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Sample records for air mass dilution

  1. 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...

  2. 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...

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

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Measurement Instruments Flow-Related Measurements § 1065.240 Dilution air and diluted exhaust flow meters. (a) Application. Use a diluted exhaust flow... 40 Protection of Environment 33 2014-07-01 2014-07-01 false Dilution air and diluted exhaust...

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

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Measurement Instruments Flow-Related Measurements § 1065.240 Dilution air and diluted exhaust flow meters. (a) Application. Use a diluted exhaust flow... 40 Protection of Environment 32 2010-07-01 2010-07-01 false Dilution air and diluted exhaust...

  9. 40 CFR 1065.240 - Dilution air and diluted exhaust flow meters.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Measurement Instruments Flow-Related Measurements § 1065.240 Dilution air and diluted exhaust flow meters. (a) Application. Use a diluted exhaust flow... 40 Protection of Environment 34 2012-07-01 2012-07-01 false Dilution air and diluted exhaust...

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

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Measurement Instruments Flow-Related Measurements § 1065.240 Dilution air and diluted exhaust flow meters. (a) Application. Use a diluted exhaust flow... 40 Protection of Environment 34 2013-07-01 2013-07-01 false Dilution air and diluted exhaust...

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

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Measurement Instruments Flow-Related Measurements § 1065.240 Dilution air and diluted exhaust flow meters. (a) Application. Use a diluted exhaust flow... 40 Protection of Environment 33 2011-07-01 2011-07-01 false Dilution air and diluted exhaust...

  12. 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.

  13. 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.

  14. 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

  15. Ignition of hydrogen-air mixture diluted by silane

    NASA Astrophysics Data System (ADS)

    Tropin, D. A.; Fedorov, A. V.

    2016-10-01

    The calculations of ignition delay time of hydrogen-air mixture diluted silane based on our previously physical and mathematical models of ignition and combustion of silane / hydrogen / oxygen / nitrogen mixtures, which takes into account detailed kinetics were carried out. It was shown that low temperatures up to 2200K silane addition in hydrogen-air mixture leads to a monotonic decrease in ignition delay time. However, at the temperatures greater than 2200K there is the opposite effect: an addition of a small amount of silane (~20%) in a hydrogen-air mixture leads to a greater decreasing of the ignition delay time compared with mixtures with a large amount of silane (>20%).

  16. 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.

  17. What's All the Talc About? Air Entrainment in Dilute Pyroclastic Density Currents

    NASA Astrophysics Data System (ADS)

    Marshall, B. J.; Andrews, B. J.; Fauria, K.

    2015-12-01

    A quantitative understanding of air entrainment is critical to predicting the behaviors of dilute Pyroclastic Density Currents (PDCs), including runout distance, liftoff, and mass fractionation into co-PDC plumes. We performed experiments in an 8.5x6x2.6 meter tank using 20 micron talc powder over a range of conditions to describe air entrainment as a function of temperature, duration and mass flux. The experiments are reproducible and are scaled with respect to the densimetric and thermal Richardson numbers (Ri and RiT), Froude number, thermal to kinetic energy density ratio (TEb/KE), Stokes number, and Settling number, such that they are dynamically similar to natural dilute PDCs. Experiments are illuminated with a swept laser sheet and imaged at 1000 Hz to create 3D reconstructions of the currents, with ~1-2 cm resolution, at up to 1.5 Hz. An array of 30 high-frequency thermocouples record the precise temperature in the currents at 3 Hz. Bulk entrainment rates are calculated based on measured current volumes, surface areas, temperatures and velocities. Entrainment rates vary from ~0-0.9 and do not show simple variation with TEb/KE, Ri, or RiT. Entrainment does, however, increase with decreasing eruption duration and increasing mass flux. Our results suggest that current heads entrain air more efficiently than current bodies (>0.5 compared to ~0.1). Because shorter duration currents have proportionally larger heads, their bulk entrainment rates are controlled by those heads, whereas longer duration currents are dominated by their bodies. Our experiments demonstrate that air entrainment, which exerts a fundamental control on PDC runout and liftoff, varies spatially and temporally within PDCs.

  18. Dilution

    PubMed Central

    Lavie, Nilli; Torralbo, Ana

    2010-01-01

    Load theory of attention proposes that distractor processing is reduced in tasks with high perceptual load that exhaust attentional capacity within task-relevant processing. In contrast, tasks of low perceptual load leave spare capacity that spills over, resulting in the perception of task-irrelevant, potentially distracting stimuli. Tsal and Benoni (2010) find that distractor response competition effects can be reduced under conditions with a high search set size but low perceptual load (due to a singleton color target). They claim that the usual effect of search set size on distractor processing is not due to attentional load but instead attribute this to lower level visual interference. Here, we propose an account for their findings within load theory. We argue that in tasks of low perceptual load but high set size, an irrelevant distractor competes with the search nontargets for remaining capacity. Thus, distractor processing is reduced under conditions in which the search nontargets receive the spillover of capacity instead of the irrelevant distractor. We report a new experiment testing this prediction. Our new results demonstrate that, when peripheral distractor processing is reduced, it is the search nontargets nearest to the target that are perceived instead. Our findings provide new evidence for the spare capacity spillover hypothesis made by load theory and rule out accounts in terms of lower level visual interference (or mere “dilution”) for cases of reduced distractor processing under low load in displays of high set size. We also discuss additional evidence that discounts the viability of Tsal and Benoni's dilution account as an alternative to perceptual load. PMID:21133554

  19. 40 CFR 1066.610 - Dilution air background correction.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... interval. x CO = amount of CO measured in the sample over the test interval. a = atomic hydrogen-to-carbon... = atomic oxygen-to-carbon ratio of the test fuel. You may measure b or use default values from Table 1 of.... ER28AP14.102 (d) Determine the time-weighted dilution factor, DF w, over the duty cycle using the...

