical recoveries ranged from 10.4 to 218.1% for serum and 22.1 to 370.0% for CSF. The method's accuracy ranged from 82.4 to 128.5% for serum matrix and 90.7 to 127.7% for CSF matrix. All intra- and inter-day coefficients of variation were below 15%. These results demonstrate that the new method is capable of quantifying endogenous serum and CSF levels of a heterogeneous group of compounds spanning a wide range of concentrations. The method was used to determine the physiological levels of target analytes in serum and CSF samples from 18 individuals, demonstrating its reliability and potential usefulness in large-scale epidemiological studies.

  14. Determination of mycotoxins in milk-based products and infant formula using stable isotope dilution assay and liquid chromatography tandem mass spectrometry.

    PubMed

    Zhang, Kai; Wong, Jon W; Hayward, Douglas G; Vaclavikova, Marta; Liao, Chia-Ding; Trucksess, Mary W

    2013-07-01

    A stable isotope dilution assay and liquid chromatography tandem mass spectrometry (LC-MS/MS) method was developed and validated for the determination of 12 mycotoxins, aflatoxins B₁, B₂, G₁, G₂, and M₁, deoxynivalenol, fumonisins B₁, B₂, and B₃, ochratoxin A, T-2 toxin, and zearalenone, in milk-based infant formula and foods. Samples were fortified with 12 ¹³C uniformly labeled mycotoxins ([¹³C]-mycotoxins) that correspond to the 12 target mycotoxins and prepared by dilution and filtration, followed by LC-MS/MS analysis. Quantitation was achieved using the relative response factors of [¹³C]-mycotoxins and target mycotoxins. The average recoveries in fortified milk, milk-based infant formula, milk powder, and baby yogurt of aflatoxins B₁, B₂, G₁, and G₂ (2, 10, and 50 μg/kg), aflatoxin M₁ (0.5, 2.5, and 12.5 μg/kg), deoxynivalenol, fumonisins B₁, B₂, and B₃ (40, 200, and 1000 μg/kg), ochratoxin A, T-2 toxin, and zearalenone (20, 100, and 500 μg/kg), range from 89 to 126% with RSDs of <20%. The individual recoveries in the four fortified matrices range from 72% (fumonisin B₃, 20 μg/kg, milk-based infant formula) to 136% (T-2 toxin, 20 μg/kg, milk powder), with RSDs ranging from 2 to 25%. The limits of quantitation (LOQs) were from 0.01 μg/kg (aflatoxin M₁) to 2 (fumonisin B₁) μg/kg. Aflatoxin M₁ was detected in two European Reference materials at 0.127 ± 0.013 μg/kg (certified value = 0.111 ± 0.018 μg/kg) and 0.46 ± 0.04 μg/kg (certified value = 0.44 ± 0.06 μg/kg), respectively. In 60 local market samples, aflatoxins B₁ (1.14 ± 0.10 μg/kg) and B₂ (0.20 ± 0.03 μg/kg) were detected in one milk powder sample. Aflatoxin M₁ was detected in three imported samples (condensed milk, milk-based infant formula, and table cream), ranging from 0.10 to 0.40 μg/kg. The validated method provides sufficient selectivity, sensitivity, accuracy, and reproducibility to screen for aflatoxin M₁ at nanograms per

  15. Determination of As and Se in crude oil diluted in xylene by inductively coupled plasma mass spectrometry using a dynamic reaction cell for interference correction on 80Se

    NASA Astrophysics Data System (ADS)

    de Albuquerque, Fernanda Inda; Duyck, Christiane B.; Fonseca, Teresa Cristina O.; Saint'Pierre, Tatiana D.

    2012-05-01

    Arsenic and selenium can be found in crude oils and represent an important source of pollution when released to the environment during any stage of extraction or refinery. These elements present low sensitivity in the direct determination by inductively coupled plasma mass spectrometry (ICP-MS), due to their high ionization potential, and are also prone to spectral interferences. Hydride generation (HG) can be alternatively employed for the separation of these analytes from the sample matrix and introduction into the instrument. However, the required sample preparation usually increases the analysis time. In this work, a method was developed for the determination of As and Se in crude oil by ICP-MS, after sample dilution in xylene. The use of a dynamic reaction cell (DRC) allowed for the overcoming of Ar2+ interference on 80Se, but was not necessary for As, since interference on m/z 75 was not observed. The optimized operational conditions for 75As and 80Se were: 1350 W of RF power, 0.4 L min- 1 of Ar nebulizer and 0.7 L min- 1 of Ar auxiliary flow rates. The DRC conditions for 80Se were 0.5 L min- 1 of methane and rejection parameter q (Rpq) of 0.2. The analyses were carried out by analyte addition and the limits of detection (LOD) were 0.04 μg kg- 1 for As and 0.1 μg kg- 1 for Se. The accuracy was verified by the analysis of residual fuel oil certified material, with agreement at a 95% confidence level. Nine Brazilian crude oil samples were analyzed and the results compared to those obtained by hydride generation ICP-MS. In this case, samples were decomposed with nitric acid in a digester block, the analytes pre-reduced with HCl 6 mol L- 1 and the determination carried out by external calibration. Although better instrumental LODs were obtained by HG (0.002 μg kg- 1 of As and 0.04 μg kg- 1 of Se), the direct determination of As and Se in crude oil diluted in xylene by DRC-ICP-MS showed to be an adequate and a faster method.

  16. Doping control analysis of 46 polar drugs in horse plasma and urine using a 'dilute-and-shoot' ultra high performance liquid chromatography-high resolution mass spectrometry approach.

    PubMed

    Kwok, Wai Him; Choi, Timmy L S; Kwok, Karen Y; Chan, George H M; Wong, Jenny K Y; Wan, Terence S M

    2016-06-17

    The high sensitivity of ultra high performance liquid chromatography coupled with high resolution mass spectrometry (UHPLC-HRMS) allows the identification of many prohibited substances without pre-concentration, leading to the development of simple and fast 'dilute-and-shoot' methods for doping control for human and equine sports. While the detection of polar drugs in plasma and urine is difficult using liquid-liquid or solid-phase extraction as these substances are poorly extracted, the 'dilute-and-shoot' approach is plausible. This paper describes a 'dilute-and-shoot' UHPLC-HRMS screening method to detect 46 polar drugs in equine urine and plasma, including some angiotensin-converting enzyme (ACE) inhibitors, sympathomimetics, anti-epileptics, hemostatics, the new doping agent 5-aminoimidazole-4-carboxamide-1-β-d-ribofuranoside (AICAR), as well as two threshold substances, namely dimethyl sulfoxide and theobromine. For plasma, the sample (200μL) was protein precipitated using trichloroacetic acid, and the resulting supernatant was diluted using Buffer A with an overall dilution factor of 3. For urine, the sample (20μL) was simply diluted 50-fold with Buffer A. The diluted plasma or urine sample was then analysed using a UHPLC-HRMS system in full-scan ESI mode. The assay was validated for qualitative identification purpose. This straightforward and reliable approach carried out in combination with other screening procedures has increased the efficiency of doping control analysis in the laboratory. Moreover, since the UHPLC-HRMS data were acquired in full-scan mode, the method could theoretically accommodate an unlimited number of existing and new doping agents, and would allow a retrospectively search for drugs that have not been targeted at the time of analysis. PMID:27180888

  17. A novel strategy for Cr(III) and Cr(VI) analysis in dietary supplements by speciated isotope dilution mass spectrometry.

    PubMed

    Unceta, Nora; Astorkia, Maider; Abrego, Zuriñe; Gómez-Caballero, Alberto; Goicolea, M Aránzazu; Barrio, Ramón J

    2016-07-01

    In recent years, Cr speciation in dietary supplements has become decisive in the evaluation of their health risks. Despite being an beneficial micronutrient, Cr(III) can be toxic at living organisms at high concentrations, while Cr(VI) is known to be highly toxic and carcinogenic. The main objective of this work was to optimize an analytical methodology for the extraction and accurate quantification of Cr(III) and Cr(VI) in dietary supplements. The extraction of Cr species was carried out with 50mM EDTA solution on a hotplate under optimized conditions. Special attention was paid to bidirectional species transformations. No noticeable oxidation of Cr(III) into Cr(VI) was observed and the reduction to Cr(III) only occurred at very high Cr(VI) concentrations. Cr(III) as Cr(EDTA)(-) complex was chromatographically separated from Cr(VI), retained as CrO4(2-), on an anion exchange column coupled to inductively coupled plasma mass spectrometry (LC-ICP-MS). The limit of quantification (0.08µgg(-1)) was below the limit established for Cr enriched yeasts by the European Union. Eleven dietary supplements were analyzed and Cr(III) and Cr(VI) quantification was carried out by external calibration monitoring (52)Cr isotope and by speciated isotope dilution mass spectrometry (SIDMS) adding (50)Cr(III) and (53)Cr(VI) spikes. Total Cr was also quantified by ICP-MS and mass balance between total Cr and the sum of Cr(III) and Cr(VI) was achieved. In eight of the eleven tested supplements Cr(III) calculated amounts were higher than those indicated by the manufacturer, but only one of them exceeded the 250µgday(-1) recommended by World Health Organization (WHO). In contrast, it is worth noting that Cr(VI) amounts beyond the recommendations of the European Union for Cr enriched yeasts were found in five supplements. These results revealed that more accurate and rigorous quality assurance protocols should be applied to the testing of the final products, including the analysis of both

  18. A novel strategy for Cr(III) and Cr(VI) analysis in dietary supplements by speciated isotope dilution mass spectrometry.

    PubMed

    Unceta, Nora; Astorkia, Maider; Abrego, Zuriñe; Gómez-Caballero, Alberto; Goicolea, M Aránzazu; Barrio, Ramón J

    2016-07-01

    In recent years, Cr speciation in dietary supplements has become decisive in the evaluation of their health risks. Despite being an beneficial micronutrient, Cr(III) can be toxic at living organisms at high concentrations, while Cr(VI) is known to be highly toxic and carcinogenic. The main objective of this work was to optimize an analytical methodology for the extraction and accurate quantification of Cr(III) and Cr(VI) in dietary supplements. The extraction of Cr species was carried out with 50mM EDTA solution on a hotplate under optimized conditions. Special attention was paid to bidirectional species transformations. No noticeable oxidation of Cr(III) into Cr(VI) was observed and the reduction to Cr(III) only occurred at very high Cr(VI) concentrations. Cr(III) as Cr(EDTA)(-) complex was chromatographically separated from Cr(VI), retained as CrO4(2-), on an anion exchange column coupled to inductively coupled plasma mass spectrometry (LC-ICP-MS). The limit of quantification (0.08µgg(-1)) was below the limit established for Cr enriched yeasts by the European Union. Eleven dietary supplements were analyzed and Cr(III) and Cr(VI) quantification was carried out by external calibration monitoring (52)Cr isotope and by speciated isotope dilution mass spectrometry (SIDMS) adding (50)Cr(III) and (53)Cr(VI) spikes. Total Cr was also quantified by ICP-MS and mass balance between total Cr and the sum of Cr(III) and Cr(VI) was achieved. In eight of the eleven tested supplements Cr(III) calculated amounts were higher than those indicated by the manufacturer, but only one of them exceeded the 250µgday(-1) recommended by World Health Organization (WHO). In contrast, it is worth noting that Cr(VI) amounts beyond the recommendations of the European Union for Cr enriched yeasts were found in five supplements. These results revealed that more accurate and rigorous quality assurance protocols should be applied to the testing of the final products, including the analysis of both

  19. In vivo prediction of goat kids body composition from the deuterium oxide dilution space determined by isotope-ratio mass spectrometry.

    PubMed

    Lerch, S; Lastel, M L; Grandclaudon, C; Brechet, C; Rychen, G; Feidt, C

    2015-09-01

    Deuterium oxide dilution space (DOS) determination is one of the most accurate methods for in vivo estimation of ruminant body composition. However, the time-consuming vacuum sublimation of blood preceding infrared spectroscopy analysis, which is traditionally used to determine deuterium oxide (DO) concentration, limits its current use. The use of isotope-ratio mass spectrometry (IRMS) to determine the deuterium enrichment and thus quantify DO in plasma could counteract this limitation by reducing the sample preparation for plasma deproteinisation through centrifugal filters. The aim of this study was to validate the DOS technique using IRMS in growing goat kids to establish in vivo prediction equations of body composition. Seventeen weaned male Alpine goat kids (8.6 wk old) received a hay-based diet supplemented with 2 types of concentrates providing medium ( = 9) or high ( = 8) energy levels. Kids were slaughtered at 14.0 ( = 1, medium-energy diet), 17.2 ( = 4, medium-energy diet, and = 4, high-energy diet), or 21.2 wk of age ( = 4, medium-energy diet, and = 4, high-energy diet). Two days before slaughter, DOS was determined after an intravenous injection of 0.2 g DO/kg body mass (BM) and the resulting study of DO dilution kinetics from 4 plasma samples (+5, +7, +29, and +31 h after injection). The deuterium enrichment was analyzed by IRMS. After slaughter, the gut contents were discarded, the empty body (EB) was minced, and EB water, lipid, protein, ash, and energy contents were measured by chemical analyses. Prediction equations for body components measured postmortem were computed from in vivo BM and DOS. The lack of postmortem variation of fat-free EB composition was confirmed (mean of 75.3% [SD 0.6] of water), and the proportion of lipids in the EB tended ( = 0.06) to be greater for the high-energy diet (13.1%) than for the medium-energy diet (11.1%). There was a close negative relationship (residual CV [rCV] = 3.9%, = 0.957) between EB water and lipid

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

    SciTech Connect

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

    2014-04-11

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

  1. Analysis of advanced glycation endproducts in dairy products by isotope dilution liquid chromatography-electrospray tandem mass spectrometry. The particular case of carboxymethyllysine.

    PubMed

    Delatour, Thierry; Hegele, Jörg; Parisod, Véronique; Richoz, Janique; Maurer, Sarah; Steven, Matthew; Buetler, Timo

    2009-03-20

    A fully validated multiple-transition recording isotope dilution liquid chromatography-electrospray tandem mass spectrometry (LC-MS/MS) method for the simultaneous quantitative determination of N(epsilon)-carboxymethyllysine (CML) and lysine in dairy products is described. Internal standards were [N-1',2'-(13)C(2)]CML and [1,2,3,4,5,6-(13)C(6)-2,6-(15)N(2)]lysine, and the method was validated by evaluating the selectivity, linearity, precision (repeatability and reproducibility) and trueness, using both powder and liquid products. For liquid dairy products, the repeatability and reproducibility was 2.79% and 11.0%, while 4.85% and 4.92% were determined for powder dairy products, respectively. The trueness of the method ranged from -9.6% to -3.6% for powder and from -0.99% to 6.8% for liquid dairy products. The limit of detection for CML was estimated to be 8 ng CML per mg protein while the limit of quantification was 27 ng CML per mg protein. The method encompasses a proteolytic cleavage mediated by enzymatic digestion to reach a complete release of the amino acids prior to a sample cleanup based on solid phase extraction, and followed by LC-MS/MS analysis of CML and lysine residues. To ensure a suitable performance of the enzymatic digestion, CML measurements were compared to values obtained with an acid hydrolysis-mediated proteolysis. Finally, the method was employed for the analysis of CML in various dairy products. The values compare well to the data available in the literature when similar methods were used, even if some discrepancies were observed upon comparison with the results obtained by other techniques such as enzyme-linked immunosorbent assay and GC-MS.

  2. Determination of eugenol in fish and shrimp muscle tissue by stable isotope dilution assay and solid-phase extraction coupled gas chromatography-triple quadrupole mass spectrometry.

    PubMed

    Li, Jincheng; Liu, Huan; Wang, Chaoying; Wu, Lidong; Liu, Dan

    2016-09-01

    In this study, we developed a new method for the accurate quantification of eugenol in fish samples based on stable isotope dilution assay (SIDA) and solid-phase extraction (SPE) coupled gas chromatography-triple quadrupole mass spectrometry (SIDA-SPE-GC-MS/MS). Due to the difference of matrix effect (ME), it was difficult to determine accurately the level of eugenol residue in different fish and shrimp samples based on external standard calibration method. SIDA was applied to compensate matrix effect (ME) that eugenol-d3 was used as internal standard (IS). Freshwater fish (carp, channel catfish), marine fish (turbot), and shrimp (Penaeus vannawei) were used for the method validation. The average recoveries of eugenol were in the range of 94.7 to 109.78 % when the spiking levels were 10, 50, and 200 μg kg(-1). The inter-day and intra-day precisions were in the range of 1.15-8.19 and 0.71-8.45 %. The limit of detection (LOD) and the limit of quantification (LOQ) were approximately 2.5 and 5.0 μg kg(-1). This method was applied to the real fish samples assay obtained from aquaculture markets in Beijing, China. Eugenol residue was found in two fish samples with the levels at 6.2 and 7.7 μg kg(-1), respectively. Graphical abstract Determination of eugenol in fish and shrimp muscle tissue. PMID:27531030

  3. Quantification of key red blood cell folates from subjects with defined MTHFR 677C>T genotypes using stable isotope dilution liquid chromatography/mass spectrometry

    PubMed Central

    Huang, Yuehua; Khartulyari, Stefanie; Morales, Megan E.; Stanislawska-Sachadyn, Anna; Von Feldt, Joan M.; Whitehead, Alexander S.; Blair, Ian A.

    2014-01-01

    Red blood cell (RBC) folate levels are established at the time of erythropoiesis and therefore provide a surrogate biomarker for the average folate status of an individual over the preceding four months. Folates are present as folylpolyglutamates, highly polar molecules that cannot be secreted from the RBCs, and must be converted into their monoglutamate forms prior to analysis. This was accomplished using an individual’s plasma pteroylpolyglutamate hydrolase by lysing the RBCs in whole blood at pH 5 in the presence of ascorbic acid. Quantitative conversion of formylated tetrahydrofolate derivatives into the stable 5,10-methenyltetrahydrofolate (5,10-MTHF) form was conducted at pH 1.5 in the presence of [13C5]-5-formyltetrahydrofolate. The resulting [13C5]-5,10-MTHF was then used as an internal standard for the formylated forms of tetrahydrofolate that had been converted into 5,10-MTHF as well any 5,10-MTHF that had been present in the original sample. A stable isotope dilution liquid chromatography-multiple reaction monitoring/mass spectrometry method was validated and then used for the accurate and precise quantification of RBC folic acid, 5-methyltetrahydrofolate (5-MTHF), tetrahydrofolate (THF), and 5,10-MTHF. The method was sensitive and robust and was used to assess the relationship between different methylenetetrahydrofolate reductase (MTHFR) 677C>T genotypes and RBC folate phenotypes. Four distinct RBC folate phenotypes could be identified. These were classified according to the relative amounts of individual RBC folates as type I (5-MTHF >95%; THF <5%; 5,10-MTHF <5%), type II (5-MTHF <95%; THF 5% to 20%; 5,10-MTHF <5%), type III (5-MTHF >55%; THF >20%; 5,10-MTHF >5%), and type IV (5-MTHF <55%; THF >20%; 5,10-MTHF >5%). PMID:18634122

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

    PubMed

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

    2015-07-01

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

  5. Measurement of attogram quantities of 231Pa in dissolved and particulate fractions of seawater by isotope dilution thermal ionization mass spectroscopy.

    PubMed

    Shen, Chuan-Chou; Cheng, Hai; Edwards, R Lawrence; Moran, S Bradley; Edmonds, Henrietta N; Hoff, John A; Thomas, Rebecca B

    2003-03-01

    A technique has been developed to quantify ultratrace 231Pa (50-2000 ag; 1 ag = 10(-18) g) concentrations in seawater using isotope-dilution thermal ionization mass spectrometry (TIMS). The method is a modification of a process developed by Pickett et al. (Pickett, D. A.; Murrell, M. T.; Williams, R. W. Anal. Chem. 1994, 66, 1044-1049) and extends the technique to very low levels of protactinium. The procedural blank is 16 +/- 15 ag (2sigma), and the ionization efficiency (ions generated/atom loaded) approaches 0.5%. Measurement time is <1 h. The amount of 231Pa needed to produce 231Pa data with an uncertainty of +/-4-12% is 100-1000 ag (approximately 3 x 10(5) to 3 x 10(6) atoms). Replicate measurements made on known standards and seawater samples demonstrate that the analytical precision approximates that expected from counting statistics and that, based on detection limits of 38 and 49 ag, protactinium can be detected in a minimum sample size of surface seawater of approximately 2 L for suspended particulate matter and <0.1 L for filtered (<0.4 microm) seawater, respectively. The concentration of 231Pa (tens of attograms per liter) can be determined with an uncertainty of +/-5-10% (2sigma) for suspended particulate matter filtered from 5 to 10 L of seawater. For the dissolved fraction, 0.5-1 L of seawater yields 231Pa measurements with a precision of 1-10%. Sample size requirements are orders of magnitude less than traditional decay-counting techniques and significantly less than previously reported ICP-MS techniques. Our technique can also be applied to other environmental samples, including cave waters, rivers, and igneous rocks.

  6. Measurement of attogram quantities of 231Pa in dissolved and particulate fractions of seawater by isotope dilution thermal ionization mass spectroscopy.

    PubMed

    Shen, Chuan-Chou; Cheng, Hai; Edwards, R Lawrence; Moran, S Bradley; Edmonds, Henrietta N; Hoff, John A; Thomas, Rebecca B

    2003-03-01

    A technique has been developed to quantify ultratrace 231Pa (50-2000 ag; 1 ag = 10(-18) g) concentrations in seawater using isotope-dilution thermal ionization mass spectrometry (TIMS). The method is a modification of a process developed by Pickett et al. (Pickett, D. A.; Murrell, M. T.; Williams, R. W. Anal. Chem. 1994, 66, 1044-1049) and extends the technique to very low levels of protactinium. The procedural blank is 16 +/- 15 ag (2sigma), and the ionization efficiency (ions generated/atom loaded) approaches 0.5%. Measurement time is <1 h. The amount of 231Pa needed to produce 231Pa data with an uncertainty of +/-4-12% is 100-1000 ag (approximately 3 x 10(5) to 3 x 10(6) atoms). Replicate measurements made on known standards and seawater samples demonstrate that the analytical precision approximates that expected from counting statistics and that, based on detection limits of 38 and 49 ag, protactinium can be detected in a minimum sample size of surface seawater of approximately 2 L for suspended particulate matter and <0.1 L for filtered (<0.4 microm) seawater, respectively. The concentration of 231Pa (tens of attograms per liter) can be determined with an uncertainty of +/-5-10% (2sigma) for suspended particulate matter filtered from 5 to 10 L of seawater. For the dissolved fraction, 0.5-1 L of seawater yields 231Pa measurements with a precision of 1-10%. Sample size requirements are orders of magnitude less than traditional decay-counting techniques and significantly less than previously reported ICP-MS techniques. Our technique can also be applied to other environmental samples, including cave waters, rivers, and igneous rocks. PMID:12641225

  7. Determination of urinary cortisol, cortisone and 6-sulfatoxymelatonin using dilute and shoot ultra-high pressure liquid chromatography-tandem mass spectrometry.

    PubMed

    Sniecinska-Cooper, Anna Maria; Shah, Ajit Jesang; Dimitriou, Dagmara; Iles, Ray Kruse; Butler, Stephen Andrew; Bayford, Richard

    2015-01-26

    Human sleep is a natural part of every individual's life. Clear relationship between sleep and endocrine system has been already established. In particular, melatonin and cortisol are known to affect and regulate sleep/wake patterns. Here we report the development of an ultra-high pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous measurement of 6-sulfatoxymelatonin (MT6s), cortisol and cortisone in urine. A separate method was developed for measurement of creatinine in urine. These levels were used to normalise the levels of analytes. First void morning urine samples were collected from 24 healthy volunteers. Samples were diluted 1:1 in water prior to injection onto reversed-phase C18 column and analysed using UHPLC-MS/MS method. Linear calibrations were obtained for all analytes with correlation coefficient in the range 0.998-0.999. The observed concentration was found to be in the range 92-105% for cortisol, 92-107% for cortisone and between 93 and 120% for MT6s of the reference levels. The total run time of 6 min with all peaks of interest eluting within 3 min was obtained. This demonstrates the feasibility of utilising the method for large multi-scale studies, where high throughput is required for studying the circadian rhythm of melatonin and cortisol secretion. These hormones play significant role in circadian rhythm and sleep/wake cycle; therefore it is important to monitor the levels of these endocrine markers in individuals suffering from sleep disorders. It is also beneficial with clinical applications to analyse melatonin and cortisol simultaneously in order to assess their interrelationships of these substances, such as their effect on diurnal rhythm and sleep.

  8. Protein quantitation using Ru-NHS ester tagging and isotope dilution high-pressure liquid chromatography-inductively coupled plasma mass spectrometry determination.

    PubMed

    Liu, Rui; Lv, Yi; Hou, Xiandeng; Yang, Lu; Mester, Zoltan

    2012-03-20

    An accurate, simple, and sensitive method for the direct determination of proteins by nonspecies specific isotope dilution and external calibration high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICPMS) is described. The labeling of myoglobin (17 kDa), transferrin (77 kDa), and thyroglobulin (670 kDa) proteins was accomplished in a single-step reaction with a commercially available bis(2,2'-bipyridine)-4'-methyl-4-carboxybipyridine-ruthenium N-succinimidyl ester-bis(hexafluorophosphate) (Ru-NHS ester). Using excess amounts of Ru-NHS ester compared to the protein concentration at optimized labeling conditions, constant ratios for Ru to proteins were obtained. Bioconjugate solutions containing both labeled and unlabeled proteins as well as excess Ru-NHS ester reagent were injected onto a size exclusion HPLC column for separation and ICPMS detection without any further treatment. A (99)Ru enriched spike was used for nonspecies specific ID calibration. The accuracy of the method was confirmed at various concentration levels. An average recovery of 100% ± 3% (1 standard deviation (SD), n = 9) was obtained with a typical precision of better than 5% RSD at 100 μg mL(-1) for nonspecies specific ID. Detection limits (3SD) of 1.6, 3.2, and 7.0 fmol estimated from three procedure blanks were obtained for myoglobin, transferrin, and thyroglobulin, respectively. These detection limits are suitable for the direct determination of intact proteins at trace levels. For simplicity, external calibration was also tested. Good linear correlation coefficients, 0.9901, 0.9921, and 0.9980 for myoglobin, transferrin, and thyroglobulin, respectively, were obtained. The measured concentrations of proteins in a solution were in good agreement with their volumetrically prepared values. To the best of our knowledge, this is the first application of nonspecies specific ID for the accurate and direct determination of proteins using a Ru-NHS ester

  9. Achieving comparability with IFCC reference method for the measurement of hemoglobin A1c by use of an improved isotope-dilution mass spectrometry method.

    PubMed

    Liu, Hong; Wong, Lingkai; Yong, Sharon; Liu, Qinde; Lee, Tong Kooi

    2015-10-01

    The development of reference measurement methods for hemoglobin A1c (HbA1c) is important for quality assurance in diabetes management. The IFCC reference method using purified proteins as calibration standards is the recommended accuracy-based reference method for the standardization of HbA1c measurement. We developed a highly precise and accurate liquid chromatography-isotope-dilution tandem mass spectrometry (LC-IDMS/MS) procedure, which can serve as an alternative accuracy-based method for HbA1c measurement. In this method, enzymatic proteolysis was applied to sample preparation, followed by LC-IDMS/MS measurement of hemoglobin A0 (HbA0) and HbA1c, using two "signature" hexapeptides for calibration. The concentrations of the signature hexapeptide calibration solutions were, in turn, determined using a hydrolysis method with HCl, followed by LC-IDMS/MS measurement using amino acid solutions as calibration standards. These solutions were gravimetrically prepared from pure amino acid certified reference materials (CRMs). The developed LC-IDMS/MS method was used in participation in an IFCC ring trial for reference laboratories (RELA 2013 and 2014) for HbA1c, where our results were compared with those using the IFCC reference method. The deviations were found to be 0.4-1.7 mmol mol(-1) [or 0.04-0.16% in National Glygohemoglobin Standardization Program (NGSP) units], revealing good comparability with the IFCC reference method. The relative expanded uncertainty of the LC-IDMS/MS was in the range of 2.6% to 2.8% (1.6% to 2.2% after converting to NGSP units). With excellent method precision, good comparability with the IFCC reference method, and a small measurement uncertainty, the developed LC-IDMS/MS method may be used as an alternative accuracy-based reference method for HbA1c measurement.

  10. Determination of eugenol in fish and shrimp muscle tissue by stable isotope dilution assay and solid-phase extraction coupled gas chromatography-triple quadrupole mass spectrometry.

    PubMed

    Li, Jincheng; Liu, Huan; Wang, Chaoying; Wu, Lidong; Liu, Dan

    2016-09-01

    In this study, we developed a new method for the accurate quantification of eugenol in fish samples based on stable isotope dilution assay (SIDA) and solid-phase extraction (SPE) coupled gas chromatography-triple quadrupole mass spectrometry (SIDA-SPE-GC-MS/MS). Due to the difference of matrix effect (ME), it was difficult to determine accurately the level of eugenol residue in different fish and shrimp samples based on external standard calibration method. SIDA was applied to compensate matrix effect (ME) that eugenol-d3 was used as internal standard (IS). Freshwater fish (carp, channel catfish), marine fish (turbot), and shrimp (Penaeus vannawei) were used for the method validation. The average recoveries of eugenol were in the range of 94.7 to 109.78 % when the spiking levels were 10, 50, and 200 μg kg(-1). The inter-day and intra-day precisions were in the range of 1.15-8.19 and 0.71-8.45 %. The limit of detection (LOD) and the limit of quantification (LOQ) were approximately 2.5 and 5.0 μg kg(-1). This method was applied to the real fish samples assay obtained from aquaculture markets in Beijing, China. Eugenol residue was found in two fish samples with the levels at 6.2 and 7.7 μg kg(-1), respectively. Graphical abstract Determination of eugenol in fish and shrimp muscle tissue.

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

    SciTech Connect

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

    2007-01-15

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

  12. Determination of urinary cortisol, cortisone and 6-sulfatoxymelatonin using dilute and shoot ultra-high pressure liquid chromatography-tandem mass spectrometry.

    PubMed

    Sniecinska-Cooper, Anna Maria; Shah, Ajit Jesang; Dimitriou, Dagmara; Iles, Ray Kruse; Butler, Stephen Andrew; Bayford, Richard

    2015-01-26

    Human sleep is a natural part of every individual's life. Clear relationship between sleep and endocrine system has been already established. In particular, melatonin and cortisol are known to affect and regulate sleep/wake patterns. Here we report the development of an ultra-high pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous measurement of 6-sulfatoxymelatonin (MT6s), cortisol and cortisone in urine. A separate method was developed for measurement of creatinine in urine. These levels were used to normalise the levels of analytes. First void morning urine samples were collected from 24 healthy volunteers. Samples were diluted 1:1 in water prior to injection onto reversed-phase C18 column and analysed using UHPLC-MS/MS method. Linear calibrations were obtained for all analytes with correlation coefficient in the range 0.998-0.999. The observed concentration was found to be in the range 92-105% for cortisol, 92-107% for cortisone and between 93 and 120% for MT6s of the reference levels. The total run time of 6 min with all peaks of interest eluting within 3 min was obtained. This demonstrates the feasibility of utilising the method for large multi-scale studies, where high throughput is required for studying the circadian rhythm of melatonin and cortisol secretion. These hormones play significant role in circadian rhythm and sleep/wake cycle; therefore it is important to monitor the levels of these endocrine markers in individuals suffering from sleep disorders. It is also beneficial with clinical applications to analyse melatonin and cortisol simultaneously in order to assess their interrelationships of these substances, such as their effect on diurnal rhythm and sleep. PMID:25531866

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

    PubMed

    Regueiro, Jorge; Wenzl, Thomas

    2015-10-01

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

  14. Quantitation of the sulfur mustard metabolites 1,1'-sulfonylbis[2-(methylthio)ethane] and thiodiglycol in urine using isotope-dilution Gas chromatography-tandem mass spectrometry.

    PubMed

    Boyer, Anne E; Ash, Doris; Barr, Dana B; Young, Carrie L; Driskell, W J; Whitehead, Ralph D; Ospina, Maria; Preston, Kerry E; Woolfitt, Adrian R; Martinez, Rodolfo A; Silks, L A Pete; Barr, John R

    2004-01-01

    Sulfur mustard (HD), or bis(2-chloroethyl)sulfide, has several urinary metabolites that can be measured to assess human exposure. These metabolites include the simple hydrolysis product thiodiglycol (TDG) and its oxidative analogue, TDG-sulfoxide, as well as metabolites of the glutathione/b-lyase pathway 1,1'-sulfonylbis[2-(methyl-sulfinyl)ethane] (SBMSE) and 1-methyl-sulfinyl-2-[(methylthio)ethyl-sulfonyl]ethane (MSMTESE). Current methods focus on either the TDG or the b-lyase metabolites. We have developed a single method that measures products of both metabolic branches, with the reduced compound of SBMSE and MSMTESE, 1,1'-sulfonylbis [2(methylthio)ethane] (SBMTE), as the definitive analyte and TDG as a confirmation analyte. Sample preparation included b-glucuronidase hydrolysis for TDG-glucuronide conjugates, titanium trichloride reduction of sulfoxides to SBMTE and TDG, solid-phase extraction, and a chemical derivatization. We analyzed samples using gas chromatography-tandem mass spectrometry with quantitation using isotope-dilution calibration. The method limits of detection for TDG and SBMTE were 0.5 ng/mL and 0.25 ng/mL, respectively, with relative standard deviations of less than 10%. Urine samples from individuals with no known exposure to mustard agent HD had measurable concentrations of TDG, but no SBMTE was detected. The geometric mean concentration of TDG was 3.43 ng/mL, with concentrations ranging from < 0.5 ng/mL to 20 ng/mL. PMID:15239851

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

    PubMed

    Regueiro, Jorge; Wenzl, Thomas

    2015-10-01

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

  16. Influence of the relative optical air mass on ultraviolet erythemal irradiance

    NASA Astrophysics Data System (ADS)

    Antón, M.; Serrano, A.; Cancillo, M. L.; García, J. A.

    2009-12-01

    The main objective of this article is to analyze the relationship between the transmissivity for ultraviolet erythemal irradiance (UVER) and the relative optical air mass at Badajoz (Southwestern Spain). Thus, a power expression between both variables is developed, which analyses in detail how atmospheric transmission is influenced by the total ozone column (TOC) and the atmospheric clearness. The period of analysis extends from 2001 to 2005. The experimental results indicate that clearness conditions play an important role in the relationship between UVER transmissivity and the relative optical air mass, while the effect of TOC is much smaller for this data set. In addition, the results show that UVER transmissivity is more sensitive to changes in atmospheric clearness than to TOC variability. Changes in TOC values higher than 15% cause UVER trasnmissivity to vary between 14% and 22%, while changes between cloud-free and overcast conditions produce variations in UVER transmissivity between 68% and 74% depending on the relative optical air mass.

  17. Towards absolute quantification of therapeutic monoclonal antibody in serum by LC-MS/MS using isotope-labeled antibody standard and protein cleavage isotope dilution mass spectrometry.

    PubMed

    Heudi, Olivier; Barteau, Samuel; Zimmer, Dieter; Schmidt, Joerg; Bill, Kurt; Lehmann, Natalie; Bauer, Christian; Kretz, Olivier

    2008-06-01

    Although LC-MS methods are increasingly used for the absolute quantification of proteins, the lack of appropriate internal standard (IS) hinders the development of rapid and standardized analytical methods for both in vitro and in vivo studies. Here, we have developed a novel method for the absolute quantification of a therapeutic protein, which is monoclonal antibody (mAb). The method combines liquid chromatography tandem mass spectrometry (LC-MS/MS) and protein cleavage isotope dilution mass spectrometry with the isotope-labeled mAb as IS. The latter was identical to the analyzed mAb with the exception that each threonine contains four (13)C atoms and one (15)N atom. Serum samples were spiked with IS prior to the overnight trypsin digestion and subsequent sample cleanup. Sample extracts were analyzed on a C18 ACE column (150 mm x 4.6 mm) using an LC gradient time of 11 min. Endogenous mAb concentrations were determined by calculating the peak height ratio of its signature peptide to the corresponding isotope-labeled peptide. The linear dynamic range was established between 5.00 and 1000 microg/mL mAb with accuracy and precision within +/-15% at all concentrations and below +/-20% at the LLOQ (lower limit of quantification). The overall method recovery in terms of mAb was 14%. The losses due to sample preparation (digestion and purification) were 72% from which about 32% was due to the first step of the method, the sample digestion. This huge loss during sample preparation strongly emphasizes the necessity to employ an IS right from the beginning. Our method was successfully applied to the mAb quantification in marmoset serum study samples, and the precision obtained on duplicate samples was, in most cases, below 20%. The comparison with enzyme-linked immunosorbent assay (ELISA) showed higher exposure in terms of AUC and Cmax with the LC-MS/MS method. Possible reasons for this discrepancy are discussed in this study. The results of this study indicate that our LC

  18. Thin-Film Air-Mass-Flow Sensor of Improved Design Developed

    NASA Technical Reports Server (NTRS)

    Fralick, Gustave C.; Wrbanek, John D.; Hwang, Danny P.

    2003-01-01

    Researchers at the NASA Glenn Research Center have developed a new air-mass-flow sensor to solve the problems of existing mass flow sensor designs. NASA's design consists of thin-film resistors in a Wheatstone bridge arrangement. The resistors are fabricated on a thin, constant-thickness airfoil to minimize disturbance to the airflow being measured. The following photograph shows one of NASA s prototype sensors. In comparison to other air-mass-flow sensor designs, NASA s thin-film sensor is much more robust than hot wires, causes less airflow disturbance than pitot tubes, is more accurate than vane anemometers, and is much simpler to operate than thermocouple rakes. NASA s thin-film air-mass-flow sensor works by converting the temperature difference seen at each leg of the thin-film Wheatstone bridge into a mass-flow rate. The following figure shows a schematic of this sensor with air flowing around it. The sensor operates as follows: current is applied to the bridge, which increases its temperature. If there is no flow, all the arms are heated equally, the bridge remains in balance, and there is no signal. If there is flow, the air passing over the upstream legs of the bridge reduces the temperature of the upstream legs and that leads to reduced electrical resistance for those legs. After the air has picked up heat from the upstream legs, it continues and passes over the downstream legs of the bridge. The heated air raises the temperature of these legs, increasing their electrical resistance. The resistance difference between the upstream and downstream legs unbalances the bridge, causing a voltage difference that can be amplified and calibrated to the airflow rate. Separate sensors mounted on the airfoil measure the temperature of the airflow, which is used to complete the calculation for the mass of air passing by the sensor. A current application for air-mass-flow sensors is as part of the intake system for an internal combustion engine. A mass-flow sensor is

  19. Interaction of mid-latitude air masses with the polar dome area during RACEPAC and NETCARE

    NASA Astrophysics Data System (ADS)

    Bozem, Heiko; Hoor, Peter; Koellner, Franziska; Kunkel, Daniel; Schneider, Johannes; Schulz, Christiane; Herber, Andreas; Borrmann, Stephan; Wendisch, Manfred; Ehrlich, Andre; Leaitch, Richard; Willis, Megan; Burkart, Julia; Thomas, Jennie; Abbatt, Jon

    2016-04-01

    We present aircraft based trace gas measurements in the Arctic during RACEPAC (2014) and NETCARE (2014 and 2015) with the Polar 6 aircraft of Alfred Wegener Institute (AWI) covering an area from 134°W to 17°W and 68°N to 83°N. We focus on cloud, aerosol and general transport processes of polluted air masses into the high Arctic. Based on CO and CO2 measurements and kinematic 10-day back trajectories as well as Flexpart particle dispersion modeling we analyze the transport regimes of mid-latitude air masses traveling to the high Arctic prevalent during spring (RACEPAC 2014, NETCARE 2015) and summer (NETCARE 2014). In general more northern parts of the high Arctic (Lat > 75°N) were relatively unaffected from mid-latitude air masses. In contrast, regions further south are influenced by air masses from Asia and Russia (eastern part of Canadian Arctic and European Arctic) as well as from North America (central and western parts of Canadian Arctic). The transition between the mostly isolated high Arctic and more southern regions indicated by tracer gradients is remarkably sharp. This allows for a chemical definition of the Polar dome based on the variability of CO and CO2 as a marker. Isentropic surfaces that slope from the surface to higher altitudes in the high Arctic form the polar dome that represents a transport barrier for mid-latitude air masses to enter the lower troposphere in the high Arctic. Synoptic-scale weather systems frequently disturb this transport barrier and foster the exchange between air masses from the mid-latitudes and polar regions. This can finally lead to enhanced pollution levels in the lower polar troposphere. Mid-latitude pollution plumes from biomass burning or flaring entering the polar dome area lead to an enhancement of 30% of the observed CO mixing ratio within the polar dome area.

  20. Thermodynamics of Dilute Solutions.

    ERIC Educational Resources Information Center

    Jancso, Gabor; Fenby, David V.

    1983-01-01

    Discusses principles and definitions related to the thermodynamics of dilute solutions. Topics considered include dilute solution, Gibbs-Duhem equation, reference systems (pure gases and gaseous mixtures, liquid mixtures, dilute solutions), real dilute solutions (focusing on solute and solvent), terminology, standard states, and reference systems.…

  1. Air mass flow estimation in turbocharged diesel engines from in-cylinder pressure measurement

    SciTech Connect

    Desantes, J.M.; Galindo, J.; Guardiola, C.; Dolz, V.

    2010-01-15

    Air mass flow determination is needed for the control of current internal combustion engines. Current methods are based on specific sensors (as hot wire anemometers) or indirect estimation through manifold pressure. With the availability of cylinder pressure sensors for engine control, methods based on them can be used for replacing or complementing standard methods. Present paper uses in cylinder pressure increase during the intake stroke for inferring the trapped air mass. The method is validated on two different turbocharged diesel engines and compared with the standard methods. (author)

  2. Apparatus and method for generating large mass flow of high temperature air at hypersonic speeds

    NASA Technical Reports Server (NTRS)

    Sabol, A. P.; Stewart, R. B. (Inventor)

    1973-01-01

    High temperature, high mass air flow and a high Reynolds number test air flow in the Mach number 8-10 regime of adequate test flow duration is attained by pressurizing a ceramic-lined storage tank with air to a pressure of about 100 to 200 atmospheres. The air is heated to temperatures of 7,000 to 8,000 R prior to introduction into the tank by passing the air over an electric arc heater means. The air cools to 5,500 to 6,000 R while in the tank. A decomposable gas such as nitrous oxide or a combustible gas such as propane is injected into the tank after pressurization and the heated pressurized air in the tank is rapidly released through a Mach number 8-10 nozzle. The injected gas medium upon contact with the heated pressurized air effects an exothermic reaction which maintains the pressure and temperature of the pressurized air during the rapid release.

  3. The Use of Red Green Blue (RGB) Air Mass Imagery to Investigate the Role of Stratospheric Air in a Non-Convective Wind Event

    NASA Technical Reports Server (NTRS)

    Berndt, Emily; Zavodsky, Bradley; Molthan, Andrew; Jedlovec, Gary

    2013-01-01

    AIRS ozone and model PV analysis confirm the stratospheric air in RGB Air Mass imagery. Trajectories confirm winds south of the low were distinct from CCB driven winds. Cross sections connect the tropopause fold, downward motion, and high nearsurface winds. Comparison to conceptual models show Shapiro-Keyser features and sting jet characteristics were observed in a storm that impacted the U.S. East Coast. RGB Air Mass imagery can be used to identify stratospheric air and regions susceptible to tropopause folding and attendant non-convective winds.

  4. Isotope dilution liquid chromatography-tandem mass spectrometry for simultaneous identification and quantification of beta-casomorphin 5 and beta-casomorphin 7 in yoghurt.