  20. An isotopic dilution approach for 1,3-butadiene tailpipe emissions and ambient air monitoring.

    PubMed

    Riservato, Manuela; Rolla, Antonio; Davoli, Enrico

    2004-01-01

    An isotopic dilution approach for 1,3-butadiene analysis in gaseous samples is presented. The methodology is based on active sampling on sorbent tubes and subsequent analysis by thermal desorption into a gas chromatography/mass spectrometry system. By adding a perdeuterated internal standard onto the sorbent tubes before sampling, and using mass spectrometric detection, the methodology gives high accuracy for this unstable analyte. The method has been used to monitor 1,3-butadiene ambient air concentrations in a residential area in proximity to a heavy-traffic roadway over a one-week period, for comparison with other traffic-related pollutants analysed by standard procedures. It has also been used to determine tailpipe emissions of two vehicles by standard emission testing procedures in a dynamometer. These vehicles were chosen as examples of low- and high-end emission rate vehicles, i.e., an old no-catalytic converter Otto engine and a new direct-injection diesel engine with catalytic converter. Exhaust gas emissions were 0.052 and 35.85 mg/km, reflecting differences in fuel, engine design, age, and presence (or not) of a catalytic abatement system. The ambient air results showed a weekly average concentration of 1,3-butadiene of 0.53 microg/m(3).

  1. High-throughput chemical residue analysis by fast extraction and dilution flow injection mass spectrometry.

    PubMed

    Nanita, Sergio C

    2011-01-21

    Fast extraction and dilution flow injection mass spectrometry (FED-FI-MS) is presented as a technique to increase throughput in quantitative multiresidue screening in complex matrices, while meeting current analytical method quality requirements.

  2. 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)

  3. Effects of CO2/N2 dilution on laminar burning velocity of stoichiometric DME-air mixture at elevated temperatures.

    PubMed

    Mohammed, Abdul Naseer; Juhany, Khalid A; Kumar, Sudarshan; Kishore, V Ratna; Mohammad, Akram

    2017-03-21

    The laminar burning velocity of CO2/N2 diluted stoichiometric dimethyl ether (DME) air mixtures is determined experimentally at atmospheric pressure and elevated mixture temperatures using a mesoscale high aspect-ratio diverging channel with inlet dimensions of 25mm×2mm. In this method, planar flames at different initial temperatures (Tu) were stabilized inside the channel using an external electric heater. The magnitude of burning velocities was acquired by measuring the flame position and initial temperature. The mass conservation of the mixture entering the inlet and the stationary planar flame front is applied to obtain the laminar burning velocity. Laminar burning velocity at different initial mixture temperatures is plotted with temperature ratio (Tu/Tu,o), where a reference temperature (Tu,o) of 300K is used. Enhancement in the laminar burning velocity is observed with mixture temperature for DME-air mixtures with CO2 and N2 dilutions. A significant decrease in the burning velocity and slight increase in temperature exponent of the stoichiometric DME-air mixture was observed with dilution at same temperatures. The addition of CO2 has profound influence when compared to N2 addition on both burning velocity and temperature exponent.

  4. 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.

  5. Magnetic Field Modulated Photoreflectance Study of the Electron Effective Mass in Dilute Nitride Semiconductors

    SciTech Connect

    Mori, N.; Hiejima, K.; Kubo, H.; Patane, A.; Eaves, L.

    2011-12-23

    Magnetic field modulated photoreflectance measurements are performed on the dilute nitride semiconductor Ga(AsN) in quantizing magnetic fields. From the measured cyclotron energies, the conduction band effective mass and its dependence on the nitrogen content are determined. The effective mass is found to become significantly heavier in samples with high nitrogen composition (>0.1%).

  6. Boundary-layer isotope dilution/mass balance methods for measurement of nocturnal methane emissions from grazing sheep

    NASA Astrophysics Data System (ADS)

    Harvey, M. J.; Brailsford, G. W.; Bromley, A. M.; Lassey, K. R.; Mei, Z.; Kristament, I. S.; Reisinger, A. R.; Walker, C. F.; Kelliher, F. M.

    Following advances with methods for 13C/ 12C isotopic analysis of methane in small (⩽4 L) air samples, new isotope dilution techniques are proposed for measurement of methane emissions at the paddock scale from grazing ruminant animals. These techniques combine measurement of the isotopic δ13CH 4 composition of air samples with a non-intrusive mass balance method applied in the nocturnal boundary layer. Flux estimates from trials using the isotope dilution techniques are compared with estimates based on scaling up individual animal emission measurements using a rumen gas tracer technique. The methane flux assessed by the latter technique ranged from 35 to 70 mg (CH 4) m -2 d -1 with a stocking density between 10 and 20 sheep ha -1. The isotope dilution based nocturnal boundary-layer estimates generally agreed to better than a factor of 2 and usually to within 20% of the average of individual animal emission rate per unit area of paddock. Both static and advecting mass balance methods are developed. In the advecting case, the upwind/downwind contrast in δ13C was typically 0.2-0.5‰. Care was necessary with air sampling to avoid error in this small contrast contributing to error in the flux. Agreement between concentration- and isotope-based nocturnal boundary layer methods and the sheep breath measurements indicated that sample representativeness was generally good. Factors which affect the accuracy of the method are examined and include variability in nocturnal mixing height, the assumed δ13CH 4 composition of the source sheep breath and diurnal patterns in sheep emission. This paper establishes new techniques useful in the paddock to landscape scale although widespread application awaits further development of technology for rapid and repeatable field analysis of δ13CH 4 in small samples.

  7. 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.

  8. Effectiveness of in-room air filtration and dilution ventilation for tuberculosis infection control

    SciTech Connect

    Miller-Leiden, S.; Lobascio, C.; Nazaroff, W.W.; Macher, J.M.

    1996-09-01

    Tuberculosis (TB) is a public health problem that may pose substantial risks to health care workers and others. TB infection occurs by inhalation of airborne bacteria emitted by persons with active disease. We experimentally evaluated the effectiveness of in-room air filtration systems, specifically portable air filters (PAFs) and ceiling-mounted air filters (CMAFs), in conjunction with dilution ventilation, for controlling TB exposure in high-risk settings. For each experiment, a test aerosol was continuously generated and released into a full-sized room. With the in-room air filter and room ventilation system operating, time-averaged airborne particle concentrations were measured at several points. The effectiveness of in-room air filtration plus ventilation was determined by comparing particle concentrations with and without device operation. The four PAFs and three CMAFs we evaluated reduced room-average particle concentrations, typically by 30% to 90%, relative to a baseline scenario with two air-changes per hour of ventilation (outside air) only. Increasing the rate of air flow recirculating through the filter and/or air flow from the ventilation did not always increase effectiveness. Concentrations were generally higher near the emission source than elsewhere in the room. Both the air flow configuration of the filter and its placement within the room were important. 46 refs., 12 figs., 1 tab.

  9. Mechanisms of mass transport during coalescence-induced microfluidic drop dilution

    NASA Astrophysics Data System (ADS)

    Wang, William S.; Vanapalli, Siva A.

    2016-10-01

    Confinement-guided coalescence of drops in microfluidic devices is an effective means to manipulate the composition of individual droplets. Recently, Sun et al. [Lab Chip 11, 3949 (2011), 10.1039/c1lc20709a] have shown that coalescence between a long moving plug and an array of parked droplets in a microfluidic network can be used to flexibly manipulate the composition of the static droplet arrays. However, the transport mechanisms underlying this complex dilution process have not been elucidated. In this study, we develop phenomenological models and perform particle-based numerical simulations to identify the key mass transfer mechanisms influencing the concentration profiles of drops during coalescence-induced drop dilution. Motivated by experimental observations, in the simulations we consider (i) advection within the moving plug, (ii) diffusion in the moving plug and parked droplets, (iii) fluid advection due to initiation of coalescence, and (iv) advection in the coalesced plug due to the continuous phase flowing through the gutters in noncircular microchannels. We find that the dilution process is dominated by diffusion, recirculation in the moving plug, and gutter-flow-induced advection, but is only weakly affected by coalescence-induced advection. We show that the control parameters regulating dilution can be divided into those influencing the duration of mass transfer (e.g., plug length and velocity) and those affecting the rate of mass transfer (e.g., diffusion and gutter-flow-induced advection). Finally, we demonstrate that our simulations are able to predict droplet concentration profiles in experiments. The results from this study will allow better design of drop dilution microfluidic devices. Furthermore, the identification of gutter-flow-induced advection as an alternative mass transfer mechanism in two-phase flows could potentially lead to more efficient means of oil recovery from droplets trapped in porous media.

  10. 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.

  11. Laminar Flame Velocity and Temperature Exponent of Diluted DME-Air Mixture

    NASA Astrophysics Data System (ADS)

    Naseer Mohammed, Abdul; Anwar, Muzammil; Juhany, Khalid A.; Mohammad, Akram

    2017-03-01

    In this paper, the laminar flame velocity and temperature exponent diluted dimethyl ether (DME) air mixtures are reported. Laminar premixed mixture of DME-air with volumetric dilutions of carbon dioxides (CO2) and nitrogen (N2) are considered. Experiments were conducted using a preheated mesoscale high aspect-ratio diverging channel with inlet dimensions of 25 mm × 2 mm. In this method, flame velocities are extracted from planar flames that were stabilized near adiabatic conditions inside the channel. The flame velocities are then plotted against the ratio of mixture temperature and the initial reference temperature. A non-linear power law regression is observed suitable. This regression analysis gives the laminar flame velocity at the initial reference temperature and temperature exponent. Decrease in the laminar flame velocity and increase in temperature exponent is observed for CO2 and N2 diluted mixtures. The addition of CO2 has profound influence when compared to N2 addition on both flame velocity and temperature exponent. Numerical prediction of the similar mixture using a detailed reaction mechanism is obtained. The computational mechanism predicts higher magnitudes for laminar flame velocity and smaller magnitudes of temperature exponent compared to experimental data.

  12. 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.

  13. 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.

  14. 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.

  15. Age of air and air exchange efficiency in high-rise urban areas and its link to pollutant dilution

    NASA Astrophysics Data System (ADS)

    Hang, Jian; Li, Yuguo

    2011-10-01

    By means of computational fluid dynamic (CFD) simulations, this paper investigated how rural winds transport relatively clean air into high-rise urban areas to dilute airborne pollutants. Two ventilation concepts for indoor environments were applied: the age of air to quantify the time taken by rural young air to reach a given place after it enters an urban area and the air exchange efficiency to evaluate the efficiency of rural winds flushing the entire urban canopy layer. Several square building arrays with street aspect ratios (building height/street width, H/ W) ranging from 1.5 to 5.3 and building area densities of 0.25 (medium) or 0.4 (compact) were considered as the approaching wind is parallel to the main street whose length varies from street scales to neighborhood scales (330-510 m to 1.03-1.65 km in full-scale). Results show that considerable young rural air enters windward entries but a major fraction of air is vertically driven out as flowing deeper into such high-rise building arrays. So air exchange efficiencies are less than 50% in street-scale arrays, and smaller in longer (neighborhood-scale) or narrower arrays. For the neighborhood-scale medium arrays, considering the power-law velocity profile in the upstream free flow, a taller array gains a larger inflow rate across its windward entry and experiences younger air and greater air exchange efficiency than a lower one. If all buildings are theoretically open-based in a neighborhood-scale compact array, air becomes much younger everywhere and the air exchange efficiency doubles. In arrays of buildings with different heights, the secondary streets in front of taller buildings get younger air due to the downward flows within them. Although further investigations are still required before providing a practical framework, this paper is one of the first attempts to find ways in improving the ventilation performance in high-rise cities like Hong Kong.

  16. Nonluminous diffusion flame of diluted acetylene in oxygen-enriched air

    SciTech Connect

    Sugiyama, G.

    1994-12-31

    A soot-reducing mechanism of fuel dilution and oxygen enrichment in laminar diffusion flames is suggested. Analysis using the Burke-Schumann theory for the shape of over ventilated diffusion flames has shown that there is a critical ratio of stoichiometric coefficients of the fuel and the oxidizer under which the gas flows from the fuel side to the oxidizer side throughout the flame. When this condition is satisfied, the soot growth region vanishes. A similar result is also found in a numerical simulation for diffusion flames that do not satisfy the Burke-Schumann assumption of uniform flow field. KIVA code is used for that purpose. The theoretically predicted direction of gas-flow across the flame sheet is verified in an experiment in a coaxial-flow diffusion flame. Soot cloud and velocity fields are visualized through a laser sheet method in the experiment. The fuel is a mixture of acetylene and nitrogen. The oxidizer is a mixture of oxygen and nitrogen. The compositions of the reactants are controlled so that the adiabatic flame temperature is kept constant to avoid the effect of temperature change. Experimental results show substantial reduction of scattered light intensity by fuel dilution and oxygen enrichment. When a sufficient amount of nitrogen is added to the fuel, nonluminous blue flames are obtained. At higher oxygen concentrations, blue flames are obtained at higher flame temperature region. When oxygen concentration in the oxidizer is 70 vol.%, blue flames are obtained up to 2,250 K. The critical condition of the reactants for nonluminous flames agrees with the theoretical prediction when the oxidizer is ordinary air. In oxygen-enriched conditions, the fuel must be diluted more, than theoretically predicted.