    PubMed

    Nguyen, D D; Solah, V A; Johnson, S K; Charrois, J W A; Busetti, F

    2014-03-01

    A highly selective and sensitive liquid chromatography-tandem mass spectrometry method was developed and validated for the simultaneous identification and quantification of beta-casomorphin 5 (BCM5) and beta-casomorphin 7 (BCM7) in yoghurt. The method used deuterium labelled BCM5-d10 and BCM7-d10 as surrogate standards for confident identification and accurate and quantification of these analytes in yoghurt. Linear responses for BCM5 and BCM7 (R(2)=0.9985 and 0.9986, respectively) was observed in the range 0.01-10ng/μL. The method limits of detection (MLDs) in yoghurt extracts were found to be 0.5 and 0.25ng/g for BCM5 and BCM7, respectively. Analyses of spiked samples were used to provide confirmation of accuracy and precision of the analytical method. Recoveries relative to the surrogate standards of these spikes were in the range of 95-106% for BCM5 and 103-109% for BCM7. Precision from analysis of spiked samples was expressed as relative standard deviation (%RSD) and values were in the range 1-16% for BCM5 and 1-6% for BCM7. Inter-day reproducibility was between 2.0-6.4% for BCM5 and between 3.2-6.1% for BCM7. The validated isotope dilution LC-MS/MS method was used to measure BCM5 and BCM7 in ten commercial and laboratory prepared samples of yoghurt and milk. Neither BCM5 nor BCM7 was detected in commercial yoghurts. However, they were observed in milk and laboratory prepared yoghurts and interestingly their levels decreased during processing. BCM5 decreased from 1.3ng/g in milk to 1.1ng/g in yoghurt made from that milk at 0day storage and

  5. Inert gas purgebox for Fourier transform ion cyclotron resonance mass spectrometry of air-sensitive solids

    NASA Astrophysics Data System (ADS)

    May, Michael A.; Marshall, Alan G.

    1994-03-01

    A sealed rigid ``purgebox'' makes it possible to load air- and/or moisture-sensitive solids into the solids probe inlet of a Fourier transform ion cyclotron resonance (FT/ICR) mass spectrometer. A pelletized sample is transferred (in a sealed canister) from a commercial drybox to a Lucite(R) purgebox. After the box is purged with inert gas, an attached glove manipulator is used to transfer the sample from the canister to the solids probe of the mass spectrometer. Once sealed inside the inlet, the sample is pre-evacuated and then passed into the high vacuum region of the instrument at ˜10-7 Torr. The purgebox is transparent, portable, and readily assembled/disassembled. Laser desorption FT/ICR mass spectra of the air- and moisture-sensitive solids, NbCl5. NbCl2(C5H5)2, and Zr(CH3)2(C5H5)2 are obtained without significant oxidation. The residual water vapor concentration inside the purgebox was measured as 100±20 ppm after a 90-min purge with dry nitrogen gas. High-resolution laser desorption/ionization mass spectrometry of air-sensitive solids becomes feasible with the present purgebox interface. With minor modification of the purgebox geometry, the present method could be adapted to any mass spectrometer equipped with a solid sample inlet.

  6. Airborne mass spectrometers: four decades of atmospheric and space research at the Air Force research laboratory.

    PubMed

    Viggiano, A A; Hunton, D E

    1999-11-01

    Mass spectrometry is a versatile research tool that has proved to be extremely useful for exploring the fundamental nature of the earth's atmosphere and ionosphere and in helping to solve operational problems facing the Air Force and the Department of Defense. In the past 40 years, our research group at the Air Force Research Laboratory has flown quadrupole mass spectrometers of many designs on nearly 100 sounding rockets, nine satellites, three Space Shuttles and many missions of high-altitude research aircraft and balloons. We have also used our instruments in ground-based investigations of rocket and jet engine exhaust, combustion chemistry and microwave breakdown chemistry. This paper is a review of the instrumentation and techniques needed for space research, a summary of the results from many of the experiments, and an introduction to the broad field of atmospheric and space mass spectrometry in general. PMID:10548806

  7. Airborne mass spectrometers: four decades of atmospheric and space research at the Air Force research laboratory.

    PubMed

    Viggiano, A A; Hunton, D E

    1999-11-01

    Mass spectrometry is a versatile research tool that has proved to be extremely useful for exploring the fundamental nature of the earth's atmosphere and ionosphere and in helping to solve operational problems facing the Air Force and the Department of Defense. In the past 40 years, our research group at the Air Force Research Laboratory has flown quadrupole mass spectrometers of many designs on nearly 100 sounding rockets, nine satellites, three Space Shuttles and many missions of high-altitude research aircraft and balloons. We have also used our instruments in ground-based investigations of rocket and jet engine exhaust, combustion chemistry and microwave breakdown chemistry. This paper is a review of the instrumentation and techniques needed for space research, a summary of the results from many of the experiments, and an introduction to the broad field of atmospheric and space mass spectrometry in general.

  8. Air

    MedlinePlus

    ... do to protect yourself from dirty air . Indoor air pollution and outdoor air pollution Air can be polluted indoors and it can ... this chart to see what things cause indoor air pollution and what things cause outdoor air pollution! Indoor ...

  9. Measuring Air-water Interfacial Area for Soils Using the Mass Balance Surfactant-tracer Method

    PubMed Central

    Araujo, Juliana B.; Mainhagu, Jon; Brusseau, Mark L.

    2015-01-01

    There are several methods for conducting interfacial partitioning tracer tests to measure air-water interfacial area in porous media. One such approach is the mass balance surfactant tracer method. An advantage of the mass-balance method compared to other tracer-based methods is that a single test can produce multiple interfacial area measurements over a wide range of water saturations. The mass-balance method has been used to date only for glass beads or treated quartz sand. The purpose of this research is to investigate the effectiveness and implementability of the mass-balance method for application to more complex porous media. The results indicate that interfacial areas measured with the mass-balance method are consistent with values obtained with the miscible-displacement method. This includes results for a soil, for which solid-phase adsorption was a significant component of total tracer retention. PMID:25950136

  10. Turbulent heat and mass transfers across a thermally stratified air-water interface

    NASA Technical Reports Server (NTRS)

    Papadimitrakis, Y. A.; Hsu, Y.-H. L.; Wu, J.

    1986-01-01

    Rates of heat and mass transfer across an air-water interface were measured in a wind-wave research facility, under various wind and thermal stability conditions (unless otherwise noted, mass refers to water vapor). Heat fluxes were obtained from both the eddy correlation and the profile method, under unstable, neutral, and stable conditions. Mass fluxes were obtained only under unstable stratification from the profile and global method. Under unstable conditions the turbulent Prandtl and Schmidt numbers remain fairly constant and equal to 0.74, whereas the rate of mass transfer varies linearly with bulk Richardson number. Under stable conditions the turbulent Prandtl number rises steadily to a value of 1.4 for a bulk Richardson number of about 0.016. Results of heat and mass transfer, expressed in the form of bulk aerodynamic coefficients with friction velocity as a parameter, are also compared with field data.

  11. Measuring air-water interfacial area for soils using the mass balance surfactant-tracer method.

    PubMed

    Araujo, Juliana B; Mainhagu, Jon; Brusseau, Mark L

    2015-09-01

    There are several methods for conducting interfacial partitioning tracer tests to measure air-water interfacial area in porous media. One such approach is the mass balance surfactant tracer method. An advantage of the mass-balance method compared to other tracer-based methods is that a single test can produce multiple interfacial area measurements over a wide range of water saturations. The mass-balance method has been used to date only for glass beads or treated quartz sand. The purpose of this research is to investigate the effectiveness and implementability of the mass-balance method for application to more complex porous media. The results indicate that interfacial areas measured with the mass-balance method are consistent with values obtained with the miscible-displacement method. This includes results for a soil, for which solid-phase adsorption was a significant component of total tracer retention.

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

    PubMed

    Grey, L; Nguyen, B; Yang, P

    2001-01-01

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

  13. MISR Aerosol Air Mass Type Mapping over Mega-City: Validation and Applications

    NASA Astrophysics Data System (ADS)

    Patadia, F.; Kahn, R. A.

    2010-12-01

    Most aerosol air-quality monitoring in mega-city environments is done from scattered ground stations having detailed chemical and optical sampling capabilities. Satellite instruments such as the Multi-angle Imaging SpectroRadiometer (MISR) can retrieve total-column Aerosol Optical Depth (AOD), along with some information about particle microphysical properties. Although the particle property information from MISR is much less detailed than that obtained from the ground sampling stations, the coverage is extensive, making it possible to put individual surface observations into the context of regional aerosol air mass types. This paper presents an analysis of MISR aerosol observations made coincident with aircraft and ground-based instruments during the INTEX-B field campaign. These detailed comparisons of satellite aerosol property retrievals against dedicated field measurements provide the opportunity to validate the retrievals quantitatively at a regional level, and help to improve aerosol representation in retrieval algorithms. Validation of MISR retrieved AOD and other aerosol properties over the INTEX-B study region in and around Mexico City will be presented. MISR’s ability to distinguish among aerosol air mass types will be discussed. The goal of this effort is to use the MISR aerosol property retrievals for mapping both aerosol air mass type and AOD gradients in mega-city environments over the decade-plus that MISR has made global observations.

  14. Establishing Lagrangian Connections between Observations within Air Masses Crossing the Atlantic during the ICARTT Experiment

    NASA Technical Reports Server (NTRS)

    Methven, J.; Arnold, S. R.; Stohl, A.; Evans, M. J.; Avery, M.; Law, K.; Lewis, A. C.; Monks, P. S.; Parrish, D.; Reeves, C.; Schlager, H.; Atlas, E.; Blake, D.; Coe, H.; Cohen, R. C.; Crosier, J.; Flocke, F.; Holloway, J. S.; Hopkins, J. R.; Huber, G.; McQuaid, J.; Purvis, R.; Rappengluck, B.; Ryerson, T. B.; Sachse, G. W.

    2006-01-01

    The International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)-Lagrangian experiment was conceived with an aim to quantify the effects of photochemistry and mixing on the transformation of air masses in the free troposphere away from emissions. To this end attempts were made to intercept and sample air masses several times during their journey across the North Atlantic using four aircraft based in New Hampshire (USA), Faial (Azores) and Creil (France). This article begins by describing forecasts using two Lagrangian models that were used to direct the aircraft into target air masses. A novel technique is then used to identify Lagrangian matches between flight segments. Two independent searches are conducted: for Lagrangian model matches and for pairs of whole air samples with matching hydrocarbon fingerprints. The information is filtered further by searching for matching hydrocarbon samples that are linked by matching trajectories. The quality of these coincident matches is assessed using temperature, humidity and tracer observations. The technique pulls out five clear Lagrangian cases covering a variety of situations and these are examined in detail. The matching trajectories and hydrocarbon fingerprints are shown and the downwind minus upwind differences in tracers are discussed.

  15. Stable isotope composition of waters in the Great Basin, United States 1. Air-mass trajectories

    USGS Publications Warehouse

    Friedman, I.; Harris, J.M.; Smith, G.I.; Johnson, C.A.

    2002-01-01

    Isentropic trajectories, calculated using the NOAA/Climate Monitoring and Diagnostics Laboratory's isentropic transport model, were used to determine air-parcel origins and the influence of air mass trajectories on the isotopic composition of precipitation events that occurred between October 1991 and September 1993 at Cedar City, Utah, and Winnemucca, Nevada. Examination of trajectories that trace the position of air parcels backward in time for 10 days indicated five distinct regions of water vapor origin: (1) Gulf of Alaska and North Pacific, (2) central Pacific, (3) tropical Pacific, (4) Gulf of Mexico, and (5) continental land mass. Deuterium (??D) and oxygen-18 (??18O) analyses were made of precipitation representing 99% of all Cedar City events. Similar analyses were made on precipitation representing 66% of the precipitation falling at Winnemucca during the same period. The average isotopic composition of precipitation derived from each water vapor source was determined. More than half of the precipitation that fell at both sites during the study period originated in the tropical Pacific and traveled northeast to the Great Basin; only a small proportion traversed the Sierra Nevada. The isotopic composition of precipitation is determined by air-mass origin and its track to the collection station, mechanism of droplet formation, reequilibration within clouds, and evaporation during its passage from cloud to ground. The Rayleigh distillation model can explain the changes in isotopic composition of precipitation as an air mass is cooled pseudo-adiabatically during uplift. However, the complicated processes that take place in the rapidly convecting environment of cumulonimbus and other clouds that are common in the Great Basin, especially in summer, require modification of this model because raindrops that form in the lower portion of those clouds undergo isotopic change as they are elevated to upper levels of the clouds from where they eventually drop to the

  16. Mass spectrometry of solid samples in open air using combined laser ionization and ambient metastable ionization

    NASA Astrophysics Data System (ADS)

    He, X. N.; Xie, Z. Q.; Gao, Y.; Hu, W.; Guo, L. B.; Jiang, L.; Lu, Y. F.

    2012-01-01

    Mass spectrometry of solid samples in open air was carried out using combined laser ionization and metastable ionization time-of-flight mass spectrometry (LI-MI-TOFMS) in ambient environment for qualitative and semiquantitative (relative analyte information, not absolute information) analysis. Ambient metastable ionization using a direct analysis in realtime (DART) ion source was combined with laser ionization time-of-flight mass spectrometry (LI-TOFMS) to study the effects of combining metastable and laser ionization. A series of metallic samples from the National Institute of Standards and Technology (NIST 494, 495, 498, 499, and 500) and a pure carbon target were characterized using LI-TOFMS in open air. LI-MI-TOFMS was found to be superior to laser-induced breakdown spectroscopy (LIBS). Laser pulse energies between 10 and 200 mJ at the second harmonic (532 nm) of an Nd:YAG laser were applied in the experiment to obtain a high degree of ionization in plasmas. Higher laser pulse energy improves signal intensities of trace elements (such as Fe, Cr, Mn, Ni, Ca, Al, and Ag). Data were analyzed by numerically calculating relative sensitivity coefficients (RSCs) and limit of detections (LODs) from mass spectrometry (MS) and LIBS spectra. Different parameters, such as boiling point, ionization potential, RSC, LOD, and atomic weight, were shown to analyze the ionization and MS detection processes in open air.

  17. Serial Dilution Simulation Lab

    ERIC Educational Resources Information Center

    Keler, Cynthia; Balutis, Tabitha; Bergen, Kim; Laudenslager, Bryanna; Rubino, Deanna

    2010-01-01

    Serial dilution is often a difficult concept for students to understand. In this short dry lab exercise, students perform serial dilutions using seed beads. This exercise helps students gain skill at performing dilutions without using reagents, bacterial cultures, or viral cultures, while being able to visualize the process.

  18. Study of single and combined mass-sensitive observables of cosmic ray induced extensive air showers

    NASA Astrophysics Data System (ADS)

    Rastegarzadeh, G.; Nemati, M.

    2016-03-01

    In this study, combinations of the global arrival time, (Δτ_{global}), pseudorapidity, and lateral density distribution (ρ_{μ}) of muons, which are three mass-sensitive observables of cosmic ray induced extensive air showers, have been used as new parameters to study the primary mass discrimination around the knee energies (100 TeV-10 PeV). This is a simulation-based study and the simulations have been performed for the KASCADE array at Karlsruhe and the Alborz-I array at Tehran to study the effect of the altitude on the quality of the primary mass discrimination. The merit factors of the single and combined three mass-sensitive observables have been calculated to compare the discrimination power of combined and single observables. We have used the CORSIKA 7.4 code to simulate the extensive air showers (EASs) sample sets. Considering all aspects of our study, it is found that the ratio of the global time to the lateral density distribution of the muons gives better results than other ratios; also in the case of single observables, the muon density gives better results compared with the other observables. Also it is shown that below 1 PeV primary energies, the ratio of the muon global time to the muon density (Δτ_{global}/ρ_{μ}) results in a better mass discrimination relative to the muon density only.

  19. Neonatal Presentation of an Air-Filled Neck Mass that Enlarges with Valsalva: A Case Report

    PubMed Central

    Patel, Jasminkumar Bharatbhai; Kilbride, Howard; Paulson, Lorien

    2015-01-01

    Branchial cleft cysts are common causes of congenital neck masses in the pediatric population. However, neonatal presentation of branchial cleft cysts is uncommon, but recognizable secondary to acute respiratory distress from airway compression or complications secondary to infection. We report a 1-day-old infant presenting with an air-filled neck mass that enlarged with Valsalva and was not associated with respiratory distress. The infant was found to have a third branchial cleft cyst with an internal opening into the pyriform sinus. The cyst was conservatively managed with endoscopic surgical decompression and cauterization of the tract and opening. We review the embryology of branchial cleft cysts and current management. PMID:26495186

  20. Air Mass Origin in the Arctic and its Response to Future Warming

    NASA Astrophysics Data System (ADS)

    Orbe, C.; Newman, P. A.; Waugh, D. W.; Holzer, M. B.; Oman, L.; Polvani, L. M.; Li, F.

    2014-12-01

    Long-range transport from Northern Hemisphere (NH) midlatitudes plays a key role in setting the distributions of trace species and aerosols in the Arctic. While comprehensive models project a strengthening and poleward shift in the midlatitude tropospheric jets in response to future warming, relatively little attention has been paid to assessing the large-scale transport response in the Arctic. A natural way to quantify transport and its future changes is in terms of rigorously defined air masses that partition air according to where it last contacted the planetary boundary layer (PBL). Here we present climatologies of Arctic air mass origin for NH winter and summer, computed from two integrations of the Goddard Earth Observing System chemistry-climate model (GEOSCCM) subject to present-day and future climate forcings. The modeled transport response to A1B greenhouse-gas induced warming reveals that in the future ~10% more air in the Arctic will originate over NH midlatitudes, with a slighter weaker albeit significant increase in winter compared to summer. Our results indicate that transport changes alone may lead to "cleaner" Arctic winters, as air will be 5-10% more likely to have last contacted the PBL over the East Pacific and the Atlantic Oceans and less likely to have originated over Europe and North America. Conversely, in future summers the air mass fractions originating over Asia and North America increase by ~10%, indicating that Arctic pollutant levels may be enhanced owing solely to changes in transport. In particular, our results suggest that more stringent emissions caps may be needed to combat enhanced transport into the Arctic from Asia, where increases in black carbon emissions have already posed concerns. Future changes in air mass fractions are interpreted in terms of large-scale circulation responses that are consistent with CMIP5 multi-model mean projections - namely, upward and poleward shifted meridional transient eddies in future winters and

  1. Measurement of mass attenuation coefficients in air by application of detector linearity tests

    NASA Astrophysics Data System (ADS)

    Peele, A. G.; Chantler, C. T.; Paterson, D.; McMahon, P. J.; Irving, T. H.; Lin, J. J.; Nugent, K. A.; Brunton, A. N.; McNulty, I.

    2002-10-01

    Accurate knowledge of x-ray mass attenuation coefficients is essential for studies as diverse as atomic physics, materials science, and radiation safety. However, a significant discrepancy exists between theoretical tabulated results for air at soft x-ray energies. We outline a precision measurement of the mass attenuation coefficients for air at various energies using two types of detectors and a simple test of detector response. We discuss whether sufficient accuracy can be obtained using this data to distinguish between competing theoretical estimates. In the process, we investigate the intensity response of two common synchrotron x-ray detectors: an x ray to optical charge-coupled device camera using a crystal scintillator and an x-ray sensitive photodiode.

  2. Estimation of whole lemon mass transfer parameters during hot air drying using different modelling methods

    NASA Astrophysics Data System (ADS)

    Torki-Harchegani, Mehdi; Ghanbarian, Davoud; Sadeghi, Morteza

    2015-08-01

    To design new dryers or improve existing drying equipments, accurate values of mass transfer parameters is of great importance. In this study, an experimental and theoretical investigation of drying whole lemons was carried out. The whole lemons were dried in a convective hot air dryer at different air temperatures (50, 60 and 75 °C) and a constant air velocity (1 m s-1). In theoretical consideration, three moisture transfer models including Dincer and Dost model, Bi- G correlation approach and conventional solution of Fick's second law of diffusion were used to determine moisture transfer parameters and predict dimensionless moisture content curves. The predicted results were then compared with the experimental data and the higher degree of prediction accuracy was achieved by the Dincer and Dost model.

  3. Spatial variability of hailfalls in France: an analysis of air mass retro-trajectories

    NASA Astrophysics Data System (ADS)

    Hermida, Lucía; Merino, Andrés; Sánchez, José Luis; Berthet, Claude; Dessens, Jean; López, Laura; Fernández-González, Sergio; Gascón, Estíbaliz; García-Ortega, Eduardo

    2014-05-01

    Hail is the main meteorological risk in south-west France, with the strongest hailfalls being concentrated in just a few days. Specifically, this phenomenon occurs most often and with the greatest severity in the Midi-Pyrénées area. Previous studies have revealed the high spatial variability of hailfall in this part of France, even leading to different characteristics being recorded on hailpads that were relatively close together. For this reason, an analysis of the air mass trajectories was carried out at ground level and at altitude, which subsequently led to the formation of the hail recorded by these hailpads. It is already known that in the study zone, the trajectories of the storms usually stretch for long distances and are oriented towards the east, leading to hailstones with diameters in excess of 3 cm, and without any change in direction above 3 km. We analysed different days with hail precipitation where there was at least one stone with a diameter of 3 cm or larger. Using the simulations from these days, an analysis of the backward trajectories of the air masses was carried out. We used the HYSPLIT (Hybrid Single Particle Lagrangian Integrated Trajectory Model) to determine the origin of the air masses, and tracked them toward each of the hailpads that were hit during the day studied. The height of the final points was the height of the impacted hailpads. Similarly, the backward trajectories for different heights were also established. Finally, the results show how storms that affect neighbouring hailpads come from very different air masses; and provide a deeper understanding of the high variability that affects the characteristics of hailfalls. Acknowledgements The authors would like to thank the Regional Government of Castile-León for its financial support through the project LE220A11-2. This study was supported by the following grants: GRANIMETRO (CGL2010-15930); MICROMETEO (IPT-310000-2010-22).

  4. Impacts of Typhoon and Air-Mass Pathways on Rainwater Chemical Compositions

    NASA Astrophysics Data System (ADS)

    Cheng, M.; You, C.

    2006-12-01

    To assess the importance of chemical fluxes on trace elements by wet precipitation, we have collected time- series rain waters between 06/20/04 and 09/20/05 for ICPMS and IC measurements. The sampling site is located at Tainan city in southwest Taiwan and there were four typhoons, namely Mindulle, Rananim, Aere, and Haima, hit the island during this period. Combining trace element compositions with HYSPLIT model for air-mass transportation designed by NOAA, we were able to understand possible source, flux and migration pathway of pollutants in rainwater. Our results show that seasalt contribution and trace element fluxes were higher during typhoon events. The Na and Pb flux varied largely, between 0.03~1388 and 0.0002~2000 mg/m2/day respectively, depended on the pathways of air mass trajectory and wind strength. It is clear that typhoons carry not only sea spray but also major anthropogenic pollutants from south Asia. Among the four typhoons, the Mindulle carried the largest fluxes of seasalt and trace elements while Rananim was weak in strength and brought the lowest Na and Pb due to less degree of mixing with air mass on land. The calculated enriched factors normalized to seawater (EFsea) were near unity for Na and Mg, but were much larger for K and Ca possibly due to crust source contamination and biomass burning. The EFcrust or EFsea values of various trace metals (e.g., V, Cr, Mn, Co, Ni, Cu, Zn, As, Ba and Pb were all significantly larger than 10 indicating the importance of anthropogenic sources. Interestingly, the PCA results confirm that rain waters with similar chemical characteristics have shared common air mass backward trajectory history.

  5. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways

    PubMed Central

    Liu, D. X.; Liu, Z. C.; Chen, C.; Yang, A. J.; Li, D.; Rong, M. Z.; Chen, H. L.; Kong, M. G.

    2016-01-01

    Plasma-liquid interaction is a critical area of plasma science and a knowledge bottleneck for many promising applications. In this paper, the interaction between a surface air discharge and its downstream sample of deionized water is studied with a system-level computational model, which has previously reached good agreement with experimental results. Our computational results reveal that the plasma-induced aqueous species are mainly H+, nitrate, nitrite, H2O2 and O3. In addition, various short-lived aqueous species are also induced, regardless whether they are generated in the gas phase first. The production/loss pathways for aqueous species are quantified for an air gap width ranging from 0.1 to 2 cm, of which heterogeneous mass transfer and liquid chemistry are found to play a dominant role. The short-lived reactive oxygen species (ROS) and reactive nitrogen species (RNS) are strongly coupled in liquid-phase reactions: NO3 is an important precursor for short-lived ROS, and in turn OH, O2− and HO2 play a crucial role for the production of short-lived RNS. Also, heterogeneous mass transfer depends strongly on the air gap width, resulting in two distinct scenarios separated by a critical air gap of 0.5 cm. The liquid chemistry is significantly different in these two scenarios. PMID:27033381

  6. Mass transfer characteristics of bisporus mushroom ( Agaricus bisporus) slices during convective hot air drying

    NASA Astrophysics Data System (ADS)

    Ghanbarian, Davoud; Baraani Dastjerdi, Mojtaba; Torki-Harchegani, Mehdi

    2016-05-01

    An accurate understanding of moisture transfer parameters, including moisture diffusivity and moisture transfer coefficient, is essential for efficient mass transfer analysis and to design new dryers or improve existing drying equipments. The main objective of the present study was to carry out an experimental and theoretical investigation of mushroom slices drying and determine the mass transfer characteristics of the samples dried under different conditions. The mushroom slices with two thicknesses of 3 and 5 mm were dried at air temperatures of 40, 50 and 60 °C and air flow rates of 1 and 1.5 m s-1. The Dincer and Dost model was used to determine the moisture transfer parameters and predict the drying curves. It was observed that the entire drying process took place in the falling drying rate period. The obtained lag factor and Biot number indicated that the moisture transfer in the samples was controlled by both internal and external resistance. The effective moisture diffusivity and the moisture transfer coefficient increased with increasing air temperature, air flow rate and samples thickness and varied in the ranges of 6.5175 × 10-10 to 1.6726 × 10-9 m2 s-1 and 2.7715 × 10-7 to 3.5512 × 10-7 m s-1, respectively. The validation of the Dincer and Dost model indicated a good capability of the model to describe the drying curves of the mushroom slices.

  7. Quantifying energy and mass transfer in crop canopies: sensors for measurement of temperature and air velocity

    NASA Technical Reports Server (NTRS)

    Bugbee, B.; Monje, O.; Tanner, B.

    1996-01-01

    Here we report on the in situ performance of inexpensive, miniature sensors that have increased our ability to measure mass and energy fluxes from plant canopies in controlled environments: 1. Surface temperature. Canopy temperature measurements indicate changes in stomatal aperture and thus latent and sensible heat fluxes. Infrared transducers from two manufacturers (Exergen Corporation, Newton, MA; and Everest Interscience, Tucson, AZ, USA) have recently become available. Transducer accuracy matched that of a more expensive hand-held infrared thermometer. 2. Air velocity varies above and within plant canopies and is an important component in mass and energy transfer models. We tested commercially-available needle, heat-transfer anemometers (1 x 50 mm cylinder) that consist of a fine-wire thermocouple and a heater inside a hypodermic needle. The needle is heated and wind speed determined from the temperature rise above ambient. These sensors are particularly useful in measuring the low wind speeds found within plant canopies. 3. Accurate measurements of air temperature adjacent to plant leaves facilitates transport phenomena modeling. We quantified the effect of radiation and air velocity on temperature rise in thermocouples from 10 to 500 micrometers. At high radiation loads and low wind speeds, temperature errors were as large as 7 degrees C above air temperature.

  8. Quantifying energy and mass transfer in crop canopies: sensors for measurement of temperature and air velocity.

    PubMed

    Bugbee, B; Monje, O; Tanner, B

    1996-01-01

    Here we report on the in situ performance of inexpensive, miniature sensors that have increased our ability to measure mass and energy fluxes from plant canopies in controlled environments: 1. Surface temperature. Canopy temperature measurements indicate changes in stomatal aperture and thus latent and sensible heat fluxes. Infrared transducers from two manufacturers (Exergen Corporation, Newton, MA; and Everest Interscience, Tucson, AZ, USA) have recently become available. Transducer accuracy matched that of a more expensive hand-held infrared thermometer. 2. Air velocity varies above and within plant canopies and is an important component in mass and energy transfer models. We tested commercially-available needle, heat-transfer anemometers (1 x 50 mm cylinder) that consist of a fine-wire thermocouple and a heater inside a hypodermic needle. The needle is heated and wind speed determined from the temperature rise above ambient. These sensors are particularly useful in measuring the low wind speeds found within plant canopies. 3. Accurate measurements of air temperature adjacent to plant leaves facilitates transport phenomena modeling. We quantified the effect of radiation and air velocity on temperature rise in thermocouples from 10 to 500 micrometers. At high radiation loads and low wind speeds, temperature errors were as large as 7 degrees C above air temperature. PMID:11538791

  9. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways

    NASA Astrophysics Data System (ADS)

    Liu, D. X.; Liu, Z. C.; Chen, C.; Yang, A. J.; Li, D.; Rong, M. Z.; Chen, H. L.; Kong, M. G.

    2016-04-01

    Plasma-liquid interaction is a critical area of plasma science and a knowledge bottleneck for many promising applications. In this paper, the interaction between a surface air discharge and its downstream sample of deionized water is studied with a system-level computational model, which has previously reached good agreement with experimental results. Our computational results reveal that the plasma-induced aqueous species are mainly H+, nitrate, nitrite, H2O2 and O3. In addition, various short-lived aqueous species are also induced, regardless whether they are generated in the gas phase first. The production/loss pathways for aqueous species are quantified for an air gap width ranging from 0.1 to 2 cm, of which heterogeneous mass transfer and liquid chemistry are found to play a dominant role. The short-lived reactive oxygen species (ROS) and reactive nitrogen species (RNS) are strongly coupled in liquid-phase reactions: NO3 is an important precursor for short-lived ROS, and in turn OH, O2‑ and HO2 play a crucial role for the production of short-lived RNS. Also, heterogeneous mass transfer depends strongly on the air gap width, resulting in two distinct scenarios separated by a critical air gap of 0.5 cm. The liquid chemistry is significantly different in these two scenarios.

  10. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways.

    PubMed

    Liu, D X; Liu, Z C; Chen, C; Yang, A J; Li, D; Rong, M Z; Chen, H L; Kong, M G

    2016-01-01

    Plasma-liquid interaction is a critical area of plasma science and a knowledge bottleneck for many promising applications. In this paper, the interaction between a surface air discharge and its downstream sample of deionized water is studied with a system-level computational model, which has previously reached good agreement with experimental results. Our computational results reveal that the plasma-induced aqueous species are mainly H(+), nitrate, nitrite, H2O2 and O3. In addition, various short-lived aqueous species are also induced, regardless whether they are generated in the gas phase first. The production/loss pathways for aqueous species are quantified for an air gap width ranging from 0.1 to 2 cm, of which heterogeneous mass transfer and liquid chemistry are found to play a dominant role. The short-lived reactive oxygen species (ROS) and reactive nitrogen species (RNS) are strongly coupled in liquid-phase reactions: NO3 is an important precursor for short-lived ROS, and in turn OH, O2(-) and HO2 play a crucial role for the production of short-lived RNS. Also, heterogeneous mass transfer depends strongly on the air gap width, resulting in two distinct scenarios separated by a critical air gap of 0.5 cm. The liquid chemistry is significantly different in these two scenarios. PMID:27033381

  11. Measurements of CO in an aircraft experiment and their correlation with biomass burning and air mass origin in South America

    NASA Astrophysics Data System (ADS)

    Boian, C.; Kirchhoff, V. W. J. H.

    Carbon monoxide (CO) measurements are obtained in an aircraft experiment during 1-7 September 2000, conducted over Central Brazil in a special region of anticyclonic circulation. This is a typical transport regime during the dry season (July-September), when intense biomass burning occurs, and which gives origin to the transport of burning poluents from the source to distant regions. This aircraft experiment included in situ measurements of CO concentrations in three different scenarios: (1) areas of fresh biomass burning air masses, or source areas; (2) areas of aged biomass burning air masses; and (3) areas of clean air or pristine air masses. The largest CO concentrations were of the order of 450 ppbv in the source region near Conceicao do Araguaia (PA), and the smallest value near 100 ppbv, was found in pristine air masses, for example, near the northeast coastline (clean air, or background region). The observed concentrations were compared to the number of fire pixels seen by the AVHRR satellite instrument. Backward isentropic trajectories were used to determine the origin of the air masses at each sampling point. From the association of the observed CO mixing ratios, fire pixels and air mass trajectories, the previous scenarios may be subdivided as follows: (1a) source regions of biomass burning with large CO concentrations; (1b) regions with few local fire pixels and absence of contributions by transport. Areas with these characteristics include the northeast region of Brazil; (1c) regions close to the source region and strongly affected by transport (region of Para and Amazonas); (2) regions that have a consistent convergence of air masses, that have traveled over biomass burning areas during a few days (western part of the Cerrado region); (3a) Pristine air masses with origin from the ocean; (3b) regions with convergent transport that has passed over areas of no biomass burning, such as frontal weather systems in the southern regions.

  12. Influence of drying air parameters on mass transfer characteristics of apple slices

    NASA Astrophysics Data System (ADS)

    Beigi, Mohsen

    2016-10-01

    To efficiently design both new drying process and equipment and/or to improve the existing systems, accurate values of mass transfer characteristics are necessary. The present study aimed to investigate the influence of drying air parameters (i.e. temperature, velocity and relative humidity) on effective diffusivity and convective mass transfer coefficient of apple slices. The Dincer and Dost model was used to determine the mass transfer characteristics. The obtained Biot number indicated that the moisture transfer in the apple slices was controlled by both internal and external resistance. The effective diffusivity and mass transfer coefficient values obtained to be in the ranges of 7.13 × 10-11-7.66 × 10-10 and 1.46 × 10-7-3.39 × 10-7 m s-1, respectively and the both of them increased with increasing drying air temperature and velocity, and decreasing relative humidity. The validation of the model showed that the model predicted the experimental drying curves of the samples with a good accuracy.

  13. Influence of drying air parameters on mass transfer characteristics of apple slices

    NASA Astrophysics Data System (ADS)

    Beigi, Mohsen

    2015-12-01

    To efficiently design both new drying process and equipment and/or to improve the existing systems, accurate values of mass transfer characteristics are necessary. The present study aimed to investigate the influence of drying air parameters (i.e. temperature, velocity and relative humidity) on effective diffusivity and convective mass transfer coefficient of apple slices. The Dincer and Dost model was used to determine the mass transfer characteristics. The obtained Biot number indicated that the moisture transfer in the apple slices was controlled by both internal and external resistance. The effective diffusivity and mass transfer coefficient values obtained to be in the ranges of 7.13 × 10-11-7.66 × 10-10 and 1.46 × 10-7-3.39 × 10-7 m s-1, respectively and the both of them increased with increasing drying air temperature and velocity, and decreasing relative humidity. The validation of the model showed that the model predicted the experimental drying curves of the samples with a good accuracy.

  14. Small-size mass spectrometer for determining gases and volatile compounds in air during breathing

    NASA Astrophysics Data System (ADS)

    Kogan, V. T.; Kozlenok, A. V.; Chichagov, Yu. V.; Antonov, A. S.; Lebedev, D. S.; Bogdanov, A. A.; Moroshkin, V. S.; Berezina, A. V.; Viktorova-Leclerc, O. S.; Vlasov, S. A.; Tubol'tsev, Yu. V.

    2015-10-01

    We describe an automated mass spectrometer for diagnostics of deceases from the composition of exhaled air. It includes a capillary system, which performs a rapid direct feeding of the sample to the instrument without changing substantially its composition and serves for studying the dynamics of variation of the ratio between various components of exhaled air. The membrane system for introducing the sample is intended for determining low concentrations of volatile organic compounds which are biomarkers of pathologies. It is characterized by selective transmittance and ensures the detection limits of target compounds at the parts per million-parts per billion (ppm-ppb) level. A static mass analyzer operating on permanent magnets possesses advantages important for mobile devices as compared to its dynamic analogs: it is more reliable in operation, has a larger dynamic range, and can be used for determining the concentration of components in the mixture one-by-one or simultaneously. The curvilinear output boundary of the magnetic lens of the mass analyzer makes it possible to reduce its weight and size by 2.5 times without deteriorating the mass resolution. We report on the results of testing of the instrument and consider the possibility of its application for early detection of deceases of respiratory and blood circulation system, gastrointestinal tract, and endocrine system.

  15. Microfluidic serial dilution ladder.

    PubMed

    Ahrar, Siavash; Hwang, Michelle; Duncan, Philip N; Hui, Elliot E

    2014-01-01

    Serial dilution is a fundamental procedure that is common to a large number of laboratory protocols. Automation of serial dilution is thus a valuable component for lab-on-a-chip systems. While a handful of different microfluidic strategies for serial dilution have been reported, approaches based on continuous flow mixing inherently consume larger amounts of sample volume and chip real estate. We employ valve-driven circulatory mixing to address these issues and also introduce a novel device structure to store each stage of the dilution process. The dilution strategy is based on sequentially mixing the rungs of a ladder structure. We demonstrate a 7-stage series of 1 : 1 dilutions with R(2) equal to 0.995 in an active device area of 1 cm(2).

  16. The mathematics of dilution.

    PubMed

    Chatterjee, Barun Kumar

    2014-04-01

    The major objection to homeopathic medicine is that the doses of medicine prescribed in some cases are too dilute for any active ingredient to be present. The medicines would hence be rendered inactive, necessitating novel explanations for the action. A further examination of dilution in the light of the Langmuir equation shows that homeopathic medicines may not be as dilute as a simplistic application of Avogadro's Principle suggests, due to surface effects.

  17. On the origin and destination of atmospheric moisture and air mass over the Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Chen, Bin; Xu, Xiang-De; Yang, Shuai; Zhang, Wei

    2012-12-01

    The Tibet Plateau (TP) is a key region that imposes profound impacts on the atmospheric water cycle and energy budget of Asia, even the global climate. In this work, we develop a climatology of origin (destination) of air mass and moisture transported to (from) the TP using a Lagrangian moisture diagnosis combined with the forward and backward atmospheric tracking schemes. The climatology is derived from 6-h particle positions based on 5-year (2005-2009) seasonal summer trajectory dataset from the Lagrangian particle dispersion model FLEXPART using NCEP/GFS data as input, where the regional model atmosphere was globally filled with particles. The results show that (1) the dominant origin of the moisture supplied to the TP is a narrow tropical-subtropical band in the extended Arabian Sea covering a long distance from the Indian subcontinent to the Southern Hemisphere. Two additional moisture sources are located in the northwestern part of TP and the Bay of Bengal and play a secondary role. This result indicates that the moisture transporting to the TP more depends on the Indian summer monsoon controlled by large-scale circulation. (2) The moisture departing from the TP can be transported rapidly to East Asia, including East China, Korea, Japan, and even East Pacific. The qualitative similarity between the regions of diagnosed moisture loss and the pattern of the observed precipitation highlights the robustness of the role of the TP on precipitation over East Asia. (3) In contrast to the moisture origin confined in the low level, the origin and fate of whole column air mass over the TP is largely controlled by a strong high-level Asian anticyclone. The results show that the TP is a crossroad of air mass where air enters mainly from the northwest and northeast and continues in two separate streams: one goes southwestwards over the Indian Ocean and the other southeastwards through western North Pacific. Both of them partly enter the trade wind zone, which manifests the

  18. Air flow assisted ionization for remote sampling of ambient mass spectrometry and its application.

    PubMed

    He, Jiuming; Tang, Fei; Luo, Zhigang; Chen, Yi; Xu, Jing; Zhang, Ruiping; Wang, Xiaohao; Abliz, Zeper

    2011-04-15

    Ambient ionization methods are an important research area in mass spectrometry (MS) analysis. Under ambient conditions, the gas flow and atmospheric pressure significantly affect the transfer and focusing of ions. The design and implementation of air flow assisted ionization (AFAI) as a novel and effective, remote sampling method for ambient mass spectrometry are described herein. AFAI benefits from a high extracting air flow rate. A systematic investigation of the extracting air flow in the AFAI system has been carried out, and it has been demonstrated not only that it plays a role in the effective capture and remote transport of charged droplets, but also that it promotes desolvation and ion formation, and even prevents ion fragmentation during the ionization process. Moreover, the sensitivity of remote sampling ambient MS analysis was improved significantly by the AFAI method. Highly polar and nonpolar molecules, including dyes, pharmaceutical samples, explosives, drugs of abuse, protein and volatile compounds, have been successfully analyzed using AFAI-MS. The successful application of the technique to residue detection on fingers, large object analysis and remote monitoring in real time indicates its potential for the analysis of a variety of samples, especially large objects. The ability to couple this technique with most commercially available MS instruments with an API interface further enhances its broad applicability.

  19. Seasonality of new particle formation in Vienna, Austria - Influence of air mass origin and aerosol chemical composition

    NASA Astrophysics Data System (ADS)

    Wonaschütz, Anna; Demattio, Anselm; Wagner, Robert; Burkart, Julia; Zíková, Naděžda; Vodička, Petr; Ludwig, Wolfgang; Steiner, Gerhard; Schwarz, Jaroslav; Hitzenberger, Regina

    2015-10-01

    The impact of air mass origin and season on aerosol chemical composition and new particle formation and growth events (NPF events) in Vienna, Austria, is investigated using impactor samples from short-term campaigns and two long-term number size distribution datasets. The results suggest that air mass origin is most important for bulk PM concentrations, chemical composition of the coarse fraction (>1.5 μm) and the mass size distribution, and less important for chemical composition of the fine fraction (<1.5 μm). Continental air masses (crustal elements) were distinguished from air masses of marine origin (traces of sea salt). NPF events were most frequent in summer (22% of measurement days), and least frequent in winter (3% of measurement days). They were associated with above-average solar radiation and ozone concentrations, but were largely independent of PM2.5. Air mass origin was a secondary influence on NPF, largely through its association with meteorological conditions. Neither a strong dependence on the PM2.5 loading of the air masses, nor indications of a source area for NPF precursors outside the city were found.

  20. Community air monitoring for pesticides-part 2: multiresidue determination of pesticides in air by gas chromatography, gas chromatography-mass spectrometry, and liquid chromatography-mass spectrometry.

    PubMed

    Hengel, Matt; Lee, P

    2014-03-01

    Two multiresidue methods were developed to determine pesticides in air collected in California. Pesticides were trapped using XAD-4 resin and extracted with ethyl acetate. Based on an analytical method from the University of California Davis Trace Analytical Laboratory, pesticides were detected by analyzing the extract by gas chromatography-mass spectrometry (GC-MS) to determine chlorothalonil, chlorthal-dimethyl, cycloate, dicloran, dicofol, EPTC, ethalfluralin, iprodione, mefenoxam, metolachlor, PCNB, permethrin, pronamide, simazine, trifluralin, and vinclozolin. A GC with a flame photometric detector was used to determine chlorpyrifos, chlorpyrifos oxon, diazinon, diazinon oxon, dimethoate, dimethoate oxon, fonophos, fonophos oxon, malathion, malathion oxon, naled, and oxydemeton. Trapping efficiencies ranged from 78 to 92 % for low level (0.5 μg) and 37-104 % for high level (50 and 100 μg) recoveries. Little to no degradation of compounds occurred over 31 days; recoveries ranged from 78 to 113 %. In the California Department of Food and Agriculture (CDFA) method, pesticides were detected by analyzing the extract by GC-MS to determine chlorothalonil, chlorpyrifos, cypermethrin, dichlorvos, dicofol, endosulfan 1, endosulfan sulfate, oxyfluorfen, permethrin, propargite, and trifluralin. A liquid chromatograph coupled to a MS was used to determine azinphos-methyl, chloropyrifos oxon, DEF, diazinon, diazinon oxon, dimethoate, dimethoate oxon, diuron, EPTC, malathion, malathion oxon, metolachlor, molinate, norflurazon, oryzalin, phosmet, propanil, simazine and thiobencarb. Trapping efficiencies for compounds determined by the CDFA method ranged from 10 to 113, 22 to 114, and 56 to 132 % for 10, 5, and 2 μg spikes, respectively. Storage tests yielded 70-170 % recovery for up to 28 days. These multiresidue methods represent flexible, sensitive, accurate, and cost-effective ways to determine residues of various pesticides in ambient air. PMID:24370860

  1. Optimization of solar cells for air mass zero operation and a study of solar cells at high temperatures, phase 2

    NASA Technical Reports Server (NTRS)

    Hovel, H.; Woodall, J. M.