  17. Steroid hormone levels in pregnancy and 1 year postpartum using isotope dilution tandem mass spectrometry

    PubMed Central

    Soldin, Offie P.; Guo, Tiedong; Weiderpass, Elisabete; Tractenberg, Rochelle E.; Hilakivi-Clarke, Leena; Soldin, Steven J.

    2013-01-01

    Objective To establish normal, trimester-specific reference intervals for serum 17β-estradiol, progesterone (P), 17α-hydroxyprogesterone, cortisol, 11-deoxycortisol, androstenedione, DHEA, and DHEAS, measured simultaneously using isotope dilution tandem mass spectrometry. Design Sequential cohort study. Patient(s) Healthy women undergoing a normal pregnancy (age, 25–38 years; mean, 30 years) attending a prenatal well clinic at gestation weeks 12, 22, and 32 and approximately 1 year postpartum. Main Outcome Measure(s) Trimester-specific reference intervals of endogenous steroid hormones analyzed using an isotope dilution tandem mass spectrometer equipped with an atmospheric pressure photoionization source with deuterium-labeled internal standards. Result(s) Serum estradiol, P, 17α-hydroxyprogesterone, and 11-deoxycortisol increased throughout pregnancy; cortisol increased up to the second trimester and then remained steady, while androstenedione increased by 80 percent by gestation week 12, then remained constant. Serum DHEA-S decreased by 50% by the third trimester. Conclusion(s) Trimester-specific reference intervals are reported for eight serum steroids. The ratios of individual serum hormone concentrations during pregnancy relative to their 1-year postpartum concentrations illustrate the expected normal trends of changes in hormone concentrations during pregnancy. PMID:16169406

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

    SciTech Connect

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

    1985-11-15

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

  19. Air dilution, under calm, of spreading dense vapor from an instantaneous spill of volatile liquid

    SciTech Connect

    Carrier, G.F.; Fendell, F.E.; Fink, S.F. IV

    1998-07-01

    The objective is to estimate the time after release until dilution with air of a combustible vapor results in the local concentration being everywhere below the fuel-lean flammability limit. For an instantaneous release of sufficient liquid volume, the authors anticipate (and can justify a posteriori) that a balance of inertial and buoyant forces constitutes an excellent approximation to the conservation of momentum for the gravity-current dynamics of the spilled liquid and evolved vapor [until the (cylindrical-)radial spread results in liquid and vapor layers so thin that a viscous-buoyant balance is more appropriate]. Whereas virtually all previous analyses of wind-free dense-fluid dispersion take the initial condition to be a uniform-fluid spill in the configuration of a right-circular cylinder, and eventually a selfsimilar behavior, based parametrically only on the fixed spill-occupied volume and the effective gravitational acceleration, evolves, the authors adopt an initial spilled-fluid configuration in the form of a finite-radius mound, with the layer thickness monotonically decreasing with increasing radial distance and smoothly vanishing at finite radius. They find that no selfsimilar behavior evolves; furthermore, they find that at all times the thickness of the spilled-fluid layer would decrease monotonically with radius, from the axis of symmetry to the spilled-fluid-layer front. Also, whereas virtually all simple gas-cloud models are of box type, and take the contents to be spatially homogeneous, they investigate the spatial inhomogeneity of the vapor content of a cloud formed by evaporation, and show that distribution of the ambient-air-diluted vapor is well approximated as decreasing with increasing height as a Gaussian function, with peak concentration on the axis at all times.

  20. 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.

  1. 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.

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

    SciTech Connect

    Beals, D.M.

    1992-09-01

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

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

    SciTech Connect

    Beals, D.M.

    1992-01-01

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

  4. Screening of dimethoate in food by isotope dilution and electrospray ionization tandem mass spectrometry.

    PubMed

    Mazzotti, Fabio; Di Donna, Leonardo; Macchione, Barbara; Maiuolo, Loredana; Perri, Enzo; Sindona, Giovanni

    2009-05-01

    Crop control is an important issue in both developed and developing countries. An environmentally friendly approach is represented by the so-called Integrated Pest Management (IPM), whereby synthetic pesticides are only applied as a last resort, under the strict control of suitable experts. European and US regulatory authorities, such as the US EPA, are constantly assessing the risks of exposure to the organophosphate (OP) class of pesticides and, among these, specifically dimethoate. The use of dimethoate is still allowed in many crops, including olives, which once was based in the Mediterranean area but now is expanding rapidly throughout the world. An important aspect of IPM protocols is represented by the availability of reliable and sensitive methods to detect pesticides residues. This paper describes an isotope dilution dimethoate assay based on the application of electrospray ionization tandem mass spectrometry (ESI-MS/MS) by means of a deuterium-labeled internal standard.

  5. 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.

  6. Quantification of four artificial sweeteners in Finnish surface waters with isotope-dilution mass spectrometry.

    PubMed

    Perkola, Noora; Sainio, Pirjo

    2014-01-01

    The artificial sweeteners sucralose (SCL), acesulfame (ACS), saccharin (SAC), and cyclamate (CYC) have been detected in environmental waters in Europe and North America. Higher environmental levels are expected in view of the increasing consumption of these food additives. In this study, an isotope-dilution mass spectrometry (IDMS) LC-MS/MS method was developed and validated for quantifying the four artificial sweeteners in boreal lakes (n = 3) and rivers (n = 12). The highest concentrations of ACS, SAC, CYC and SCL were 9,600, 490, 210 and 1000 ng/L, respectively. ACS and SAC were detected in all studied samples, and CYC and SCL in 98% and 56% of the samples. Seasonal trends of ACS and SAC were observed in some rivers. ACS and SCL concentrations in rivers correlated linearly with population equivalents of the wastewater treatment plants in the catchment areas, whereas SAC and CYC concentrations depend more on the source.

  7. [Determination of nicotinamide in formula milk powder using liquid chromatography-isotope dilution mass spectrometry].

    PubMed

    Huang, Ting; Zhang, Wei; Liu, Yang; Liu, Jun

    2007-11-01

    It is important to determine trace compounds in complex matrices. Internal standards are often introduced to circumvent loss of analytes during the preparation to achieve accurate measurement. Isotope internal standards are better than other types of internal standards, due to its high similarity to analyte in chemical properties. By introducing isotope-labeled nicotinamide, as an internal standard, a method for determining nicotinamide in formula milk powder by liquid chromatography-isotope dilution mass spectrometry (LC-IDMS) was developed with a relative standard deviation of 0.94%. The results suggested that the developed LC-IDMS method has high accuracy, high specificity, high repeatability, and is suitable for the determination of vitamins in complex matrices. This method was used to perform international comparison for CCQM-P78, and the result was consistent with that of international laboratories.

  8. Precise determination of seawater calcium using isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Liu, Hou-Chun; You, Chen-Feng; Cai, Wei-Jun; Chung, Chuan-Hsiung; Huang, Kuo-Fang; Chen, Bao-Shan; Li, Yen

    2014-02-21

    We describe a method for rapid, precise and accurate determination of calcium ion (Ca(2+)) concentration in seawater using isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). A 10 μL aliquot of seawater was spiked with an appropriate (43)Ca enriched solution for (44)Ca/(43)Ca ID-ICP-MS analyses, using an Element XR (Thermo Fisher Scientific), operated at low resolution in E-scan acquisition mode. A standard-sample bracketing technique was applied to correct for potential mass discrimination and ratio drift at every 5 samples. A precision of better than 0.05% for within-run and 0.10% for duplicate measurements of the IAPSO seawater standard was achieved using 10 μL solutions with a measuring time less than 3 minutes. Depth profiles of seawater samples collected from the Arctic Ocean basin were processed and compared with results obtained by the classic ethylene glycol tetra-acetic acid (EGTA) titration. Our new ID-ICP-MS data agreed closely with the conventional EGTA data, with the latter consistently displaying 1.5% excess Ca(2+) values, possibly due to a contribution of interference from Mg(2+) and Sr(2+) in the EGTA titration. The newly obtained Sr/Ca profiles reveal sensitive water mass mixing in the upper oceanic column to reflect ice melting in the Arctic region. This novel technique provides a tool for seawater Ca(2+) determination with small sample size, high throughput, excellent internal precision and external reproducibility.

  9. Plasticization and antiplasticization of polymer melts diluted by low molar mass species

    NASA Astrophysics Data System (ADS)

    Stukalin, Evgeny B.; Douglas, Jack F.; Freed, Karl F.

    2010-02-01

    An analysis of glass formation for polymer melts that are diluted by structured molecular additives is derived by using the generalized entropy theory, which involves a combination of the Adam-Gibbs model and the direct computation of the configurational entropy based on a lattice model of polymer melts that includes monomer structural effects. Our computations indicate that the plasticization and antiplasticization of polymer melts depend on the molecular properties of the additive. Antiplasticization is accompanied by a "toughening" of the glass mixture relative to the pure polymer, and this effect is found to occur when the diluents are small species with strongly attractive interactions with the polymer matrix. Plasticization leads to a decreased glass transition temperature Tg and a "softening" of the fragile host polymer in the glass state. Plasticization is prompted by small additives with weakly attractive interactions with the polymer matrix. However, the latter situation can lead to phase separation if the attractive interactions are sufficiently strong. The shifts in Tg of polystyrene diluted by fully flexible short oligomers (up to 20% mass of diluent) are evaluated from the computations, along with the relative changes in the isothermal compressibility at Tg (a softening or toughening effect) to characterize the extent to which the additives act as antiplasticizers or plasticizers. The theory predicts that a decreased fragility can accompany both antiplasticization and plasticization of the glass by molecular additives. The general reduction in the Tg of polymers by molecular additives is rationalized by analyzing the influence of the diluent's properties (cohesive energy, chain length, and stiffness) on glass formation in fluid mixtures and the variation of fragility is discussed in relation to changes in the molecular packing in diluted polymer melts. Our description of constant temperature glass formation upon increasing the diluent concentration

  10. 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.

  11. 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.

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

    PubMed

    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.

  13. 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.

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

    PubMed

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

    2012-04-01

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

  15. 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.

  16. Elemental composition of different air masses over Jeju Island, South Korea

    NASA Astrophysics Data System (ADS)

    Kang, Jeongwon; Choi, Man-Sik; Yi, Hi-Il; Jeong, Kap-Sik; Chae, Jung-Sun; Cheong, Chang-Sik

    2013-03-01

    We investigated the characteristics (concentrations and compositional changes) of atmospheric elements in total suspended particulates through source-receptor relationships using cluster analyses to classify air mass back-trajectories arriving at Gosan, Jeju Island, South Korea, from October 2003 to December 2008. Five trajectory clusters were chosen to explain the transport regimes. Continental outflows of natural and anthropogenic aerosols from Asian dust source regions and eastern China during the colder period could increase element concentrations at Gosan. Elemental levels at Gosan decreased in air masses that passed over marine regions (East China Sea, Pacific Ocean/southern side of Kyushu Island in Japan, and East Sea/southern side of South Korea) during the warmer rainy period due to lower source intensity and dilution by the marine air mass. Anthropogenic pollutants were often major components in air masses passing over marine regions. Air mass characterization by elemental concentration and composition revealed that enrichment by non-sea-salt sulfur in the air mass originated from eastern China, indicative of the main sulfur emitter in northeast Asia. The apportionment of V and Ni by principal component analysis as a marker of heavy oil combustion suggested different residence times and deposition rates from other anthropogenic components in the air. Regionally intermediate concentrations of pollutants were found in the atmosphere over the Korean peninsula.

  17. 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.

  18. 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).