    1976-01-01

    Crystal growth procedures, fabrication techniques, and theoretical analysis were developed in order to make GaAlAs-GaAs solar cell structures which exhibit high performance at air mass 0 illumination and high temperature conditions.

  2. Evidence for widespread tropospheric Cl chemistry in free tropospheric air masses from the South China Sea

    NASA Astrophysics Data System (ADS)

    Baker, Angela K.; Sauvage, Carina; Thorenz, Ute R.; Brenninkmeijer, Carl A. M.; Oram, David E.; van Velthoven, Peter; Zahn, Andreas; Williams, Jonathan

    2015-04-01

    While the primary global atmospheric oxidant is the hydroxyl radical (OH), under certain circumstances chlorine radicals (Cl) can compete with OH and perturb the oxidative cycles of the troposphere. During flights between Bangkok, Thailand and Kuala Lumpur, Malaysia conducted over two fall/winter seasons (November 2012 - March 2013 and November 2013 - January 2014) the IAGOS-CARIBIC (www.caribic-atmospheric.com) observatory consistently encountered free tropospheric air masses (9-11 km) originating over the South China Sea which had non-methane hydrocarbon (NMHC) signatures characteristic of processing by Cl. These signatures were observed in November and December of both years, but were not seen in other months, suggesting that oxidation by Cl is a persistent seasonal feature in this region. These Cl signatures were observed over a range of ~1500 km indicating a large-scale phenomenon. In this region, where transport patterns facilitate global redistribution of pollutants and persistent deep convection creates a fast-track for cross-tropopause transport, there exists the potential for regional chemistry to have impacts further afield. Here we use observed relationships between NMHCs to estimate the significance and magnitude of Cl oxidation in this region. From the relative depletions of NMHCs in these air masses we infer OH to Cl ratios of 83±28 to 139±40 [OH]/[Cl], which we believe represents an upper limit, based on the technique employed. At a predicted average [OH] of 1.5×106 OH cm-3 this corresponds to an average (minimum) [Cl] exposure of 1-2×104 Cl cm-3 during air mass transport. Lastly, in addition to estimating Cl abundances we have used IAGOS-CARIBIC observations to elucidate whether the origin of this Cl is predominantly natural or anthropogenic.

  3. Diode laser-based air mass flux sensor for subsonic aeropropulsion inlets

    NASA Astrophysics Data System (ADS)

    Miller, Michael F.; Kessler, William J.; Allen, Mark G.

    1996-08-01

    An optical air mass flux sensor based on a compact, room-temperature diode laser in a fiber-coupled delivery system has been tested on a full-scale gas turbine engine. The sensor is based on simultaneous measurements of O 2 density and Doppler-shifted velocity along a line of sight across the inlet duct. Extensive tests spanning engine power levels from idle to full afterburner demonstrate accuracy and precision of the order of 1 2 of full scale in density, velocity, and mass flux. The precision-limited velocity at atmospheric pressure was as low as 40 cm s. Multiple data-reduction procedures are quantitatively compared to suggest optimal strategies for flight sensor packages.

  4. Characteristics of dimethylsulfide, ozone, aerosols, and cloud condensation nuclei in air masses over the northwestern Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Nagao, Ippei; Matsumoto, Kiyoshi; Tanaka, Hiroshi

    1999-05-01

    Long-term measurements of several trace gases and aerosols were carried out from December 1994 to October 1996 at Ogasawara Hahajima Island over the northwestern Pacific Ocean. The continental impact on the concentrations of sulfur compounds, ozone (O3), and cloud condensation nuclei (CCN) was estimated on the basis of the classification of air mass into seven types by isentropic trajectory analysis. From May to October, the air mass originating from the central North Pacific Ocean is predominant and regarded as the clean marine air for the concentrations of sulfur compounds and CCN. From the results of the molar ratio of methane sulfonic acid to non-sea-salt sulfate (NSS) and the positive correlation between dimethylsulfide (DMS) and CCN in this air mass it can be concluded that DMS largely contributes to the production of NSS and CCN. On the other hand, continental and anthropogenic substances are preferably transported to the northwestern Pacific Ocean by the predominant continental air mass from November to March. The enhancement of concentrations by the outflow from the Asian continent are estimated by a factor of 2.8 for O3, 3.9 for SO2, 3.5 for CCN activated at 0.5% supersaturation (0.5% CCN), 4.7 for 1.0% CCN, and 5.5 for NSS. Moreover, the CCN supersaturation spectra are also affected by the continental substances resulting in factor 2 of enhancement of cloud droplet number concentration. The diurnal variations of DMS and O3 for each air mass show a pattern of daytime minimum and nighttime maximum, which are typically found in remote ocean, even though those amplitudes are different for each air mass. Consequently, it can be concluded that the influence of nitric oxides (NOx) for the daytime O3 production and nitrate (NO3) radical for the nighttime oxidation of DMS are small even in the continental air mass.

  5. A workflow for multiclass determination of 256 pesticides in essential oils by liquid chromatography tandem mass spectrometry using evaporation and dilution approaches: Application to lavandin, lemon and cypress essential oils.

    PubMed

    Fillatre, Yoann; Rondeau, David; Daguin, Antoine; Communal, Pierre-Yves

    2016-01-01

    This paper describes the determination of 256 multiclass pesticides in cypress and lemon essential oils (EOs) by the way of liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS) analysis using the scheduled selected reaction monitoring mode (sSRM) available on a hybrid quadrupole linear ion trap (QLIT) mass spectrometer. The performance of a sample preparation of lemon and cypress EOs based on dilution or evaporation under nitrogen assisted by a controlled heating were assessed. The best limits of quantification (LOQs) were achieved with the evaporation under nitrogen method giving LOQs≤10µgL(-1) for 91% of the pesticides. In addition the very satisfactory results obtained for recovery, repeatability and linearity showed that for EOs of relatively low evaporation temperature, a sample preparation based on evaporation under nitrogen is well adapted and preferable to dilution. By compiling these results with those previously published by some of us on lavandin EO, we proposed a workflow dedicated to multiresidue determination of pesticides in various EOs by LC-ESI/sSRM. Among the steps involved in this workflow, the protocol related to mass spectrometry proposes an alternative confirmation method to the classical SRM ratio criteria based on a sSRM survey scan followed by an information-dependent acquisition using the sensitive enhanced product ion (EPI) scan to generate MS/MS spectra then compared to a reference. The submitted workflow was applied to the case of lemon EOs samples highlighting for the first time the simultaneous detection of 20 multiclass pesticides in one EO. Some pesticides showed very high concentration levels with amounts greatly exceeding the mgL(-1).

  6. Phenylboronic Acid Solid Phase Extraction Cleanup and Isotope Dilution Liquid Chromatography-Tandem Mass Spectrometry for the Determination of Florfenicol Amine in Fish Muscles.

    PubMed

    Sin, Della Wai-Mei; Ho, Clare; Wong, Yiu-Tung

    2015-01-01

    Florfenicol (FFC) residues in foods are regulated as the sum of florfenicol and its metabolites measured as florfenicol amine (FFA). An isotope dilution LC-MS/MS method utilizing phenylboronic acid (PBA) SPE cleanup is established for the accurate determination of FFA in fish muscles (i.e., salmon and tilapia) after acid catalyzed hydrolysis. Comparisons of the PBA SPE cleanup procedure with other cleanup procedures such as mixed-mode cationic (MCX) SPE and solid supported liquid-liquid extraction were performed. Quantification of FFA in fish muscles was accomplished by using matrix-matched calibration with FFA-D3 as the internal standard. The method was validated with FFA fortified fish muscles at three different levels (50, 100, and 200 μg/kg). Conversion of FFC to FFA by acid catalyzed hydrolysis was evaluated and found to be ≥88%. The recoveries of FFA in fish muscles at the three fortification levels ranged from 89 to 106%, and RSDs were ≤9% in all cases. The LOD values in salmon and tilapia muscles were 0.13 and 1.64 μg/kg, respectively. The LOQ values in salmon and tilapia muscles were 0.29 and 4.13 μg/kg, respectively. This method is suitable for the application in routine control of FFC in fishes according to its residue definition.

  7. Solitary fibrous tumor of the pleura manifesting as an air-containing cystic mass: radiologic and histopathologic correlation.

    PubMed

    Baek, Ji Eun; Ahn, Myeong Im; Lee, Kyo Young

    2013-01-01

    Solitary fibrous tumor (SFT) is a rare mesenchymal neoplasm that typically presents as a well-defined lobular soft tissue mass commonly arising from the pleura. We report an extremely rare case of an SFT containing air arising from the right major fissure in a 58-year-old woman. Chest CT showed an ovoid air-containing cystic mass with an internal, homogeneously enhancing solid nodule. To our knowledge, this is the first case in the literature. The histopathologic findings were correlated with the radiologic findings, and the mechanism of air retention within the tumor is discussed.

  8. Mixture model-based atmospheric air mass classification: a probabilistic view of thermodynamic profiles

    NASA Astrophysics Data System (ADS)

    Pernin, Jérôme; Vrac, Mathieu; Crevoisier, Cyril; Chédin, Alain

    2016-10-01

    Air mass classification has become an important area in synoptic climatology, simplifying the complexity of the atmosphere by dividing the atmosphere into discrete similar thermodynamic patterns. However, the constant growth of atmospheric databases in both size and complexity implies the need to develop new adaptive classifications. Here, we propose a robust unsupervised and supervised classification methodology of a large thermodynamic dataset, on a global scale and over several years, into discrete air mass groups homogeneous in both temperature and humidity that also provides underlying probability laws. Temperature and humidity at different pressure levels are aggregated into a set of cumulative distribution function (CDF) values instead of classical ones. The method is based on a Gaussian mixture model and uses the expectation-maximization (EM) algorithm to estimate the parameters of the mixture. Spatially gridded thermodynamic profiles come from ECMWF reanalyses spanning the period 2000-2009. Different aspects are investigated, such as the sensitivity of the classification process to both temporal and spatial samplings of the training dataset. Comparisons of the classifications made either by the EM algorithm or by the widely used k-means algorithm show that the former can be viewed as a generalization of the latter. Moreover, the EM algorithm delivers, for each observation, the probabilities of belonging to each class, as well as the associated uncertainty. Finally, a decision tree is proposed as a tool for interpreting the different classes, highlighting the relative importance of temperature and humidity in the classification process.

  9. Variation in particulate PAHs levels and their relation with the transboundary movement of the air masses.

    PubMed

    Ravindra, Khaiwal; Wauters, Eric; Van Grieken, René

    2008-06-25

    The levels of particulate polycyclic aromatic hydrocarbons (PAHs) were determined with a fast analytical approach to study their seasonal variations at Menen (Belgium) during 2003; they were found to be 5-7 times higher in January, February and December, in comparison to May, June and August. The annual average concentration of the sum of 16 US Environmental Protection Agency (EPA) criteria PAHs was 6.7 ng/m3 and around 63% of it was found to be probably carcinogenic to humans. The application of diagnostic ratio and principal component analysis showed vehicular emission as a major source. An increased ratio of 'combustion PAHs' to 'total EPA-PAHs' during the winter season indicated towards combustion activities. Further, the differences in PAHs concentration were assessed with relation to backward air mass trajectories, which show that the levels of PAHs increase when there is an air mass movement from Central and Western Europe and a fall when the trajectories spend most of their 4-day time over the Atlantic Ocean or in the Arctic region.

  10. Precipitation chemistry and corresponding transport patterns of influencing air masses at Huangshan Mountain in East China

    NASA Astrophysics Data System (ADS)

    Shi, ChunE; Deng, Xueliang; Yang, Yuanjian; Huang, Xiangrong; Wu, Biwen

    2014-09-01

    One hundred and ten samples of rainwater were collected for chemical analysis at the summit of Huangshan Mountain, a high-altitude site in East China, from July 2010 to June 2011. The volume-weighted-mean (VWM) pH for the whole sampling period was 5.03. SO{4/2-} and Ca2+ were the most abundant anion and cation, respectively. The ionic concentrations varied monthly with the highest concentrations in winter/spring and the lowest in summer. Evident inter-correlations were found among most ions, indicating the common sources for some species and fully mixing characteristics of the alpine precipitation chemistry. The VWM ratio of [SO{4/2-}]/[NO{3/-}] was 2.54, suggesting the acidity of rainwater comes from both nitric and sulfuric acids. Compared with contemporary observations at other alpine continental sites in China, the precipitation at Huangshan Mountain was the least polluted, with the lowest ionic concentrations. Trajectories to Huangshan Mountain on rainy days could be classified into six groups. The rainwater with influencing air masses originating in Mongolia was the most polluted with limited effect. The emissions of Jiangxi, Anhui, Zhejiang and Jiangsu provinces had a strong influence on the overall rain chemistry at Huangshan Mountain. The rainwater with influencing air masses from Inner Mongolia was heavily polluted by anthropogenic pollutants.

  11. Impact of maritime air mass trajectories on the Western European coast urban aerosol.

    PubMed

    Almeida, S M; Silva, A I; Freitas, M C; Dzung, H M; Caseiro, A; Pio, C A

    2013-01-01

    Lisbon is the largest urban area in the Western European coast. Due to this geographical position the Atlantic Ocean serves as an important source of particles and plays an important role in many atmospheric processes. The main objectives of this study were to (1) perform a chemical characterization of particulate matter (PM2.5) sampled in Lisbon, (2) identify the main sources of particles, (3) determine PM contribution to this urban area, and (4) assess the impact of maritime air mass trajectories on concentration and composition of respirable PM sampled in Lisbon. During 2007, PM2.5 was collected on a daily basis in the center of Lisbon with a Partisol sampler. The exposed Teflon filters were measured by gravimetry and cut into two parts: one for analysis by instrumental neutron activation analysis (INAA) and the other by ion chromatography (IC). Principal component analysis (PCA) and multilinear regression analysis (MLRA) were used to identify possible sources of PM2.5 and determine mass contribution. Five main groups of sources were identified: secondary aerosols, traffic, calcium, soil, and sea. Four-day backtracking trajectories ending in Lisbon at the starting sampling time were calculated using the HYSPLIT model. Results showed that maritime transport scenarios were frequent. These episodes were characterized by a significant decrease of anthropogenic aerosol concentrations and exerted a significant role on air quality in this urban area.

  12. Optimized combination of dilution and refined QuEChERS to overcome matrix effects of six types of tea for determination eight neonicotinoid insecticides by ultra performance liquid chromatography-electrospray tandem mass spectrometry.

    PubMed

    Jiao, Weiting; Xiao, Yu; Qian, Xiaosan; Tong, Mengmeng; Hu, Yizheng; Hou, Ruyan; Hua, Rimao

    2016-11-01

    Liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) is a primary tool for analysis of low volatility compounds in complex matrices. However, complex matrices, such as different types of tea, complicate analysis through ionization suppression or enhancement. In this study, sample preparation by a refined QuEChERS method combined with a dilution strategy removed almost all matrix effects caused by six types of tea. Tea samples were soaked with water and extracted with acetonitrile, cleaned up with a combination of PVPP (160mg) and GCB (20mg), and dried. Dried extracts were diluted with 20mL acetonitrile/water (15:85, v/v) before analysis by UPLC-MS/MS. The average recoveries of eight neonicotinoid insecticides (dinotefuran, nitenpyram, thiamethoxam, imidacloprid, clothianidin, imidaclothiz, acetamiprid, and thiacloprid) ranged from 66.3 to 108.0% from tea samples spiked at 0.01-0.5mgkg(-1). Relative standard deviations were below 16% for all recovery tests. The limit of quantification ranged from 0.01 to 0.05mgkg(-1). PMID:27211616

  13. Optimized combination of dilution and refined QuEChERS to overcome matrix effects of six types of tea for determination eight neonicotinoid insecticides by ultra performance liquid chromatography-electrospray tandem mass spectrometry.

    PubMed

    Jiao, Weiting; Xiao, Yu; Qian, Xiaosan; Tong, Mengmeng; Hu, Yizheng; Hou, Ruyan; Hua, Rimao

    2016-11-01

    Liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) is a primary tool for analysis of low volatility compounds in complex matrices. However, complex matrices, such as different types of tea, complicate analysis through ionization suppression or enhancement. In this study, sample preparation by a refined QuEChERS method combined with a dilution strategy removed almost all matrix effects caused by six types of tea. Tea samples were soaked with water and extracted with acetonitrile, cleaned up with a combination of PVPP (160mg) and GCB (20mg), and dried. Dried extracts were diluted with 20mL acetonitrile/water (15:85, v/v) before analysis by UPLC-MS/MS. The average recoveries of eight neonicotinoid insecticides (dinotefuran, nitenpyram, thiamethoxam, imidacloprid, clothianidin, imidaclothiz, acetamiprid, and thiacloprid) ranged from 66.3 to 108.0% from tea samples spiked at 0.01-0.5mgkg(-1). Relative standard deviations were below 16% for all recovery tests. The limit of quantification ranged from 0.01 to 0.05mgkg(-1).

  14. Air mass distribution and the heterogeneity of the climate change signal in the Hudson Bay/Foxe Basin region, Canada

    NASA Astrophysics Data System (ADS)

    Leung, Andrew; Gough, William

    2016-08-01

    The linkage between changes in air mass distribution and temperature trends from 1971 to 2010 is explored in the Hudson Bay/Foxe Basin region. Statistically significant temperature increases were found of varying spatial and temporal magnitude. Concurrent statistically significant changes in air mass frequency at the same locations were also detected, particularly in the declining frequency of dry polar (DP) air. These two sets of changes were found to be linked, and we thus conclude that the heterogeneity of the climatic warming signal in the region is at least partially the result of a fundamental shift in the concurrent air mass frequency in addition to global and regional changes in radiative forcing due to increases in long-lived greenhouse gases.

  15. Trends and sources vs air mass origins in a major city in South-western Europe: Implications for air quality management.

    PubMed

    Fernández-Camacho, R; de la Rosa, J D; Sánchez de la Campa, A M

    2016-05-15

    This study presents a 17-years air quality database comprised of different parameters corresponding to the largest city in the south of Spain (Seville) where atmospheric pollution is frequently attributed to traffic emissions and is directly affected by Saharan dust outbreaks. We identify the PM10 contributions from both natural and anthropogenic sources in this area associated to different air mass origins. Hourly, daily and seasonal variation of PM10 and gaseous pollutant concentrations (CO, NO2 and SO2), all of them showing negative trends during the study period, point to the traffic as one of the main sources of air pollution in Seville. Mineral dust, secondary inorganic compounds (SIC) and trace elements showed higher concentrations under North African (NAF) air mass origins than under Atlantic. We observe a decreasing trend in all chemical components of PM10 under both types of air masses, NAF and Atlantic. Principal component analysis using more frequent air masses in the area allows the identification of five PM10 sources: crustal, regional, marine, traffic and industrial. Natural sources play a more relevant role during NAF events (20.6 μg · m(-3)) than in Atlantic episodes (13.8 μg · m(-3)). The contribution of the anthropogenic sources under NAF doubles the one under Atlantic conditions (33.6 μg · m(-3) and 15.8 μg · m(-3), respectively). During Saharan dust outbreaks the frequent accumulation of local anthropogenic pollutants in the lower atmosphere results in poor air quality and an increased risk of mortality. The results are relevant when analysing the impact of anthropogenic emissions on the exposed population in large cities. The increase in potentially toxic elements during Saharan dust outbreaks should also be taken into account when discounting the number of exceedances attributable to non-anthropogenic or natural origins.

  16. Trends and sources vs air mass origins in a major city in South-western Europe: Implications for air quality management.

    PubMed

    Fernández-Camacho, R; de la Rosa, J D; Sánchez de la Campa, A M

    2016-05-15

    This study presents a 17-years air quality database comprised of different parameters corresponding to the largest city in the south of Spain (Seville) where atmospheric pollution is frequently attributed to traffic emissions and is directly affected by Saharan dust outbreaks. We identify the PM10 contributions from both natural and anthropogenic sources in this area associated to different air mass origins. Hourly, daily and seasonal variation of PM10 and gaseous pollutant concentrations (CO, NO2 and SO2), all of them showing negative trends during the study period, point to the traffic as one of the main sources of air pollution in Seville. Mineral dust, secondary inorganic compounds (SIC) and trace elements showed higher concentrations under North African (NAF) air mass origins than under Atlantic. We observe a decreasing trend in all chemical components of PM10 under both types of air masses, NAF and Atlantic. Principal component analysis using more frequent air masses in the area allows the identification of five PM10 sources: crustal, regional, marine, traffic and industrial. Natural sources play a more relevant role during NAF events (20.6 μg · m(-3)) than in Atlantic episodes (13.8 μg · m(-3)). The contribution of the anthropogenic sources under NAF doubles the one under Atlantic conditions (33.6 μg · m(-3) and 15.8 μg · m(-3), respectively). During Saharan dust outbreaks the frequent accumulation of local anthropogenic pollutants in the lower atmosphere results in poor air quality and an increased risk of mortality. The results are relevant when analysing the impact of anthropogenic emissions on the exposed population in large cities. The increase in potentially toxic elements during Saharan dust outbreaks should also be taken into account when discounting the number of exceedances attributable to non-anthropogenic or natural origins. PMID:26930305

  17. Quantification of methane in humid air and exhaled breath using selected ion flow tube mass spectrometry.

    PubMed

    Dryahina, Kseniya; Smith, D; Spanel, P

    2010-05-15

    In selected ion flow tube mass spectrometry, SIFT-MS, analyses of humid air and breath, it is essential to consider and account for the influence of water vapour in the media, which can be profound for the analysis of some compounds, including H(2)CO, H(2)S and notably CO(2). To date, the analysis of methane has not been considered, since it is known to be unreactive with H(3)O(+) and NO(+), the most important precursor ions for SIFT-MS analyses, and it reacts only slowly with the other available precursor ion, O(2) (+). However, we have now experimentally investigated methane analysis and report that it can be quantified in both air and exhaled breath by exploiting the slow O(2) (+)/CH(4) reaction that produces CH(3)O(2) (+) ions. We show that the ion chemistry is significantly influenced by the presence of water vapour in the sample, which must be quantified if accurate analyses are to be performed. Thus, we have carried out a study of the loss rate of the CH(3)O(2) (+) analytical ion as a function of sample humidity and deduced an appropriate kinetics library entry that provides an accurate analysis of methane in air and breath by SIFT-MS. However, the associated limit of detection is rather high, at 0.2 parts-per-million, ppm. We then measured the methane levels, together with acetone levels, in the exhaled breath of 75 volunteers, all within a period of 3 h, which shows the remarkable sample throughput rate possible with SIFT-MS. The mean methane level in ambient air is seen to be 2 ppm with little spread and that in exhaled breath is 6 ppm, ranging from near-ambient levels to 30 ppm, with no significant variation with age and gender. Methane can now be included in the wide ranging analyses of exhaled breath that are currently being carried out using SIFT-MS.

  18. Aerosols in Polluted versus Nonpolluted Air Masses: Long-Range Transport and Effects on Clouds.

    NASA Astrophysics Data System (ADS)

    Pueschel, R. F.; van Valin, C. C.; Castillo, R. C.; Kadlecek, J. A.; Ganor, E.

    1986-12-01

    To assess the influence of anthropogenic aerosols on the physics and chemistry of clouds in the northeastern United State, aerosol and cloud-drop size distributions, elemental composition of aerosols as a function of size, and ionic content of cloud water were measured on Whiteface Mountain, New York, during the summers of 1981 and 1982. In several case studies, the data were cross-correlated with different air mass types-background continental, polluted continental, and maritime-that were advected to the sampling site. The results are the following (1) Anthropogenic sources hundreds of kilometers upwind cause the small-particle (accumulation) mode number to increase from hundreds to thousands per cubic centimeter and the mass loading to increase from a few to several tens of micrograms per cubic meter, mostly in the form of sulfur aerosols. (ii) A significant fraction of anthropogenic sulfur aerosols appears to act as cloud condensation nuclei (CCN) to affect the cloud drop concentration. (iii) Clouds in Atlantic maritime air masses have cloud drop spectra that are markedly different from those measured in continental clouds. The drop concentration is significantly lower, and the drop size spectra are heavily skewed toward large drops. (iv) Effects of anthropogenic pollutants on cloud water ionic composition are an increase of nitrate by a factor of 50, an increase of sulfate by more than one order of magnitude, and an increase of ammonium ion by a factor of 7. The net effect of the changes in ionic concentrations is an increase in cloud water acidity. An anion deficit even in maritime clouds suggests an unknown, possibly biogenic, source that could be responsible for a pH below neutral, which is frequently observed in nonpolluted clouds.

  19. Finite element analysis of an inflatable torus considering air mass structural element

    NASA Astrophysics Data System (ADS)

    Gajbhiye, S. C.; Upadhyay, S. H.; Harsha, S. P.

    2014-01-01

    Inflatable structures, also known as gossamer structures, are at high boom in the current space technology due to their low mass and compact size comparing to the traditional spacecraft designing. Internal pressure becomes the major source of strength and rigidity, essentially stiffen the structure. However, inflatable space based membrane structure are at high risk to the vibration disturbance due to their low structural stiffness and material damping. Hence, the vibration modes of the structure should be known to a high degree of accuracy in order to provide better control authority. In the past, most of the studies conducted on the vibration analysis of gossamer structures used inaccurate or approximate theories in modeling the internal pressure. The toroidal shaped structure is one of the important key element in space application, helps to support the reflector in space application. This paper discusses the finite-element analysis of an inflated torus. The eigen-frequencies are obtained via three-dimensional small-strain elasticity theory, based on extremum energy principle. The two finite-element model (model-1 and model-2) have cases have been generated using a commercial finite-element package. The structure model-1 with shell element and model-2 with the combination of the mass of enclosed fluid (air) added to the shell elements have been taken for the study. The model-1 is computed with present analytical approach to understand the convergence rate and the accuracy. The convergence study is made available for the symmetric modes and anti-symmetric modes about the centroidal-axis plane, meeting the eigen-frequencies of an inflatable torus with the circular cross section. The structural model-2 is introduced with air mass element and analyzed its eigen-frequency with different aspect ratio and mode shape response using in-plane and out-plane loading condition are studied.

  20. The Use of Red Green Blue Air Mass Imagery to Investigate the Role of Stratospheric Air in a Non-Convective Wind Event

    NASA Technical Reports Server (NTRS)

    Berndt, E. B.; Zavodsky, B. T.; Moltham, A. L.; Folmer, M. J.; Jedlovec, G. J.

    2014-01-01

    The investigation of non-convective winds associated with passing extratropical cyclones and the formation of the sting jet in North Atlantic cyclones that impact Europe has been gaining interest. Sting jet research has been limited to North Atlantic cyclones that impact Europe because it is known to occur in Shapiro-Keyser cyclones and theory suggests it does not occur in Norwegian type cyclones. The global distribution of sting jet cyclones is unknown and questions remain as to whether cyclones with Shapiro-Keyser characteristics that impact the United States develop features similar to the sting jet. Therefore unique National Aeronautics and Space Administration (NASA) products were used to analyze an event that impacted the Northeast United States on 09 February 2013. Moderate Resolution Imaging Spectroradiometer (MODIS) Red Green Blue (RGB) Air Mass imagery and Atmospheric Infrared Sounder (AIRS) ozone data were used in conjunction with NASA's global Modern Era-Retrospective Analysis for Research and Applications (MERRA) reanalysis and higher-resolution regional 13-km Rapid Refresh (RAP) data to analyze the role of stratospheric air in producing high winds. The RGB Air Mass imagery and a new AIRS ozone anomaly product were used to confirm the presence of stratospheric air. Plan view and cross sectional plots of wind, potential vorticity, relative humidity, omega, and frontogenesis were used to analyze the relationship between stratospheric air and high surface winds during the event. Additionally, the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model was used to plot trajectories to determine the role of the conveyor belts in producing the high winds. Analyses of new satellite products, such as the RGB Air Mass imagery, show the utility of future GOES-R products in forecasting non-convective wind events.

  1. Fullerene Soot in Eastern China Air: Results from Soot Particle-Aerosol Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Wang, J.; Ge, X.; Chen, M.; Zhang, Q.; Yu, H.; Sun, Y.; Worsnop, D. R.; Collier, S.

    2015-12-01

    In this work, we present for the first time, the observation and quantification of fullerenes in ambient airborne particulate using an Aerodyne Soot Particle - Aerosol Mass Spectrometer (SP-AMS) deployed during 2015 winter in suburban Nanjing, a megacity in eastern China. The laser desorption and electron impact ionization techniques employed by the SP-AMS allow us to differentiate various fullerenes from other aerosol components. Mass spectrum of the identified fullerene soot is consisted by a series of high molecular weight carbon clusters (up to m/z of 2000 in this study), almost identical to the spectral features of commercially available fullerene soot, both with C70 and C60 clusters as the first and second most abundant species. This type of soot was observed throughout the entire study period, with an average mass loading of 0.18 μg/m3, accounting for 6.4% of the black carbon mass, 1.2% of the total organic mass. Temporal variation and diurnal pattern of fullerene soot are overall similar to those of black carbon, but are clearly different in some periods. Combining the positive matrix factorization, back-trajectory and analyses of the meteorological parameters, we identified the petrochemical industrial plants situating upwind from the sampling site, as the major source of fullerene soot. In this regard, our findings imply the ubiquitous presence of fullerene soot in ambient air of industry-influenced area, especially the oil and gas production regions. This study also offers new insights into the characterization of fullerenes from other environmental samples via the advanced SP-AMS technique.

  2. Number size distribution of aerosols at Mt. Huang and Nanjing in the Yangtze River Delta, China: Effects of air masses and characteristics of new particle formation

    NASA Astrophysics Data System (ADS)

    Wang, Honglei; Zhu, Bin; Shen, Lijuan; An, Junlin; Yin, Yan; Kang, Hanqing

    2014-12-01

    Aerosol number spectra in the range of 10 nm-10 μm were observed at Mt. Huang (Aug. 15-Sep. 15) and Nanjing (Oct. 13-Nov. 15) by a wide-range particle spectrometer (WPS) in 2011. Based on the backward trajectories obtained using the HYSPLIT model, the transport pathways of observed air masses during the study periods were classified into the following four groups: maritime air mass, continental air mass, marine-continental mixed air mass and local air mass. The variations in the aerosol number spectrum and the new particle formation (NPF) events for various types of air masses were discussed, along with meteorological data. The results showed that the average number concentration was 12,540 cm- 3 at Nanjing and only 2791 cm- 3 at Mt. Huang. The aerosol number concentration in Nanjing was 3-7 times higher than that in Mt. Huang; the large discrepancy was in the range of 10-100 nm. Different types of air masses had different effects on number concentration distribution. The number concentration of aerosols was higher in marine air masses, continental air masses and continental-marine mixed air masses at 10-50 nm, 100-500 nm and 50-200 nm, respectively. Under the four types of air masses, the aerosol size spectra had bimodal distributions in Nanjing and unimodal distributions in Mt. Huang (except under continental air masses: HT1). The effects of the diverse air masses on aerosol size segments of the concentration peak in Mt. Huang were stronger than those in Nanjing. The local air masses were dominant at these two sites and accounted for 44% of the total air masses. However, the aerosol number concentration was the lowest in Mt. Huang and the highest in Nanjing when local air masses were present. The number concentrations for foreign air masses increased at Mt. Huang and decreased at Nanjing. Different types of air masses had greater effects on the aerosol spectrum distribution at Mt. Huang than at Nanjing. During the NPF events, the particle growth rates at Mt

  3. An Air Mass Based Approach to the Establishment of Spring Season Synoptic Characteristics in the Northeast United States

    NASA Astrophysics Data System (ADS)

    Zander, R.; Messina, A.; Godek, M. L.

    2012-12-01

    The spring season is indicative of marked meteorological, ecological, and biological changes across the Northeast United States. The onset of spring coincides with distinct meteorological phenomena including an increase in severe weather events and snow meltwaters that can cause localized flooding and other costly damages. Increasing and variable springtime temperatures also influence Northeast tourist operations and agricultural productivity. Even with the vested interest of industry in the season and public awareness of the dynamic characteristics of spring, the definition of spring remains somewhat arbitrary. The primary goal of this research is to obtain a synoptic meteorological definition of the spring season through an assessment of air mass frequency over the past 60 years. A secondary goal examines the validity of recent speculations that the onset and termination of spring has changed in recent decades, particularly since 1975. The Spatial Synoptic Classification is utilized to define daily air masses over the region. Annual and seasonal baseline frequencies are identified and their differences are acquired to characterize the season. Seasonal frequency departures of the early and late segments of the period of record around 1975 are calculated and examined for practical and statistical significance. The daily boundaries of early and late spring are then isolated and frequencies are obtained for these periods. Boundary frequencies are assessed across the period of record to identify important changes in the season's initiation and termination through time. Results indicate that the Northeast spring season is dominated by dry air masses, mainly the Dry Moderate and Dry Polar types. Significant differences in seasonal air mass frequency are also observed through time. Prior to 1975, higher frequencies of polar air mass types are detected while after 1975 there is an increase in the frequencies of both moderate and tropical types. This finding is also

  4. Atmospheric Thickness Variability During Air Mass Conditions and Winter Snow Events at Albany, NY: 2002-2012

    NASA Astrophysics Data System (ADS)

    Dubbs, A. M.; Swift, S.; Godek, M. L.

    2014-12-01

    A winter weather parameter that is underutilized in the prediction of Northeast snowfall events is critical thickness. Knowledge of atmospheric thickness values during snowfall can benefit the accuracy of winter forecasts, especially if thickness layer ranges at times without precipitation are known. This investigation aims to better understand atmospheric thickness variations in the 1000-500, 1000-700, and 1000-850 hPa layers at Albany, New York during snowfall with differing air mass conditions. Since snow can occur alongside a variety of air mass environments, distinctions in layer thickness between air mass types and critical levels will be examined. Pairing air mass information with an improved understanding of thicknesses may allow forecasters to determine normal snowfall conditions of the atmosphere and decipher when anomalous conditions are occurring alongside heavier snows. Daily geopotential height data are examined alongside Spatial Synoptic Classification weather types over the past decade. Air mass frequencies are computed and baseline thicknesses are established for non-snow days, days with snow and liquid precipitation, and days with only snowfall. Thicknesses are compared to those computed for seven air mass types and differences layers are examined for continuity. For the three air masses identified as prevalent during heavy snow, light-to-heavy and early-to-late season snowfall categories are established and thickness variations are evaluated against non-snow days for significant differences. Results indicate that the differences in layer thicknesses are comparable for all precipitation and non-snow days but around 40 geopotential meters less for pure-snow days. For air masses present during snow, layer thicknesses can vary by over 100 gpm with type. Isolating polar varieties, approximately 50 gpm thickness differences are found in pure-snow days. Comparable differences are detected between the moderate and polar types and the continuity between

  5. Composition of air masses in Fuerteventura (Canary Islands) according to their origins

    SciTech Connect

    Patier, R.F.; Diez Hernandez, P.; Diaz Ramiro, E.; Ballesteros, J.S.; Santos-Alves, S.G. dos

    1994-12-31

    The Centro Nacional de Sanidad Ambiental has among their duties the background atmospheric pollution monitoring in Spain. To do so, the laboratory has set up 6 field stations in the Iberian Peninsula. In these stations, both gaseous and particulate pollutants are currently analyzed. However, there is a lack of data about the atmospheric pollution in the Canary, where they are a very strong influence of natural emissions from sea and the Saharan desert, mixed with anthropogenic ones. Therefore, during the ASTEX/MAGE project the CNSA established a station in Fuerteventura island, characterized by the nonexistence of man-made emissions, to measure some atmospheric pollutants, in order to foresee their origins. In this study, the authors analyzed some pollutants that are used to obtain a clue about the sources of air masses such as gaseous ozone and metallic compounds (vanadium, iron and manganese) in the atmospheric aerosol fractionated by size.

  6. Operational performance of a low cost, air mass 2 solar simulator

    NASA Technical Reports Server (NTRS)

    Yass, K.; Curtis, H. B.

    1975-01-01

    Modifications and improvements on a low cost air mass 2 solar simulator are discussed. The performance characteristics of total irradiance, uniformity of irradiance, spectral distribution, and beam subtense angle are presented. The simulator consists of an array of tungsten halogen lamps hexagonally spaced in a plane. A corresponding array of plastic Fresnel lenses shapes the output beam such that the simulator irradiates a 1.2 m by 1.2 m area with uniform collimated irradiance. Details are given concerning individual lamp output measurements and placement of the lamps. Originally, only the direct component of solar irradiance was simulated. Since the diffuse component may affect the performance of some collectors, the capability to simulate it is being added. An approach to this diffuse addition is discussed.

  7. Progress Toward a Global, EOS-Era Aerosol Air Mass Type Climatology

    NASA Technical Reports Server (NTRS)

    Kahn, Ralph A.

    2012-01-01

    The MISR and MODIS instruments aboard the NASA Earth Observing System's Terra Satellite have been collecting data containing information about the state of Earth's atmosphere and surface for over eleven years. Data from these instruments have been used to develop a global, monthly climatology of aerosol amount that is widely used as a constraint on climate models, including those used for the 2007 IPCC assessment report. The next frontier in assessing aerosol radiative forcing of climate is aerosol type, and in particular, the absorption properties of major aerosol air masses. This presentation will focus on the prospects for constraining aerosol type globally, and the steps we are taking to apply a combination of satellite and suborbital data to this challenge.

  8. Simultaneous measurement of mass and rotation of trapped absorbing particles in air.

    PubMed

    Bera, Sudipta K; Kumar, Avinash; Sil, Souvik; Saha, Tushar Kanti; Saha, Tanumoy; Banerjee, Ayan

    2016-09-15

    We trap absorbing micro-particles in air by photophoretic forces generated using a single loosely focused Gaussian trapping beam. We measure a component of the radial Brownian motion of a trapped particle cluster and determine the power spectral density, mean squared displacement, and normalized position and velocity autocorrelation functions to characterize the photophoretic body force in a quantitative fashion for the first time. The trapped particles also undergo spontaneous rotation due to the action of this force. This is evident from the spectral density that displays clear peaks at the rotation and the particles' inertial resonance frequencies. We fit the spectral density to the well-known analytical function derived from the Langevin equation, measure the resonance and rotation frequencies, and determine the values for particle mass that we verify at different trapping laser powers with reasonable accuracy. PMID:27628396

  9. Identification of aerosol types over an urban site based on air-mass trajectory classification

    NASA Astrophysics Data System (ADS)

    Pawar, G. V.; Devara, P. C. S.; Aher, G. R.

    2015-10-01

    Columnar aerosol properties retrieved from MICROTOPS II Sun Photometer measurements during 2010-2013 over Pune (18°32‧N; 73°49‧E, 559 m amsl), a tropical urban station in India, are analyzed to identify aerosol types in the atmospheric column. Identification/classification is carried out on the basis of dominant airflow patterns, and the method of discrimination of aerosol types on the basis of relation between aerosol optical depth (AOD500 nm) and Ångström exponent (AE, α). Five potential advection pathways viz., NW/N, SW/S, N, SE/E and L have been identified over the observing site by employing the NOAA-HYSPLIT air mass back trajectory analysis. Based on AE against AOD500 nm scatter plot and advection pathways followed five major aerosol types viz., continental average (CA), marine continental average (MCA), urban/industrial and biomass burning (UB), desert dust (DD) and indeterminate or mixed type (MT) have been identified. In winter, sector SE/E, a representative of air masses traversed over Bay of Bengal and Eastern continental Indian region has relatively small AOD (τpλ = 0.43 ± 0.13) and high AE (α = 1.19 ± 0.15). These values imply the presence of accumulation/sub-micron size anthropogenic aerosols. During pre-monsoon, aerosols from the NW/N sector have high AOD (τpλ = 0.61 ± 0.21), and low AE (α = 0.54 ± 0.14) indicating an increase in the loading of coarse-mode particles over Pune. Dominance of UB type in winter season for all the years (i.e. 2010-2013) may be attributed to both local/transported aerosols. During pre-monsoon seasons, MT is the dominant aerosol type followed by UB and DD, while the background aerosols are insignificant.

  10. AUTOMATED DECONVOLUTION OF COMPOSITE MASS SPECTRA OBTAINED WITH AN OPEN-AIR IONIZATIONS SOURCE BASED ON EXACT MASSES AND RELATIVE ISOTIPIC ABUNDANCES

    EPA Science Inventory

    Chemicals dispersed by accidental, deliberate, or weather-related events must be rapidly identified to assess health risks. Mass spectra from high levels of analytes obtained using rapid, open-air ionization by a Direct Analysis in Real Time (DART®) ion source often contain

  11. Bioaccumulation Potential Of Air Contaminants: Combining Biological Allometry, Chemical Equilibrium And Mass-Balances To Predict Accumulation Of Air Pollutants In Various Mammals

    SciTech Connect

    Veltman, Karin; McKone, Thomas E.; Huijbregts, Mark A.J.; Hendriks, A. Jan

    2009-03-01

    In the present study we develop and test a uniform model intended for single compartment analysis in the context of human and environmental risk assessment of airborne contaminants. The new aspects of the model are the integration of biological allometry with fugacity-based mass-balance theory to describe exchange of contaminants with air. The developed model is applicable to various mammalian species and a range of chemicals, while requiring few and typically well-known input parameters, such as the adult mass and composition of the species, and the octanol-water and air-water partition coefficient of the chemical. Accumulation of organic chemicals is typically considered to be a function of the chemical affinity forlipid components in tissues. Here, we use a generic description of chemical affinity for neutral and polar lipids and proteins to estimate blood-air partition coefficients (Kba) and tissue-air partition coefficients (Kta) for various mammals. This provides a more accurate prediction of blood-air partition coefficients, as proteins make up a large fraction of total blood components. The results show that 75percent of the modeled inhalation and exhalation rate constants are within a factor of 2 from independent empirical values for humans, rats and mice, and 87percent of the predicted blood-air partition coefficients are within a factor of 5 from empirical data. At steady-state, the bioaccumulation potential of air pollutants is shown to be mainly a function of the tissue-air partition coefficient and the biotransformation capacity of the species and depends weakly on the ventilation rate and the cardiac output of mammals.

  12. Ring waves as a mass transport mechanism in air-driven core-annular flows.

    PubMed

    Camassa, Roberto; Forest, M Gregory; Lee, Long; Ogrosky, H Reed; Olander, Jeffrey

    2012-12-01

    Air-driven core-annular fluid flows occur in many situations, from lung airways to engineering applications. Here we study, experimentally and theoretically, flows where a viscous liquid film lining the inside of a tube is forced upwards against gravity by turbulent airflow up the center of the tube. We present results on the thickness and mean speed of the film and properties of the interfacial waves that develop from an instability of the air-liquid interface. We derive a long-wave asymptotic model and compare properties of its solutions with those of the experiments. Traveling wave solutions of this long-wave model exhibit evidence of different mass transport regimes: Past a certain threshold, sufficiently large-amplitude waves begin to trap cores of fluid which propagate upward at wave speeds. This theoretical result is then confirmed by a second set of experiments that show evidence of ring waves of annular fluid propagating over the underlying creeping flow. By tuning the parameters of the experiments, the strength of this phenomenon can be adjusted in a way that is predicted qualitatively by the model.

  13. Synoptic patterns and air mass transport during ozone episodes in northwestern Iberia.

    PubMed

    Saavedra, S; Rodríguez, A; Taboada, J J; Souto, J A; Casares, J J

    2012-12-15

    High levels of ozone are frequently measured at the Galicia (NW Iberian Peninsula) air quality monitoring stations from March to October. However, there have been very few studies on surface ozone in the northwestern Iberian Peninsula, most likely because the climate of this region is not favourable to photochemical ozone generation. The occurrence of these episodes may be related to either local-scale photochemical pollution or regional-scale transport from other polluted regions. In addition, high ozone episodes usually are developed under specific synoptic conditions. The main purposes of this study are to characterise the atmospheric conditions that lead to the ozone episodes in this region and to identify possible advection paths of ozone and precursors. A surface hourly ozone dataset (2002-2007) measured at rural sites in Galicia was analysed to identify high ozone episodes together with their associated synoptic patterns using a subjective classification with 23 different synoptic types. The synoptic weather patterns revealed that most of the episodes occur with high surface pressures centred over the British Isles and/or Central Europe while a high-altitude anticyclonic ridge crosses the Peninsula from North Africa, causing easterly or southeasterly winds. This analysis was completed with 3-day backward air mass trajectories obtained with HYSPLIT to assess the contribution of long-range transport, resulting in the following main routes: Mediterranean-Peninsular, South Atlantic-Portuguese, local and French-Cantabric.

  14. Enantiomeric signatures of organochlorine pesticides in Asian, trans-Pacific, and western U.S. air masses.

    PubMed

    Genualdi, Susan A; Simonich, Staci L Massey; Primbs, Toby K; Bidleman, Terry F; Jantunen, Liisa M; Ryoo, Keon-Sang; Zhu, Tong

    2009-04-15

    The enantiomeric signatures of organochlorine pesticides were measured in air masses from Okinawa, Japan and three remote locations in the Pacific Northwestern United States: Cheeka Peak Observatory (CPO), a marine boundary layer site on the Olympic Peninsula of Washington at 500 m above sea level (m.a.s.l); Mary's Peak Observatory (MPO), a site at 1250 m.a.s.l in Oregon's Coast range; and Mt. Bachelor Observatory (MBO), a site at 2763 m.a.s.l in Oregon's Cascade range. The enantiomeric signatures of composite soil samples, collected from China, South Korea, and the western U.S. were also measured. The data from chiral analysis was expressed asthe enantiomeric fraction, defined as (+) enantiomer/(sum of the (+) and (-) enantiomers), where a racemic composition has EF = 0.5. Racemic alpha-hexachlorocyclohexane (alpha-HCH) was measured in Asian air masses at Okinawa and in Chinese and South Korean soils. Nonracemic alpha-HCH (EF = 0.528 +/- 0.0048) was measured in regional air masses at CPO, and may reflect volatilization from the Pacific Ocean and regional soils. However, during trans-Pacific transport events at CPO, the alpha-HCH EFs were significantly more racemic (EF = 0.513 +/- 0.0003, p < 0.001). Racemic alpha-HCH was consistently measured at MPO and MBO in trans-Pacific air masses that had spent considerable time in the free troposphere. The alpha-HCH EFs in CPO, MPO, and MBO air masses were negatively correlated (p = 0.0017) with the amount of time the air mass spent above the boundary layer, along the 10-day back air mass trajectory, prior to being sampled. This suggests that, on the West coast of the U.S., the alpha-HCH in the free troposphere is racemic. Racemic signatures of cis- and trans-chlordane were measured in air masses at all four air sampling sites, suggesting that Asian and U.S. urban areas continue to be sources of chlordane that has not yet been biotransformed. PMID:19475954

  15. Enantiomeric Signatures of Organochlorine Pesticides in Asian, Trans-Pacific and Western U.S. Air Masses

    PubMed Central

    Genualdi, Susan A.; Massey Simonich, Staci L.; Primbs, Toby K.; Bidleman, Terry F.; Jantunen, Liisa M.; Ryoo, Keon-Sang; Zhu, Tong

    2009-01-01

    The enantiomeric signatures of organochlorine pesticides were measured in air masses from Okinawa, Japan and three remote locations in the Pacific Northwestern U.S.: Cheeka Peak Observatory (CPO), a marine boundary layer site on the Olympic Peninsula of Washington at 500 meters above sea level (m.a.s.l); Mary’s Peak Observatory (MPO), a site at 1250 m.a.s.l in Oregon’s Coast range; and Mt. Bachelor Observatory (MBO), a site at 2763 m.a.s.l in Oregon’s Cascade range. The enantiomeric signatures of composite soil samples, collected from China, South Korea, and the western U.S. were also measured. The data from chiral analysis was expressed as the enantiomeric fraction (1), defined as (+) enantiomer/(sum of the (+) and (−) enantiomers), where a racemic composition has EF = 0.5. Racemic α-hexachlorocyclohexane (α-HCH) was measured in Asian air masses at Okinawa and in Chinese and South Korean soils. Non-racemic α-HCH (EF = 0.528 ± 0.0048) was measured in regional air masses at CPO, and may reflect volatilization from the Pacific Ocean and regional soils. However, during trans-Pacific transport events at CPO, the α-HCH EFs were significantly more racemic (EF = 0.513 ± 0.0003, p < 0.001). Racemic α-HCH was consistently measured at MPO and MBO in trans-Pacific air masses that had spent considerable time in the free troposphere. The α-HCH EFs in CPO, MPO, and MBO air masses were negatively correlated (p = 0.0017) with the amount of time the air mass spent above the boundary layer, along the 10-day back air mass trajectory, prior to being sampled. This suggests that, on the West coast of the U.S., the α-HCH in the free troposphere is racemic. Racemic signatures of cis- and trans-chlordane were measured in air masses at all four air sampling sites, suggesting that Asian and U.S. urban areas continue to be sources of chlordane that has not yet been biotransformed. PMID:19475954

  16. Enantiomeric signatures of organochlorine pesticides in Asian, trans-Pacific, and western U.S. air masses.

    PubMed

    Genualdi, Susan A; Simonich, Staci L Massey; Primbs, Toby K; Bidleman, Terry F; Jantunen, Liisa M; Ryoo, Keon-Sang; Zhu, Tong

    2009-04-15

    The enantiomeric signatures of organochlorine pesticides were measured in air masses from Okinawa, Japan and three remote locations in the Pacific Northwestern United States: Cheeka Peak Observatory (CPO), a marine boundary layer site on the Olympic Peninsula of Washington at 500 m above sea level (m.a.s.l); Mary's Peak Observatory (MPO), a site at 1250 m.a.s.l in Oregon's Coast range; and Mt. Bachelor Observatory (MBO), a site at 2763 m.a.s.l in Oregon's Cascade range. The enantiomeric signatures of composite soil samples, collected from China, South Korea, and the western U.S. were also measured. The data from chiral analysis was expressed asthe enantiomeric fraction, defined as (+) enantiomer/(sum of the (+) and (-) enantiomers), where a racemic composition has EF = 0.5. Racemic alpha-hexachlorocyclohexane (alpha-HCH) was measured in Asian air masses at Okinawa and in Chinese and South Korean soils. Nonracemic alpha-HCH (EF = 0.528 +/- 0.0048) was measured in regional air masses at CPO, and may reflect volatilization from the Pacific Ocean and regional soils. However, during trans-Pacific transport events at CPO, the alpha-HCH EFs were significantly more racemic (EF = 0.513 +/- 0.0003, p < 0.001). Racemic alpha-HCH was consistently measured at MPO and MBO in trans-Pacific air masses that had spent considerable time in the free troposphere. The alpha-HCH EFs in CPO, MPO, and MBO air masses were negatively correlated (p = 0.0017) with the amount of time the air mass spent above the boundary layer, along the 10-day back air mass trajectory, prior to being sampled. This suggests that, on the West coast of the U.S., the alpha-HCH in the free troposphere is racemic. Racemic signatures of cis- and trans-chlordane were measured in air masses at all four air sampling sites, suggesting that Asian and U.S. urban areas continue to be sources of chlordane that has not yet been biotransformed.

  17. The determination of carbon dioxide concentration using atmospheric pressure ionization mass spectrometry/isotopic dilution and errors in concentration measurements caused by dryers.

    PubMed

    DeLacy, Brendan G; Bandy, Alan R

    2008-01-01

    An atmospheric pressure ionization mass spectrometry/isotopically labeled standard (APIMS/ILS) method has been developed for the determination of carbon dioxide (CO(2)) concentration. Descriptions of the instrumental components, the ionization chemistry, and the statistics associated with the analytical method are provided. This method represents an alternative to the nondispersive infrared (NDIR) technique, which is currently used in the atmospheric community to determine atmospheric CO(2) concentrations. The APIMS/ILS and NDIR methods exhibit a decreased sensitivity for CO(2) in the presence of water vapor. Therefore, dryers such as a nafion dryer are used to remove water before detection. The APIMS/ILS method measures mixing ratios and demonstrates linearity and range in the presence or absence of a dryer. The NDIR technique, on the other hand, measures molar concentrations. The second half of this paper describes errors in molar concentration measurements that are caused by drying. An equation describing the errors was derived from the ideal gas law, the conservation of mass, and Dalton's Law. The purpose of this derivation was to quantify errors in the NDIR technique that are caused by drying. Laboratory experiments were conducted to verify the errors created solely by the dryer in CO(2) concentration measurements post-dryer. The laboratory experiments verified the theoretically predicted errors in the derived equations. There are numerous references in the literature that describe the use of a dryer in conjunction with the NDIR technique. However, these references do not address the errors that are caused by drying.

  18. The determination of carbon dioxide concentration using atmospheric pressure ionization mass spectrometry/isotopic dilution and errors in concentration measurements caused by dryers.

    PubMed

    DeLacy, Brendan G; Bandy, Alan R

    2008-01-01

    An atmospheric pressure ionization mass spectrometry/isotopically labeled standard (APIMS/ILS) method has been developed for the determination of carbon dioxide (CO(2)) concentration. Descriptions of the instrumental components, the ionization chemistry, and the statistics associated with the analytical method are provided. This method represents an alternative to the nondispersive infrared (NDIR) technique, which is currently used in the atmospheric community to determine atmospheric CO(2) concentrations. The APIMS/ILS and NDIR methods exhibit a decreased sensitivity for CO(2) in the presence of water vapor. Therefore, dryers such as a nafion dryer are used to remove water before detection. The APIMS/ILS method measures mixing ratios and demonstrates linearity and range in the presence or absence of a dryer. The NDIR technique, on the other hand, measures molar concentrations. The second half of this paper describes errors in molar concentration measurements that are caused by drying. An equation describing the errors was derived from the ideal gas law, the conservation of mass, and Dalton's Law. The purpose of this derivation was to quantify errors in the NDIR technique that are caused by drying. Laboratory experiments were conducted to verify the errors created solely by the dryer in CO(2) concentration measurements post-dryer. The laboratory experiments verified the theoretically predicted errors in the derived equations. There are numerous references in the literature that describe the use of a dryer in conjunction with the NDIR technique. However, these references do not address the errors that are caused by drying. PMID:18574165

  19. Body mass penalties in the physical fitness tests of the Army, Air Force, and Navy.

    PubMed

    Vanderburgh, Paul M; Crowder, Todd A

    2006-08-01

    Recent research has empirically documented a consistent penalty against heavier service members for events identical or similar to those in the physical fitness tests of the Army, Air Force, and Navy. These penalties, which are not related to body fatness, are based on biological scaling models and have a physiological basis. Using hypothetical cases, we quantified the penalties for men, with body mass of 60 vs. 90 kg, and women, 45 vs. 75 kg, to be 15% to 20% for the fitness tests of these three services. Such penalties alone can adversely affect awards and promotions for heavier service members. To deal equitably with these penalties in a practical manner, we offer two recommendations, i.e., (1) implementation of revised fitness tests with balanced events, in which the penalties of one event for heavier service members are balanced by an equal and opposite bias against lighter service members, or (2) development of correction factors that can be multiplied by raw scores to yield adjusted scores free of body mass bias.

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

    PubMed

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

    2015-09-01

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

  1. Characteristics of tyre dust in polluted air: Studies by single particle mass spectrometry (ATOFMS)

    NASA Astrophysics Data System (ADS)

    Dall'Osto, Manuel; Beddows, David C. S.; Gietl, Johanna K.; Olatunbosun, Oluremi A.; Yang, Xiaoguang; Harrison, Roy M.

    2014-09-01

    There is a paucity of quantitative knowledge on the contributions of non-exhaust (abrasion and re-suspension) sources to traffic emissions. Abrasive emissions can be broadly categorised as tyre wear, brake wear and road dust/road surface wear. Current research often considers road dust and tyre dust as externally mixed particles, the former mainly composed of mineral matter and the latter solely composed of mainly organic matter and some trace elements. The aim of this work was to characterise tyre wear from both laboratory and field studies by using Aerosol Time-Of-Flight Mass Spectrometry (ATOFMS). Real-time single particle chemical composition was obtained from a set of rubber tyres rotating on a metal surface. Bimodal particle number size distributions peaking at 35 nm and 85 nm were obtained from SMPS/APS measurements over the range 6-20,000 nm. ATOFMS mass spectra of tyre wear in the particle size range 200-3000 nm diameter show peaks due to exo-sulphur compounds, nitrate, Zn and ions of high molecular weight (m/z > 100) attributed to organic polymers. Two large ATOFMS datasets collected from a number of outdoor studies were examined. The former was constituted of 48 road dust samples collected on the roads of London. The latter consisted of ATOFMS ambient air field studies from Europe, overall composed of more than 2,000,000 single particle mass spectra. The majority (95%) of tyre wear particles present in the road dust samples and atmospheric samples are internally mixed with metals (Li, Na, Ca, Fe, Ti), as well as phosphate. It is concluded that the interaction of tyres with the road surface creates particles internally mixed from two sources: tyre rubber and road surface materials. Measurements of the tyre rubber component alone may underestimate the contribution of tyre wear to concentrations of airborne particulate matter. The results presented are especially relevant for urban aerosol source apportionment and PM2.5 exposure assessment.

  2. Study Case of Air-Mass Modification over Poland and Romania Observed by the Means of Multiwavelength Raman Depolarization Lidars

    NASA Astrophysics Data System (ADS)

    Costa-Surós, Montserrat; Janicka, Lucja; Stachlewska, Iwona S.; Nemuc, Anca; Talianu, Camelia; Heese, Birgit; Engelmann, Ronny

    2016-06-01

    An air-mass modification, on its way from Poland to Romania, observed between 19-21 July 2014 is discussed. The air-mass was investigated using data of two multi-wavelength lidars capable of performing regular elastic, depolarization and Raman measurements in Warsaw, Poland, and in Magurele, Romania. The analysis was focused on evaluating optical properties of aerosol in order to search for similarities and differences in the vertical profiles describing the atmospheric layers above the two stations within given period.

  3. Simultaneous determination of 19 triazine pesticides and degradation products in processed cereal samples from Chinese total diet study by isotope dilution-high performance liquid chromatography-linear ion trap mass spectrometry.

    PubMed

    Li, Peng; Yang, Xin; Miao, Hong; Zhao, Yunfeng; Liu, Wei; Wu, Yongning

    2013-06-01

    A selective and sensitive isotope dilution-high performance liquid chromatography-linear ion trap mass spectrometry (Isotope Dilution-HPLC-LIT-MS(3)) method was developed for the simultaneous determination of 19 triazine pesticides and their degradation products in processed cereal samples from Chinese total diet study (TDS). The method integrated the addition of isotope internal standards, liquid-liquid extraction (LLE), clean-up with MCX solid-phase extraction (SPE) cartridges and HPLC-LIT-MS(3) analysis with selected reaction monitoring (SRM) mode. Matrix-matched calibration curves showed good linearity (R(2)≥0.9940) verified by applying the Mandel's fitting test (p>0.087) performed at the 95% confidence level. Decision limits (CCαs) and detection capabilities (CCβs) of the 19 triazine pesticides and their degradation products fell in the ranges of 0.0020-0.4200 μg kg(-1) and 0.0024-0.4500 μg kg(-1), respectively. Recoveries ranged from 70.1% to 112.8%, with the relative standard deviations (RSDs) ranging from 1.5% to 13.5%. Furthermore, the proposed method was applied to analyzing the proposed cereal samples from the fourth Chinese TDS. Eleven triazines were detected in six cereal samples with the concentrations ranging from 0.013 to 0.987 μg kg(-1). This method can also be used for the further determination of the triazines in other food group composites, and ultimately served as a methodological foundation for assessing the triazines in the average Chinese diet in the general population. PMID:23684466

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

    PubMed

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

    2015-10-01

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

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

    PubMed

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

    2015-10-01

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

  6. Development and validation of a new analytical method for the determination of 1,4-dichlorobenzene in honey by gas chromatography-isotope dilution mass spectrometry after steam-distillation.

    PubMed

    Botitsi, E V; Kormali, P N; Kontou, S N; Economou, A; Tsipi, D F

    2006-10-01

    A simple, fast, sensitive and robust analytical method using gas chromatography (GC)-isotope dilution mass spectrometry (MS) was developed and validated for the identification and quantification of 1,4-dichlorobenzene (p-DCB) residues in honey samples. The proposed methodology is based on steam-distillation using a Clevenger-type apparatus followed by gas chromatography-mass spectrometry (GC-MS) in the selected ion monitoring (SIM) mode employing the isotopically labeled analogue d4-1,4-dichlorobenzene (d4-p-DCB) as internal standard (IS). Validation of the method was performed in two different GC-MS systems, using quadrupole MS (QMS) and ion-trap MS (ITMS) detectors, with no statistically significant differences between two. Recoveries were better than 91% with percent relative standard deviations lower than 12%. The instrumental limits of detection were 1 microg kg(-1) in the GC-ITMS system and 0.6 microg kg(-1) in the GC-QMS system. The expanded uncertainty was estimated as 17% at the currently accepted "action level" of 10 microg kg(-1). The method was applied to the analysis of 310 honey samples in an extensive national monitoring study. A quality control (QC) system applied during the assays has demonstrated a good performance and long-term stability over a period of more than 8 months of continuous operation.

  7. Development and validation of a new analytical method for the determination of 1,4-dichlorobenzene in honey by gas chromatography-isotope dilution mass spectrometry after steam-distillation.

    PubMed

    Botitsi, E V; Kormali, P N; Kontou, S N; Economou, A; Tsipi, D F

    2006-10-01

    A simple, fast, sensitive and robust analytical method using gas chromatography (GC)-isotope dilution mass spectrometry (MS) was developed and validated for the identification and quantification of 1,4-dichlorobenzene (p-DCB) residues in honey samples. The proposed methodology is based on steam-distillation using a Clevenger-type apparatus followed by gas chromatography-mass spectrometry (GC-MS) in the selected ion monitoring (SIM) mode employing the isotopically labeled analogue d4-1,4-dichlorobenzene (d4-p-DCB) as internal standard (IS). Validation of the method was performed in two different GC-MS systems, using quadrupole MS (QMS) and ion-trap MS (ITMS) detectors, with no statistically significant differences between two. Recoveries were better than 91% with percent relative standard deviations lower than 12%. The instrumental limits of detection were 1 microg kg(-1) in the GC-ITMS system and 0.6 microg kg(-1) in the GC-QMS system. The expanded uncertainty was estimated as 17% at the currently accepted "action level" of 10 microg kg(-1). The method was applied to the analysis of 310 honey samples in an extensive national monitoring study. A quality control (QC) system applied during the assays has demonstrated a good performance and long-term stability over a period of more than 8 months of continuous operation. PMID:17723727

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

    USGS Publications Warehouse

    Matsumoto, A.; Hinkley, T.K.

    1997-01-01

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

  9. Assay of 25-hydroxy vitamin D3-1 alpha-hydroxylase in pig kidney mitochondria using isotope dilution-mass spectrometry

    SciTech Connect

    Holmberg, I.; Saarem, K.; Pedersen, J.I.; Bjoerkhem, I.

    1986-12-01

    An assay of 1 alpha-hydroxylation of 25-hydroxy vitamin D3 in pig kidney mitochondria, based on selected ion monitoring, has been developed. Trideuterium-labeled 1,25-dihydroxy vitamin D3 was synthesized and used as internal standard. This standard was added immediately after incubation of 25-hydroxy vitamin D3 with the mitochondrial fraction. The incubation extracts were purified by high-performance liquid chromatography. After formation of the trimethylsilyl derivative, the product was quantitated by mass fragmentography using the ion at m/z 452 and m/z 455. With the use of this assay it was found that formation of 1,25-dihydroxy vitamin D3 was linear with the amount of mitochondrial protein and time of incubation. Substrate saturation was obtained at about 20 microM of 25-hydroxy vitamin D3. The maximal rate of conversion obtained under the conditions employed was about 0.1 pmol/mg protein X minute.

  10. Helium dilution refrigeration system

    DOEpatents

    Roach, Patrick R.; Gray, Kenneth E.

    1988-01-01

    A helium dilution refrigeration system operable over a limited time period, and recyclable for a next period of operation. The refrigeration system is compact with a self-contained pumping system and heaters for operation of the system. A mixing chamber contains .sup.3 He and .sup.4 He liquids which are precooled by a coupled container containing .sup.3 He liquid, enabling the phase separation of a .sup.3 He rich liquid phase from a dilute .sup.3 He-.sup.4 He liquid phase which leads to the final stage of a dilution cooling process for obtaining low temperatures. The mixing chamber and a still are coupled by a fluid line and are maintained at substantially the same level with the still cross sectional area being smaller than that of the mixing chamber. This configuration provides maximum cooling power and efficiency by the cooling period ending when the .sup.3 He liquid is depleted from the mixing chamber with the mixing chamber nearly empty of liquid helium, thus avoiding unnecessary and inefficient cooling of a large amount of the dilute .sup.3 He-.sup.4 He liquid phase.

  11. Helium dilution refrigeration system

    DOEpatents

    Roach, P.R.; Gray, K.E.

    1988-09-13

    A helium dilution refrigeration system operable over a limited time period, and recyclable for a next period of operation is disclosed. The refrigeration system is compact with a self-contained pumping system and heaters for operation of the system. A mixing chamber contains [sup 3]He and [sup 4]He liquids which are precooled by a coupled container containing [sup 3]He liquid, enabling the phase separation of a [sup 3]He rich liquid phase from a dilute [sup 3]He-[sup 4]He liquid phase which leads to the final stage of a dilution cooling process for obtaining low temperatures. The mixing chamber and a still are coupled by a fluid line and are maintained at substantially the same level with the still cross sectional area being smaller than that of the mixing chamber. This configuration provides maximum cooling power and efficiency by the cooling period ending when the [sup 3]He liquid is depleted from the mixing chamber with the mixing chamber nearly empty of liquid helium, thus avoiding unnecessary and inefficient cooling of a large amount of the dilute [sup 3]He-[sup 4]He liquid phase. 2 figs.

  12. Dilution, Concentration, and Flotation

    ERIC Educational Resources Information Center

    Liang, Ling; Schmuckler, Joseph S.

    2004-01-01

    As both classroom teaching practice and literature show, many students have difficulties learning science concepts such as density. Here are some investigations that identify the relationship between density and floating through experimenting with successive dilution of a liquid, or the systematic change of concentration of a saltwater solution.…

  13. Effect of the detector dead-time uncertainty on the analytical result of minor elements in low-alloy steel by isotope dilution/ICP sector field mass spectrometry.

    PubMed

    Nonose, Naoko; Hioki, Akiharu; Chiba, Koichi

    2014-01-01

    In the present study the effects of the detector dead-time and its uncertainties on the accuracy and uncertainty of isotope dilution mass spectrometry (IDMS) were considered through an interlaboratory study on the analysis of low-alloy steel by using an ICP-sector field mass spectrometer. Also, an optimized mixing ratio of the sample and the spike to obtain highly precise results was theoretically and experimentally investigated. The detector dead-time used in the interlaboratory study showed a negative value. However, it less affected the trueness of the analytical result if the dead-time correction for the measured isotope ratio was done properly. As many researchers have pointed out, the detector dead-time showed a clear mass dependence. Therefore, it is desirable to check the dead-time in every target element by using assay standards or isotopic standards, which would lead to an accurate result even if the detector dead-time is a negative value. On the other hand, the effect of the uncertainty of the detector dead-time can be minimized when both isotope ratios and ICP-MS signals of the [sample + spike] blend in IDMS are equal to those of [spike + assay standard] in reverse IDMS. From standpoints of error magnification theory and the precision of the isotope ratio measurement, an optimized isotope ratio of the sample-spike blend would be 1.0 for an element with a large difference in ten times and more between the atomic fractions of two isotopes used for IDMS. In the case of an element with no significant difference between the atomic fractions of two isotopes, an optimized isotope ratio can be calculated by a formula expressed as a function of the atomic fractions of the sample and the spike as well as the signal of ICP-MS.

  14. On the association between daily mortality and air mass types in Athens, Greece during winter and summer

    NASA Astrophysics Data System (ADS)

    Kassomenos, Pavlos A.; Gryparis, Alexandros; Katsouyanni, Klea

    2007-03-01

    In this study, we examined the short-term effects of air mass types on mortality in Athens, Greece. An objective air mass types classification was used, based on meteorological parameters measured at the surface. Mortality data were treated with generalized additive models (GAM) and extending Poisson regression, using a LOESS smoother to control for the confounding effects of seasonal patterns, adjusting also for temperature, long-term trends, day of the week, and ambient particle concentrations. The introduced air mass classification explains the daily variation of mortality to a statistically significant degree. The highest daily mortality was observed on days characterized by southerly flow conditions for both the cold (increase in relative risk for mortality 9%; with a 95% confidence interval: 3-14%), and the warm period (7%; with a 95% confidence interval: 2-13%) of the year. The northeasterly flow is associated with the lowest mortality. Effects on mortality, independent of temperature, are observed mainly for lag 0 during the cold period, but persist longer during the warm period. Not adjusting for temperature and/or ambient particle levels slightly alters the results, which then reflect the known temperature and particle effects, already reported in the literature. In conclusion, we find that air mass types have independent effects on mortality for both the cold and warm season and may be used to predict weather-related adverse health effects.

  15. Caucasian children's fat mass: routine anthropometry v. air-displacement plethysmography.

    PubMed

    Michels, Nathalie; Huybrechts, Inge; Bammann, Karin; Lissner, Lauren; Moreno, Luis; Peeters, Maarten; Sioen, Isabelle; Vanaelst, Barbara; Vyncke, Krishna; De Henauw, Stefaan

    2013-04-28

    The present paper will use fat mass percentage (FM%) obtained via BOD POD® air-displacement plethysmography (FMADP%) to examine the relative validity of (1) anthropometric measurements/indices and (2) of FM% assessed with equations (FMeq%) based on skinfold thickness and bioelectrical impedance (BIA). In 480 Belgian children (aged 5-11 years) weight, height, skinfold thickness (triceps and subscapular), body circumferences (mid-upper arm, waist and hip), foot-to-foot BIA (Tanita®) and FMADP% were measured. Anthropometric measurements and calculated indices were compared with FMADP%. Next, published equations were used to calculate FMeq% using impedance (equations of Tanita®, Tyrrell, Shaefer and Deurenberg) or skinfold thickness (equations of Slaughter, Goran, Dezenberg and Deurenberg). Both indices and equations performed better in girls than in boys. For both sexes, the sum of skinfold thicknesses resulted in the highest correlation with FMADP%, followed by triceps skinfold, arm fat area and subscapular skinfold. In general, comparing FMeq% with FMADP% indicated mostly an age and sex effect, and an increasing underestimation but less dispersion with increasing FM%. The Tanita® impedance equation and the Deurenberg skinfold equation performed the best, although none of the used equations were interchangeable with FMADP%. In conclusion, the sum of triceps and subscapular skinfold thickness is recommended as marker of FM% in the absence of specialised technologies. Nevertheless, the higher workload, cost and survey management of an immobile device like the BOD POD® remains justified.

  16. Background NO/sub x/ mixing ratios in air masses over the North Atlantic ocean

    SciTech Connect

    Helas, G.; Warneck, P.

    1981-08-20

    A chemiluminescence analyzer was used to measure NO/sub x/ mixing ratios at the west coast of Ireland. Two measurement modes allowed the determination of NO and NO/sub x/ = NO+NO/sub 2/. In a third mode using a molybdenum converter, higher signals were observed than was in the second mode indicating that nitrogen compounds other than NO+NO/sub 2/ are registered. They are denoted 'excess NO/sub x/'. The average NO/sub 2/ mixing ratio for a week period was 101 +- 87 pptv. In pure marine air masses identified by means of trajectory calculations, the NO/sub 2/ mixing ratios were lower and exhibited in addition a diurnal variation with nighttime values of 37 +- 6 pptv and average values of 87 +- 47 pptv. Possible origins of the diurnal variation are discussed. For such conditions, the NO mixing ratio generally was unmeasurably small, certainly less than 10 pptv. The excess NO/sub x/ is also higher during the day compared with nighttime values of about 70 pptv. Further studies are required to identify the compounds involved.

  17. New Directions: Questions surrounding suspended particle mass used as a surrogate for air quality and for regulatory control of ambient urban air pollution

    NASA Astrophysics Data System (ADS)

    Hoare, John L.

    2014-07-01

    The original choice of particulate matter mass (PM) as a realistic surrogate for gross air pollution has gradually evolved into routine use nowadays of epidemiologically-based estimates of the monetary and other benefits expected from regulating urban air quality. Unfortunately, the statistical associations facilitating such calculations usually are based on single indices of air pollution whereas the health effects themselves are more broadly based causally. For this and other reasons the economic benefits of control tend to be exaggerated. Primarily because of their assumed inherently inferior respirability, particles ≥10 μm are generally excluded from such considerations. Where the particles themselves are chemically heterogeneous, as in an urban context, this may be inappropriate. Clearly all air-borne particles, whether coarse or fine, are susceptible to inhalation. Hence, the possibility exists for any adhering potentially harmful semi-volatile substances to be subsequently de-sorbed in vivo thereby facilitating their transport deeper into the lungs. Consequently, this alone may be a sufficient reason for including rather than rejecting during air quality monitoring the relatively coarse 10-100 μm particle fraction, ideally in conjunction with routine estimation of the gaseous co-pollutants thereby facilitating a multi-pollutant approach apropos regulation.

  18. Variations of the glacio-marine air mass front in West Greenland through water vapor isotopes

    NASA Astrophysics Data System (ADS)

    Kopec, B. G.; Lauder, A. M.; Posmentier, E. S.; Feng, X.

    2012-12-01

    While the isotopic distribution of precipitation has been widely used for research in hydrology, paleoclimatology, and ecology for decades, intensive isotopic studies of atmospheric water vapor has only recently been made possible by spectral-based technology. New instrumentation based on this technology opens up many opportunities to investigate short-term atmospheric dynamics involving the water cycle and moisture transport. We deployed a Los Gatos Water Vapor Isotope Analyzer (WVIA) at Kangerlussuaq, Greenland from July 21 to August 15, and measured the water vapor concentration and its isotopic ratios continuously at 10s intervals. A Danish Meteorological Institute site is located about 1 km from the site of the deployment, and meteorological data is collected at 30 min intervals. During the observation period, the vapor concentration of the ambient air ranges from 5608.4 to 11189.4 ppm; dD and d18O range from -254.5 to -177.7 ‰ and -34.2 to -23.2 ‰, respectively. The vapor content (dew point) and the isotopic ratios are both strongly controlled by the wind direction. The easterly winds are associated with dry, isotopically depleted air masses formed over the glacier, while westerly winds are associated with moist and isotopically enriched air masses from the marine/fjord surface. This region typically experiences katabatic winds off of the ice sheet to the east. However, during some afternoons, the wind shifts 180 degrees, blowing off the fjord to the west. This wind switch marks the onset of a sea breeze, and significant isotopic enrichment results. Enrichment in deuterium is up to 60 ‰ with a mean of 15‰, and oxygen-18 is enriched by 3‰ on average and up to 8 ‰. Other afternoons have no change in wind, and only small changes in humidity and vapor isotopic ratios. The humidity and isotopic variations suggest the local atmosphere circulation is dominated by relatively high-pressure systems above the cold glaciers and cool sea surface, and diurnal

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

    PubMed

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

    2015-04-01

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

  20. The impact of mass flow and masking on the pressure drop of air filter in heavy-duty diesel engine

    NASA Astrophysics Data System (ADS)

    Hoseeinzadeh, Sepideh; Gorji-Bandpy, Mofid

    2012-04-01

    This paper presents a computational fluid dynamics (CFD) calculation approach to predict and evaluate the impact of the mass-flow inlet on the pressure drop of turbocharger`s air filtfer in heavy-duty diesel engine. The numerical computations were carried out using a commercial CFD program whereas the inlet area of the air filter consisted of several holes connected to a channel. After entering through the channel, the air passes among the holes and enters the air filter. The effect of masking holes and hydraulic diameter is studied and investigated on pressure drop. The results indicate that pressure drop increase with decreasing of hydraulic diameter and masking of the holes has considerable affect on the pressure drop.

  1. Fast and solvent-free quantitation of boar taint odorants in pig fat by stable isotope dilution analysis-dynamic headspace-thermal desorption-gas chromatography/time-of-flight mass spectrometry.

    PubMed

    Fischer, Jochen; Haas, Torsten; Leppert, Jan; Lammers, Peter Schulze; Horner, Gerhard; Wüst, Matthias; Boeker, Peter

    2014-09-01

    Boar taint is a specific off-odour of boar meat products, known to be caused by at least three unpleasant odorants, with very low odour thresholds. Androstenone is a boar pheromone produced in the testes, whereas skatole and indole originate from the microbial breakdown of tryptophan in the intestinal tract. A new procedure, applying stable isotope dilution analysis (SIDA) and dynamic headspace-thermal desorption-gas chromatography/time-of-flight mass spectrometry (dynHS-TD-GC/TOFMS) for the simultaneous quantitation of these boar taint compounds in pig fat was elaborated and validated in this paper. The new method is characterised by a simple and solvent-free dynamic headspace sampling. The deuterated compounds d3-androstenone, d3-skatole and d6-indole were used as internal standards to eliminate matrix effects. The method validation performed revealed low limits of detection (LOD) and quantitation (LOQ) with high accuracy and precision, thus confirming the feasibility of the new dynHS-TD-GC/TOFMS approach for routine analysis. PMID:24731353

  2. Analysis of natural-occurring and synthetic sexual hormones in sludge-amended soils by matrix solid-phase dispersion and isotope dilution gas chromatography-tandem mass spectrometry.

    PubMed

    Albero, Beatriz; Sánchez-Brunete, Consuelo; Miguel, Esther; Pérez, Rosa A; Tadeo, José L

    2013-03-29

    A sensitive analytical method is presented for the simultaneous determination of four synthetic estrogens and six steroid hormones in sludge-amended soil. The method employs matrix solid-phase dispersion (MSPD) followed by isotope dilution gas chromatography-tandem mass spectrometry injecting a large volume sample (10μL) after trimethylsilyl derivatization, using the solvent vent mode. It affords good resolution, high sensitivity and reproducibility and freedom from interferences even from complex matrices as soil amended with sewage sludge. The limits of detection (LODs) ranged from 10 to 300pgg(-1) with testosterone and progesterone having the highest limits. Soil amended with sewage sludge was spiked at 2, 10, 25 and 50ngg(-1) and the recoveries after MSPD with acetonitrile:methanol (90:10, v/v), ranged from 80 to 110% with relative standard deviations ≤9%. The method was applied to the analysis of six soil samples collected from agricultural plots and forested fields that had been amended with sewage sludge using isotopically labeled surrogates. Three of the synthetic estrogens studied were found at least in one of the six samples analyzed and trans-androsterone and estrone were the only natural hormones detected, although at very low levels (≤0.4ngg(-1)). PMID:23465128

  3. Automated on-line column-switching high performance liquid chromatography isotope dilution tandem mass spectrometry method for the quantification of bisphenol A, bisphenol F, bisphenol S, and 11 other phenols in urine.

    PubMed

    Zhou, Xiaoliu; Kramer, Joshua P; Calafat, Antonia M; Ye, Xiaoyun

    2014-01-01

    Human exposure to bisphenol A (BPA) is widespread. However, in recent years, bisphenol analogs such as bisphenol S (BPS) and bisphenol F (BPF) are replacing BPA in the production of some consumer products. Because human exposure to these alternative bisphenols may occur, biomonitoring of these bisphenol analogs is warranted. In the present study, we developed and validated a sensitive and selective method that uses on-line solid phase extraction coupled to high performance liquid chromatography-isotope dilution tandem mass spectrometry with peak focusing to measure BPA, BPF, BPS, and 11 other environmental phenols in urine. The method required a small amount of sample (100μL) and minimal sample pretreatment. The limits of detection were 0.03ng/mL (BPS), 0.06ng/mL (BPF), 0.10ng/mL (BPA), and ranged from 0.1ng/mL to 1.0ng/mL for the other 11 phenols. In 100 urine samples collected in 2009-2012 from a convenience group of anonymous adults in the United States, of the three bisphenols, we detected BPA at the highest frequency and median concentrations (95%, 0.72ng/mL), followed by BPS (78%, 0.13ng/mL) and BPF (55%, 0.08ng/mL). This sensitive, rugged, and labor and cost-effective method could be used for the analysis of large number of samples for epidemiologic studies.

  4. Simultaneous measurement of testosterone, androstenedione and dehydroepiandrosterone (DHEA) in serum and plasma using Isotope-Dilution 2-Dimension Ultra High Performance Liquid-Chromatography Tandem Mass Spectrometry (ID-LC-MS/MS).

    PubMed

    Büttler, Rahel M; Martens, Frans; Kushnir, Mark M; Ackermans, Mariette T; Blankenstein, Marinus A; Heijboer, Annemieke C

    2015-01-01

    The adrenal and gonadal androgens, testosterone, androstenedione and dehydroepiandrosterone (DHEA) play an important role in sexual development as well as in other processes. We developed a method for simultaneous quantitative analysis of serum and plasma testosterone, androstenedione and DHEA levels using Isotope-Dilution Liquid-Chromatography Tandem Mass Spectrometry (ID-LC-MS/MS). Samples underwent liquid-liquid extraction and were analyzed on an Acquity 2D-UPLC-System and a Xevo TQ-S tandem mass spectrometer (Waters). The intra-assay and inter-assay coefficients of variation were <4.0%, <6.3% and <7.0% and <6.0%, <8.1% and <7.7% for testosterone, androstenedione and DHEA, respectively. Inter-assay CVs at the lower limit were 10.6%, 16.9% and 9.0% for testosterone (0.10nmol/L), androstenedione (0.10nmol/L) and DHEA (1.0nmol/L), respectively. Recoveries of spiked analytes were 93-107%. The present testosterone method compared well (y=1.00x-0.04; r=0.998) to a published ID-LC-MS/MS method for testosterone in our lab. The latter method being concordant with a published reference method (Bui et al., 2013). The present method compared well to a published ID-LC-MS/MS method (Kushnir et al., 2010) (y=1.06x-0.06; r=0.996 for testosterone; y=1.04x-0.04; r=0.995 for androstenedione and y=1.03x+0.01; r=0.991 for DHEA). In conclusion, we developed a sensitive and accurate ID-LC-MS/MS method to simultaneously measure serum testosterone, androstenedione and DHEA in serum and plasma.

  5. Development, validation and application of a stable isotope dilution liquid chromatography electrospray ionization/selected reaction monitoring/mass spectrometry (SID-LC/ESI/SRM/MS) method for quantification of keto-androgens in human serum.

    PubMed

    Tamae, Daniel; Byrns, Michael; Marck, Brett; Mostaghel, Elahe A; Nelson, Peter S; Lange, Paul; Lin, Daniel; Taplin, Mary-Ellen; Balk, Steven; Ellis, William; True, Larry; Vessella, Robert; Montgomery, Bruce; Blair, Ian A; Penning, Trevor M

    2013-11-01

    Prostate cancer is the most frequently diagnosed form of cancer in males in the United States. The disease is androgen driven and the use of orchiectomy or chemical castration, known as androgen deprivation therapy (ADT) has been employed for the treatment of advanced prostate cancer for over 70 years. Agents such as GnRH agonists and non-steroidal androgen receptor antagonists are routinely used in the clinic, but eventually relapse occurs due to the emergence of castration-resistant prostate cancer. With the appreciation that androgen signaling still persists in these patients and the development of new therapies such as abiraterone and enzalutamide that further suppresses androgen synthesis or signaling, there is a renewed need for sensitive and specific methods to quantify androgen precursor and metabolite levels to assess drug efficacy. We describe the development, validation and application of a stable isotope dilution liquid chromatography electrospray ionization selected reaction monitoring mass spectrometry (SID-LC/ESI/SRM/MS) method for quantification of serum keto-androgens and their sulfate and glucuronide conjugates using Girard-T oxime derivatives. The method is robust down to 0.2-4pg on column, depending on the androgen metabolite quantified, and can also quantify dehydroepiandrosterone sulfate (DHEA-S) in only 1μL of serum. The clinical utility of this method was demonstrated by analyzing serum androgens from patients enrolled in a clinical trial assessing combinations of pharmacological agents to maximally suppress gonadal and adrenal androgens (Targeted Androgen Pathway Suppression, TAPS clinical trial). The method was validated by correlating the results obtained with a hydroxylamine derivatization procedure coupled with tandem mass spectrometry using selected reaction monitoring that was conducted in an independent laboratory.

  6. Band anticrossing in dilute nitrides

    SciTech Connect

    Shan, W.; Yu, K.M.; Walukiewicz, W.; Wu, J.; Ager III, J.W.; Haller, E.E.

    2003-12-23

    Alloying III-V compounds with small amounts of nitrogen leads to dramatic reduction of the fundamental band-gap energy in the resulting dilute nitride alloys. The effect originates from an anti-crossing interaction between the extended conduction-band states and localized N states. The interaction splits the conduction band into two nonparabolic subbands. The downward shift of the lower conduction subband edge is responsible for the N-induced reduction of the fundamental band-gap energy. The changes in the conduction band structure result in significant increase in electron effective mass and decrease in the electron mobility, and lead to a large enhance of the maximum doping level in GaInNAs doped with group VI donors. In addition, a striking asymmetry in the electrical activation of group IV and group VI donors can be attributed to mutual passivation process through formation of the nearest neighbor group-IV donor nitrogen pairs.

  7. Chiral Signatures of Anthropogenic Semi-Volatile Organic Compounds in Asian, trans- Pacific, and Pacific Northwestern Air Masses

    NASA Astrophysics Data System (ADS)

    Genualdi, S.; Primbs, T.; Bidleman, T.; Jantunen, L.; Simonich, S.

    2006-12-01

    The goal of this research is to use the chiral signatures of Semi-Volatile Organic Compounds (SOCs) to distinguish between new and old sources in Asian, trans-Pacific, and regional air masses. During 2004, a six week air sampling campaign was conducted at a remote site in Okinawa, Japan to determine the chemical composition of Eurasian air masses. During 2003 and 2004, high volume air samples were collected at three different locations in the Pacific Northwest of the United States. These sampling locations were; Mary's Peak Observatory (MPO) located at 1250m in the Oregon Coast Range, Mt. Bachelor located at 2800m in Oregon's Cascade Range, and Cheeka Peak Observatory (CPO) located at 500m in the state of Washington. The air samples consisted of both polyurethane foam and XAD-2 resin to collect the gas phase SOCs, and glass fiber filters to collect the particulate phase SOCs. The samples were extracted using accelerated solvent extraction and enantiomer fractions were determined using GCMS-ECNI with the use of a BGB Analytik chiral column. The chiral SOCs, á-Hexachlorocyclohexane, cis and trans chlordane, heptachlor epoxide, and o'p' DDT, were measured, the enantiomer ratios were determined, and potential new and historical sources of these compounds were identified.

  8. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    SciTech Connect

    Morrison, Glenn C.

    1999-12-01

    {sup {minus}7}, 10{sup {minus}5}, and 10{sup {minus}5} respectively. To understand how internal surface area influences the equivalent reaction probability of whole carpet, a model of ozone diffusion into and reaction with internal carpet components was developed. This was then used to predict apparent reaction probabilities for carpet. He combines this with a modified model of turbulent mass transfer developed by Liu, et al. to predict deposition rates and indoor ozone concentrations. The model predicts that carpet should have an equivalent reaction probability of about 10{sup {minus}5}, matching laboratory measurements of the reaction probability. For both carpet and duct materials, surfaces become progressively quenched (aging), losing the ability to react or otherwise take up ozone. He evaluated the functional form of aging and find that the reaction probability follows a power function with respect to the cumulative uptake of ozone. To understand ozone aging of surfaces, he developed several mathematical descriptions of aging based on two different mechanisms. The observed functional form of aging is mimicked by a model which describes ozone diffusion with internal reaction in a solid. He shows that the fleecy nature of carpet materials in combination with the model of ozone diffusion below a fiber surface and internal reaction may explain the functional form and the magnitude of power function parameters observed due to ozone interactions with carpet. The ozone induced aldehyde emissions, measured from duct materials, were combined with an indoor air quality model to show that concentrations of aldehydes indoors may approach odorous levels. He shows that ducts are unlikely to be a significant sink for ozone due to the low reaction probability in combination with the short residence time of air in ducts.