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

    PubMed Central

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

    2014-01-01

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

  20. Isotope dilution gas chromatography/mass spectrometry method for determination of pyrethroids in apple juice.

    PubMed

    Wong, Siu-kay; Yu, Kwok-chiu; Lam, Chi-ho

    2010-03-01

    This paper presents the development of a highly precise and accurate analytical method for the determination of three matrix-bound pyrethroids, namely, cypermethrin, permethrin, and bifenthrin, using an isotope dilution gas chromatography/mass spectrometry technique. Identification of the analytes was confirmed under selective ion monitoring mode by the presence of two dominant ion fragments within specific time windows and matching of relative ion intensities of the ions concerned in samples and calibration standards. Quantitation was based on the measurement of concentration ratios of the natural and isotope analogues in the sample and calibration blends. Intraday and interday repeatabilities of replicate analyses of the pyethroids in an apple juice sample were below 0.5%. The expanded relative uncertainty ranged from 3 to 6%, which was significantly lower than the range obtained using internal or external calibration methods. As a labeled analogue is not available for bifenthrin, bifenthrin was determined using labeled cis-permethrin as the internal standard. The results were counterchecked by a gas chromatography-electron capture detection technique using PCB 209 as the internal standard. The method developed was applied to a recent pilot study organized by CCQM and the results were consistent with those of other participants.

  1. Impact of Isotope Dilution Mass Spectrometry (IDMS) Standardization on Carboplatin Dose and Adverse Events

    PubMed Central

    Lawson, Justin; Switchenko, Jeffrey M.; McKibbin, Trevor; Harvey, R. Donald

    2017-01-01

    BACKGROUND When using area under the concentration-time curve-based strategies for dosing carboplatin, accurate estimation of glomerular filtration rate is required for determining dose. Commonly, the Cockcroft–Gault equation is used, which is dependent on measurement of serum creatinine (SCr). Because analysis of SCr changed to an isotope dilution mass spectrometry (IDMS) standard, we sought to determine the impact of this assay change on carboplatin dosing and related toxicity. METHODS This was a single-center, retrospective chart review of adults treated with carboplatin between April 2008 and April 2010 divided into cohorts that initiated carboplatin before or after IDMS standardization. End points included grade 3 thrombocytopenia, decrease in platelet count, and hospitalization and were evaluated in cohorts based on concomitant chemotherapy. RESULTS The chart review identified 158 patients, with 63 patients in the pre-IDMS group and 95 patients in the post-IDMS group. Average SCr (pre 1.01 mg/dl vs post 0.86 mg/dl, p<0.001) and average carboplatin dose (pre 580 mg vs post 703 mg, p<0.001) were significantly different between the groups. The frequency of grade 3 thrombocytopenia was not statistically significant across three partner chemotherapy cohorts before and after IDMS implementation. CONCLUSION IDMS standardization led to an overall decrease in SCr with subsequent increase in carboplatin doses. However, no increase in recorded adverse events was observed, suggesting that the clinical relevance in toxicity from higher doses was minimal. PMID:27130286

  2. 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.

  3. 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…

  4. Potential impact of a 500-mL water bolus and body mass on plasma osmolality dilution.

    PubMed

    Sollanek, Kurt J; Kenefick, Robert W; Cheuvront, Samuel N; Axtell, Robert S

    2011-09-01

    A methodological discrepancy exists in the hydration assessment literature regarding the establishment of euhydration, as some investigations utilize a pre-hydration technique, while others do not (overnight fluid/food fast). However, the degree that plasma osmolality (P (osm)) dilutes when using the pre-hydration method and how body mass/composition might influence the results is not known. Thirty subjects (22 M, 8 F; 20 ± 2 years (mean ± SD); 1.8 ± 0.1 m; 75.8 ± 13.5 kg) had P (osm) measured after an 8-h food and fluid fast (overnight fast) and 90 min after a 500-mL (4-9 mL/kg) water bolus (pre-hydration). From pre- to post-bolus, participants' P (osm) declined from 297 ± 3.5 to 295 ± 3.8 mmol/kg (p < 0.05; ∆ -1.7 ± 3.5 mmol/kg). One-third of the sample diluted to more than -3 mmol/kg. The effect of body mass on P (osm) dilution was investigated by comparing dilution in the ten lightest (62.8 ± 3.4 kg) and heaviest (92.0 ± 9.8 kg) participants; however, the change between the light (∆ -1.9 ± 3.8 mmol/kg) versus heavy groups (∆ -1.1 ± 3.0 mmol/kg) was not different (p > 0.05). The correlation between body mass or total body water and change in P (osm) was weak (p > 0.05), as was the correlation between relative fluid intake based on mass and change in P (osm) (p > 0.05). The two methodologies appear to produce similar P (osm) values when measured in most individuals. However, the potential for significant dilution (>3 mmol/kg) should be considered when choosing the pre-hydration methodology.

  5. Evolution of Southern Hemisphere spring air masses observed by HALOE

    NASA Technical Reports Server (NTRS)

    Pierce, R. Bradley; Grose, William L.; Russell, James M., III; Tuck, Adrian F.

    1994-01-01

    The evolution of Southern Hemisphere air masses observed by the Halogen Occultation Experiment (HALOE) during September 21 through October 15, 1992, is investigated using isentropic trajectories computed from United Kingdom Meteorological Office (UKMO) assimilated winds and temperatures. Maps of constituent concentrations are obtained by accumulation of air masses from previous HALOE occultations. Lagged correlations between initial and subsequent HALOE observations of the same air mass are used to validate the air mass trajectories. High correlations are found for lag times as large as 10 days. Frequency distributions of the air mass constituent concentrations are used to examine constituent distributions in and around the Southern Hemisphere polar vortex.

  6. 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.

  7. 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.

  8. Isentropic analysis of polar cold air mass streams

    NASA Astrophysics Data System (ADS)

    Iwasaki, Toshiki; Kanno, Yuki

    2015-04-01

    1. Introduction A diagnostic method is presented of polar cold air mass streams defined below a threshold potential temperature. The isentropic threshold facilitates a Lagrangian view of the cold air mass streams from diabatic generation to disappearance. 2. Mass-weighted isentropic zonal mean (MIM) cold air streams In winter hemispheres, MIM's mass stream functions show a distinct extratropical direct (ETD) cell in addition to the Hadley cell. The mass stream functions have local maxima at around (280K, 45N) for NH winter and, around (280K, 50S) for SH winter. Thus, =280K may be appropriate to a threshold of the polar cold air mass for both hemispheres. The high-latitude downward motion indicates the diabatic generation of cold air mass, whereas the mid-latitude equatorward flow does its outbreak. The strength of equatorward flow is under significant control of wave-mean flow interactions. 3. Geographical distribution of the cold air mass streams in the NH winter In the NH winter, the polar cold air mass flux has two distinct mainstreams, hereafter called as East Asian (EA) stream and the North American (NA) stream. The former grows over the northern part of the Eurasian continent, turns down southeastward toward East Asia and disappears over the western North Pacific Ocean. The latter grows over the Arctic Ocean, flows toward the East Coast of North America and disappears over the western North Atlantic Ocean. These coincide well with main routes of cold surges. 4. Comparison between NH and SH winter streams The cold air mass streams in NH winter are more asymmetric than those in SH winter. The NH total cold air mass below =280K is about 1.5 times greater than the SH one. These come mainly from the topography and land-sea distribution. The mid-latitude mountains steer the cold air mass streams on the northern sides and enhance the residence time over its genesis region.