  9. Overview of aerosol properties associated with air masses sampled by the ATR-42 during the EUCAARI campaign (2008)

    NASA Astrophysics Data System (ADS)

    Crumeyrolle, S.; Schwarzenboeck, A.; Roger, J. C.; Sellegri, K.; Burkhart, J. F.; Stohl, A.; Gomes, L.; Quennehen, B.; Roberts, G.; Weigel, R.; Villani, P.; Pichon, J. M.; Bourrianne, T.; Laj, P.

    2013-05-01

    Within the frame of the European Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) project, the Météo-France aircraft ATR-42 performed 22 research flights over central Europe and the North Sea during the intensive observation period in May 2008. For the campaign, the ATR-42 was equipped to study the aerosol physical, chemical, hygroscopic and optical properties, as well as cloud microphysics. For the 22 research flights, retroplume analyses along the flight tracks were performed with FLEXPART in order to classify air masses into five sectors of origin, allowing for a qualitative evaluation of emission influence on the respective air parcel. This study shows that the extensive aerosol parameters (aerosol mass and number concentrations) show vertical decreasing gradients and in some air masses maximum mass concentrations (mainly organics) in an intermediate layer (1-3 km). The observed mass concentrations (in the boundary layer (BL): between 10 and 30 μg m-3; lower free troposphere (LFT): 0.8 and 14 μg m-3) are high especially in comparison with the 2015 European norms for PM2.5 (25 μg m-3) and with previous airborne studies performed over England (Morgan et al., 2009; McMeeking et al., 2012). Particle number size distributions show a larger fraction of particles in the accumulation size range in the LFT compared to BL. The chemical composition of submicron aerosol particles is dominated by organics in the BL, while ammonium sulphate dominates the submicron aerosols in the LFT, especially in the aerosol particles originated from north-eastern Europe (~ 80%), also experiencing nucleation events along the transport. As a consequence, first the particle CCN acting ability, shown by the CCN/CN ratio, and second the average values of the scattering cross sections of optically active particles (i.e. scattering coefficient divided by the optical active particle concentration) are increased in the LFT compared to BL.

  10. Influence of the ozone profile above Madrid (Spain) on Brewer estimation of ozone air mass factor

    NASA Astrophysics Data System (ADS)

    Antón, M.; López, M.; Costa, M. J.; Serrano, A.; Bortoli, D.; Bañón, M.; Vilaplana, J. M.; Silva, A. M.

    2009-08-01

    The methodology used by Brewer spectroradiometers to estimate the ozone column is based on differential absorption spectroscopy. This methodology employs the ozone air mass factor (AMF) to derive the total ozone column from the slant path ozone amount. For the calculating the ozone AMF, the Brewer algorithm assumes that the ozone layer is located at a fixed height of 22 km. However, for a real specific site the ozone presents a certain profile, which varies spatially and temporally depending on the latitude, altitude and dynamical conditions of the atmosphere above the site of measurements. In this sense, this work address the reliability of the mentioned assumption and analyses the influence of the ozone profiles measured above Madrid (Spain) in the ozone AMF calculations. The approximated ozone AMF used by the Brewer algorithm is compared with simulations obtained using the libRadtran radiative transfer model code. The results show an excellent agreement between the simulated and the approximated AMF values for solar zenith angle lower than 75°. In addition, the relative differences remain lower than 2% at 85°. These good results are mainly due to the fact that the altitude of the ozone layer assumed constant by the Brewer algorithm for all latitudes notably can be considered representative of the real profile of ozone above Madrid (average value of 21.7±1.8 km). The operational ozone AMF calculations for Brewer instruments are limited, in general, to SZA below 80°. Extending the usable SZA range is especially relevant for Brewer instruments located at high mid-latitudes.

  11. An automated gas chromatography time-of-flight mass spectrometry instrument for the quantitative analysis of halocarbons in air

    NASA Astrophysics Data System (ADS)

    Obersteiner, F.; Bönisch, H.; Engel, A.

    2015-09-01

    We present the characterization and application of a new gas chromatography-time-of-flight mass spectrometry instrument (GC-TOFMS) for the quantitative analysis of halocarbons in air samples. The setup comprises three fundamental enhancements compared to our earlier work (Hoker et al., 2015): (1) full automation, (2) a mass resolving power R = m/Δ m of the TOFMS (Tofwerk AG, Switzerland) increased up to 4000 Th/Th and (3) a fully accessible data format of the mass spectrometric data. Automation in combination with the accessible data allowed an in-depth characterization of the instrument. Mass accuracy was found around 5 ppm after automatic recalibration of the mass axis in each measurement. A TOFMS configuration giving R = 3500 was chosen to provide an R-to-sensitivity ratio suitable for our purpose. Calculated detection limits were as low as a few femtograms as mass traces could be made highly specific for selected molecule fragments with the accurate mass information. The precision for substance quantification was 0.15 % at the best for an individual measurement and in general mainly determined by the signal-to-noise ratio of the chromatographic peak. The TOFMS was found to be linear within a concentration range from about 1 pg to 1 ng of analyte per Liter of air. At higher concentrations, non-linearities of a few percent were observed (precision level: 0.2 %) but could be attributed to a potential source within the detection system. A straight-forward correction for those non-linearities was applied in data processing, again by exploiting the accurate mass information. Based on the overall characterization results, the GC-TOFMS instrument was found to be very well-suited for the task of quantitative halocarbon trace gas observation and a big step forward compared to scanning, low resolution quadrupole MS and a TOFMS technique reported to be non-linear and restricted by a small dynamical range.

  12. Interdecadal linkages between Pacific decadal oscillation and interhemispheric air mass oscillation and their possible connections with East Asian Monsoon

    NASA Astrophysics Data System (ADS)

    Lu, C.

    2015-12-01

    The Pacific decadal oscillation (PDO) recently emerged in the literature as a robust signal in the Northern Hemisphere climate variability. Many studies reported that the relationships between PDO and East Asian monsoon (EAM) and climate variability in China are significant. However, the possible mechanisms are still unclear. The present study investigates the interdecadal relationship between Pacific decadal oscillation (PDO) and interhemispheric air mass imbalance or oscillation (IHO) between the Northern and Southern Hemispheres. The possible connection of PDO and IHO with both East Asian monsoon and climate variability in China are also assessed in this study. It is found that the interdecadal components (11-38 years) of PDO, IHO, and EAM contribute large variance to low frequency variations, and they are well-matched with each other on (inter)decadal timescale. In particular, their negative phases mainly appeared in the 1970s and late 1990s, while positive phase in period from 1980s to mid 1990s. Decadal change of global mean air columnar temperature may be the key factor for the notable difference between PDO and IHO from mid 1970s to mid 1990s. The spatial distributions of PDO and IHO associated surface air temperature and surface pressure anomalies exhibit highly similar and large scale characteristics, indicative of their intimate linkage with air mass redistribution over global domain especially over 300S-500N. The PDO associated columnar integral of velocity potential anomalies that maintain the air mass redistribution, show a dipole pattern with air mass flux emanating mainly from the eastern hemisphere to the Pacific regions in positive PDO phase. This contributes to hemispherical and land-sea mass exchange and redistribution, and also leads to the decadal displacement of both upward and downward branch of Walker circulation. In positive phase of PDO, an anomalous anticyclone is found in the Mongolian region in both boreal summer and winter seasons

  13. Influence of air mass source region on nanoparticle events and hygroscopicity in central Virginia, U.S.

    NASA Astrophysics Data System (ADS)

    O'Halloran, T. L.; Fuentes, J. D.; Collins, D. R.; Cleveland, M. J.; Keene, W. C.

    During autumn, 2006, variation in the frequency of aerosol nucleation events, as inferred from nanoparticle growth events, and associated hygroscopicity were investigated as a function of air mass transport history at a mixed deciduous forest in central Virginia, U.S. Above-canopy size distributions of aerosols between 0.012 and 0.700 μm diameter, size-resolved particle hygroscopicity at eight dry diameters between 0.012 and 0.400 μm, and cloud condensation nuclei (CCN) activity were characterized. Air mass back trajectories were clustered to identify source regions. Growth events were most frequent in fast-moving air masses (mean = 9 m s -1) that originated over the north central U.S. Under these flow regimes, mean values for preexisting sub-μm aerosol number concentrations (4700 cm -3), corresponding surface area (142 μm 2 cm -3), air temperature (6.2 °C), and relative humidity (RH, 49.4%) were relatively low compared to other regimes. Under stagnant flow conditions (mean = 3 m s -1), mean number concentrations were higher (>6000 cm -3) and size fractions <0.1 μm diameter exhibited enhanced hygroscopicity compared to other source regions. These results indicate that precursors emitted into relatively clean, cold, and dry air transported over the southeastern U.S. reacted to form condensable intermediates that subsequently produced new aerosols via nucleation and growth. This pathway was an important source for CCN. During events in October, nanoparticles were produced in greater numbers and grew more rapidly compared to November and December.

  14. On the relationship between Arctic ice clouds and polluted air masses over the North Slope of Alaska in April 2008

    NASA Astrophysics Data System (ADS)

    Jouan, C.; Pelon, J.; Girard, E.; Ancellet, G.; Blanchet, J. P.; Delanoë, J.

    2014-02-01

    Recently, two types of ice clouds (TICs) properties have been characterized using the Indirect and Semi-Direct Aerosol Campaign (ISDAC) airborne measurements (Alaska, April 2008). TIC-2B were characterized by fewer (< 10 L-1) and larger (> 110 μm) ice crystals, and a larger ice supersaturation (> 15%) compared to TIC-1/2A. It has been hypothesized that emissions of SO2 may reduce the ice nucleating properties of ice nuclei (IN) through acidification, resulting in a smaller concentration of larger ice crystals and leading to precipitation (e.g., cloud regime TIC-2B). Here, the origin of air masses forming the ISDAC TIC-1/2A (1 April 2008) and TIC-2B (15 April 2008) is investigated using trajectory tools and satellite data. Results show that the synoptic conditions favor air masses transport from three potential SO2 emission sources into Alaska: eastern China and Siberia where anthropogenic and biomass burning emissions, respectively, are produced, and the volcanic region of the Kamchatka/Aleutians. Weather conditions allow the accumulation of pollutants from eastern China and Siberia over Alaska, most probably with the contribution of acidic volcanic aerosol during the TIC-2B period. Observation Monitoring Instrument (OMI) satellite observations reveal that SO2 concentrations in air masses forming the TIC-2B were larger than in air masses forming the TIC-1/2A. Airborne measurements show high acidity near the TIC-2B flight where humidity was low. These results support the hypothesis that acidic coating on IN could be at the origin of the formation of TIC-2B.

  15. On the relationship between Arctic ice clouds and polluted air masses over the north slope of Alaska in April 2008

    NASA Astrophysics Data System (ADS)

    Jouan, C.; Pelon, J.; Girard, E.; Ancellet, G.; Blanchet, J. P.; Delanoë, J.

    2013-02-01

    Recently, two Types of Ice Clouds (TICs) properties have been characterized using ISDAC airborne measurements (Alaska, April 2008). TIC-2B were characterized by fewer (<10 L-1) and larger (>110 μm) ice crystals, a larger ice supersaturation (>15%) and a fewer ice nuclei (IN) concentration (<2 order of magnitude) when compared to TIC-1/2A. It has been hypothesized that emissions of SO2 may reduce the ice nucleating properties of IN through acidification, resulting to a smaller concentration of larger ice crystals and leading to precipitation (e.g. cloud regime TIC-2B) because of the reduced competition for the same available moisture. Here, the origin of air masses forming the ISDAC TIC-1/2A (1 April 2008) and TIC-2B (15 April 2008) is investigated using trajectory tools and satellite data. Results show that the synoptic conditions favor air masses transport from the three potentials SO2 emission areas to Alaska: eastern China and Siberia where anthropogenic and biomass burning emission respectively are produced and the volcanic region from the Kamchatka/Aleutians. Weather conditions allow the accumulation of pollutants from eastern China/Siberia over Alaska, most probably with the contribution of acid volcanic aerosol during the TIC-2B period. OMI observations reveal that SO2 concentrations in air masses forming the TIC-2B were larger than in air masses forming the TIC-1/2A. Airborne measurements show high acidity near the TIC-2B flight where humidity was low. These results strongly support the hypothesis that acidic coating on IN are at the origin of the formation of TIC-2B.

  16. Highly sensitive isotope-dilution liquid-chromatography-electrospray ionization-tandem-mass spectrometry approach to study the drug-mediated modulation of dopamine and serotonin levels in Caenorhabditis elegans.

    PubMed

    Schumacher, Fabian; Chakraborty, Sudipta; Kleuser, Burkhard; Gulbins, Erich; Schwerdtle, Tanja; Aschner, Michael; Bornhorst, Julia

    2015-11-01

    Dopamine (DA) and serotonin (SRT) are monoamine neurotransmitters that play a key role in regulating the central and peripheral nervous system. Their impaired metabolism has been implicated in several neurological disorders, such as Parkinson's disease and depression. Consequently, it is imperative to monitor changes in levels of these low-abundant neurotransmitters and their role in mediating disease. For the first time, a rapid, specific and sensitive isotope-dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for the quantification of DA and SRT in the nematode Caenorhabditis elegans (C. elegans). This model organism offers a unique approach for studying the effect of various drugs and environmental conditions on neurotransmitter levels, given by the conserved DA and SRT biology, including synaptic release, trafficking and formation. We introduce a novel sample preparation protocol incorporating the usage of sodium thiosulfate in perchloric acid as extraction medium that assures high recovery of the relatively unstable neurotransmitters monitored. Moreover, the use of both deuterated internal standards and the multiple reaction monitoring (MRM) technique allows for unequivocal quantification. Thereby, to the best of our knowledge, we achieve a detection sensitivity that clearly exceeds those of published DA and SRT quantification methods in various matrices. We are the first to show that exposure of C. elegans to the monoamine oxidase B (MAO-B) inhibitor selegiline or the catechol-O-methyltransferase (COMT) inhibitor tolcapone, in order to block DA and SRT degradation, resulted in accumulation of the respective neurotransmitter. Assessment of a behavioral output of the dopaminergic system (basal slowing response) corroborated the analytical LC-MS/MS data. Thus, utilization of the C. elegans model system in conjunction with our analytical method is well-suited to investigate drug-mediated modulation of the DA and

  17. Highly sensitive isotope-dilution liquid-chromatography-electrospray ionization-tandem-mass spectrometry approach to study the drug-mediated modulation of dopamine and serotonin levels in Caenorhabditis elegans.

    PubMed

    Schumacher, Fabian; Chakraborty, Sudipta; Kleuser, Burkhard; Gulbins, Erich; Schwerdtle, Tanja; Aschner, Michael; Bornhorst, Julia

    2015-11-01

    Dopamine (DA) and serotonin (SRT) are monoamine neurotransmitters that play a key role in regulating the central and peripheral nervous system. Their impaired metabolism has been implicated in several neurological disorders, such as Parkinson's disease and depression. Consequently, it is imperative to monitor changes in levels of these low-abundant neurotransmitters and their role in mediating disease. For the first time, a rapid, specific and sensitive isotope-dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for the quantification of DA and SRT in the nematode Caenorhabditis elegans (C. elegans). This model organism offers a unique approach for studying the effect of various drugs and environmental conditions on neurotransmitter levels, given by the conserved DA and SRT biology, including synaptic release, trafficking and formation. We introduce a novel sample preparation protocol incorporating the usage of sodium thiosulfate in perchloric acid as extraction medium that assures high recovery of the relatively unstable neurotransmitters monitored. Moreover, the use of both deuterated internal standards and the multiple reaction monitoring (MRM) technique allows for unequivocal quantification. Thereby, to the best of our knowledge, we achieve a detection sensitivity that clearly exceeds those of published DA and SRT quantification methods in various matrices. We are the first to show that exposure of C. elegans to the monoamine oxidase B (MAO-B) inhibitor selegiline or the catechol-O-methyltransferase (COMT) inhibitor tolcapone, in order to block DA and SRT degradation, resulted in accumulation of the respective neurotransmitter. Assessment of a behavioral output of the dopaminergic system (basal slowing response) corroborated the analytical LC-MS/MS data. Thus, utilization of the C. elegans model system in conjunction with our analytical method is well-suited to investigate drug-mediated modulation of the DA and

  18. Quantification of viral proteins of the avian H7 subtype of influenza virus: an isotope dilution mass spectrometry method applicable for producing more rapid vaccines in the case of an influenza pandemic.

    PubMed

    Santana, Wanda I; Williams, Tracie L; Winne, Emily K; Pirkle, James L; Barr, John R

    2014-05-01

    Vaccination is the most effective means to prevent influenza and its serious complications. Influenza viral strains undergo rapid mutations of the surface proteins hemagglutinin (HA) and neuraminidase (NA) requiring vaccines to be frequently updated to include current circulating strains. It is nearly impossible to predict which strains will be circulating in the next influenza season. It is, therefore, imperative that the process of producing a vaccine be streamlined and as swift as possible. We have developed an isotope dilution mass spectrometry (IDMS) method to quantify HA and NA in H7N7, H7N2, and H7N9 influenza. The IDMS method involves enzymatic digestion of viral proteins and the specific detection of evolutionarily conserved target peptides. The four target peptides that were initially chosen for analysis of the HA protein of H7N2 and H7N7 subtypes were conserved and available for analysis of the H7N9 subtype that circulated in China in the spring of 2013. Thus, rapid response to the potential pandemic was realized. Quantification of a protein is performed by employing multiple peptides to ensure that the enzymatic digestion of the protein is efficient in the region of the target peptides, verify the accuracy of the measurement, and provide flexibility in the case of amino acid changes among newly emerging strains. The IDMS method is an accurate, sensitive, and selective method to quantify the amount of HA and NA antigens in primary liquid standards, crude allantoic fluid, purified virus samples, and final vaccine presentations.

  19. Features of air masses associated with the deposition of Pseudomonas syringae and Botrytis cinerea by rain and snowfall.

    PubMed

    Monteil, Caroline L; Bardin, Marc; Morris, Cindy E

    2014-11-01

    Clarifying the role of precipitation in microbial dissemination is essential for elucidating the processes involved in disease emergence and spread. The ecology of Pseudomonas syringae and its presence throughout the water cycle makes it an excellent model to address this issue. In this study, 90 samples of freshly fallen rain and snow collected from 2005-2011 in France were analyzed for microbiological composition. The conditions favorable for dissemination of P. syringae by this precipitation were investigated by (i) estimating the physical properties and backward trajectories of the air masses associated with each precipitation event and by (ii) characterizing precipitation chemistry, and genetic and phenotypic structures of populations. A parallel study with the fungus Botrytis cinerea was also performed for comparison. Results showed that (i) the relationship of P. syringae to precipitation as a dissemination vector is not the same for snowfall and rainfall, whereas it is the same for B. cinerea and (ii) the occurrence of P. syringae in precipitation can be linked to electrical conductivity and pH of water, the trajectory of the air mass associated with the precipitation and certain physical conditions of the air mass (i.e. temperature, solar radiation exposure, distance traveled), whereas these predictions are different for B. cinerea. These results are pertinent to understanding microbial survival, emission sources and atmospheric processes and how they influence microbial dissemination.

  20. Influence of power ultrasound application on mass transport and microstructure of orange peel during hot air drying

    NASA Astrophysics Data System (ADS)

    Ortuño, Carmen; Pérez-Munuera, Isabel; Puig, Ana; Riera, Enrique; Garcia-Perez, J. V.

    2010-01-01

    Power ultrasound application on convective drying of foodstuffs may be considered an emergent technology. This work deals with the influence of power ultrasound on drying of natural materials addressing the kinetic as well as the product's microstructure. Convective drying kinetics of orange peel slabs (thickness 5.95±0.41 mm) were carried out at 40 ∘C and 1 m/s with (US) and without (AIR) power ultrasound application. A diffusion model considering external resistance to mass transfer was considered to describe drying kinetics. Fresh, US and AIR dried samples were analyzed using Cryo-SEM. Results showed that drying kinetics of orange peel were significantly improved by the application of power ultrasound. From modeling, it was observed a significant (p¡0.05) increase in both mass transfer coefficient and effective moisture diffusivity. The effects on mass transfer properties were confirmed from microestructural observations. In the cuticle surface, the pores were obstructed by wax components scattering, which evidence the ultrasonic effects on the interfaces. The cells of the flavedo were compressed and large intercellular air spaces were generated in the albedo facilitating water transfer through it.

  1. Features of air masses associated with the deposition of Pseudomonas syringae and Botrytis cinerea by rain and snowfall

    PubMed Central

    Monteil, Caroline L; Bardin, Marc; Morris, Cindy E

    2014-01-01

    Clarifying the role of precipitation in microbial dissemination is essential for elucidating the processes involved in disease emergence and spread. The ecology of Pseudomonas syringae and its presence throughout the water cycle makes it an excellent model to address this issue. In this study, 90 samples of freshly fallen rain and snow collected from 2005–2011 in France were analyzed for microbiological composition. The conditions favorable for dissemination of P. syringae by this precipitation were investigated by (i) estimating the physical properties and backward trajectories of the air masses associated with each precipitation event and by (ii) characterizing precipitation chemistry, and genetic and phenotypic structures of populations. A parallel study with the fungus Botrytis cinerea was also performed for comparison. Results showed that (i) the relationship of P. syringae to precipitation as a dissemination vector is not the same for snowfall and rainfall, whereas it is the same for B. cinerea and (ii) the occurrence of P. syringae in precipitation can be linked to electrical conductivity and pH of water, the trajectory of the air mass associated with the precipitation and certain physical conditions of the air mass (i.e. temperature, solar radiation exposure, distance traveled), whereas these predictions are different for B. cinerea. These results are pertinent to understanding microbial survival, emission sources and atmospheric processes and how they influence microbial dissemination. PMID:24722630

  2. Constraining Aerosol Optical Models Using Ground-Based, Collocated Particle Size and Mass Measurements in Variable Air Mass Regimes During the 7-SEAS/Dongsha Experiment

    NASA Technical Reports Server (NTRS)

    Bell, Shaun W.; Hansell, Richard A.; Chow, Judith C.; Tsay, Si-Chee; Wang, Sheng-Hsiang; Ji, Qiang; Li, Can; Watson, John G.; Khlystov, Andrey

    2012-01-01

    During the spring of 2010, NASA Goddard's COMMIT ground-based mobile laboratory was stationed on Dongsha Island off the southwest coast of Taiwan, in preparation for the upcoming 2012 7-SEAS field campaign. The measurement period offered a unique opportunity for conducting detailed investigations of the optical properties of aerosols associated with different air mass regimes including background maritime and those contaminated by anthropogenic air pollution and mineral dust. What appears to be the first time for this region, a shortwave optical closure experiment for both scattering and absorption was attempted over a 12-day period during which aerosols exhibited the most change. Constraints to the optical model included combined SMPS and APS number concentration data for a continuum of fine and coarse-mode particle sizes up to PM2.5. We also take advantage of an IMPROVE chemical sampler to help constrain aerosol composition and mass partitioning of key elemental species including sea-salt, particulate organic matter, soil, non sea-salt sulphate, nitrate, and elemental carbon. Our results demonstrate that the observed aerosol scattering and absorption for these diverse air masses are reasonably captured by the model, where peak aerosol events and transitions between key aerosols types are evident. Signatures of heavy polluted aerosol composed mostly of ammonium and non sea-salt sulphate mixed with some dust with transitions to background sea-salt conditions are apparent in the absorption data, which is particularly reassuring owing to the large variability in the imaginary component of the refractive indices. Extinctive features at significantly smaller time scales than the one-day sample period of IMPROVE are more difficult to reproduce, as this requires further knowledge concerning the source apportionment of major chemical components in the model. Consistency between the measured and modeled optical parameters serves as an important link for advancing remote

  3. OMI tropospheric NO2 air mass factors over South America: effects of biomass burning aerosols

    NASA Astrophysics Data System (ADS)

    Castellanos, P.; Boersma, K. F.; Torres, O.; de Haan, J. F.

    2015-03-01

    Biomass burning is an important and uncertain source of aerosols and NOx (NO + NO2) to the atmosphere. OMI observations of tropospheric NO2 are essential for characterizing this emissions source, but inaccuracies in the retrieval of NO2 tropospheric columns due to the radiative effects of aerosols, especially light-absorbing carbonaceous aerosols, are not well understood. It has been shown that the O2-O2 effective cloud fraction and pressure retrieval is sensitive to aerosol optical and physical properties, including aerosol optical depth (AOD). Aerosols implicitly influence the tropospheric air mass factor (AMF) calculations used in the NO2 retrieval through the effective cloud parameters used in the independent pixel approximation. In this work, we explicitly account for the effects of biomass burning aerosols in the tropospheric NO2 AMF calculation by including collocated aerosol extinction vertical profile observations from the CALIOP instrument, and aerosol optical depth (AOD) and single scattering albedo (SSA) retrieved by the OMI near-UV aerosol algorithm (OMAERUV) in the DISAMAR radiative transfer model for cloud-free scenes. Tropospheric AMFs calculated with DISAMAR were benchmarked against AMFs reported in the Dutch OMI NO2 (DOMINO) retrieval; the mean and standard deviation (SD) of the difference was 0.6 ± 8%. Averaged over three successive South American biomass burning seasons (2006-2008), the spatial correlation in the 500 nm AOD retrieved by OMI and the 532 nm AOD retrieved by CALIOP was 0.6, and 72% of the daily OMAERUV AOD observations were within 0.3 of the CALIOP observations. Overall, tropospheric AMFs calculated with observed aerosol parameters were on average 10% higher than AMFs calculated with effective cloud parameters. For effective cloud radiance fractions less than 30%, or effective cloud pressures greater than 800 hPa, the difference between tropospheric AMFs based on implicit and explicit aerosol parameters is on average 6 and 3

  4. Dispersion serial dilution methods using the gradient diluter device.

    PubMed

    Walling, Leslie; Schulz, Craig; Johnson, Michael

    2012-12-01

    A solute aspirated into a prefilled tube of diluent undergoes a dilution effect known as dispersion. Traditionally the effects of dispersion have been considered a negative consequence of using liquid-filled fixed-tip liquid handlers. We present a novel device and technique that utilizes the effects of dispersion to the benefit of making dilutions. The device known as the Gradient Diluter extends the dilution range of practical serial dilutions to six orders of magnitude in final volumes as low as 10 μL. Presented are the device, dispersion methods, and validation tests using fluorescence detection of sulforhodamine and the high-performance liquid chromatography/ultraviolet detection of furosemide. In addition, a T-cell inhibition assay of a relevant downstream protein is used to demonstrate IC(50) curves made with the Gradient Diluter compare favorably with those generated by hand.

  5. An ion-drag air mass-flow sensor for automotive applications

    SciTech Connect

    Malaczynski, G.W.; Schroeder, T. )

    1992-04-01

    An air-flow meter, developed primarily for the measurement of intake air flow into an internal combustion engine, is described. The well-known process of corona ion deflection in a gas flow together with proper electrode geometry and a detection scheme provides the conceptual basis for a humidity-insensitive ionic air-flow sensor. Output characteristics of the sensor, such as response time and range of operation, are discussed and compared with those of a production hot-wore meter for the type that is currently used with electronic fuel injection systems.

  6. Surface analysis using a new plasma assisted desorption/ionisation source for mass spectrometry in ambient air

    NASA Astrophysics Data System (ADS)

    Bowfield, A.; Barrett, D. A.; Alexander, M. R.; Ortori, C. A.; Rutten, F. M.; Salter, T. L.; Gilmore, I. S.; Bradley, J. W.

    2012-06-01

    The authors report on a modified micro-plasma assisted desorption/ionisation (PADI) device which creates plasma through the breakdown of ambient air rather than utilising an independent noble gas flow. This new micro-PADI device is used as an ion source for ambient mass spectrometry to analyse species released from the surfaces of polytetrafluoroethylene, and generic ibuprofen and paracetamol tablets through remote activation of the surface by the plasma. The mass spectra from these surfaces compare favourably to those produced by a PADI device constructed using an earlier design and confirm that the new ion source is an effective device which can be used to achieve ambient mass spectrometry with improved spatial resolution.

  7. Diluted magnetic semiconductors

    NASA Astrophysics Data System (ADS)

    Anderson, James R.

    1990-03-01

    Growth and physical properties of diluted magnetic semiconductors (DMS) were investigated. Growth included Bridgman, solid state recrystallization, and liquid phase epitaxy of Mercury(1-x)Manganese(x)Telluride and Mercury(1-x-y)Manganese(x)Cadmium(y)Telluride. Very uniform crystals were produced by solid state recrystallization. Physical properties studied included magnetization, optical response, and magnetotransport. From magnetization, the exchange interactions among magnetic ions have been deduced. Modulated spectroscopy gave details of the electronic structure of DMS and the quality of the material was indicated by the line widths. Magnetotransport, carried out in some cases to 30 T, showed a large negative magnetoresistance and subsequent increase. The Hg(1-x-y)Mn(x)Cd(y)Te has considerable promise for avalanche photodiodes between 1.2 and 1.8 micrometers.

  8. Dilution jet mixing program

    NASA Technical Reports Server (NTRS)

    Srinivasan, R.; Coleman, E.; Johnson, K.

    1984-01-01

    Parametric tests were conducted to quantify the mixing of opposed rows of jets (two-sided injection) in a confined cross flow. Results show that jet penetrations for two sided injections are less than that for single-sided injections, but the jet spreading rates are faster for a given momentum ratio and orifice plate. Flow area convergence generally enhances mixing. Mixing characteristics with asymmetric and symmetric convergence are similar. For constant momentum ratio, the optimum S/H(0) with in-line injections is one half the optimum value for single sided injections. For staggered injections, the optimum S/H(0) is twice the optimum value for single-sided injection. The correlations developed predicted the temperature distributions within first order accuracy and provide a useful tool for predicting jet trajectory and temperature profiles in the dilution zone with two-sided injections.

  9. Mass

    SciTech Connect

    Quigg, Chris

    2007-12-05

    In the classical physics we inherited from Isaac Newton, mass does not arise, it simply is. The mass of a classical object is the sum of the masses of its parts. Albert Einstein showed that the mass of a body is a measure of its energy content, inviting us to consider the origins of mass. The protons we accelerate at Fermilab are prime examples of Einsteinian matter: nearly all of their mass arises from stored energy. Missing mass led to the discovery of the noble gases, and a new form of missing mass leads us to the notion of dark matter. Starting with a brief guided tour of the meanings of mass, the colloquium will explore the multiple origins of mass. We will see how far we have come toward understanding mass, and survey the issues that guide our research today.

  10. Chemical and Trajectory Analysis of an Air Mass Plume from Asia

    NASA Astrophysics Data System (ADS)

    Guo, J. J.; Marrero, J. E.; Blake, D. R.

    2014-12-01

    Tracking the source of pollution events is important in understanding the transport of pollution plumes and impact on areas far from the source. Previous studies have shown that the rising contribution of Asian air pollution to the US has increased the number of days that pollution events exceed National Ambient Air Quality Standards (NAAQS). Whole air samples collected over the Edwards Air Force Base during a June 2014 NASA Student Airborne Research Program (SARP) flight exhibited enhancements in the concentrations of several compounds between 23-32 thousand feet. Chemical tracer analysis of these high altitude samples reveal that the air does not correspond to California emitted air. Chemical signatures in the plume, including high levels of OCS, chloroform, and methyl chloride, and low levels of methyl bromide, indicate that the plume was most heavily influence by coal combustion with contributions from biomass burning events from Asia. Low concentrations of ethene at the high altitude despite enhanced concentrations of ethane and ethyne suggest that this plume was aged. Further analysis of the plume using meteorological wind trajectories reveal that the plume had originated in China approximately 4-5 days prior. This is faster than results from previous studies that had found a Spring transport time of approximately 6 days.

  11. A Comparison of the Red Green Blue (RGB) Air Mass Imagery and Hyperspectral Infrared Retrieved Profiles and NOAA G-IV Dropsondes

    NASA Technical Reports Server (NTRS)

    Berndt, Emily; Folmer, Michael; Dunion, Jason

    2014-01-01

    RGB air mass imagery is derived from multiple channels or paired channel differences. The combination of channels and channel differences means the resulting imagery does not represent a quantity or physical parameter such as brightness temperature in conventional single channel imagery. Without a specific quantity to reference, forecasters are often confused as to what RGB products represent. Hyperspectral infrared retrieved profiles and NOAA G-IV dropsondes provide insight about the vertical structure of the air mass represented on the RGB air mass imagery and are a first step to validating the imagery.

  12. Effects of dilution on vehicle emissions of primary particles

    NASA Astrophysics Data System (ADS)

    Hayden, K. L.; Li, S.; Liggio, G.; McCurdy, M.; Chan, T.; Rostkowski, J.

    2009-12-01

    Dilution of primary aerosols from vehicles into the ambient atmosphere can change their physical and chemical characteristics. In order to study these processes, experiments were conducted in an engine testing facility at Environment Canada in Ottawa, Ontario. Exhaust from a light duty diesel engine was vented into a constant volume sampling (CVS) system where it underwent primary dilution at an ambient temperature of 25oC, leading to a primary dilution ratio of 10-15. From the CVS, the exhaust was further diluted using a combination of a Dekati ejection diluter and mixing with zero air in a flow tube, achieving secondary dilution ratios of up to 3000. Particle and gas measurements were made through multi-ports in the CVS and the flow tube using an SMPS, FMPS, AMS, and SP2, and instruments to measure CO, CO2, NOx, and total hydrocarbons (THC). Preliminary results indicate that regardless of dilution ratios, primary particles contain significant amounts of organic material that appear to reside on small black carbon cores. With increasing dilution ratios, the primary particle sizes become progressively smaller, suggesting volatilization of the adsorbed organic material. Results from various engine operating modes (simulating different driving conditions) will be presented.

  13. Dilute oxygen combustion. Phase I report

    SciTech Connect

    1997-10-01

    A novel burner, in which fuel (natural gas) and oxidant (oxygen or air) are separately injected into a furnace, shows promise for achieving very low nitrogen oxide(s) (NO{sub x}) emissions for commercial furnace applications. The dilute oxygen combustion (DOC) burner achieves very low NO{sub x} through in-furnace dilution of the oxidant stream prior to combustion, resulting in low flame temperatures, thus inhibiting thermal NO{sub x} production. The results of a fundamental and applied research effort on the development of the DOC burner are presented. In addition, the results of a market survey detailing the potential commercial impact of the DOC system are disclosed. The fundamental aspects of the burner development project involved examining the flame characteristics of a natural gas turbulent jet in a high-temperature ({approximately}1366 K) oxidant (7-27% O{sub 2} vol. wet). Specifically, the mass entrainment rate, the flame lift-off height, the velocity field and major species field of the jet were evaluated as a function of surrounding-gas temperature and composition. The measured entrainment rate of the fuel jet decreased with increasing oxygen content in the surrounding high-temperature oxidant, and was well represented by the d{sup +} scaling correlation found in the literature. The measured flame lift-off height decreased with increasing oxygen content and increasing temperature of the surrounding gas. An increase in surrounding-gas oxygen content and/or temperature inhibited the velocity decay within the jet periphery as a function of axial distance as compared to isothermal turbulent jets. However, the velocity measurements were only broadly represented by the d{sup +} scaling correlation. Several DOC burner configurations were tested in a laboratory-scale furnace at a nominal firing rate of 185 kW ({approximately}0.63 MMBtu/h). The flue gas composition was recorded as a function of furnace nitrogen content, furnace temperature, burner geometric

  14. Dilute Oxygen Combustion Phase 2 Final Report

    SciTech Connect

    Ryan, H.M.; Riley, M.F.; Kobayashi, H.

    2005-09-30

    A novel burner, in which fuel (natural gas) and oxidant (oxygen or air) are separately injected into a furnace, shows promise for achieving very low nitrogen oxide(s) (NOx) emissions for commercial furnace applications. The dilute oxygen combustion (DOC) burner achieves very low NOx through in-furnace dilution of the oxidant stream prior to combustion, resulting in low flame temperatures, thus inhibiting thermal NOx production. The results of a fundamental and applied research effort on the development of the DOC burner are presented. In addition, the results of a market survey detailing the potential commercial impact of the DOC system are disclosed. The fundamental aspects of the burner development project involved examining the flame characteristics of a natural gas turbulent jet in a high-temperature (~1366 K) oxidant (7-27% O2 vol. wet). Specifically, the mass entrainment rate, the flame lift-off height, the velocity field and major species field of the jet were evaluated as a function of surrounding-gas temperature and composition. The measured entrainment rate of the fuel jet decreased with increasing oxygen content in the surrounding high-temperature oxidant, and was well represented by the d+ scaling correlation found in the literature. The measured flame lift-off height decreased with increasing oxygen content and increasing temperature of the surrounding gas. An increase in surrounding-gas oxygen content and/or temperature inhibited the velocity decay within the jet periphery as a function of axial distance as compared to isothermal turbulent jets. However, the velocity measurements were only broadly represented by the d+ scaling correlation. Several DOC burner configurations were tested in a laboratory-scale furnace at a nominal firing rate of 185 kW (~0.63 MMBtu/h). The flue gas composition was recorded as a function of furnace nitrogen content, furnace temperature, burner geometric arrangement, firing rate, and fuel injection velocity. NOx emissions

  15. Dilute Oxygen Combustion Phase I Final Report

    SciTech Connect

    Ryan, H.M.; Riley, M.F.; Kobayashi, H.

    1997-10-31

    A novel burner, in which fuel (natural gas) and oxidant (oxygen or air) are separately injected into a furnace, shows promise for achieving very low nitrogen oxide(s) (NOx) emissions for commercial furnace applications. The dilute oxygen combustion (DOC) burner achieves very low NOx through in-furnace dilution of the oxidant stream prior to combustion, resulting in low flame temperatures, thus inhibiting thermal NOx production. The results of a fundamental and applied research effort on the development of the DOC burner are presented. In addition, the results of a market survey detailing the potential commercial impact of the DOC system are disclosed. The fundamental aspects of the burner development project involved examining the flame characteristics of a natural gas turbulent jet in a high-temperature (~1366 K) oxidant (7-27% O2 vol. wet). Specifically, the mass entrainment rate, the flame lift-off height, the velocity field and major species field of the jet were evaluated as a function of surrounding-gas temperature and composition. The measured entrainment rate of the fuel jet decreased with increasing oxygen content in the surrounding high-temperature oxidant, and was well represented by the d+ scaling correlation found in the literature. The measured flame lift-off height decreased with increasing oxygen content and increasing temperature of the surrounding gas. An increase in surrounding-gas oxygen content and/or temperature inhibited the velocity decay within the jet periphery as a function of axial distance as compared to isothermal turbulent jets. However, the velocity measurements were only broadly represented by the d+ scaling correlation. Several DOC burner configurations were tested in a laboratory-scale furnace at a nominal firing rate of 185 kW (~0.63 MMBtu/h). The flue gas composition was recorded as a function of furnace nitrogen content, furnace temperature, burner geometric arrangement, firing rate, and fuel injection velocity. NOx emissions

  16. Long-term Trend of Cold Air Mass Amount below a Designated Potential Temperature in Northern and Southern Hemisphere Winters with 7 Different Reanalysis Datasets

    NASA Astrophysics Data System (ADS)

    Kanno, Y.; Abdillah, M. R.; Iwasaki, T.

    2015-12-01

    This study addresses that the hemispheric total cold air mass amount defined below a threshold potential temperature of 280 K is a good indicator of the long-term trend of climate change in the polar region. We demonstrate quantitative analyses of warming trend in the Northern Hemisphere (NH) and Southern Hemisphere (SH) winters, using 7 different reanalysis datasets (JRA-55, JRA-55C, JRA-55AMIP, ERA-interim, CFSR, JRA-25, NCEP-NCAR). Hemispheric total cold air mass amount in the NH winter exhibit a statistically significant decreasing trend in all reanalysis datasets at a rate about -1.37 to -0.77% per decade over the period 1959-2012 and at a rate about -1.57 to -0.82% per decade over 1980-2012. There is no statistically significant trend in the equatorward cold air mass flux across latitude of 45N, which is an indicator for hemispheric-scale cold air outbreak, over the period 1980-2012 except for NCEP-NCAR reanalysis dataset which shows substantial decreasing trend of about -3.28% per decade. The spatial distribution of the long-term trend of cold air mass amount in the NH winter is almost consistent among reanalysis datasets except for JRA-55AMIP over the period 1980-2012. Cold air mass amount increases over Central Siberia, Kamchatka peninsula, and Bering Sea, while it decreases over Norwegian Sea, Barents Sea, Kara Sea, Greenland, Canada, Northern part of United States, and East Asia. In the SH winter, on the other hand, there is a large discrepancy in hemispheric total cold air mass amount and equatorward cold air mass flux across latitude of 50S over the period 1980-2010 among reanalysis datasets. This result indicate that there is a large uncertainty in the long-term trend of cold air mass amount in the SH winter.

  17. Use of Chiral Signatures of Organochlorine Pesticides in Asian, Trans-Pacific, and Western U.S. Air Masses to Identify Source Regions

    NASA Astrophysics Data System (ADS)

    Simonich, S.; Genualdi, S.; Primbs, T.; Ryoo, K.; Bidleman, T.; Jantunen, L.

    2008-12-01

    Chiral signatures of organochlorine pesticides were measured in air masses on Okinawa Japan and three remote locations in the Pacific Northwestern U.S.: Cheeka Peak Observatory (CPO), a coastal site on the Olympic Peninsula of Washington at 500 m; Mary's Peak Observatory (MPO), a site at 1250 m in Oregon's Coast range; and Mt. Bachelor Observatory (MBO), a site at 2300 m in Oregon's Cascade range. The chiral signature of composite soil samples collected from agricultural areas in China and South Korea were also measured. Racemic alpha-HCH was measured in Asian air masses and soil from China and South Korea. Non-racemic (enantiomer fraction (EF) = 0.528 ± 0.0048) alpha-HCH was measured in regional air masses at CPO, a marine boundary layer site, and may reflect volatilization from the Pacific Ocean and regional soils. However, during trans-Pacific transport events at CPO, the EFs were significantly (p-value <0.001) more racemic (EF = 0.513 ± 0.0003). Racemic alpha-HCH was consistently measured in trans- Pacific air masses at MPO and MBO. The alpha-HCH EFs in CPO, MPO, and MBO air masses were positively correlated (p-value = 0.0017) with the amount of time the air mass spent above the boundary layer along the 10-day back air mass trajectory prior to being sampled. This suggests that the alpha-HCH in the free troposphere is racemic. The racemic signatures of cis and trans chlordane in air masses at all four air sampling sites suggest that Asian and U.S. urban areas continue to be sources of chlordanes that have not yet undergone biotransformation.

  18. Retrospective screening of pesticide metabolites in ambient air using liquid chromatography coupled to high-resolution mass spectrometry.

    PubMed

    López, Antonio; Yusà, Vicent; Millet, Maurice; Coscollà, Clara

    2016-04-01

    A new methodology for the retrospective screening of pesticide metabolites in ambient air was developed, using liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (UHPLC-HRMS), including two systematic workflows (i) post-run target screening (suspect screening) and (ii) non-target screening. An accurate-mass database was built and used for the post-run screening analysis. The database contained 240 pesticide metabolites found in different matrixes such as air, soil, water, plants, animals and humans. For non-target analysis, a "fragmentation-degradation" relationship strategy was selected. The proposed methodology was applied to 31 air samples (PM10) collected in the Valencian Region (Spain). In the post-target analysis 34 metabolites were identified, of which 11 (3-ketocarburan, carbofuran-7-phenol, carbendazim, desmethylisoproturon, ethiofencarb-sulfoxide, malaoxon, methiocarb-sulfoxide, N-(2-ethyl-6-methylphenyl)-L-alanine, omethoate, 2-hydroxy-terbuthylazine, and THPAM) were confirmed using analytical standards. The semiquantitative estimated concentration ranged between 6.78 and 198.31 pg m(-3). Likewise, two unknown degradation products of malaoxon and fenhexamid were elucidated in the non-target screening. PMID:26838378

  19. Origin of atmospheric aerosols at the Pierre Auger Observatory using studies of air mass trajectories in South America

    NASA Astrophysics Data System (ADS)

    Aab, A.; Abreu, P.; Aglietta, M.; Ahlers, M.; Ahn, E. J.; Albuquerque, I. F. M.; Allekotte, I.; Allen, J.; Allison, P.; Almela, A.; Alvarez Castillo, J.; Alvarez-Muñiz, J.; Alves Batista, R.; Ambrosio, M.; Aminaei, A.; Anchordoqui, L.; Andringa, S.; Antičić, T.; Aramo, C.; Arqueros, F.; Asorey, H.; Assis, P.; Aublin, J.; Ave, M.; Avenier, M.; Avila, G.; Badescu, A. M.; Barber, K. B.; Bardenet, R.; Bäuml, J.; Baus, C.; Beatty, J. J.; Becker, K. H.; Bellido, J. A.; BenZvi, S.; Berat, C.; Bertou, X.; Biermann, P. L.; Billoir, P.; Blanco, F.; Blanco, M.; Bleve, C.; Blümer, H.; Boháčová, M.; Boncioli, D.; Bonifazi, C.; Bonino, R.; Borodai, N.; Brack, J.; Brancus, I.; Brogueira, P.; Brown, W. C.; Buchholz, P.; Bueno, A.; Buscemi, M.; Caballero-Mora, K. S.; Caccianiga, B.; Caccianiga, L.; Candusso, M.; Caramete, L.; Caruso, R.; Castellina, A.; Cataldi, G.; Cazon, L.; Cester, R.; Cheng, S. H.; Chiavassa, A.; Chinellato, J. A.; Chudoba, J.; Cilmo, M.; Clay, R. W.; Cocciolo, G.; Colalillo, R.; Collica, L.; Coluccia, M. R.; Conceição, R.; Contreras, F.; Cooper, M. J.; Coutu, S.; Covault, C. E.; Criss, A.; Cronin, J.; Curutiu, A.; Dallier, R.; Daniel, B.; Dasso, S.; Daumiller, K.; Dawson, B. R.; de Almeida, R. M.; De Domenico, M.; de Jong, S. J.; De La Vega, G.; de Mello Junior, W. J. M.; de Mello Neto, J. R. T.; De Mitri, I.; de Souza, V.; de Vries, K. D.; del Peral, L.; Deligny, O.; Dembinski, H.; Dhital, N.; Di Giulio, C.; Di Matteo, A.; Diaz, J. C.; Díaz Castro, M. L.; Diep, P. N.; Diogo, F.; Dobrigkeit, C.; Docters, W.; D'Olivo, J. C.; Dong, P. N.; Dorofeev, A.; dos Anjos, J. C.; Dova, M. T.; Ebr, J.; Engel, R.; Erdmann, M.; Escobar, C. O.; Espadanal, J.; Etchegoyen, A.; Facal San Luis, P.; Falcke, H.; Fang, K.; Farrar, G.; Fauth, A. C.; Fazzini, N.; Ferguson, A. P.; Fick, B.; Figueira, J. M.; Filevich, A.; Filipčič, A.; Foerster, N.; Fox, B. D.; Fracchiolla, C. E.; Fraenkel, E. D.; Fratu, O.; Fröhlich, U.; Fuchs, B.; Gaior, R.; Gamarra, R. F.; Gambetta, S.; García, B.; Garcia Roca, S. T.; Garcia-Gamez, D.; Garcia-Pinto, D.; Garilli, G.; Gascon Bravo, A.; Gemmeke, H.; Ghia, P. L.; Giammarchi, M.; Giller, M.; Gitto, J.; Glaser, C.; Glass, H.; Gomez Albarracin, F.; Gómez Berisso, M.; Gómez Vitale, P. F.; Gonçalves, P.; Gonzalez, J. G.; Gookin, B.; Gorgi, A.; Gorham, P.; Gouffon, P.; Grebe, S.; Griffith, N.; Grillo, A. F.; Grubb, T. D.; Guardincerri, Y.; Guarino, F.; Guedes, G. P.; Hansen, P.; Harari, D.; Harrison, T. A.; Harton, J. L.; Haungs, A.; Hebbeker, T.; Heck, D.; Herve, A. E.; Hill, G. C.; Hojvat, C.; Hollon, N.; Holt, E.; Homola, P.; Hörandel, J. R.; Horvath, P.; Hrabovský, M.; Huber, D.; Huege, T.; Insolia, A.; Isar, P. G.; Jansen, S.; Jarne, C.; Josebachuili, M.; Kadija, K.; Kambeitz, O.; Kampert, K. H.; Karhan, P.; Kasper, P.; Katkov, I.; Kégl, B.; Keilhauer, B.; Keivani, A.; Kemp, E.; Kieckhafer, R. M.; Klages, H. O.; Kleifges, M.; Kleinfeller, J.; Knapp, J.; Krause, R.; Krohm, N.; Krömer, O.; Kruppke-Hansen, D.; Kuempel, D.; Kunka, N.; La Rosa, G.; LaHurd, D.; Latronico, L.; Lauer, R.; Lauscher, M.; Lautridou, P.; Le Coz, S.; Leão, M. S. A. B.; Lebrun, D.; Lebrun, P.; Leigui de Oliveira, M. A.; Letessier-Selvon, A.; Lhenry-Yvon, I.; Link, K.; López, R.; Lopez Agüera, A.; Louedec, K.; Lozano Bahilo, J.; Lu, L.; Lucero, A.; Ludwig, M.; Lyberis, H.; Maccarone, M. C.; Malacari, M.; Maldera, S.; Maller, J.; Mandat, D.; Mantsch, P.; Mariazzi, A. G.; Marin, V.; Mariş, I. C.; Marquez Falcon, H. R.; Marsella, G.; Martello, D.; Martin, L.; Martinez, H.; Martínez Bravo, O.; Martraire, D.; Masías Meza, J. J.; Mathes, H. J.; Matthews, J.; Matthews, J. A. J.; Matthiae, G.; Maurel, D.; Maurizio, D.; Mayotte, E.; Mazur, P. O.; Medina, C.; Medina-Tanco, G.; Melissas, M.; Melo, D.; Menichetti, E.; Menshikov, A.; Messina, S.; Meyhandan, R.; Mićanović, S.; Micheletti, M. I.; Middendorf, L.; Minaya, I. A.; Miramonti, L.; Mitrica, B.; Molina-Bueno, L.; Mollerach, S.; Monasor, M.; Monnier Ragaigne, D.; Montanet, F.; Morales, B.; Morello, C.; Moreno, J. C.; Mostafá, M.; Moura, C. A.; Muller, M. A.; Müller, G.; Münchmeyer, M.; Mussa, R.; Navarra, G.; Navarro, J. L.; Navas, S.; Necesal, P.; Nellen, L.; Nelles, A.; Neuser, J.; Nhung, P. T.; Niechciol, M.; Niemietz, L.; Niggemann, T.; Nitz, D.; Nosek, D.; Nožka, L.; Oehlschläger, J.; Olinto, A.; Oliveira, M.; Ortiz, M.; Pacheco, N.; Pakk Selmi-Dei, D.; Palatka, M.; Pallotta, J.; Palmieri, N.; Parente, G.; Parra, A.; Pastor, S.; Paul, T.; Pech, M.; Pȩkala, J.; Pelayo, R.; Pepe, I. M.; Perrone, L.; Pesce, R.; Petermann, E.; Petrera, S.; Petrolini, A.; Petrov, Y.; Piegaia, R.; Pierog, T.; Pieroni, P.; Pimenta, M.; Pirronello, V.; Platino, M.; Plum, M.; Pontz, M.; Porcelli, A.; Preda, T.; Privitera, P.; Prouza, M.; Quel, E. J.; Querchfeld, S.; Quinn, S.; Rautenberg, J.; Ravel, O.; Ravignani, D.; Revenu, B.; Ridky, J.; Riggi, S.; Risse, M.; Ristori, P.; Rivera, H.; Rizi, V.; Roberts, J.; Rodrigues de Carvalho, W.; Rodriguez Cabo, I.; Rodriguez Fernandez, G.; Rodriguez Martino, J.; Rodriguez Rojo, J.; Rodríguez-Frías, M. D.; Ros, G.; Rosado, J.; Rossler, T.; Roth, M.; Rouillé-d'Orfeuil, B.; Roulet, E.; Rovero, A. C.; Rühle, C.; Saffi, S. J.; Saftoiu, A.; Salamida, F.; Salazar, H.; Salesa Greus, F.; Salina, G.; Sánchez, F.; Sanchez-Lucas, P.; Santo, C. E.; Santos, E.; Santos, E. M.; Sarazin, F.; Sarkar, B.; Sarmento, R.; Sato, R.; Scharf, N.; Scherini, V.; Schieler, H.; Schiffer, P.; Schmidt, A.; Scholten, O.; Schoorlemmer, H.; Schovánek, P.; Schröder, F. G.; Schulz, A.; Schulz, J.; Sciutto, S. J.; Scuderi, M.; Segreto, A.; Settimo, M.; Shadkam, A.; Shellard, R. C.; Sidelnik, I.; Sigl, G.; Sima, O.; Śmiałkowski, A.; Šmída, R.; Snow, G. R.; Sommers, P.; Sorokin, J.; Spinka, H.; Squartini, R.; Srivastava, Y. N.; Stanič, S.; Stapleton, J.; Stasielak, J.; Stephan, M.; Straub, M.; Stutz, A.; Suarez, F.; Suomijärvi, T.; Supanitsky, A. D.; Šuša, T.; Sutherland, M. S.; Swain, J.; Szadkowski, Z.; Szuba, M.; Tapia, A.; Tartare, M.; Taşcău, O.; Thao, N. T.; Tiffenberg, J.; Timmermans, C.; Tkaczyk, W.; Todero Peixoto, C. J.; Toma, G.; Tomankova, L.; Tomé, B.; Tonachini, A.; Torralba Elipe, G.; Torres Machado, D.; Travnicek, P.; Tridapalli, D. B.; Trovato, E.; Tueros, M.; Ulrich, R.; Unger, M.; Valdés Galicia, J. F.; Valiño, I.; Valore, L.; van Aar, G.; van den Berg, A. M.; van Velzen, S.; van Vliet, A.; Varela, E.; Vargas Cárdenas, B.; Varner, G.; Vázquez, J. R.; Vázquez, R. A.; Veberič, D.; Verzi, V.; Vicha, J.; Videla, M.; Villaseñor, L.; Wahlberg, H.; Wahrlich, P.; Wainberg, O.; Walz, D.; Watson, A. A.; Weber, M.; Weidenhaupt, K.; Weindl, A.; Werner, F.; Westerhoff, S.; Whelan, B. J.; Widom, A.; Wieczorek, G.; Wiencke, L.; Wilczyńska, B.; Wilczyński, H.; Will, M.; Williams, C.; Winchen, T.; Wundheiler, B.; Wykes, S.; Yamamoto, T.; Yapici, T.; Younk, P.; Yuan, G.; Yushkov, A.; Zamorano, B.; Zas, E.; Zavrtanik, D.; Zavrtanik, M.; Zaw, I.; Zepeda, A.; Zhou, J.; Zhu, Y.; Zimbres Silva, M.; Ziolkowski, M.; Curci, G.

    2014-11-01

    The Pierre Auger Observatory is making significant contributions towards understanding the nature and origin of ultra-high energy cosmic rays. One of its main challenges is the monitoring of the atmosphere, both in terms of its state variables and its optical properties. The aim of this work is to analyse aerosol optical depth τa(z) values measured from 2004 to 2012 at the observatory, which is located in a remote and relatively unstudied area of Pampa Amarilla, Argentina. The aerosol optical depth is in average quite low - annual mean τa(3.5 km) ∼ 0.04 - and shows a seasonal trend with a winter minimum - τa(3.5 km) ∼ 0.03 -, and a summer maximum - τa(3.5 km) ∼ 0.06 -, and an unexpected increase from August to September - τa(3.5 km) ∼ 0.055. We computed backward trajectories for the years 2005 to 2012 to interpret the air mass origin. Winter nights with low aerosol concentrations show air masses originating from the Pacific Ocean. Average concentrations are affected by continental sources (wind-blown dust and urban pollution), whilst the peak observed in September and October could be linked to biomass burning in the northern part of Argentina or air pollution coming from surrounding urban areas.

  20. Thermal desorption-gas chromatography-mass spectrometry method to determine phthalate and organophosphate esters from air samples.

    PubMed

    Aragón, M; Borrull, F; Marcé, R M

    2013-08-16

    A method based on thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) has been developed to determine four organophosphate esters, seven phthalate esters, and bis(2-ethylhexyl) adipate in the gas phase from harbour and urban air samples. The method involves the sampling of 1.5L of air in a Tenax TA sorbent tube followed by thermal desorption (using a Tenax TA cryogenic trap) coupled to gas chromatography-mass spectrometry. The repeatability of the method expressed as %RSD (n=3) is less than 15% and the MQLs are between 0.007μgm(-3) (DMP, TBP, BBP, TPP and DnOP) and 6.7μgm(-3) (DEHP). The method was successfully applied in two areas (urban and harbour) testing two and three points in each one, respectively. Some of these compounds were found in both urban and harbour samples. Di-(2-ethylhexyl)phthalate was the most abundant compound found in both areas at concentration levels between 6.7μgm(-3) and 136.4μgm(-3). This study demonstrates that thermal desorption is an efficient method for the determination of these semi-volatile compounds in the gas phase fraction of air samples.

  1. Retrospective screening of pesticide metabolites in ambient air using liquid chromatography coupled to high-resolution mass spectrometry.

    PubMed

    López, Antonio; Yusà, Vicent; Millet, Maurice; Coscollà, Clara

    2016-04-01

    A new methodology for the retrospective screening of pesticide metabolites in ambient air was developed, using liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (UHPLC-HRMS), including two systematic workflows (i) post-run target screening (suspect screening) and (ii) non-target screening. An accurate-mass database was built and used for the post-run screening analysis. The database contained 240 pesticide metabolites found in different matrixes such as air, soil, water, plants, animals and humans. For non-target analysis, a "fragmentation-degradation" relationship strategy was selected. The proposed methodology was applied to 31 air samples (PM10) collected in the Valencian Region (Spain). In the post-target analysis 34 metabolites were identified, of which 11 (3-ketocarburan, carbofuran-7-phenol, carbendazim, desmethylisoproturon, ethiofencarb-sulfoxide, malaoxon, methiocarb-sulfoxide, N-(2-ethyl-6-methylphenyl)-L-alanine, omethoate, 2-hydroxy-terbuthylazine, and THPAM) were confirmed using analytical standards. The semiquantitative estimated concentration ranged between 6.78 and 198.31 pg m(-3). Likewise, two unknown degradation products of malaoxon and fenhexamid were elucidated in the non-target screening.

  2. Influence of trans-boundary biomass burning impacted air masses on submicron particle number concentrations and size distributions

    NASA Astrophysics Data System (ADS)

    Betha, Raghu; Zhang, Zhe; Balasubramanian, Rajasekhar

    2014-08-01

    Submicron particle number concentration (PNC) and particle size distribution (PSD) in the size range of 5.6-560 nm were investigated in Singapore from 27 June 2009 through 6 September 2009. Slightly hazy conditions lasted in Singapore from 6 to 10 August. Backward air trajectories indicated that the haze was due to the transport of biomass burning impacted air masses originating from wild forest and peat fires in Sumatra, Indonesia. Three distinct peaks in the morning (08:00-10:00), afternoon (13:00-15:00) and evening (16:00-20:00) were observed on a typical normal day. However, during the haze period no distinct morning and afternoon peaks were observed and the PNC (39,775 ± 3741 cm-3) increased by 1.5 times when compared to that during non-haze periods (26,462 ± 6017). The morning and afternoon peaks on the normal day were associated with the local rush hour traffic while the afternoon peak was induced by new particle formation (NPF). Diurnal profiles of PNCs and PSDs showed that primary particle peak diameters were large during the haze (60 nm) period when compared to that during the non-haze period (45.3 nm). NPF events observed in the afternoon period on normal days were suppressed during the haze periods due to heavy particle loading in atmosphere caused by biomass burning impacted air masses.

  3. OMI tropospheric NO2 air mass factors over South America: effects of biomass burning aerosols

    NASA Astrophysics Data System (ADS)

    Castellanos, P.; Boersma, K. F.; Torres, O.; de Haan, J. F.

    2015-09-01

    Biomass burning is an important and uncertain source of aerosols and NOx (NO + NO2) to the atmosphere. Satellite observations of tropospheric NO2 are essential for characterizing this emissions source, but inaccuracies in the retrieval of NO2 tropospheric columns due to the radiative effects of aerosols, especially light-absorbing carbonaceous aerosols, are not well understood. It has been shown that the O2-O2 effective cloud fraction and pressure retrieval is sensitive to aerosol optical and physical properties, including aerosol optical depth (AOD). Aerosols implicitly influence the tropospheric air mass factor (AMF) calculations used in the NO2 retrieval through the effective cloud parameters used in the independent pixel approximation. In this work, we explicitly account for the effects of biomass burning aerosols in the Ozone Monitoring Instrument (OMI) tropospheric NO2 AMF calculation for cloud-free scenes. We do so by including collocated aerosol extinction vertical profile observations from the CALIOP instrument, and aerosol optical depth (AOD) and single scattering albedo (SSA) retrieved by the OMI near-UV aerosol algorithm (OMAERUV) in the DISAMAR radiative transfer model. Tropospheric AMFs calculated with DISAMAR were benchmarked against AMFs reported in the Dutch OMI NO2 (DOMINO) retrieval; the mean and standard deviation of the difference was 0.6 ± 8 %. Averaged over three successive South American biomass burning seasons (2006-2008), the spatial correlation in the 500 nm AOD retrieved by OMI and the 532 nm AOD retrieved by CALIOP was 0.6, and 68 % of the daily OMAERUV AOD observations were within 30 % of the CALIOP observations. Overall, tropospheric AMFs calculated with observed aerosol parameters were on average 10 % higher than AMFs calculated with effective cloud parameters. For effective cloud radiance fractions less than 30 %, or effective cloud pressures greater than 800 hPa, the difference between tropospheric AMFs based on implicit and

  4. An automated gas chromatography time-of-flight mass spectrometry instrument for the quantitative analysis of halocarbons in air

    NASA Astrophysics Data System (ADS)

    Obersteiner, F.; Bönisch, H.; Engel, A.

    2016-01-01

    We present the characterization and application of a new gas chromatography time-of-flight mass spectrometry instrument (GC-TOFMS) for the quantitative analysis of halocarbons in air samples. The setup comprises three fundamental enhancements compared to our earlier work (Hoker et al., 2015): (1) full automation, (2) a mass resolving power R = m/Δm of the TOFMS (Tofwerk AG, Switzerland) increased up to 4000 and (3) a fully accessible data format of the mass spectrometric data. Automation in combination with the accessible data allowed an in-depth characterization of the instrument. Mass accuracy was found to be approximately 5 ppm in mean after automatic recalibration of the mass axis in each measurement. A TOFMS configuration giving R = 3500 was chosen to provide an R-to-sensitivity ratio suitable for our purpose. Calculated detection limits are as low as a few femtograms by means of the accurate mass information. The precision for substance quantification was 0.15 % at the best for an individual measurement and in general mainly determined by the signal-to-noise ratio of the chromatographic peak. Detector non-linearity was found to be insignificant up to a mixing ratio of roughly 150 ppt at 0.5 L sampled volume. At higher concentrations, non-linearities of a few percent were observed (precision level: 0.2 %) but could be attributed to a potential source within the detection system. A straightforward correction for those non-linearities was applied in data processing, again by exploiting the accurate mass information. Based on the overall characterization results, the GC-TOFMS instrument was found to be very well suited for the task of quantitative halocarbon trace gas observation and a big step forward compared to scanning, quadrupole MS with low mass resolving power and a TOFMS technique reported to be non-linear and restricted by a small dynamical range.

  5. Air mass origin and its influence on radionuclide activities ( 7Be and 210Pb) in aerosol particles at a coastal site in the western Mediterranean

    NASA Astrophysics Data System (ADS)

    Dueñas, C.; Orza, J. A. G.; Cabello, M.; Fernández, M. C.; Cañete, S.; Pérez, M.; Gordo, E.

    2011-07-01

    Studies of radionuclide activities in aerosol particles provide a means for evaluating the integrated effects of transport and meteorology on the atmospheric loadings of substances with different sources. Measurements of aerosol mass concentration and specific activities of 7Be and 210Pb in aerosols at Málaga (36° 43' 40″ N; 4° 28' 8″ W) for the period 2000-2006 were used to obtain the relationships between radionuclide activities and airflow patterns by comparing the data grouped by air mass trajectory clusters. The average concentration values of 7Be and 210Pb over the 7 year period have been found to be 4.6 and 0.58 mBq m -3, respectively, with mean aerosol mass concentration of 53.6 μg m -3. The identified air flow types arriving at Málaga reflect the transitional location of the Iberian Peninsula and show significant differences in radionuclide activities. Air concentrations of both nuclides and the aerosol mass concentration are controlled predominantly by the synoptic scenarios leading to the entrance of dust-laden continental flows from northern Africa and the arrival of polar maritime air masses, as implied by the strong correlations found between the monthly frequencies of the different air masses and the specific activities of both radionuclides. Correlations between activity concentrations and precipitation are significant though lower than with air masses.

  6. [Determination of volatile organic compounds in ambient air by thermal desorption-gas chromatography-triple quadrupole tandem mass spectrometry].

    PubMed

    Feng, Lili; Hu, Xiaofang; Yu, Xiaojuan; Zhang, Wenying

    2016-02-01

    A method was established for the simultaneous determination of 23 volatile organic compounds (VOCs) in ambient air with combination of thermal desorption (TD) and gas chromatography-triple quadrupole tandem mass spectrometry (GC-MS/MS). The air samples were collected by active sampling method using Tenax-TA sorbent tubes, and desorbed by thermal desorption. The analytes were determined by GC-MS/MS in selected reaction monitoring (SRM) mode, and internal standard method was applied to quantify the VOCs. The results of all the 23 VOCs showed good linearities in low level (0. 01-1 ng) and high level (1-100 ng) with all the correlation coefficients (r2) more than 0. 99. The method quantification limits were between 0. 000 08-1 µg/m3. The method was validated by means of recovery experiments (n = 6) at three spiked levels of 2, 10 and 50 ng. The recoveries between 77% and 124% were generally obtained. The relative standard deviations (RSDs) in all cases were lower than 20%, except for chlorobenzene at the low spiked level. The developed method was applied to determine VOCs in ambient air collected at three sites in Shanghai. Several compounds, like benzene, toluene, ethylbenzene, m-xylenes, p-xylenes, styrene, 1, 2, 4-trimethylbenzene and hexachlorobutadiene were detected and confirmed in all the samples analyzed. The method is highly accurate, reliable and sensitive for monitoring the VOCs in ambient air. PMID:27382728

  7. Measurement of volatile plant compounds in field ambient air by thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Cai, Xiao-Ming; Xu, Xiu-Xiu; Bian, Lei; Luo, Zong-Xiu; Chen, Zong-Mao

    2015-12-01

    Determination of volatile plant compounds in field ambient air is important to understand chemical communication between plants and insects and will aid the development of semiochemicals from plants for pest control. In this study, a thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method was developed to measure ultra-trace levels of volatile plant compounds in field ambient air. The desorption parameters of TD, including sorbent tube material, tube desorption temperature, desorption time, and cold trap temperature, were selected and optimized. In GC-MS analysis, the selected ion monitoring mode was used for enhanced sensitivity and selectivity. This method was sufficiently sensitive to detect part-per-trillion levels of volatile plant compounds in field ambient air. Laboratory and field evaluation revealed that the method presented high precision and accuracy. Field studies indicated that the background odor of tea plantations contained some common volatile plant compounds, such as (Z)-3-hexenol, methyl salicylate, and (E)-ocimene, at concentrations ranging from 1 to 3400 ng m(-3). In addition, the background odor in summer was more abundant in quality and quantity than in autumn. Relative to previous methods, the TD-GC-MS method is more sensitive, permitting accurate qualitative and quantitative measurements of volatile plant compounds in field ambient air. PMID:26493981

  8. Measurement of volatile plant compounds in field ambient air by thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Cai, Xiao-Ming; Xu, Xiu-Xiu; Bian, Lei; Luo, Zong-Xiu; Chen, Zong-Mao

    2015-12-01

    Determination of volatile plant compounds in field ambient air is important to understand chemical communication between plants and insects and will aid the development of semiochemicals from plants for pest control. In this study, a thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method was developed to measure ultra-trace levels of volatile plant compounds in field ambient air. The desorption parameters of TD, including sorbent tube material, tube desorption temperature, desorption time, and cold trap temperature, were selected and optimized. In GC-MS analysis, the selected ion monitoring mode was used for enhanced sensitivity and selectivity. This method was sufficiently sensitive to detect part-per-trillion levels of volatile plant compounds in field ambient air. Laboratory and field evaluation revealed that the method presented high precision and accuracy. Field studies indicated that the background odor of tea plantations contained some common volatile plant compounds, such as (Z)-3-hexenol, methyl salicylate, and (E)-ocimene, at concentrations ranging from 1 to 3400 ng m(-3). In addition, the background odor in summer was more abundant in quality and quantity than in autumn. Relative to previous methods, the TD-GC-MS method is more sensitive, permitting accurate qualitative and quantitative measurements of volatile plant compounds in field ambient air.

  9. Method to simultaneously determine the sphingosine 1-phosphate breakdown product (2E)-hexadecenal and its fatty acid derivatives using isotope-dilution HPLC-electrospray ionization-quadrupole/time-of-flight mass spectrometry.

    PubMed

    Neuber, Corinna; Schumacher, Fabian; Gulbins, Erich; Kleuser, Burkhard

    2014-09-16

    Sphingosine 1-phosphate (S1P), a bioactive lipid involved in various physiological processes, can be irreversibly degraded by the membrane-bound S1P lyase (S1PL) yielding (2E)-hexadecenal and phosphoethanolamine. It is discussed that (2E)-hexadecenal is further oxidized to (2E)-hexadecenoic acid by the long-chain fatty aldehyde dehydrogenase ALDH3A2 (also known as FALDH) prior to activation via coupling to coenzyme A (CoA). Inhibition or defects in these enzymes, S1PL or FALDH, result in severe immunological disorders or the Sjögren-Larsson syndrome, respectively. Hence, it is of enormous importance to simultaneously determine the S1P breakdown product (2E)-hexadecenal and its fatty acid metabolites in biological samples. However, no method is available so far. Here, we present a sensitive and selective isotope-dilution high performance liquid chromatography-electrospray ionization-quadrupole/time-of-flight mass spectrometry method for simultaneous quantification of (2E)-hexadecenal and its fatty acid metabolites following derivatization with 2-diphenylacetyl-1,3-indandione-1-hydrazone and 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide. Optimized conditions for sample derivatization, chromatographic separation, and MS/MS detection are presented as well as an extensive method validation. Finally, our method was successfully applied to biological samples. We found that (2E)-hexadecenal is almost quantitatively oxidized to (2E)-hexadecenoic acid, that is further activated as verified by cotreatment of HepG2 cell lysates with (2E)-hexadecenal and the acyl-CoA synthetase inhibitor triacsin C. Moreover, incubations of cell lysates with deuterated (2E)-hexadecenal revealed that no hexadecanoic acid is formed from the aldehyde. Thus, our method provides new insights into the sphingolipid metabolism and will be useful to investigate diseases known for abnormalities in long-chain fatty acid metabolism, e.g., the Sjögren-Larsson syndrome, in more detail. PMID:25137547

  10. Abundance of four sulfur mustard-DNA adducts ex vivo and in vivo revealed by simultaneous quantification in stable isotope dilution-ultrahigh performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Yue, Lijun; Wei, Yuxia; Chen, Jia; Shi, Huiqin; Liu, Qin; Zhang, Yajiao; He, Jun; Guo, Lei; Zhang, Tingfen; Xie, Jianwei; Peng, Shuangqing

    2014-04-21

    Sulfur mustard (SM) is a highly reactive alkylating vesicant and causes blisters upon contact with skin, eyes, and respiratory organs. It covalently links with DNAs by forming four mono- or cross-link adducts. In this article, the reference standards of SM-DNA adducts and deuterated analogues were first synthesized with simplified procedures containing only one or two steps and using less toxic chemical 2-(2-chloroethylthio)ethanol or nontoxic chemical thiodiglycol as starting materials. A sensitive and high-throughput simultaneous quantification method of N(7)-[2-[(2-hydroxyethyl)thio]-ethyl]guanine (N(7)-HETEG), O(6)-[2-[(2-hydroxyethyl)thio]-ethyl]guanine (O(6)-HETEG), N(3)-[2-[(2-hydroxyethyl)thio]-ethyl]adenine (N(3)-HETEA), and bis[2-(guanin-7-yl)ethyl]sulfide (Bis-G) in the Sprague-Dawley rat derma samples was developed by stable isotope dilution-ultrahigh performance liquid chromatography-tandem mass spectrometry (ID-UPLC-MS/MS) with the aim of revealing the real metabolic behaviors of four adducts. The method was validated, the limit of detection (S/N ratio greater than 10) was 0.01, 0.002, 0.04, and 0.11 fmol on column for N(7)-HETEG, O(6)-HETEG, Bis-G, and N(3)-HETEA, respectively, and the lower limit of quantification (S/N ratio greater than 20) was 0.04, 0.01, 0.12, and 0.33 fmol on column for N(7)-HETEG, O(6)-HETEG, Bis-G, and N(3)-HETEA, respectively. The accuracy of this method was determined to be 76% to 129% (n = 3), and both the interday (n = 6) and intraday (n = 7) precisions were less than 10%. The method was further applied for the quantifications of four adducts in the derma of adult male Sprague-Dawley rats exposed to SM ex vivo and in vivo, and all adducts had time- and dose-effect relationships. To the best of our knowledge, this is the first time that the real presented status of four DNA adducts was simultaneously revealed by the MS-based method, in which Bis-G showed much higher abundance than the result previously reported and N(3

  11. Comprehensive profiling of mercapturic acid metabolites from dietary acrylamide as short-term exposure biomarkers for evaluation of toxicokinetics in rats and daily internal exposure in humans using isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Zhang, Yu; Wang, Qiao; Cheng, Jun; Zhang, Jingshun; Xu, Jiaojiao; Ren, Yiping

    2015-09-24

    Mercapturic acid metabolites from dietary acrylamide are important short-term exposure biomarkers for evaluating the in vivo toxicity of acrylamide. Most of studies have focused on the measurement of two metabolites, N-acetyl-S-(2-carbamoylethyl)-L-cysteine (AAMA) and N-acetyl-S-(2-carbamoyl-2-hydroxyethyl)-L-cysteine (GAMA). Thus, the comprehensive profile of acrylamide urinary metabolites cannot be fully understood. We developed an isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous determination of all four mercapturic acid adducts of acrylamide and its primary metabolite glycidamide under the electroscopy ionization negative (ESI-) mode in the present study. The limit of detection (LOD) and limit of quantification (LOQ) of the analytes ranged 0.1-0.3 ng/mL and 0.4-1.0 ng/mL, respectively. The recovery rates with low, intermediate and high spiking levels were calculated as 95.5%-105.4%, 98.2%-114.0% and 92.2%-108.9%, respectively. Acceptable within-laboratory reproducibility (RSD<7.0%) substantially supported the use of current method for robust analysis. Rapid pretreatment procedures and short run time (8 min per sample) ensured good efficiency of metabolism profiling, indicating a wide application for investigating short-term internal exposure of dietary acrylamide. Our proposed UHPLC-MS/MS method was successfully applied to the toxicokinetic study of acrylamide in rats. Meanwhile, results of human urine analysis indicated that the levels of N-acetyl-S-(2-carbamoylethyl)-L-cysteine-sulfoxide (AAMA-sul), which did not appear in the mercapturic acid metabolites in rodents, were more than the sum of GAMA and N-acetyl-S-(1-carbamoyl-2-hydroxyethyl)-L-cysteine (iso-GAMA). Thus, AAMA-sul may alternatively become a specific biomarker for investigating the acrylamide exposure in humans. Current proposed method provides a substantial methodology support for comprehensive profiling of

  12. Modeling 3D conjugate heat and mass transfer for turbulent air drying of Chilean papaya in a direct contact dryer

    NASA Astrophysics Data System (ADS)

    Lemus-Mondaca, Roberto A.; Vega-Gálvez, Antonio; Zambra, Carlos E.; Moraga, Nelson O.

    2016-03-01

    A 3D model considering heat and mass transfer for food dehydration inside a direct contact dryer is studied. The k- ɛ model is used to describe turbulent air flow. The samples thermophysical properties as density, specific heat, and thermal conductivity are assumed to vary non-linearly with temperature. FVM, SIMPLE algorithm based on a FORTRAN code are used. Results unsteady velocity, temperature, moisture, kinetic energy and dissipation rate for the air flow are presented, whilst temperature and moisture values for the food also are presented. The validation procedure includes a comparison with experimental and numerical temperature and moisture content results obtained from experimental data, reaching a deviation 7-10 %. In addition, this turbulent k- ɛ model provided a better understanding of the transport phenomenon inside the dryer and sample.

  13. Stress in dilute suspensions

    NASA Technical Reports Server (NTRS)

    Passman, Stephen L.

    1989-01-01

    Generally, two types of theory are used to describe the field equations for suspensions. The so-called postulated equations are based on the kinetic theory of mixtures, which logically should give reasonable equations for solutions. The basis for the use of such theory for suspensions is tenuous, though it at least gives a logical path for mathematical arguments. It has the disadvantage that it leads to a system of equations which is underdetermined, in a sense that can be made precise. On the other hand, the so-called averaging theory starts with a determined system, but the very process of averaging renders the resulting system underdetermined. A third type of theory is proposed in which the kinetic theory of gases is used to motivate continuum equations for the suspended particles. This entails an interpretation of the stress in the particles that is different from the usual one. Classical theory is used to describe the motion of the suspending medium. The result is a determined system for a dilute suspension. Extension of the theory to more concentrated systems is discussed.

  14. Continental Land Mass Air Traffic Control (COLM ATC). [using three artificial satellite configurations

    NASA Technical Reports Server (NTRS)

    Pecar, J. A.; Henrich, J. E.

    1973-01-01

    The application of various satellite systems and techniques relative to providing air traffic control services for the continental United States was studied. Three satellite configurations were reviewed. The characteristics and capabilities of the satellites are described. The study includes consideration for the various ranging waveforms, multiple access alternatives, and the power and bandwidth required as a function of the number of users.

  15. Aerosol composition and properties variation at the ground and over the column under different air masses advection in South Italy.

    PubMed

    Pavese, G; Lettino, A; Calvello, M; Esposito, F; Fiore, S

    2016-04-01

    Aerosol composition and properties variation under the advection of different air masses were investigated, as case studies, by contemporary measurements over the atmospheric column and at the ground in a semi-rural site in South Italy. The absence of local strong sources in this area allowed to characterize background aerosol and to compare particle mixing effects under various atmospheric circulation conditions. Aerosol optical depth (AOD) and Ǻngström parameters from radiometric measurements allowed the detection and identification of polluted, dust, and volcanic atmospheric conditions. AODs were the input for a suitable model to evaluate the columnar aerosol composition, according to six main atmospheric components (water-soluble, soot, sea salt accumulation, sea salt coarse, mineral dus,t and biological). Scanning electron microscope (SEM) analysis of particulate sampled with a 13-stage impactor at the ground showed not only fingerprints typical of the different air masses but also the effects of transport and aging on atmospheric particles, suggesting processes that changed their chemical and optical properties. Background columnar aerosol was characterized by 72% of water-soluble and soot, in agreement with ground-based findings that highlighted 60% of contribution from anthropogenic carbonate particles and soot. In general, a good agreement between ground-based and columnar results was observed. Under the advection of trans-boundary air masses, water-soluble and soot were always present in columnar aerosol, whereas, in variable percentages, sea salt and mineral particles characterized both dust and volcanic conditions. At the ground, sulfates characterized the amorphous matrix produced in finer stages by the evaporation of solutions of organic and inorganic aerosols. Sulfates were also one of the key players involved in heterogeneous chemical reactions, producing complex secondary aerosol, as such clay-sulfate internally mixed particle externally mixed

  16. Detection of biological particles in ambient air using Bio-Aerosol Mass Spectrometry

    SciTech Connect

    McJimpsey, E L; Steele, P T; Coffee, K R; Fergenson, D P; Riot, V J; Woods, B W; Gard, E E; Frank, M; Tobias, H J; Lebrilla, C

    2006-03-16

    The Bio-Aerosol Mass Spectrometry (BAMS) system is an instrument used for the real time detection and identification of biological aerosols. Particles are drawn from the atmosphere directly into vacuum and tracked as they scatter light from several continuous wave lasers. After tracking, the fluorescence of individual particles is excited by a pulsed 266nm or 355nm laser. Molecules from those particles with appropriate fluorescence properties are subsequently desorbed and ionized using a pulsed 266nm laser. Resulting ions are analyzed in a dual polarity mass spectrometer. During two field deployments at the San Francisco International Airport, millions of ambient particles were analyzed and a small but significant fraction were found to have fluorescent properties similar to Bacillus spores and vegetative cells. Further separation of non-biological background particles from potential biological particles was accomplished using laser desorption/ionization mass spectrometry. This has been shown to enable some level of species differentiation in specific cases, but the creation and observation of higher mass ions is needed to enable a higher level of specificity across more species. A soft ionization technique, matrix-assisted laser desorption/ionization (MALDI) is being investigated for this purpose. MALDI is particularly well suited for mass analysis of biomolecules since it allows for the generation of molecular ions from large mass compounds that would fragment under normal irradiation. Some of the initial results from a modified BAMS system utilizing this technique are described.

  17. Plasma flame for mass purification of contaminated air with chemical and biological warfare agents

    SciTech Connect

    Uhm, Han S.; Shin, Dong H.; Hong, Yong C.

    2006-09-18

    An elimination of airborne simulated chemical and biological warfare agents was carried out by making use of a plasma flame made of atmospheric plasma and a fuel-burning flame, which can purify the interior air of a large volume in isolated spaces such as buildings, public transportation systems, and military vehicles. The plasma flame generator consists of a microwave plasma torch connected in series to a fuel injector and a reaction chamber. For example, a reaction chamber, with the dimensions of a 22 cm diameter and 30 cm length, purifies an airflow rate of 5000 lpm contaminated with toluene (the simulated chemical agent) and soot from a diesel engine (the simulated aerosol for biological agents). Large volumes of purification by the plasma flame will free mankind from the threat of airborne warfare agents. The plasma flame may also effectively purify air that is contaminated with volatile organic compounds, in addition to eliminating soot from diesel engines as an environmental application.

  18. Smart tetroons for Lagrangian air-mass tracking during ACE 1

    NASA Astrophysics Data System (ADS)

    Businger, Steven; Johnson, Randy; Katzfey, Jack; Siems, Steven; Wang, Qing

    1999-05-01

    A series of "smart" tetroons was released from shipboard during the recent ACE 1 field experiment designed to monitor changes in the sulfur budget in a remote marine boundary layer (MBL) south of Tasmania, Australia. The smart tetroons were designed at NOAA Air Resources Laboratory Field Research Division to provide air parcel tracking information. The adjective smart here refers here to the fact that the buoyancy of the tetroons automatically adjusts through the action of a pump and valves when the tetroon travels vertically outside a range of pressures set prior to tetroon release. The smart tetroon design provides GPS location, barometric pressure, temperature, relative humidity, and tetroon status data via a transponder to the NCAR C-130 research aircraft flying in the vicinity of the tetroons. In this paper we will describe (1) the design and capability of the smart tetroons and their performance during the two Lagrangian experiments conducted during ACE 1, (2) the synoptic context of the Lagrangians, including the origin of the air parcels being tracked, and (3) the results of trajectory predictions derived from the National Center for Environmental Prediction (NCEP) Global Spectral Model (GSM) and Australia's Commonwealth Scientific and Industrial Research Organization (CSIRO) Division of Atmospheric Research (DAR) limited-area model.

  19. Mass transfer of volatile organic compounds from drinking water to indoor air: The role of residential dishwashers

    SciTech Connect

    Howard-Reed, C.; Corsi, R.L.; Moya, J.

    1999-07-01

    Contaminated tap water may be a source of volatile organic compounds (VOCs) in residential indoor air. To better understand the extent and impact of chemical emissions from this source, a two-phase mass balance model was developed based on mass transfer kinetics between each phase. Twenty-nine experiments were completed using a residential dishwasher to determine model parameters. During each experiment, inflow water was spiked with a cocktail of chemical tracers with a wide range of physicochemical properties. In each case, the effects of water temperature, detergent, and dish-loading pattern on chemical stripping efficiencies and mass transfer coefficients were determined. Dishwasher headspace ventilation rates were also measured using an isobutylene tracer gas. Chemical stripping efficiencies for a single cycle ranged from 18% to 55% for acetone, from 96% to 98% for toluene, and from 97% to 98% for ethylbenzene and were consistently 100% for cyclohexane. Experimental results indicate that dishwashers have a relatively low but continuous ventilation rate that results in significant chemical storage within the headspace of the dishwasher. In conjunction with relatively high mass transfer coefficients, low ventilation rates generally lead to emissions that are limited by equilibrium conditions after approximately 1--2 min of dishwasher operation.

  20. Interaction of clothing and body mass index affects validity of air displacement plethysmography in adults

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Objective: Examine the effect of alternate clothing schemes on validity of Bod Pod to estimate percent body fat (BF) compared to dual x-ray absorptiometry (DXA), and determine if these effects differ by body mass index (BMI). Design: Cross-sectional Subjects: 132 healthy adults aged 19-81 classifi...

  1. Dilution refrigeration for space applications

    NASA Technical Reports Server (NTRS)

    Israelsson, U. E.; Petrac, D.

    1990-01-01

    Dilution refrigerators are presently used routinely in ground based applications where temperatures below 0.3 K are required. The operation of a conventional dilution refrigerator depends critically on the presence of gravity. To operate a dilution refrigerator in space many technical difficulties must be overcome. Some of the anticipated difficulties are identified in this paper and possible solutions are described. A single cycle refrigerator is described conceptually that uses forces other than gravity to function and the stringent constraints imposed on the design by requiring the refrigerator to function on the earth without using gravity are elaborated upon.

  2. Determination of cooling air mass flow for a horizontally-opposed aircraft engine installation

    NASA Technical Reports Server (NTRS)

    Miley, S. J.; Cross, E. J., Jr.; Ghomi, N. A.; Bridges, P. D.

    1979-01-01

    The relationship between the amount of cooling air flow and the corresponding flow pressure difference across an aircraft engine was investigated in flight and on the ground. The flight test results were consistent with theory, but indicated a significant installation leakage problem. A ground test blower system was used to identify and reduce the leakage. The correlation between ground test cell determined engine orifice characteristics and flight measurements showed good agreement if the engine pressure difference was based on total pressure rather than static pressure.

  3. An air-mass trajectory study of the transport of radioactivity from Fukushima to Thessaloniki, Greece and Milan, Italy

    NASA Astrophysics Data System (ADS)

    Ioannidou, A.; Giannakaki, E.; Manolopoulou, M.; Stoulos, S.; Vagena, E.; Papastefanou, C.; Gini, L.; Manenti, S.; Groppi, F.