  9. Quantitation of organophosphorus nerve agent metabolites in human urine using isotope dilution gas chromatography-tandem mass spectrometry.

    PubMed

    Driskell, W Jack; Shih, Ming; Needham, Larry L; Barr, Dana B

    2002-01-01

    An isotope dilution gas chromatography-tandem mass spectrometric (GC-MS-MS) method was developed for quantitating the urinary metabolites of the organophosphorus nerve agents sarin, soman, tabun (GA), VX, and GF. Urine samples were concentrated by codistillation with acetonitrile, derivatized by methylation with diazomethane, and analyzed by GC-MS-MS. The limits of detection were less than 4 microg/L for all the analytes except for the GA metabolite, which had a limit of detection of less than 20 microg/L.

  10. The averaging effect of odorant mixing as determined by air dilution sensory tests: a case study on reduced sulfur compounds.

    PubMed

    Kim, Ki-Hyun

    2011-01-01

    To learn more about the effects of mixing different odorants, a series of air dilution sensory (ADS) tests were conducted using four reduced sulfur compounds [RSC: hydrogen sulfide (H(2)S), methanethiol (CH(3)SH), dimethylsulfide (DMS), and dimethyldisulfide (DMDS)] at varying concentration levels. The tests were initially conducted by analyzing samples containing single individual RSCs at a wide range of concentrations. The resulting data were then evaluated to define the empirical relationship for each RSC between the dilution-to-threshold (D/T) ratio and odor intensity (OI) scaling. Based on the relationships defined for each individual RSC, the D/T ratios were estimated for a synthetic mixture of four RSCs. The effect of mixing was then examined by assessing the relative contribution of each RSC to those estimates with the aid of the actually measured D/T values. This stepwise test confirmed that the odor intensity of the synthetic mixture is not governed by the common theoretical basis (e.g., rule of additivity, synergism, or a stronger component model) but is best represented by the averaged contribution of all RSC components. The overall results of this study thus suggest that the mixing phenomenon between odorants with similar chemical properties (like RSC family) can be characterized by the averaging effect of all participants.

  11. 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.

  12. Determination of dicyandiamide in infant formula by stable isotope dilution hydrophilic interaction liquid chromatography with tandem mass spectrometry.

    PubMed

    Inoue, Koichi; Sakamoto, Tasuku; Min, Jun Zhe; Todoroki, Kenichiro; Toyo'oka, Toshimasa

    2014-08-01

    Dicyandiamide is a compound for reducing the negative effects of greenhouse gas emissions and nitrate leaching into waterways. In this study, the trace contamination of dicyandiamide in infant formula was analysed by stable isotope dilution hydrophilic interaction liquid chromatography with tandem mass spectrometry (HILIC-MS/MS). Dicyandiamide and a stable isotope internal standard were monitored by multiple reaction-monitoring with mass transitions: m/z 85→68/43 and m/z 89→71/45 in the electrospray positive ion mode. For sample preparation of the infant formula, a diluted/filtered procedure was developed for this assay. The calculated LOD and LOQ values were 0.01 or 0.05ng/mL for the standard solution, respectively. The averaged recovery and precision were 110.8% and 7.4%, respectively. This assay was applied to monitor 23 infant formulas, and the dicyandiamide contamination in one sample was detected and quantified at 79.1±1.2ng/g (ppb) powder. We suggest that it is necessary to cautiously monitor the DCD in common products from international countries.

  13. Measurement of Pyrethroid, Organophosphorus, and Carbamate Insecticides in Human Plasma using Isotope Dilution Gas Chromatography-High Resolution Mass Spectrometry

    PubMed Central

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

    2010-01-01

    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 withing ± 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. PMID:20434413

  14. Assay of tyrosol and hydroxytyrosol in olive oil by tandem mass spectrometry and isotope dilution method.

    PubMed

    Mazzotti, Fabio; Benabdelkamel, Hicham; Di Donna, Leonardo; Maiuolo, Loredana; Napoli, Anna; Sindona, Giovanni

    2012-12-01

    Hydroxytyrosol and tyrosol, the strong antioxidant present in large amount in virgin olive oil have been assayed by LC-MS/MS under MRM condition and isotope dilution method, using d(2)-labelled internal standards obtained by simple synthetic procedures. The assay has been performed under MRM condition monitoring two transitions for each analyte to improve the specificity. This paper deals with a modern approach for assaying the content of this polyphenols in virgin olive oil down to a limit of a few hundreds of parts per billion. Tyrosol and hydroxytyrosol ranged from 10 to 47ppm and from 5 to 25ppm in commercial olive oil, respectively. The accuracy (98-107%) and analytical parameters values confirm the reliability of the proposed approach. The method can be extended to any natural matrices, including mill wastes, after a simple step of sample preparation.

  15. Multilayering of Surfactant Systems at the Air-Dilute Aqueous Solution Interface.

    PubMed

    Thomas, Robert K; Penfold, Jeffrey

    2015-07-14

    In the last 15 years there have been a number of observations of surfactants adsorbed at the air-water interface with structures more complicated than the expected single monolayer. These observations, mostly made by neutron or X-ray reflectivity, show structures varying from the usual monolayer to monolayer plus one or two additional bilayers to multilayer adsorption at the surface. These observations have been assembled in this article with a view to finding some common features between the very different systems and to relating them to aspects of the bulk solution phase behavior. It is argued that multilayering is primarily associated with wetting or prewetting of the air-water interface by phases in the bulk system, whose structures depend on an overall attractive force between the constituent units. Two such phases, whose formation is assumed to be partially driven by strong specific ion binding, are a concentrated lamellar phase that forms at low concentrations and a swollen lamellar phase that is not space-filling. Multilayering phenomena at the air-water interface then offer a delicate and easy means of studying the finer details of the incompletely understood attraction that leads to these two phases, as well as an interesting new means of self-assembling surface structures. In addition, multilayering is often associated with unusual wetting characteristics. Examples of systems discussed, and in some cases their bulk phase behavior, include surfactants with multivalent metal counterions, surfactants with oligomers and polymers, surfactant with hydrophobin, dichain surfactants, lung surfactant, and the unusual system of ethanolamine and stearic acid. Two situations where the air-water surface is deliberately held out of equilibrium are also assessed for features in common with the steady-state/equilibrium observations.