    2013-08-01

    Analyses of 131I, 137Cs and 134Cs in airborne aerosols were carried out in daily samples at two different sites of investigation: Thessaloniki, Greece (40° N) and Milan, Italy (45° N) after the Fukushima accident during the period of March-April, 2011. The radionuclide concentrations were determined and studied as a function of time. The 131I concentration in air over Milan and Thessaloniki peaked on April 3-4, 2011, with observed activities 467 μBq m-3 and 497 μBq m-3, respectively. The 134Cs/137Cs activity ratio values in air were around 1 in both regions, related to the burn-up history of the damaged nuclear fuel of the destroyed nuclear reactor. The high 131I/137Cs ratio, observed during the first days after the accident, followed by lower values during the following days, reflects not only the initial release ratio but also the different volatility, attachment and removal of the two isotopes during transportation due to their different physico-chemical properties. No artificial radionuclides could be detected in air after April 28, 2011 in both regions of investigation. The different maxima of airborne 131I and 134,137Cs in these two regions were related to long-range air mass transport from Japan, across the Pacific and to Central Europe. Analysis of backward trajectories was used to confirm the arrival of artificial radionuclides following atmospheric transport and processing. HYSPLIT backward trajectories were applied for the interpretation of activity variations of measured radionuclides.

  4. Modeling syngas-fired gas turbine engines with two dilutants

    NASA Astrophysics Data System (ADS)

    Hawk, Mitchell E.

    2011-12-01

    Prior gas turbine engine modeling work at the University of Wyoming studied cycle performance and turbine design with air and CO2-diluted GTE cycles fired with methane and syngas fuels. Two of the cycles examined were unconventional and innovative. The work presented herein reexamines prior results and expands the modeling by including the impacts of turbine cooling and CO2 sequestration on GTE cycle performance. The simple, conventional regeneration and two alternative regeneration cycle configurations were examined. In contrast to air dilution, CO2 -diluted cycle efficiencies increased by approximately 1.0 percentage point for the three regeneration configurations examined, while the efficiency of the CO2-diluted simple cycle decreased by approximately 5.0 percentage points. For CO2-diluted cycles with a closed-exhaust recycling path, an optimum CO2-recycle pressure was determined for each configuration that was significantly lower than atmospheric pressure. Un-cooled alternative regeneration configurations with CO2 recycling achieved efficiencies near 50%, which was approximately 3.0 percentage points higher than the conventional regeneration cycle and simple cycle configurations that utilized CO2 recycling. Accounting for cooling of the first two turbine stages resulted in a 2--3 percentage point reduction in un-cooled efficiency, with air dilution corresponding to the upper extreme. Additionally, when the work required to sequester CO2 was accounted for, cooled cycle efficiency decreased by 4--6 percentage points, and was more negatively impacted when syngas fuels were used. Finally, turbine design models showed that turbine blades are shorter with CO2 dilution, resulting in fewer design restrictions.

  5. Quantification of the 2-deoxyribonolactone and nucleoside 5’-aldehyde products of 2-deoxyribose oxidation in DNA and cells by isotope-dilution gas chromatography mass spectrometry: Differential effects of γ-radiation and Fe2+-EDTA

    PubMed Central

    Chan, Wan; Chen, Bingzi; Wang, Lianrong; Taghizadeh, Koli; Demott, Michael S.; Dedon, Peter C.

    2010-01-01

    The oxidation of 2-deoxyribose in DNA has emerged as a critical determinant of the cellular toxicity of oxidative damage to DNA, with oxidation of each carbon producing a unique spectrum of electrophilic products. We have developed and validated an isotope-dilution gas chromatography-coupled mass spectrometry (GC-MS) method for the rigorous quantification of two major 2-deoxyribose oxidation products: the 2-deoxyribonolactone abasic site of 1’-oxidation and the nucleoside 5’-aldehyde of 5’-oxidation chemistry. The method entails elimination of these products as 5-methylene-2(5H)-furanone (5MF) and furfural, respectively, followed by derivatization with pentafluorophenylhydrazine (PFPH), addition of isotopically labeled PFPH derivatives as internal standards, extraction of the derivatives, and quantification by GC-MS analysis. The precision and accuracy of the method were validated with oligodeoxynucleotides containing the 2-deoxyribonolactone and nucleoside 5’-aldehyde lesions. Further, the well defined 2-deoxyribose oxidation chemistry of the enediyne antibiotics, neocarzinostatin and calicheamicin γ1I, was exploited in control studies, with neocarzinostatin producing 10 2-deoxyribonolactone and 300 nucleoside 5’-aldehyde per 106 nt per µM in accord with its established minor 1’- and major 5’-oxidation chemistry. Calicheamicin unexpectedly caused 1’-oxidation at a low level of 10 2-deoxyribonolactone per 106 nt per µM in addition to the expected predominance of 5’-oxidation at 560 nucleoside 5’-aldehyde per 106 nt per µM. The two hydroxyl radical-mediated DNA oxidants, γ-radiation and Fe2+-EDTA, produced nucleoside 5’-aldehyde at a frequency of 57 per 106 nt per Gy (G-value 74 nmol/J) and 3.5 per 106 nt per µM, respectively, which amounted to 40% and 35%, respectively, of total 2-deoxyribose oxidation as measured by a plasmid nicking assay. However, γ-radiation and Fe2+-EDTA produced different proportions of 2-deoxyribonolactone at 7

  6. Numerical simulation for the influence of laser-induced plasmas addition on air mass capture of hypersonic inlet

    NASA Astrophysics Data System (ADS)

    Zhao, Wei; Dou, Zhiguo; Li, Qian

    2012-03-01

    The theory of laser-induced plasmas addition to hypersonic airflow off a vehicle to increase air mass capture and improve the performance of hypersonic inlets at Mach numbers below the design value is explored. For hypersonic vehicles, when flying at mach numbers lower than the design one, we can increase the mass capture ratio of inlet through laser-induced plasmas injection to the hypersonic flow upstream of cowl lip to form a virtual cowl. Based on the theory, the model of interaction between laser-induced plasmas and hypersonic flow was established. The influence on the effect of increasing mass capture ratio was studied at different positions of laser-induced plasmas region for the external compression hypersonic inlet at Mach 5 while the design value is 6, the power of plasmas was in the range of 1-8mJ. The main results are as follows: 1. the best location of the plasma addition region is near the intersection of the nose shock of the vehicle with the continuation of the cowl line, and slightly below that line. In that case, the shock generated by the heating is close to the shock that is a reflection of the vehicle nose shock off the imaginary solid surface-extension of the cowl. 2. Plasma addition does increase mass capture, and the effect becomes stronger as more energy is added, the peak value appeared when the power of plasma was about 4mJ, when the plasma energy continues to get stronger, the mass capture will decline slowly.

  7. Diagnosis of medium chain acyl-CoA dehydrogenase deficiency by stable isotope dilution analysis of urinary acylglycines: Retrospective and prospective studies, and comparison of its accuracy to acylcarnitine identification by FAB/mass spectrometry

    SciTech Connect

    Rinaldo, P.; O'Shea, J.J.; Welch, R.D.; Tanaka, K. )

    1990-01-01

    In summary, we have demonstrated that the accurate quantitation of urinary HG and PPG by stable isotope dilution analysis is currently the most reliable method for the diagnosis of MCAD deficiency. This method is particularly useful for testing random samples from asymptomatic patients without any provocative test, and it is suitable to widely survey a fairly large population, such as patients with episodic manifestations and families with a history of SIDS.

  8. Derivation of Equivalent Continuous Dilution for Cyclic, Unsteady Driving Forces

    SciTech Connect

    Lawrence Berkeley National Laboratory; Technical University of Denmark, Department of Civil Engineering; Mortensen, Dorthe K.; Walker, Iain S.; Sherman, Max H.

    2010-12-15

    This article uses an analytical approach to determine the dilution of an unsteadily-generated solute in an unsteady solvent stream, under cyclic temporal boundary conditions. The goal is to find a simplified way of showing equivalence of such a process to a reference case where equivalent dilution is defined as a weighted average concentration. This derivation has direct applications to the ventilation of indoor spaces where indoor air quality and energy consumption cannot in general be simultaneously optimized. By solving the equation we can specify how much air we need to use in one ventilation pattern compared to another to obtain same indoor air quality. Because energy consumption is related to the amount of air exchanged by a ventilation system, the equation can be used as a first step to evaluate different ventilation patterns effect on the energy consumption. The use of the derived equation is demonstrated by representative cases of interest in both residential and non-residential buildings.

  9. Intermittency in dilute granular flows

    NASA Astrophysics Data System (ADS)

    Guo, Wenxuan; Zhang, Qiang; Wylie, Jonathan J.

    2016-07-01

    In this letter, we show that dilute granular systems can exhibit a type of intermittency that has no analogue in gas dynamics. We consider a simple system in which a very dilute set of granular particles falls under gravity through a nozzle. This setting is analogous to the classical problem of high-speed nozzle flow in the study of compressible gases. It is well known that very dilute granular systems exhibit behavior qualitatively similar to gases, and that gas flowing through a nozzle does not exhibit intermittency. Nevertheless, we show that the intermittency in dilute granular nozzle flows can occur and corresponds to complicated transitions between supersonic and subsonic regimes. We also provide detailed explanations of the mechanism underlying this phenomenon.

  10. Cluster approach to dilute magnetism

    NASA Astrophysics Data System (ADS)

    Holvorcem, Paulo R. C.; Osório, Roberto

    1988-10-01

    A cluster algebra is developed for the definition of independent correlation functions in the cluster-variation method (CVM) for the spin-1 Ising model. A scheme is then introduced for the study of site-dilute spin- {1}/{2} Ising models by means of the CVM. The procedure regards the site-dilute spin- {1}/{2} model as the spin-1 model with additional constraints due to dilution. The Desjardins-Steinsvoll algortihm is used for the transformation of the CVM equations into a set of differential equations for the independent correlation functions with the inverse temperature as parameter. The evolution of the correlation functions with temperature and the behavior of response functions such as the specific heat and the susceptability are then obtained for any degree of dilution. As an introduction to this scheme, its detailed application is presented here for the simple case of the pair approximation.

  11. Air-sea fluxes and satellite-based estimation of water masses formation

    NASA Astrophysics Data System (ADS)

    Sabia, Roberto; Klockmann, Marlene; Fernandez-Prieto, Diego; Donlon, Craig

    2015-04-01

    Recent work linking satellite-based measurements of sea surface salinity (SSS) and sea surface temperature (SST) with traditional physical oceanography has demonstrated the capability of generating routinely satellite-derived surface T-S diagrams [1] and analyze the distribution/dynamics of SSS and its relative surface density with respect to in-situ measurements. Even more recently [2,3], this framework has been extended by exploiting these T-S diagrams as a diagnostic tool to derive water masses formation rates and areas. A water mass describes a water body with physical properties distinct from the surrounding water, formed at the ocean surface under specific conditions which determine its temperature and salinity. The SST and SSS (and thus also density) at the ocean surface are largely determined by fluxes of heat and freshwater. The surface density flux is a function of the latter two and describes the change of the density of seawater at the surface. To obtain observations of water mass formation is of great interest, since they serve as indirect observations of the thermo-haline circulation. The SSS data which has become available through the SMOS [4] and Aquarius [5] satellite missions will provide the possibility of studying also the effect of temporally-varying SSS fields on water mass formation. In the present study, the formation of water masses as a function of SST and SSS is derived from the surface density flux by integrating the latter over a specific area and time period in bins of SST and SSS and then taking the derivative of the total density flux with respect to density. This study presents a test case using SMOS SSS, OSTIA SST, as well as Argo ISAS SST and SSS for comparison, heat fluxes from the NOCS Surface Flux Data Set v2.0, OAFlux evaporation and CMORPH precipitation. The study area, initially referred to the North Atlantic, is extended over two additional ocean basins and the study period covers the 2011-2012 timeframe. Yearly, seasonal

  12. Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface.

    PubMed

    Ramus, Ksenia; Kopinke, Frank-Dieter; Georgi, Anett

    2012-01-01

    The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.

  13. Dynamics of atmospheres with a non-dilute condensible component

    NASA Astrophysics Data System (ADS)

    Pierrehumbert, Raymond T.; Ding, Feng

    2016-06-01

    The diversity of characteristics for the host of recently discovered exoplanets opens up a great deal of fertile new territory for geophysical fluid dynamics, particularly when the fluid flow is coupled to novel thermodynamics, radiative transfer or chemistry. In this paper, we survey one of these new areas-the climate dynamics of atmospheres with a non-dilute condensible component, defined as the situation in which a condensible component of the atmosphere makes up a substantial fraction of the atmospheric mass within some layer. Non-dilute dynamics can occur for a wide range of condensibles, generically applying near both the inner and the outer edges of the conventional habitable zone and in connection with runaway greenhouse phenomena. It also applies in a wide variety of other planetary circumstances. We first present a number of analytical results developing some key features of non-dilute atmospheres, and then show how some of these features are manifest in simulations with a general circulation model adapted to handle non-dilute atmospheres. We find that non-dilute atmospheres have weak horizontal temperature gradients even for rapidly rotating planets, and that their circulations are largely barotropic. The relative humidity of the condensible component tends towards 100% as the atmosphere becomes more non-dilute, which has important implications for runaway greenhouse thresholds. Non-dilute atmospheres exhibit a number of interesting organized convection features, for which there is not yet any adequate theoretical understanding.

  14. Uncertainties in Modelling Glacier Melt and Mass Balances: the Role of Air Temperature Extrapolation and Type of Melt Models

    NASA Astrophysics Data System (ADS)

    Pellicciotti, F.; Ragettli, S.; Carenzo, M.; Ayala, A.; McPhee, J. P.; Stoffel, M.

    2014-12-01

    While glacier responses to climate are understood in general terms and in their main trends, model based projections are affected by the type of model used and uncertainties in the meteorological input data, among others. Recent works have attempted at improving glacio-hydrological models by including neglected processes and investigating uncertainties in their outputs. In this work, we select two knowledge gaps in current modelling practices and illustrate their importance through modelling with a fully distributed mass balance model that includes some of the state of the art approaches for calculations of glacier ablation, accumulation and glacier geometry changes. We use an advanced mass balance model applied to glaciers in the Andes of Chile, Swiss Alps and Nepalese Himalaya to investigate two issues that seem of importance for a sound assessment of glacier changes: 1) the use of physically-based models of glacier ablation (energy balance) versus more empirical models (enhanced temperature index approaches); 2) the importance of the correct extrapolation of air temperature forcing on glaciers and the large uncertainty in model outputs associated with it. The ablation models are calibrated with a large amount of data from in-situ campaigns, and distributed observations of air temperature used to calculate lapse rates and calibrate a thermodynamic model of temperature distribution. We show that no final assessment can be made of what type of melt model is more appropriate or accurate for simulation of glacier ablation at the glacier scale, not even for relatively well studied glaciers. Both models perform in a similar manner at low elevations, but important differences are evident at high elevations, where lack of data prevents a final statement on which model better represent the actual ablation amounts. Accurate characterization of air temperature is important for correct simulations of glacier mass balance and volume changes. Substantial differences are

  15. What is the role of wind pumping on heat and mass transfer rates at the air-snow interface?

    NASA Astrophysics Data System (ADS)

    Helgason, W.; Pomeroy, J. W.

    2010-12-01

    Accurate prediction of the turbulent exchange of sensible heat and water vapour between the atmosphere and snowpack remains a challenging task under all but the most ideal conditions. Heat and mass transfer coefficients that recognize the unique properties of the snow surface are warranted. A particular area requiring improvement concerns the role of the porous nature of snow which provides a large surface area for heat and mass exchange with the atmosphere. Wind-pumping has long been considered as a viable mechanism for incorporating aerosols into snowpacks; however these processes are not considered in parameterization schemes for heat and mass transfer near the surface. This study attempts to determine the degree to which wind pumping can increase the rates of heat and mass transfer to snow, and to ascertain which structural properties of the snowpack are needed for inclusion in heat and mass transfer coefficients that reflect wind pumping processes. Based upon a review of recent geophysical and engineering literature where porous surfaces are exploited for their ability to augment heat and mass transfer rates, a technical analysis was conducted. Numerous conceptual mechanisms of wind pumping were considered: topographically-induced flow; barometric pressure changes; high frequency pressure fluctuations at the surface; and steady flow in the interfacial region. A sensitivity analysis was performed, subjecting each conceptual model to varying thermal and hydraulic conditions at the air-snow interface, as well as variable micro-structural properties of snow. It is shown that the rate of heat and mass exchange is most sensitive to the interfacial thermal conditions and factors controlling the energy balance of the uppermost snow grains. The effect upon the thermal regime of the snowpack was found to be most significant for mechanisms of wind pumping that result in shorter flow paths near the surface, rather than those caused by low frequency pressure changes. In

  16. DAVINCI: Dilute Aperture VIsible Nulling Coronagraphic Imager

    NASA Technical Reports Server (NTRS)

    Shao, Michael; Levine, B. M.; Vasisht, G.; Lane, B. F.; Woodruff, R.; Vasudevan, G.; Samuele, R.; Lloyd, C. A.; Clampin, M.; Lyon, R.; Guyon, O.

    2008-01-01

    This slide presentation gives an overview of DAVINCI (Dilute Aperture VIsible Nulling Coronagraphic Imager). The presentation also includes information about dilute aperture coronagraph, and lyot efficiency.

  17. Precision of a field method for determination of pH in dilute lakes

    USGS Publications Warehouse

    Turk, J.T.

    1986-01-01

    Replicate pH measurements in three dilute lakes made during extreme conditions indicate that pH can be measured in the field with a variance due to measurement error of 0.005 unit. Error of the field technique in measuring the pH of dilute solutions in the laboratory ranges from less than 0.01 unit in dilute strong-acid solutions to about 0.05 unit in air-saturated deionized water.

  18. Seasonal variability of tritium and ion concentrations in rain at Kumamoto, Japan and back-trajectory analysis of air mass

    SciTech Connect

    Momoshima, N.; Sugihara, S.; Toyoshima, T.; Nagao, Y.; Takahashi, M.; Nakamura, Y.

    2008-07-15

    Tritium and major ion concentrations in rain were analyzed in Kumamoto (Japan)) between 2001 and 2006 to examine present tritium concentration and seasonal variation. The average tritium concentration was 0.36 {+-} 0.19 Bq/L (n=104) and higher tritium concentrations were observed in spring than the other seasons. Among the ions, non-sea-salt (nss) SO{sub 4}{sup 2}'- showed higher concentration in winter while other ions did not show marked increase in winter. Based on the back-trajectory analyses of air masses, the increase in tritium concentrations in spring arises from downward movement of naturally produced tritium from stratosphere to troposphere, while the increase of the nss-SO{sub 4}{sup 2-} concentrations in winter is due to long range transport of pollutants from China to Japan. (authors)

  19. Distinct synoptic patterns and air masses responsible for long-range desert dust transport and sea spray in Palermo, Italy

    NASA Astrophysics Data System (ADS)

    Dimitriou, K.; Paschalidou, A. K.; Kassomenos, P. A.

    2016-09-01

    Undoubtedly, anthropogenic emissions carry a large share of the risk posed on public health by particles exposure in urban areas. However, natural emissions, in the form of desert dust and sea spray, are well known to contribute significantly to the PM load recorded in many Mediterranean environments, posing an extra risk burden on public health. In the present paper, we examine the synoptic climatology in a background station in Palermo, Italy, through K-means clustering of the mean sea-level pressure (MSLP) maps, in an attempt to associate distinct synoptic patterns with increased PM10 levels. Four-day backward trajectory analysis is then applied, in order to study the origins and pathways of air masses susceptible of PM10 episodes. It is concluded that a number of atmospheric patterns result in several kind of flows, namely south, west, and slow-moving/stagnant flows, associated with long-range dust transport and sea spray.

  20. Brief Communication: Upper-air relaxation in RACMO2 significantly improves modelled interannual surface mass balance variability in Antarctica

    NASA Astrophysics Data System (ADS)

    van de Berg, Willem Jan; Medley, Brooke

    2016-03-01

    The Regional Atmospheric Climate Model (RACMO2) has been a powerful tool for improving surface mass balance (SMB) estimates from GCMs or reanalyses. However, new yearly SMB observations for West Antarctica show that the modelled interannual variability in SMB is poorly simulated by RACMO2, in contrast to ERA-Interim, which resolves this variability well. In an attempt to remedy RACMO2 performance, we included additional upper-air relaxation (UAR) in RACMO2. With UAR, the correlation to observations is similar for RACMO2 and ERA-Interim. The spatial SMB patterns and ice-sheet-integrated SMB modelled using UAR remain very similar to the estimates of RACMO2 without UAR. We only observe an upstream smoothing of precipitation in regions with very steep topography like the Antarctic Peninsula. We conclude that UAR is a useful improvement for regional climate model simulations, although results in regions with steep topography should be treated with care.

  1. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schindler, Matthias; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-01

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO2 and reduced to graphite to determine 14C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  2. Persistent organic contaminants in Saharan dust air masses in West Africa, Cape Verde and the eastern Caribbean

    USGS Publications Warehouse

    Garrison, Virginia H.; Majewski, Michael S.; Foreman, William T.; Genualdi, Susan A.; Mohammed, Azad; Massey Simonich, Stacy L.

    2014-01-01

    Anthropogenic semivolatile organic compounds (SOCs) that persist in the environment, bioaccumulate, are toxic at low concentrations, and undergo long-range atmospheric transport (LRT) were identified and quantified in the atmosphere of a Saharan dust source region (Mali) and during Saharan dust incursions at downwind sites in the eastern Caribbean (U.S. Virgin Islands, Trinidad and Tobago) and Cape Verde. More organochlorine and organophosphate pesticides (OCPPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyl (PCB) congeners were detected in the Saharan dust region than at downwind sites. Seven of the 13 OCPPs detected occurred at all sites: chlordanes, chlorpyrifos, dacthal, dieldrin, endosulfans, hexachlorobenzene (HCB), and trifluralin. Total SOCs ranged from 1.9–126 ng/m3 (mean = 25 ± 34) at source and 0.05–0.71 ng/m3 (mean = 0.24 ± 0.18) at downwind sites during dust conditions. Most SOC concentrations were 1–3 orders of magnitude higher in source than downwind sites. A Saharan source was confirmed for sampled air masses at downwind sites based on dust particle elemental composition and rare earth ratios, atmospheric back trajectory models, and field observations. SOC concentrations were considerably below existing occupational and/or regulatory limits; however, few regulatory limits exist for these persistent organic compounds. Long-term effects of chronic exposure to low concentrations of SOCs are unknown, as are possible additive or synergistic effects of mixtures of SOCs, biologically active trace metals, and mineral dust particles transported together in Saharan dust air masses.

  3. Development of portable mass spectrometer with electron cyclotron resonance ion source for detection of chemical warfare agents in air.

    PubMed

    Urabe, Tatsuya; Takahashi, Kazuya; Kitagawa, Michiko; Sato, Takafumi; Kondo, Tomohide; Enomoto, Shuichi; Kidera, Masanori; Seto, Yasuo

    2014-01-01

    A portable mass spectrometer with an electron cyclotron resonance ion source (miniECRIS-MS) was developed. It was used for in situ monitoring of trace amounts of chemical warfare agents (CWAs) in atmospheric air. Instrumental construction and parameters were optimized to realize a fast response, high sensitivity, and a small body size. Three types of CWAs, i.e., phosgene, mustard gas, and hydrogen cyanide were examined to check if the mass spectrometer was able to detect characteristic elements and atomic groups. From the results, it was found that CWAs were effectively ionized in the miniECRIS-MS, and their specific signals could be discerned over the background signals of air. In phosgene, the signals of the 35Cl+ and 37Cl+ ions were clearly observed with high dose-response relationships in the parts-per-billion level, which could lead to the quantitative on-site analysis of CWAs. A parts-per-million level of mustard gas, which was far lower than its lethal dosage (LCt50), was successfully detected with a high signal-stability of the plasma ion source. It was also found that the chemical forms of CWAs ionized in the plasma, i.e., monoatomic ions, fragment ions, and molecular ions, could be detected, thereby enabling the effective identification of the target CWAs. Despite the disadvantages associated with miniaturization, the overall performance (sensitivity and response time) of the miniECRIS-MS in detecting CWAs exceeded those of sector-type ECRIS-MS, showing its potential for on-site detection in the future. PMID:24211802

  4. Development of portable mass spectrometer with electron cyclotron resonance ion source for detection of chemical warfare agents in air.

    PubMed

    Urabe, Tatsuya; Takahashi, Kazuya; Kitagawa, Michiko; Sato, Takafumi; Kondo, Tomohide; Enomoto, Shuichi; Kidera, Masanori; Seto, Yasuo

    2014-01-01

    A portable mass spectrometer with an electron cyclotron resonance ion source (miniECRIS-MS) was developed. It was used for in situ monitoring of trace amounts of chemical warfare agents (CWAs) in atmospheric air. Instrumental construction and parameters were optimized to realize a fast response, high sensitivity, and a small body size. Three types of CWAs, i.e., phosgene, mustard gas, and hydrogen cyanide were examined to check if the mass spectrometer was able to detect characteristic elements and atomic groups. From the results, it was found that CWAs were effectively ionized in the miniECRIS-MS, and their specific signals could be discerned over the background signals of air. In phosgene, the signals of the 35Cl+ and 37Cl+ ions were clearly observed with high dose-response relationships in the parts-per-billion level, which could lead to the quantitative on-site analysis of CWAs. A parts-per-million level of mustard gas, which was far lower than its lethal dosage (LCt50), was successfully detected with a high signal-stability of the plasma ion source. It was also found that the chemical forms of CWAs ionized in the plasma, i.e., monoatomic ions, fragment ions, and molecular ions, could be detected, thereby enabling the effective identification of the target CWAs. Despite the disadvantages associated with miniaturization, the overall performance (sensitivity and response time) of the miniECRIS-MS in detecting CWAs exceeded those of sector-type ECRIS-MS, showing its potential for on-site detection in the future.

  5. Persistent organic contaminants in Saharan dust air masses in West Africa, Cape Verde and the eastern Caribbean.

    PubMed

    Garrison, V H; Majewski, M S; Foreman, W T; Genualdi, S A; Mohammed, A; Massey Simonich, S L

    2014-01-15

    Anthropogenic semivolatile organic compounds (SOCs) that persist in the environment, bioaccumulate, are toxic at low concentrations, and undergo long-range atmospheric transport (LRT) were identified and quantified in the atmosphere of a Saharan dust source region (Mali) and during Saharan dust incursions at downwind sites in the eastern Caribbean (U.S. Virgin Islands, Trinidad and Tobago) and Cape Verde. More organochlorine and organophosphate pesticides (OCPPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyl (PCB) congeners were detected in the Saharan dust region than at downwind sites. Seven of the 13 OCPPs detected occurred at all sites: chlordanes, chlorpyrifos, dacthal, dieldrin, endosulfans, hexachlorobenzene (HCB), and trifluralin. Total SOCs ranged from 1.9-126 ng/m(3) (mean = 25 ± 34) at source and 0.05-0.71 ng/m(3) (mean = 0.24 ± 0.18) at downwind sites during dust conditions. Most SOC concentrations were 1-3 orders of magnitude higher in source than downwind sites. A Saharan source was confirmed for sampled air masses at downwind sites based on dust particle elemental composition and rare earth ratios, atmospheric back trajectory models, and field observations. SOC concentrations were considerably below existing occupational and/or regulatory limits; however, few regulatory limits exist for these persistent organic compounds. Long-term effects of chronic exposure to low concentrations of SOCs are unknown, as are possible additive or synergistic effects of mixtures of SOCs, biologically active trace metals, and mineral dust particles transported together in Saharan dust air masses. PMID:24055669

  6. A mass balance method for non-intrusive measurements of surface-air trace gas exchange

    NASA Astrophysics Data System (ADS)

    Denmead, O. T.; Harper, L. A.; Freney, J. R.; Griffith, D. W. T.; Leuning, R.; Sharpe, R. R.

    A mass balance method is described for calculating gas production from a surface or volume source in a small test plot from measurements of differences in the horizontal fluxes of the gas across upwind and downwind boundaries. It employs a square plot, 24 m×24 m, with measurements of gas concentration at four heights (up to 3.5 m) along each of the four boundaries. Gas concentrations are multiplied by the appropriate vector winds to yield the horizontal fluxes at each height on each boundary. The difference between these fluxes integrated over downwind and upwind boundaries represents production. Illustrations of the method, which involve exchanges of methane and carbon dioxide, are drawn from experiments with landfills, pastures and grazing animals. Tests included calculation of recovery rates from known gas releases and comparisons with a conventional micrometeorological approach and a backward dispersion model. The method performed satisfactorily in all cases. Its sensitivity for measuring exchanges of CO 2, CH 4 and N 2O in various scenarios was examined. As employed by us, the mass balance method can suffer from errors arising from the large number of gas analyses required for a flux determination, and becomes unreliable when there are light winds and variable wind directions. On the other hand, it is non-disturbing, has a simple theoretical basis, is independent of atmospheric stability or the shape of the wind profile, and is appropriate for flux measurement in situations where conventional micrometeorological methods can not be used, e.g. for small plots, elevated point sources, and heterogeneous surface sources.

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

    PubMed

    Spesyvyi, Anatolii; Smith, David; Španěl, Patrik

    2015-12-15

    A selected ion flow-drift tube mass spectrometric analytical technique, SIFDT-MS, is described that extends the established selected ion flow tube mass spectrometry, SIFT-MS, by the inclusion of a static but variable E-field along the axis of the flow tube reactor in which the analytical ion-molecule chemistry occurs. The ion axial speed is increased in proportion to the reduced field strength E/N (N is the carrier gas number density), and the residence/reaction time, t, which is measured by Hadamard transform multiplexing, is correspondingly reduced. To ensure a proper understanding of the physics and ion chemistry underlying SIFDT-MS, ion diffusive loss to the walls of the flow-drift tube and the mobility of injected H3O(+) ions have been studied as a function of E/N. It is seen that the derived diffusion coefficient and mobility of H3O(+) ions are consistent with those previously reported. The rate coefficient has been determined at elevated E/N for the association reaction of the H3O(+) reagent ions with H2O molecules, which is the first step in the production of H3O(+)(H2O)1,2,3 reagent hydrate ions. The production of hydrated analyte ion was also experimentally investigated. The analytical performance of SIFDT-MS is demonstrated by the quantification of acetone and isoprene in exhaled breath. Finally, the essential features of SIFDT-MS and SIFT-MS are compared, notably pointing out that a much lower speed of the flow-drive pump is required for SIFDT-MS, which facilitates the development of smaller cost-effective analytical instruments for real time breath and fluid headspace analyses.

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

    PubMed

    Spesyvyi, Anatolii; Smith, David; Španěl, Patrik

    2015-12-15

    A selected ion flow-drift tube mass spectrometric analytical technique, SIFDT-MS, is described that extends the established selected ion flow tube mass spectrometry, SIFT-MS, by the inclusion of a static but variable E-field along the axis of the flow tube reactor in which the analytical ion-molecule chemistry occurs. The ion axial speed is increased in proportion to the reduced field strength E/N (N is the carrier gas number density), and the residence/reaction time, t, which is measured by Hadamard transform multiplexing, is correspondingly reduced. To ensure a proper understanding of the physics and ion chemistry underlying SIFDT-MS, ion diffusive loss to the walls of the flow-drift tube and the mobility of injected H3O(+) ions have been studied as a function of E/N. It is seen that the derived diffusion coefficient and mobility of H3O(+) ions are consistent with those previously reported. The rate coefficient has been determined at elevated E/N for the association reaction of the H3O(+) reagent ions with H2O molecules, which is the first step in the production of H3O(+)(H2O)1,2,3 reagent hydrate ions. The production of hydrated analyte ion was also experimentally investigated. The analytical performance of SIFDT-MS is demonstrated by the quantification of acetone and isoprene in exhaled breath. Finally, the essential features of SIFDT-MS and SIFT-MS are compared, notably pointing out that a much lower speed of the flow-drive pump is required for SIFDT-MS, which facilitates the development of smaller cost-effective analytical instruments for real time breath and fluid headspace analyses. PMID:26583448

  9. Atmospheric pollutants in Chiang Mai (Thailand) over a five-year period (2005-2009), their possible sources and relation to air mass movement

    NASA Astrophysics Data System (ADS)

    Chantara, Somporn; Sillapapiromsuk, Sopittaporn; Wiriya, Wan

    2012-12-01

    Monitoring and analysis of the chemical composition of air pollutants were conducted over a five-year period (2005-2009) in the sub-urban area of Chiang Mai, Thailand. This study aims to determine the seasonal variation of atmospheric ion species and gases, examine their correlations, identify possible sources and assess major air-flow patterns to the receptor. The dominant gas and particulate pollutants were NH3 (43-58%) and SO42- (39-48%), respectively. The annual mean concentrations of NH3 (μg m-3) in descending order were 4.08 (2009) > 3.32 (2007) > 2.68 (2008) > 2.47 (2006) and 1.87 (2005), while those of SO42- (μg m-3) were 2.60 (2007) > 2.20 (2006) > 1.95 (2009) > 1.75 (2008) and 1.26 (2005). Concentrations of particulate ions were analyzed by principle component analysis to find out the possible sources of air pollutants in this area. The first component of each year had a high loading of SO42- and NH4+, which probably came from fuel combustion and agricultural activity, respectively. K+, a tracer of biomass burning, also contributed to the first or the second components of each year. Concentrations of NH4+ and SO42- were well correlated (r > 0.777, p < 0.01), which lead to the conclusion that (NH4)2SO4 was a major compound present in this area. The 3-day backward trajectories of air mass arriving at Chiang Mai from 2005 to 2009 were analyzed using the hybrid single particle langrangian integrated trajectory (HYSPLIT) model and grouped by cluster analysis. The air mass data was analyzed for the dry season (n = 18; 100%). The trajectory of air mass in 2005 mainly originated locally (67%). In 2006, the recorded data showed that 56% of air mass was emitted from the western continental region of Thailand. In 2007, the percent ratios from the western and eastern continental areas were equal (39%). In 2008, 67% originated from the western continental area. In 2009, the recorded air mass mainly came from the western continental area (72%). In conclusion, the

  10. Association between indoor air pollutant exposure and blood pressure and heart rate in subjects according to body mass index.

    PubMed

    Jung, Chien-Cheng; Su, Huey-Jen; Liang, Hsiu-Hao

    2016-01-01

    This study investigates the effects of high body mass index (BMI) of subjects on individual who exhibited high cardiovascular disease indexes with blood pressure (BP) and heart rate (HR) when exposed to high levels of indoor air pollutants. We collected 115 office workers, and measured their systolic blood pressure (SBP), diastolic blood pressure (DBP) and HR at the end of the workday. The subjects were divided into three groups according to BMI: 18-24 (normal weight), 24-27 (overweight) and >27 (obese). This study also measured the levels of carbon dioxide (CO2), total volatile organic compounds (TVOC), particulate matter with an aerodynamic diameter less than 2.5μm (PM2.5), as well as the bacteria and fungi in the subjects' work-places. The pollutant effects were divided by median. Two-way analysis of variance (ANOVA) was used to analyze the health effects of indoor air pollution exposure according to BMI. Our study showed that higher levels of SBP, DBP and HR occurred in subjects who were overweight or obese as compared to those with normal weight. Moreover, there was higher level of SBP in subjects who were overweight or obese when they were exposed to higher levels of TVOC and fungi (p<0.05). We also found higher value for DBP and HR with increasing BMI to be associated with exposure to higher TVOC levels. This study suggests that individuals with higher BMI have higher cardiovascular disease risk when they are exposed to poor indoor air quality (IAQ), and specifically in terms of TVOC.

  11. Air flow-assisted ionization imaging mass spectrometry method for easy whole-body molecular imaging under ambient conditions.

    PubMed

    Luo, Zhigang; He, Jiuming; Chen, Yi; He, Jingjing; Gong, Tao; Tang, Fei; Wang, Xiaohao; Zhang, Ruiping; Huang, Lan; Zhang, Lianfeng; Lv, Haining; Ma, Shuanggang; Fu, Zhaodi; Chen, Xiaoguang; Yu, Shishan; Abliz, Zeper

    2013-03-01

    Whole-body molecular imaging is able to directly map spatial distribution of molecules and monitor its biotransformation in intact biological tissue sections. Imaging mass spectrometry (IMS), a label-free molecular imaging method, can be used to image multiple molecules in a single measurement with high specificity. Herein, a novel easy-to-implement, whole-body IMS method was developed with air flow-assisted ionization in a desorption electrospray ionization mode. The developed IMS method can effectively image molecules in a large whole-body section in open air without sample pretreatment, such as chemical labeling, section division, or matrix deposition. Moreover, the signal levels were improved, and the spatial assignment errors were eliminated; thus, high-quality whole-body images were obtained. With this novel IMS method, in situ mapping analysis of molecules was performed in adult rat sections with picomolar sensitivity under ambient conditions, and the dynamic information of molecule distribution and its biotransformation was provided to uncover molecular events at the whole-animal level. A global view of the differential distribution of an anticancer agent and its metabolites was simultaneously acquired in whole-body rat and model mouse bearing neuroglioma along the administration time. The obtained drug distribution provided rich information for identifying the targeted organs and predicting possible tumor spectrum, pharmacological activity, and potential toxicity of drug candidates.

  12. Development of analysis of volatile polyfluorinated alkyl substances in indoor air using thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Wu, Yaoxing; Chang, Victor W-C

    2012-05-18

    The study attempts to utilize thermal desorption (TD) coupled with gas chromatography-mass spectrometry (GC-MS) for determination of indoor airborne volatile polyfluorinated alkyl substances (PFASs), including four fluorinated alcohols (FTOHs), two fluorooctane sulfonamides (FOSAs), and two fluorooctane sulfonamidoethanols (FOSEs). Standard stainless steel tubes of Tenax/Carbograph 1 TD were employed for low-volume sampling and exhibited minimal breakthrough of target analytes in sample collection. The method recoveries were in the range of 88-119% for FTOHs, 86-138% for FOSAs, exhibiting significant improvement compared with other existing air sampling methods. However, the widely reported high method recoveries of FOSEs were also observed (139-210%), which was probably due to the structural differences between FOSEs and internal standards. Method detection limit, repeatability, linearity, and accuracy were reported as well. The approach has been successfully applied to routine quantification of targeted PFASs in indoor environment of Singapore. The significantly shorter sampling time enabled the observation of variations of concentrations of targeted PFASs within different periods of a day, with higher concentration levels at night while ventilation systems were shut off. This indicated the existence of indoor sources and the importance of building ventilation and air conditioning system.

  13. Identification of water-soluble polar organics in air and vehicular emitted particulate matter using ultrahigh resolution mass spectrometry and Capillary electrophoresis - mass spectrometry.

    NASA Astrophysics Data System (ADS)

    Schmitt-Kopplin, P.; Yassine, M.; Gebefugi, I.; Hertkorn, N.; Dabek-Zlotorzynska, E.

    2009-04-01

    The effects of aerosols on human health, atmospheric chemistry, and climate are among the central topics in current environmental health research. Detailed and accurate measurements of the chemical composition of air particulate matter (PM) represent a challenging analytical task. Minute sample amounts are usually composed of several main constituents and hundreds of minor and trace constituents. Moreover, the composition of individual particles can be fairly uniform or very different (internally or externally mixed aerosols), depending on their origin and atmospheric aging processes (coagulation, condensation / evaporation, chemical reaction). The aim of the presentation was the characterization of the organic matter (OM) fraction of environmental aerosols which is not accessible by GC-methods, either because of their high molecular weight, their polarity or due to thermal instability. We also describe the main chemical characteristics of complexe oligomeric organic fraction extracted from different aerosols collected in urban and rural area in Germany and Canada. Mass spectrometry (MS) became an essential tool used by many prominent leaders of the biological research community and the importance of MS to the future of biological research is now clearly evident as in the fields of Proteomics and Metabolomics. Especially Fourier Transform Ion Cyclotron Mass Spectrometry (ICR-FT/MS) is an ultrahigh resolution MS that allows new approach in the analysis of complex mixtures. The mass resolution (< 200 ppb) allowed assigning the elemental composition (C, H, O, N, S…) to each of the obtained mass peaks and thus already a description of the mixture in terms of molecular composition. This possibility is used by the authors together with a high resolution separation method of charged compounds: capillary electrophoresis. A CE-ESI-MS method using an ammonium acetate based background electrolyte (pH 4.7) was developed for the determination of isomeric benzoic acids in

  14. Large-Scale Air Mass Characteristics Observed Over the Remote Tropical Pacific Ocean During March-April 1999: Results from PEM-Tropics B Field Experiment

    NASA Technical Reports Server (NTRS)

    Browell, Edward V.; Fenn, Marta A.; Butler, Carolyn F.; Grant, William B.; Ismail, Syed; Ferrare, Richard A.; Kooi, Susan A.; Brackett, Vincent G.; Clayton, Marian B.; Avery, Melody A.

    2001-01-01

    Eighteen long-range flights over the Pacific Ocean between 38 S to 20 N and 166 E to 90 W were made by the NASA DC-8 aircraft during the NASA Pacific Exploratory Mission (PEM) Tropics B conducted from March 6 to April 18, 1999. Two lidar systems were flown on the DC-8 to remotely measure vertical profiles of ozone (O3), water vapor (H2O), aerosols, and clouds from near the surface to the upper troposphere along their flight track. In situ measurements of a wide range of gases and aerosols were made on the DC-8 for comprehensive characterization of the air and for correlation with the lidar remote measurements. The transition from northeasterly flow of Northern Hemispheric (NH) air on the northern side of the Intertropical Convergence Zone (ITCZ) to generally easterly flow of Southern Hemispheric (SH) air south of the ITCZ was accompanied by a significant decrease in O3, carbon monoxide, hydrocarbons, and aerosols and an increase in H2O. Trajectory analyses indicate that air north of the ITCZ came from Asia and/or the United States, while the air south of the ITCZ had a long residence time over the Pacific, perhaps originating over South America several weeks earlier. Air south of the South Pacific Convergence Zone (SPCZ) came rapidly from the west originating over Australia or Africa. This air had enhanced O3 and aerosols and an associated decrease in H2O. Average latitudinal and longitudinal distributions of O3 and H2O were constructed from the remote and in situ O3 and H2O data, and these distributions are compared with results from PEM-Tropics A conducted in August-October 1996. During PEM-Tropics B, low O3 air was found in the SH across the entire Pacific Basin at low latitudes. This was in strong contrast to the photochemically enhanced O3 levels found across the central and eastern Pacific low latitudes during PEM-Tropics A. Nine air mass types were identified for PEM-Tropics B based on their O3, aerosols, clouds, and potential vorticity characteristics. The

  15. Bicosomes: Bicelles in Dilute Systems

    PubMed Central

    Rodríguez, Gelen; Soria, Guadalupe; Coll, Elisenda; Rubio, Laia; Barbosa-Barros, Lucyanna; López-Iglesias, Carmen; Planas, Anna M.; Estelrich, Joan; de la Maza, Alfons; López, Olga

    2010-01-01

    Abstract Bicelles are discoidal phospholipid nanostructures at high lipid concentrations. Under dilute conditions, bicelles become larger and adopt a variety of morphologies. This work proposes a strategy to preserve the discoidal morphology of bicelles in environments with high water content. Bicelles were formed in concentrated conditions and subsequently encapsulated in liposomes. Later dilution of these new structures, called bicosomes, demonstrated that lipid vesicles were able to isolate and protect bicelles entrapped inside them from the medium. Characterization of systems before and after dilution by dynamic light-scattering spectroscopy and cryo-transmission electron microscopy showed that free bicelles changed in size and morphology, whereas encapsulated bicelles remained unaltered by the effect of dilution. Free and entrapped bicelles (containing the paramagnetic contrast agent gadodiamide) were injected into rat brain lateral ventricles. Coronal and sagittal visualization was performed by magnetic resonance imaging. Whereas rats injected with free bicelles did not survive the surgery, those injected with bicosomes did, and a hyperintensity effect due to gadodiamide was observed in the cerebrospinal fluid. These results indicate that bicosomes are a good means of preserving the morphology of bicelles under dilution conditions. PMID:20643066

  16. The influence of air temperature inversions on snowmelt and glacier mass-balance simulations, Ammassalik island, SE Greenland

    SciTech Connect

    Mernild, Sebastian Haugard; Liston, Glen

    2009-01-01

    In many applications, a realistic description of air temperature inversions is essential for accurate snow and glacier ice melt, and glacier mass-balance simulations. A physically based snow-evolution modeling system (SnowModel) was used to simulate eight years (1998/99 to 2005/06) of snow accumulation and snow and glacier ice ablation from numerous small coastal marginal glaciers on the SW-part of Ammassalik Island in SE Greenland. These glaciers are regularly influenced by inversions and sea breezes associated with the adjacent relatively low temperature and frequently ice-choked fjords and ocean. To account for the influence of these inversions on the spatiotemporal variation of air temperature and snow and glacier melt rates, temperature inversion routines were added to MircoMet, the meteorological distribution sub-model used in SnowModel. The inversions were observed and modeled to occur during 84% of the simulation period. Modeled inversions were defined not to occur during days with strong winds and high precipitation rates due to the potential of inversion break-up. Field observations showed inversions to extend from sea level to approximately 300 m a.s.l., and this inversion level was prescribed in the model simulations. Simulations with and without the inversion routines were compared. The inversion model produced air temperature distributions with warmer lower elevation areas and cooler higher elevation areas than without inversion routines due to the use of cold sea-breeze base temperature data from underneath the inversion. This yielded an up to 2 weeks earlier snowmelt in the lower areas and up to 1 to 3 weeks later snowmelt in the higher elevation areas of the simulation domain. Averaged mean annual modeled surface mass-balance for all glaciers (mainly located above the inversion layer) was -720 {+-} 620 mm w.eq. y{sup -1} for inversion simulations, and -880 {+-} 620 mm w.eq. y{sup -1} without the inversion routines, a difference of 160 mm w.eq. y

  17. Long-term measurements of particle number size distributions and the relationships with air mass history and source apportionment in the summer of Beijing

    NASA Astrophysics Data System (ADS)

    Wang, Z. B.; Hu, M.; Wu, Z. J.; Yue, D. L.; He, L. Y.; Huang, X. F.; Liu, X. G.; Wiedensohler, A.

    2013-02-01

    A series of long-term and temporary measurements were conducted to study the improvement of air quality in Beijing during Olympic Games period (8-24 August 2008). To evaluate actions taken to improve the air quality, comparisons of particle number and volume size distributions of August 2008 and 2004-2007 were performed. The total particle number and volume concentrations were 14 000 cm-3 and 37 μm3 cm-3 in August of 2008, respectively. These were reductions of 41% and 35% compared with the mean values of August 2004-2007. A cluster analysis on air mass history and source apportionment were performed, exploring reasons of the reduction of particle concentrations. Back trajectories were classified into five major clusters. Air mass from south direction are always associated with pollution events during the summertime of Beijing. In August 2008, the frequency of air mass arriving from south has been twice higher compared to the average of the previous years, these southerly air masses did however not result in elevated particle volume concentrations in Beijing. This result implied that the air mass history was not the key factor, explaining reduced particle number and volume concentrations during the Beijing 2008 Olympic Games. Four factors were found influencing particle concentrations using a Positive matrix factorization (PMF) model. They were identified to local and remote traffic emissions, combustion sources as well as secondary transformation. The reductions of the four sources were calculated to 47%, 44%, 43% and 30%, respectively. The significant reductions of particle number and volume concentrations may attribute to actions taken, focusing on primary emissions, especially related to the traffic and combustion sources.

  18. First day of an oil spill on the open sea: early mass transfers of hydrocarbons to air and water.

    PubMed

    Gros, Jonas; Nabi, Deedar; Würz, Birgit; Wick, Lukas Y; Brussaard, Corina P D; Huisman, Johannes; van der Meer, Jan R; Reddy, Christopher M; Arey, J Samuel

    2014-08-19

    During the first hours after release of petroleum at sea, crude oil hydrocarbons partition rapidly into air and water. However, limited information is available about very early evaporation and dissolution processes. We report on the composition of the oil slick during the first day after a permitted, unrestrained 4.3 m(3) oil release conducted on the North Sea. Rapid mass transfers of volatile and soluble hydrocarbons were observed, with >50% of ≤C17 hydrocarbons disappearing within 25 h from this oil slick of <10 km(2) area and <10 μm thickness. For oil sheen, >50% losses of ≤C16 hydrocarbons were observed after 1 h. We developed a mass transfer model to describe the evolution of oil slick chemical composition and water column hydrocarbon concentrations. The model was parametrized based on environmental conditions and hydrocarbon partitioning properties estimated from comprehensive two-dimensional gas chromatography (GC×GC) retention data. The model correctly predicted the observed fractionation of petroleum hydrocarbons in the oil slick resulting from evaporation and dissolution. This is the first report on the broad-spectrum compositional changes in oil during the first day of a spill at the sea surface. Expected outcomes under other environmental conditions are discussed, as well as comparisons to other models.

  19. Cyclic organic peroxides identification and trace analysis by Raman microscopy and open-air chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pena-Quevedo, Alvaro Javier

    The persistent use of cyclic organic peroxides in explosive devices has increased the interest in study these compounds. Development of methodologies for the detection of triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) has become an urgent priority. However, differences in physical properties between cyclic organic peroxides make difficult the development of a general method for peroxide analysis and detection. Following this urgency, the first general technique for the analysis of any peroxide, regarding its structural differences is reported. Characterization and detection of TATP and HMTD was performed using an Open-Air Chemical Ionization High-Resolution Time-of-Flight Mass Spectrometer. The first spectrometric analysis for tetramethylene diperoxide dicarbamide (TMDD) and other nitrogen based peroxides using Raman Microscopy and Mass Spectrometry is reported. Analysis of cyclic peroxides by GC-MS was also conducted to compare results with OACI-HRTOF data. In the OACI mass spectrum, HMTD showed a clear signal at m/z 209 MH + and a small adduct peak at m/z 226 [M+NH4]+ that allowed its detection in commercial standard solutions and lab made standards. TMDD presented a molecular peak of m/z 237 MH+ and an adduct peak of m/z 254 [M+NH4]+. TATP showed a single peak at m/z 240 [M+NH4]+, while the peak of m/z 223 or 222 was completely absent. This evidence suggests that triperoxides are stabilized by the ammonium ion. TATP samples with deuterium enrichment were analyzed to compare results that could differentiate from HMTD. Raman microscopy was used as a complementary characterization method and was an essential tool for cyclic peroxides identification, particularly for those which could not be extensively purified. All samples were characterized by Raman spectroscopy to confirm the Mass Spectrometry results. Peroxide O-O vibrations were observed around 750-970 cm-1. D18-TATP studies had identified ketone triperoxide nu(O-O) vibration around

  20. The potential of LIRIC to validate the vertical profiles of the aerosol mass concentration estimated by an air quality model

    NASA Astrophysics Data System (ADS)

    Siomos, Nikolaos; Filoglou, Maria; Poupkou, Anastasia; Liora, Natalia; Dimopoulos, Spyros; Melas, Dimitris; Chaikovsky, Anatoli; Balis, Dimitris

    2015-04-01

    Vertical profiles of the aerosol mass concentration derived by a retrieval algorithm that uses combined sunphotometer and LIDAR data (LIRIC) were used in order to validate the mass concentration profiles estimated by the air quality model CAMx. LIDAR and CIMEL measurements of the Laboratory of Atmospheric Physics of the Aristotle University of Thessaloniki were used for this validation.The aerosol mass concentration profiles of the fine and coarse mode derived by CAMx were compared with the respective profiles derived by the retrieval algorithm. For the coarse mode particles, forecasts of the Saharan dust transportation model BSC-DREAM8bV2 were also taken into account. Each of the retrieval algorithm's profiles were matched to the models' profile with the best agreement within a time window of four hours before and after the central measurement. OPAC, a software than can provide optical properties of aerosol mixtures, was also employed in order to calculate the angstrom exponent and the lidar ratio values for 355nm and 532nm for each of the model's profiles aiming in a comparison with the angstrom exponent and the lidar ratio values derived by the retrieval algorithm for each measurement. The comparisons between the fine mode aerosol concentration profiles resulted in a good agreement between CAMx and the retrieval algorithm, with the vertical mean bias error never exceeding 7 μgr/m3. Concerning the aerosol coarse mode concentration profiles both CAMx and BSC-DREAM8bV2 values are severely underestimated, although, in cases of Saharan dust transportation events there is an agreement between the profiles of BSC-DREAM8bV2 model and the retrieval algorithm.

  1. Physical and chemical processes of air masses in the Aegean Sea during Etesians: Aegean-GAME airborne campaign.

    PubMed

    Tombrou, M; Bossioli, E; Kalogiros, J; Allan, J D; Bacak, A; Biskos, G; Coe, H; Dandou, A; Kouvarakis, G; Mihalopoulos, N; Percival, C J; Protonotariou, A P; Szabó-Takács, B

    2015-02-15

    High-resolution measurements of gas and aerosols' chemical composition along with meteorological and turbulence parameters were performed over the Aegean Sea (AS) during an Etesian outbreak in the framework of the Aegean-GAME airborne campaign. This study focuses on two distinct Etesian patterns, with similarities inside the Marine Atmospheric Boundary Layer (MABL) and differences at higher levels. Under long-range transport and subsidence the pollution load is enhanced (by 17% for CO, 11% for O3, 28% for sulfate, 62% for organic mass, 47% for elemental carbon), compared to the pattern with a weaker synoptic system. Sea surface temperature (SST) was a critical parameter for the MABL structure, turbulent fluxes and pollutants' distribution at lower levels. The MABL height was below 500 m asl over the eastern AS (favoring higher accumulation), and deeper over the western AS. The most abundant components of total PM1 were sulfate (40-50%) and organics (30-45%). Higher average concentrations measured over the eastern AS (131 ± 76 ppbv for CO, 62.5 ± 4.1 ppbv for O3, 5.0 ± 1.1 μg m(-3) for sulfate, 4.7 ± 0.9 μg m(-3) for organic mass and 0.5 ± 0.2 μg m(-3) for elemental carbon). Under the weaker synoptic system, cleaner but more acidic air masses prevailed over the eastern part, while distinct aerosol layers of different signature were observed over the western part. The Aitken and accumulation modes contributed equally during the long-range transport, while the Aitken modes dominated during local or medium range transport. PMID:25460953

  2. On-line analysis of volatile chlorinated hydrocarbons in air by gas chromatography-mass spectrometry Improvements in preconcentration and injection steps.

    PubMed

    Zoccolillo, Lelio; Amendola, Luca; Insogna, Susanna; Pastorini, Elisabetta

    2010-06-11

    An analytical system composed of a cryofocusing trap injector device coupled to a gas chromatograph with mass spectrometric detection (CTI-GC-MS) specific for the on-line analysis in air of volatile chlorinated hydrocarbons (VCHCs) (dichloromethane; chloroform; 1,1,1-trichloroethane; tetrachloromethane; 1,1,2-trichloroethylene; tetrachloroethylene) was developed. The cryofocusing trap injector was the result of appropriate low cost modifications to an original purge-and-trap device to make it suitable for direct air analysis even in the case of only slightly contaminated air samples, such as those from remote zones. The CTI device can rapidly and easily be rearranged into the purge-and-trap allowing water and air analysis with the same apparatus. Air samples, collected in stainless steel canisters, were introduced directly into the CTI-GC-MS system to realize cryo-concentration (at -120 degrees C), thermal desorption (at 200 degrees C) and for the subsequent analysis of volatiles. The operating phases and conditions were customised and optimized. Recovery efficiency was optimized in terms of moisture removal, cold trap temperature and sampling mass flow. The injection of entrapped volatiles was realized through a direct transfer with high chromatographic reliability (capillary column-capillary column). These improvements allowed obtaining limits of detection (LODs) at least one order of magnitude lower than current LODs for the investigated substances. The method was successfully employed on real samples: air from urban and rural areas and air from remote zones such as Antarctica.

  3. The Potential of The Synergy of Sunphotometer and Lidar Data to Validate Vertical Profiles of The Aerosol Mass Concentration Estimated by An Air Quality Model

    NASA Astrophysics Data System (ADS)

    Siomos, N.; Filioglou, M.; Poupkou, A.; Liora, N.; Dimopoulos, S.; Melas, D.; Chaikovsky, A.; Balis, D. S.

    2016-06-01

    Vertical profiles of the aerosol mass concentration derived by the Lidar/Radiometer Inversion Code (LIRIC), that uses combined sunphotometer and lidar data, were used in order to validate the aerosol mass concentration profiles estimated by the air quality model CAMx. Lidar and CIMEL measurements performed at the Laboratory of Atmospheric Physics of the Aristotle University of Thessaloniki, Greece (40.5N, 22.9E) from the period 2013-2014 were used in this study.

  4. Dilution and the elusive baseline.

    PubMed

    Likens, Gene E; Buso, Donald C

    2012-04-17

    Knowledge of baseline conditions is critical for evaluating quantitatively the effect of human activities on environmental conditions, such as the impact of acid deposition. Efforts to restore ecosystems to prior, "pristine" condition require restoration targets, often based on some presumed or unknown baseline condition. Here, we show that rapid and relentless dilution of surface water chemistry is occurring in the White Mountains of New Hampshire, following decades of acid deposition. Extrapolating measured linear trends using a unique data set of up to 47 years, suggest that both precipitation and streamwater chemistry (r(2) >0.84 since 1985) in the Hubbard Brook Experimental Forest (HBEF) will approximate demineralized water within one to three decades. Because such dilute chemistry is unrealistic for surface waters, theoretical baseline compositions have been calculated for precipitation and streamwater: electrical conductivity of 3 and 5 μS/cm, base cation concentrations of 7 and 39 μeq/liter, acid-neutralizing capacity values of <1 and 14 μeq/liter, respectively; and pH 5.5 for both. Significantly large and rapid dilution of surface waters to values even more dilute than proposed for Pre-Industrial Revolution (PIR) conditions has important ecological, biogeochemical and water resource management implications, such as for the success of early reproductive stages of aquatic organisms.

  5. Dilution and the elusive baseline.

    PubMed

    Likens, Gene E; Buso, Donald C

    2012-04-17

    Knowledge of baseline conditions is critical for evaluating quantitatively the effect of human activities on environmental conditions, such as the impact of acid deposition. Efforts to restore ecosystems to prior, "pristine" condition require restoration targets, often based on some presumed or unknown baseline condition. Here, we show that rapid and relentless dilution of surface water chemistry is occurring in the White Mountains of New Hampshire, following decades of acid deposition. Extrapolating measured linear trends using a unique data set of up to 47 years, suggest that both precipitation and streamwater chemistry (r(2) >0.84 since 1985) in the Hubbard Brook Experimental Forest (HBEF) will approximate demineralized water within one to three decades. Because such dilute chemistry is unrealistic for surface waters, theoretical baseline compositions have been calculated for precipitation and streamwater: electrical conductivity of 3 and 5 μS/cm, base cation concentrations of 7 and 39 μeq/liter, acid-neutralizing capacity values of <1 and 14 μeq/liter, respectively; and pH 5.5 for both. Significantly large and rapid dilution of surface waters to values even more dilute than proposed for Pre-Industrial Revolution (PIR) conditions has important ecological, biogeochemical and water resource management implications, such as for the success of early reproductive stages of aquatic organisms. PMID:22455659

  6. ON-DEMAND SERIAL DILUTION USING QUANTIZED NANO/PICOLITER-SCALE DROPLETS

    SciTech Connect

    Jambovane, Sachin R.; Prost, Spencer A.; Sheen, Allison M.; Magnuson, Jon K.; Kelly, Ryan T.

    2014-10-29

    This paper describes a fully automated droplet-based microfluidic device for on-demand serial dilution that is capable of achieving a dilution ratio of >6000 (concentration ranges from 1 mM to 160nM) over 35 nanoliter-scale droplets. This serial diluter can be applied to high throughput and label-free kinetic assays by integrating with our previously developed on-demand droplet-based microfluidic with mass spectrometry detection.

  7. Hydrogen sulphide in human nasal air quantified using thermal desorption and selected ion flow tube mass spectrometry.

    PubMed

    Wondimu, Taddese; Wang, Rui; Ross, Brian

    2014-09-01

    The discovery that hydrogen sulphide (H2S) acts as a gasotransmitter when present at very low concentrations (sub-parts per billion (ppbv)) has resulted in the need to quickly quantify trace amounts of the gas in complex biological samples. Selected ion flow tube mass spectrometry (SIFT-MS) is capable of real-time quantification of H2S but many SIFT-MS instruments lack sufficient sensitivity for this application. In this study we investigate the utility of combining thermal desorption with SIFT-MS for quantifying H2S in the 0.1-1 ppbv concentration range. Human orally or nasally derived breath, and background ambient air, were collected in sampling bags and dried by passing through CaCl2 and H2S pre-concentrated using a sorbent trap optimised for the capture of this gas. The absorbed H2S was then thermally desorbed and quantified by SIFT-MS. H2S concentrations in ambient air, nasal breath and oral breath collected from 10 healthy volunteers were 0.12  ±  0.02 (mean ± SD), 0.40  ±  0.11 and 3.1  ±  2.5 ppbv respectively, and in the oral cavity H2S, quantified by SIFT-MS without pre-concentration, was present at 13.5  ±  8.6 ppbv. The oral cavity H2S correlates well with oral breath H2S but not with nasal breath H2S, suggesting that oral breath H2S derives mainly from the oral cavity but nasal breath is likely pulmonary in origin. The successful quantification of such low concentrations of H2S in nasal air using a rapid analytical procedure paves the way for the straightforward analysis of H2S in breath and may assist in elucidating the role that H2S plays in biological systems.

  8. Steadiness in Dilute Pyroclastic Density Currents

    NASA Astrophysics Data System (ADS)

    Andrews, B. J.

    2015-12-01

    Pyroclastic density currents (PDCs) are often unsteady, as evidenced by direct observations of dilute lobes or jets emerging from the fronts of larger currents and by deposits that indicate transient transport and depositional regimes. We used scaled experiments to investigate unsteadiness in dilute PDCs. The experimental currents were run in an 8.5x6.1x2.6 m tank and comprised heated or ambient temperature 20-μm talc powder turbulently suspended in air. Experiments were scaled such that densimetric and thermal Richardson numbers, Froude number, and particle Stokes and settling numbers were dynamically similar to natural dilute PDCs. Although the experiment Reynolds numbers are substantially lower than those of natural PDCs, the experiments are fully turbulent. Experiments were observed with video and high-speed cameras and high-frequency thermocouples. Currents were generated with total eruption durations of 100 s. Unsteadiness in source conditions was produced by interrupting supply for intervals, t, with durations of 1, 2.5, 5, and 10 s in the experimental runs at 35 and 70 s. When t<2.5 s, the currents are indistinguishable from currents with steady supply. In runs with t=2.5-5 s, the individual pulses comprising each current are readily apparent near the source, but decay with distance downstream until the currents appear as single (e.g. steady) flows. In experiments with t=10 s, the 3 pulses comprising each run never merge and the currents remain unsteady. Comparison with the integral turbulent timescale, τ, and current velocity, U, show that unsteadiness is persistent when t>3<τ but currents are steady when t<τ. In currents with 3τ>t>τ, unsteadiness decays such that at a distance of ~4Ut, the currents are again steady. Applied to natural dilute PDCs, our results suggest that currents and their resulting deposits, will only show evidence of unsteadiness if they are disrupted for many seconds and those breaks may "heal" over distances of 100s of meters.

  9. Influence of air mass origin on the wet deposition of nitrogen to Tampa Bay, Florida—An eight-year study

    NASA Astrophysics Data System (ADS)

    Strayer, Hillary; Smith, Ronald; Mizak, Connie; Poor, Noreen

    Rainfall delivers on the average ˜10% of the total annual nitrogen load directly to Tampa Bay, based on precipitation monitoring at a National Atmospheric Deposition Program (NADP) Atmospheric Integrated Research Monitoring Network (AIRMoN) site located adjacent to Tampa Bay in urban Tampa. We coupled the chemical analyses for 606 daily precipitation samples collected from 1996 to 2004 with corresponding air mass trajectory information to investigate if wet-deposited nitrogen originated from near versus removed source regions. Air mass trajectories were obtained using the National Oceanic and Atmospheric Administration (NOAA) HYbrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model, and were classified into six trajectory categories by the direction of their approach to Tampa Bay. Rainfall nitrate and ammonium concentrations were significantly lower for over-water air mass trajectories than for over-land trajectories as expected, but contributed to 40% of the total wet-deposited nitrogen, a likely consequence of the higher frequency of rain events for these trajectories. Average rainfall nitrate concentrations were significantly higher for air masses that stagnated over the urbanized bay region. We estimated that local sources contributed 1kgNha-1yr-1 or 25% of the total inorganic nitrogen wet-deposited to Tampa Bay.

  10. REAL TIME, ON-LINE CHARACTERIZATION OF DIESEL GENERATOR AIR TOXIC EMISSIONS BY RESONANCE ENHANCED MULTI-PHOTON IONIZATION TIME OF FLIGHT MASS SPECTROMETRY

    EPA Science Inventory

    The laser based resonance, enhanced multi-photon ionization time-of-flight mass spectrometry (REMPI-TOFMS) technique has been applied to the exhaust gas stream of a diesel generator to measure, in real time, concentration levels of aromatic air toxics. Volatile organic compounds ...

  11. Formic and Acetic Acid Observations over Colorado by Chemical Ionization Mass Spectrometry and Organic Acids' Role in Air Quality

    NASA Astrophysics Data System (ADS)

    Treadaway, V.; O'Sullivan, D. W.; Heikes, B.; Silwal, I.; McNeill, A.

    2015-12-01

    Formic acid (HFo) and acetic acid (HAc) have both natural and anthropogenic sources and a role in the atmospheric processing of carbon. These organic acids also have an increasing importance in setting the acidity of rain and snow as precipitation nitrate and sulfate concentrations have decreased. Primary emissions for both organic acids include biomass burning, agriculture, and motor vehicle emissions. Secondary production is also a substantial source for both acids especially from biogenic precursors, secondary organic aerosols (SOAs), and photochemical production from volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs). Chemical transport models underestimate organic acid concentrations and recent research has sought to develop additional production mechanisms. Here we report HFo and HAc measurements during two campaigns over Colorado using the peroxide chemical ionization mass spectrometer (PCIMS). Iodide clusters of both HFo and HAc were recorded at mass-to-charge ratios of 173 and 187, respectively. The PCIMS was flown aboard the NCAR Gulfstream-V platform during the Deep Convective Clouds and Chemistry Experiment (DC3) and aboard the NCAR C-130 during the Front Range Air Pollution and Photochemistry Experiment (FRAPPE). The DC3 observations were made in May and June 2012 extending from the surface to 13 km over the central and eastern United States. FRAPPE observations were made in July and August 2014 from the surface to 7 km over Colorado. DC3 measurements reported here are focused over the Colorado Front Range and complement the FRAPPE observations. DC3 HFo altitude profiles are characterized by a decrease up to 6 km followed by an increase either back to boundary layer mixing ratio values or higher (a "C" shape). Organic acid measurements from both campaigns are interpreted with an emphasis on emission sources (both natural and anthropogenic) over Colorado and in situ photochemical production especially ozone precursors.

  12. Measurement of urinary desmosine by isotope dilution and high performance liquid chromatography. Correlation between elastase-induced air-space enlargement in the hamster and elevation of urinary desmosine

    SciTech Connect

    Stone, P.J.; Bryan-Rhadfi, J.; Lucey, E.C.; Ciccolella, D.E.; Crombie, G.; Faris, B.; Snider, G.L.; Franzblau, C. )

    1991-08-01

    The accuracy of methods employed to measure the elastin-specific crosslinks, desmosine (DES) and isodesmosine (IDES), has been called into question because contaminants in the urine may cause elevated values. In the present study urine samples were spiked with a known amount of (14C)DES and refluxed in 6 N HCl. Sephadex G-15 chromatography of the hydrolyzed urine employed to remove contaminants. DES and IDES were quantified by high performance liquid chromatography (HPLC) as well as by amino acid analysis. The amount of isotope recovered was used to determine losses during the overall procedure and the isotope dilution to calculate the amounts of endogenous DES and IDES originally present in the urine. Because similar values were obtained by both methods, the more rapid HPLC method was used for all succeeding analyses. In one experiment, the DES amounts in urine collected from hamsters for 3 days after intratracheal treatment with human neutrophil elastase (300 micrograms) or porcine pancreatic elastase (300 micrograms) were 0.212 {plus minus} 0.012 (mean {plus minus} SEM, two measurements on a single pool) and 0.816 {plus minus} 0.005 (two measurements) microgram per hamster per day, respectively. Urine from control hamsters had a mean value of 0.074 {plus minus} 0.008 (eight measurements) microgram per hamster per day. The HNE- and PPE-treated hamsters had mean linear intercept values of 119 and 159% of control values, respectively, giving a positive correlation between increase in airspace size and elevation of urinary DES.

  13. Determination of trichloroanisole and trichlorophenol in wineries' ambient air by passive sampling and thermal desorption-gas chromatography coupled to tandem mass spectrometry.

    PubMed

    Camino-Sánchez, F J; Bermúdez-Peinado, R; Zafra-Gómez, A; Ruíz-García, J; Vílchez-Quero, J L

    2015-02-01

    The present paper describes the calibration of selected passive samplers used in the quantitation of trichlorophenol and trichloroanisole in wineries' ambient air, by calculating the corresponding sampling rates. The method is based on passive sampling with sorbent tubes and involves thermal desorption-gas chromatography-triple quadrupole mass spectrometry analysis. Three commercially available sorbents were tested using sampling cartridges with a radial design instead of axial ones. The best results were found for Tenax TA™. Sampling rates (R-values) for the selected sorbents were determined. Passive sampling was also used for accurately determining the amount of compounds present in the air. Adequate correlation coefficients between the mass of the target analytes and exposure time were obtained. The proposed validated method is a useful tool for the early detection of trichloroanisole and its precursor trichlorophenol in wineries' ambient air while avoiding contamination of wine or winery facilities.

  14. Transport Regimes of Air Masses Affecting the Tropospheric Composition of the Canadian and European Arctic During RACEPAC 2014 and NETCARE 2014/2015

    NASA Astrophysics Data System (ADS)

    Bozem, H.; Hoor, P. M.; Koellner, F.; Kunkel, D.; Schneider, J.; Schulz, C.; Herber, A. B.; Borrmann, S.; Wendisch, M.; Ehrlich, A.; Leaitch, W. R.; Willis, M. D.; Burkart, J.; Thomas, J. L.; Abbatt, J.

    2015-12-01

    The Arctic is warming much faster than any other place in the world and undergoes a rapid change dominated by a changing climate in this region. The impact of polluted air masses traveling to the Arctic from various remote sources significantly contributes to the observed climate change, in contrast there are additional local emission sources contributing to the level of pollutants (trace gases and aerosol). Processes affecting the emission and transport of these pollutants are not well understood and need to be further investigated. We present aircraft based trace gas measurements in the Arctic during RACEPAC (2014) and NETCARE (2014 and 2015) with the Polar 6 aircraft of Alfred Wegener Institute (AWI) covering an area from 134°W to 17°W and 68°N to 83°N. We focus on cloud, aerosol and general transport processes of polluted air masses into the high Arctic. Based on CO and CO2 measurements and kinematic 10-day back trajectories we analyze the transport regimes prevalent during spring (RACEPAC 2014 and NETCARE 2015) and summer (NETCARE 2014) in the observed region. Whereas the eastern part of the Canadian Arctic is affected by air masses with their origin in Asia, in the central and western parts of the Canadian and European Arctic air masses from North America are predominant at the time of the measurement. In general the more northern parts of the Arctic were relatively unaffected by pollution from mid-latitudes since air masses mostly travel within the polar dome, being quite isolated. Associated mixing ratios of CO and CO2 fit into the seasonal cycle observed at NOAA ground stations throughout the Arctic, but show a more mid-latitudinal characteristic at higher altitudes. The transition is remarkably sharp and allows for a chemical definition of the polar dome. At low altitudes, synoptic disturbances transport polluted air masses from mid-latitudes into regions of the polar dome. These air masses contribute to the Arctic pollution background, but also

  15. Development and characterisation of a state-of-the-art GOME-2 formaldehyde air-mass factor algorithm

    NASA Astrophysics Data System (ADS)

    Hewson, W.; Barkley, M. P.; Gonzalez Abad, G.; Bösch, H.; Kurosu, T.; Spurr, R.

    2015-01-01

    Space-borne observations of formaldehyde (HCHO) are frequently used to derive surface emissions of isoprene, an important biogenic volatile organic compound. The conversion of retrieved HCHO slant column concentrations from satellite line of sight measurements to vertical columns is determined through application of an air mass factor (AMF), accounting for instrument viewing geometry, radiative transfer, and vertical profile of the absorber in the atmosphere. This step in the trace gas retrieval is subject to large errors. This work presents the AMF algorithm in use at the University of Leicester (UoL), which introduces scene specific variables into a per-observation full radiative transfer AMF calculation, including increasing spatial resolution of key environmental parameter databases, input variable area weighting, instrument specific scattering weight calculation, and inclusion of an ozone vertical profile climatology. Application of these updates to HCHO slant columns from the GOME-2 instrument is shown to typically adjust the AMF by ±10%, compared to a~reference algorithm without these advanced parameterisations. Furthermore, the new UoL algorithm also incorporates a full radiative transfer error calculation for each scene to help characterise AMF uncertainties. Global median AMF errors are typically 50-60%, and are dominated by uncertainties in the HCHO profile shape and its corresponding seasonal variation.

  16. Student understanding of the volume, mass, and pressure of air within a sealed syringe in different states of compression

    NASA Astrophysics Data System (ADS)

    de Berg, Kevin Charles

    Problem-solving strategies in the physical sciences have been characterized by a dependence on algorithmic techniques often devoid of any reasoning skills. The purpose of this study was to examine student responses to a task relating to Boyle's Law for gases, which did not demand the use of a mathematical equation for its solution. Students (17- to 18-year-olds) in lower sixth form from two colleges in the Leeds district of Yorkshire in England were asked to respond to a task relating to pressure and volume measurements of air within a sealed syringe in different states of compression. Both qualitative and quantitative tasks for the sealed syringe system were examined. It was found that 34% to 38% of students did not understand the concepts of volume and mass, respectively, of a gas under such circumstances. Performance on an inverse ratio (2:1) task was shown to depend on gender and those students who performed well on the 2:1 inverse ratio task did not necessarily perform well on a different inverse ratio task when an arithmetic averaging principle was present. Tasks which draw upon qualitative knowledge as well as quantitative knowledge have the potential to reduce dependence on algorithms, particularly equation substitution and solution. The implications for instructional design are discussed.Received: 14 April 1993; Revised: 29 June 1994;

  17. Volatile garlic odor components: gas phases and adsorbed exhaled air analysed by headspace gas chromatography-mass spectrometry.

    PubMed

    Laakso, I; Seppänen-Laakso, T; Hiltunen, R; Müller, B; Jansen, H; Knobloch, K

    1989-06-01

    Combined headspace gas chromatography-mass spectrometry (HSGC-MS) was used in the analysis of garlic volatile compounds. Twenty major components were identified in the gas phases enriched by fresh, sliced garlic cloves ( ALLIUM SATIVUM L, Allioceae, Liliidae). Suspended dry garlic powder and crushed garlic, incubated in vegetable oil, revealed a different pattern since mainly the amounts of di- and trisulfides were decreased. The considerable compositional differences found in the analyses for the gas phase of garlic cloves, kept in oil, are likely associated with the poor stability of allicin in a lipophilic environment; a marked increase in the amounts of 2-propene-1-thiol, acetic acid, and ethanol was observed in the gas phase, whereas trisulfides were present in traces only. The occurrence of 2-propene-1-thiol and diallyl disulfide, the two principal sulfur components in exhaled air, also may indicate a rapid degradation of most garlic volatile components probably caused by the enzymatically active human salivary or digestive system. PMID:17262412

  18. Evaluation of chemical transport model predictions of primary organic aerosol for air masses classified by particle-component-based factor analysis

    NASA Astrophysics Data System (ADS)

    Stroud, C. A.; Moran, M. D.; Makar, P. A.; Gong, S.; Gong, W.; Zhang, J.; Slowik, J. G.; Abbatt, J. P. D.; Lu, G.; Brook, J. R.; Mihele, C.; Li, Q.; Sills, D.; Strawbridge, K. B.; McGuire, M. L.; Evans, G. J.

    2012-02-01

    Observations from the 2007 Border Air Quality and Meteorology Study (BAQS-Met 2007) in southern Ontario (ON), Canada, were used to evaluate Environment Canada's regional chemical transport model predictions of primary organic aerosol (POA). Environment Canada's operational numerical weather prediction model and the 2006 Canadian and 2005 US national emissions inventories were used as input to the chemical transport model (named AURAMS). Particle-component-based factor analysis was applied to aerosol mass spectrometer measurements made at one urban site (Windsor, ON) and two rural sites (Harrow and Bear Creek, ON) to derive hydrocarbon-like organic aerosol (HOA) factors. Co-located carbon monoxide (CO), PM2.5 black carbon (BC), and PM1 SO4 measurements were also used for evaluation and interpretation, permitting a detailed diagnostic model evaluation. At the urban site, good agreement was observed for the comparison of daytime campaign PM1 POA and HOA mean values: 1.1 μg m-3 vs. 1.2 μg m-3, respectively. However, a POA overprediction was evident on calm nights due to an overly-stable model surface layer. Biases in model POA predictions trended from positive to negative with increasing HOA values. This trend has several possible explanations, including (1) underweighting of urban locations in particulate matter (PM) spatial surrogate fields, (2) overly-coarse model grid spacing for resolving urban-scale sources, and (3) lack of a model particle POA evaporation process during dilution of vehicular POA tail-pipe emissions to urban scales. Furthermore, a trend in POA bias was observed at the urban site as a function of the BC/HOA ratio, suggesting a possible association of POA underprediction for diesel combustion sources. For several time periods, POA overprediction was also observed for sulphate-rich plumes, suggesting that our model POA fractions for the PM2.5 chemical speciation profiles may be too high for these point sources. At the rural Harrow site

  19. Simultaneous Quantification of Methylated Cytidine and Adenosine in Cellular and Tissue RNA by Nano-Flow Liquid Chromatography-Tandem Mass Spectrometry Coupled with the Stable Isotope-dilution Method

    PubMed Central

    Fu, Lijuan; Amato, Nicolas J.; Wang, Pengcheng; McGowan, Sara J.; Niedernhofer, Laura J.; Wang, Yinsheng

    2016-01-01

    The rising interest in understanding the functions, regulation and maintenance of the epitranscriptome calls for robust and accurate analytical methods for the identification and quantification of post-transcriptionally modified nucleosides in RNA. Mono-methylations of cytidine and adenosine are common post-transcriptional modifications in RNA. Herein, we developed an LC-MS/MS/MS coupled with the stable isotope-dilution method for the sensitive and accurate quantifications of 5-methylcytidine (m5C), 2′-O-methylcytidine (Cm), N6-methyladenosine (m6A) and 2′-O-methyladenosine (Am) in RNA isolated from mammalian cells and tissues. Our results showed that the distributions of the four methylated nucleosides are tissue-specific. In addition, the 2′-O-methylated ribonucleosides (Cm and Am) are present at higher levels than the corresponding methylated nucleobase products (m5C and m6A) in total RNA isolated from mouse brain, pancreas and spleen, but not mouse heart. We also found that the levels of m5C, Cm and Am are significantly lower (by 6.5-43 fold) in mRNA than in total RNA isolated from HEK293T cells, whereas the level of m6A was slightly higher (by 1.6 fold) in mRNA than in total RNA. The availability of this analytical method, in combination with genetic manipulation, may facilitate the future discovery of proteins involved in the maintenance and regulation of these RNA modifications. PMID:26158405

  20. Dynamical Threshold of Diluteness of Soft Colloids

    SciTech Connect

    Chen, Wei-Ren; Do, Changwoo; Egami, T; Falus, Peter; Li, Xin; Liu, Dazhi; Porcar, L.; Sanchez-Diaz, Luis E; Smith, Gregory Scott; Wu, Bin

    2014-01-01

    The dynamics of soft colloids in solutions is characterized by internal collective motion as well as center-of-mass diffusion. Using neutron scattering we demonstrate that the competition between the relaxation processes associated with these two degrees of freedom results in strong dependence of dynamics and structure on colloid concentration, c, well below the overlap concentration c*. Triggered by the increasing inter-particle collisions, substantial structural dehydration and slowing-down of internal dynamics occurs before geometrically defined colloidal overlap develops. This observation is surprising since it is generally believed that the internal dynamics and conformation of soft colloidal particles essentially remain invariant below c*. The competition between these two relaxation processes gives rise to a new dynamically-defined dilute threshold concentration well below c*.

  1. Size-Segregated Aerosol Composition and Mass Loading of Atmospheric Particles as Part of the Pacific Northwest 2001(PNW2001) Air Quality Study In Puget Sound

    NASA Astrophysics Data System (ADS)

    Disselkamp, R. S.; Barrie, L. A.; Shutthanadan, S.; Cliff, S.; Cahill, T.

    2001-12-01

    In mid-August, 2001, an aircraft-based air-quality study was performed in the Puget Sound, WA, area entitled PNW2001 (http://www.pnl.gov/pnw2001). The objectives of this field campaign were the following: 1. reveal information about the 3-dimensional distribution of ozone, its gaseous precursors and fine particulate matter during weather conditions favoring air pollution; 2. derive information about the accuracy of urban and biogenic emissions inventories that are used to drive the air quality forecast models; and 3. examine the accuracy of modeled ozone concentration with that observed. In support of these efforts, we collected time-averaged ( { ~}10 minute averages), size-segregated, aerosol composition and mass-loading information using ex post facto analysis techniques of synchrotron x-ray fluorescence (s-XRF), proton induced x-ray emissions(PIXE), proton elastic scattering (PESA), and scanning transmission ion microscopy (STIM). This is the first time these analysis techniques have been used together on samples collected from aircraft using an optimized 3-stage rotating drum impactor. In our presentation, we will discuss the aerosol components in three aerosol size fractions as identified by statistical analysis of multielemental data (including total mass, H, Na, Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Pb) and relate variations in these components to physical aerosol properties, other gaseous trace constituents and to air mass origin.

  2. Combining the quick, easy, cheap, effective, rugged and safe approach and clean-up by immunoaffinity column for the analysis of 15 mycotoxins by isotope dilution liquid chromatography tandem mass spectrometry.

    PubMed

    Desmarchelier, Aurélien; Tessiot, Sabine; Bessaire, Thomas; Racault, Lucie; Fiorese, Elisa; Urbani, Alessandro; Chan, Wai-Chinn; Cheng, Pearly; Mottier, Pascal

    2014-04-11

    Optimization and validation of a multi-mycotoxin method by LC-MS/MS is presented. The method covers the EU-regulated mycotoxins (aflatoxins, fumonisins, ochratoxin A, deoxynivalenol, zearalenone, T-2 and HT-2), as well as nivalenol and 3- and 15-acetyldeoxynivalenol for analysis of cereals, cocoa, oil, spices, infant formula, coffee and nuts. The proposed procedure combines two clean-up strategies: First, a generic preparation suitable for all mycotoxins based on the QuEChERS (for quick, easy, cheap, effective, rugged and safe) protocol. Second, a specific clean-up devoted to aflatoxins and ochratoxin A using immunoaffinity column (IAC) clean-up. Positive identification of mycotoxins in matrix was conducted according to the confirmation criteria defined in EU Commission Decision 2002/657/EC while quantification was performed by isotopic dilution using (13)C-labeled mycotoxins as internal standards. Limits of quantification were at or below the maximum levels set in the EC/1886/2006 document for all mycotoxin/matrix combinations under regulation. In particular, the inclusion of an IAC step allowed achieving LOQs as low as 0.05 and 0.25μg/kg in cereals for aflatoxins and ochratoxin A, respectively. Other performance parameters like linearity [(r)(2)>0.99], recovery [71-118%], precision [(RSDr and RSDiR)<33%], and trueness [78-117%] were all compliant with the analytical requirements stipulated in the CEN/TR/16059 document. Method ruggedness was proved by a verification process conducted by another laboratory. PMID:24636559

  3. Combining the quick, easy, cheap, effective, rugged and safe approach and clean-up by immunoaffinity column for the analysis of 15 mycotoxins by isotope dilution liquid chromatography tandem mass spectrometry.

    PubMed

    Desmarchelier, Aurélien; Tessiot, Sabine; Bessaire, Thomas; Racault, Lucie; Fiorese, Elisa; Urbani, Alessandro; Chan, Wai-Chinn; Cheng, Pearly; Mottier, Pascal

    2014-04-11

    Optimization and validation of a multi-mycotoxin method by LC-MS/MS is presented. The method covers the EU-regulated mycotoxins (aflatoxins, fumonisins, ochratoxin A, deoxynivalenol, zearalenone, T-2 and HT-2), as well as nivalenol and 3- and 15-acetyldeoxynivalenol for analysis of cereals, cocoa, oil, spices, infant formula, coffee and nuts. The proposed procedure combines two clean-up strategies: First, a generic preparation suitable for all mycotoxins based on the QuEChERS (for quick, easy, cheap, effective, rugged and safe) protocol. Second, a specific clean-up devoted to aflatoxins and ochratoxin A using immunoaffinity column (IAC) clean-up. Positive identification of mycotoxins in matrix was conducted according to the confirmation criteria defined in EU Commission Decision 2002/657/EC while quantification was performed by isotopic dilution using (13)C-labeled mycotoxins as internal standards. Limits of quantification were at or below the maximum levels set in the EC/1886/2006 document for all mycotoxin/matrix combinations under regulation. In particular, the inclusion of an IAC step allowed achieving LOQs as low as 0.05 and 0.25μg/kg in cereals for aflatoxins and ochratoxin A, respectively. Other performance parameters like linearity [(r)(2)>0.99], recovery [71-118%], precision [(RSDr and RSDiR)<33%], and trueness [78-117%] were all compliant with the analytical requirements stipulated in the CEN/TR/16059 document. Method ruggedness was proved by a verification process conducted by another laboratory.

  4. Transport and sedimentation in unconfined experimental dilute pyroclastic density currents

    NASA Astrophysics Data System (ADS)

    Ramirez, G.; Andrews, B. J.; Dennen, R. L.

    2013-12-01

    We present results from experiments conducted in a new facility that permits the study of large, unconfined particle laden density currents that are dynamically similar to natural dilute pyroclastic density currents (PDCs). Experiments were run in a sealed, air-filled tank measuring 8.5 m long by 6.1 m wide by 2.6 m tall. Currents were generated by feeding mixture of heated particles (5 μm aluminum oxide, 25 μm talc, 27 μm walnut shell, 76 μm glass beads) down a chute at controlled rates to produce dilute, turbulent gravity currents. Comparison of experimental currents with natural PDCs shows good agreement between Froude, densimetric and thermal Richardson, and particle Stokes and settling numbers; experimental currents have lower Reynolds numbers than natural PDCs, but are fully turbulent. Currents were illuminated with 3 orthogonal laser sheets (650, 532, and 450 nm wavelengths) and recorded with an array of HD video cameras and a high speed camera (up to 3000 fps). Deposits were mapped using a grid of sedimentation traps. We observe distinct differences between ambient temperature and warm currents: * warm currents have shorter run out distances, narrow map view distributions of currents and deposits, thicken with distance from the source, and lift off to form coignimbrite plumes; * ambient temperature currents typically travel farther, spread out radially, do not thicken greatly with transport distance, and do not form coignimbrite plumes. Long duration currents (600 s compared to 30-100 s) oscillate laterally with time (e.g. transport to the right, then the left, and back); this oscillation happens prior to any interaction with the tank walls. Isopach maps of the deposits show predictable trends in sedimentation versus distance in response to eruption parameters