  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.

  17. Violation of the mass-action law in dilute chemical systems

    NASA Astrophysics Data System (ADS)

    Brogioli, Doriano

    2013-11-01

    The mass-action law, which predicts the rates of chemical reactions, is widely used for modeling the kinetics of the chemical reactions and their stationary states, also for complex chemical reaction networks. However, violations of the mass-action equations have been reported in various cases: in confined systems with a small number of molecules, in non-ideally-stirred systems, when the reactions are limited by the diffusion, at high concentrations of reactants, or in chemical reaction networks with marginally stable mass-action equations. In this paper, I describe a new mechanism, leading to the violation of the mass-action equations, that takes place at a low concentration of at least one of the reactants; in this limit, the reaction rates can be easily inferred from the chemical reaction network. I propose that this mechanism underlies the replication stability of the hypercycles, a class of chemical reaction networks hypothetically connected with abiogenesis. I provide two simple examples of chemical reaction networks in which the mechanism leading to the violation of the mass-action law is present. I study the two chemical reaction networks by means of a simulation performed with a cellular automaton model. The results have a general validity and represent a limitation of the validity of the mass-action law, which has been overlooked up to now in the studies about the chemical reaction networks.

  18. 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

  19. 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.

  20. Quantification of nerve agent adducts with albumin in rat plasma using liquid chromatography-isotope dilution tandem mass spectrometry.

    PubMed

    Bao, Yi; Liu, Qin; Chen, Jia; Lin, Ying; Wu, Bidong; Xie, Jianwei

    2012-03-16

    A sensitive method for the determination of the organophosphorus nerve agents sarin, soman and VX adducts with tyrosine residue of albumin in rat plasma has been developed and validated using liquid chromatography-isotope dilution tandem mass spectrometry (LC-IDMS/MS). O-(O-Alkyl methylphosphonyl) tyrosine adducts and their deuterated products that were used as the internal standards were synthesised to establish the quantitative isotope-dilution method. Protein purification and solid-phase extraction (SPE) were applied to improve the recovery efficiency, reduce interference and achieve high sensitivity. The method provided a detection limit of 0.01 ng/mL for sarin and soman adducts and 0.05 ng/mL for the VX adduct. The value of the intra-day relative standard deviation over the calibration range was less than 6.16% (n=6), and that of the inter-day was less than 12.7% (n=6). The recovery varied from 86% to 111%. This sensitive method was successfully applied to the analysis of adducts in rat plasma after nerve agent exposure, and the results demonstrated the dose-effect relationships.

  1. Tunable hybrid plasma decomposition of dilute concentrations of CC14 in air

    SciTech Connect

    Truex, M.J. ); Bromberg, L.; Cohn, D.R.; Koch, M.; Patrick, R.M.; Thomas, P. . Plasma Fusion Center)

    1993-01-01

    At the Department of Energy Hanford site, a large quantity of the industrial solvent carbon tetrachloride (CC14) was used and subsequently disposed of in leaching fields. Efforts under the Volatile Organic Compound - Arid Integrated Demonstration Program (VOC-Arid ID) are directed at vapor extraction of carbon tetrachloride from the ground and its subsequent decomposition in the contaminated humid air stream. We are developing a mobile electron-beam driven plasma reactor for versatile efficient on-site decomposition of CC14 and other VOCs in carrier gases at atmospheric pressure. The decomposition of the VOCs could result in the generation of CO[sub 2], light hydrocarbons, and reactive chlorine compounds. The latter dissolve and/or dissociate in aqueous solutions.

  2. Tunable hybrid plasma decomposition of dilute concentrations of CC14 in air

    SciTech Connect

    Truex, M.J.; Bromberg, L.; Cohn, D.R.; Koch, M.; Patrick, R.M.; Thomas, P.

    1993-01-01

    At the Department of Energy Hanford site, a large quantity of the industrial solvent carbon tetrachloride (CC14) was used and subsequently disposed of in leaching fields. Efforts under the Volatile Organic Compound - Arid Integrated Demonstration Program (VOC-Arid ID) are directed at vapor extraction of carbon tetrachloride from the ground and its subsequent decomposition in the contaminated humid air stream. We are developing a mobile electron-beam driven plasma reactor for versatile efficient on-site decomposition of CC14 and other VOCs in carrier gases at atmospheric pressure. The decomposition of the VOCs could result in the generation of CO{sub 2}, light hydrocarbons, and reactive chlorine compounds. The latter dissolve and/or dissociate in aqueous solutions.

  3. Determination of benzene in soft drinks and other beverages by isotope dilution headspace gas chromatography/mass spectrometry.

    PubMed

    Cao, Xu-Liang; Casey, Valerie; Seaman, Steve; Tague, Brett; Becalski, Adam

    2007-01-01

    An automated, simple, and reproducible method was developed for the determination of benzene in soft drinks, based on isotope dilution headspace gas chromatography/mass spectrometry in the selected-ion monitoring mode. The method was used to assess benzene levels in samples of 124 soft drinks and beverages. Benzene was not detected in 60% of the 124 products. The average benzene levels in 6 products exceeded the Canadian maximum acceptable concentration of 5 microg/L for benzene in drinking water, and 2 of the 6 products had benzene levels above the World Health Organization guideline of 10 microg/L. The highest level of benzene, 23 microg/L, was found in a soft drink product specifically marketed to children.

  4. 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.

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

    SciTech Connect

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

    1981-05-01

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

  6. 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.

  7. 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.

  8. 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.

  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. 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).

  11. 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…

  12. Rapid determination of methandrostenolone in equine urine by isotope dilution liquid chromatography-tandem mass spectrometry.

    PubMed

    Edlund, O; Bowers, L; Henion, J; Covey, T R

    1989-12-29

    Urine samples were spiked with [17-methyl-2H3]methandrostenolone as internal standard and extracted with a mixture of dichloromethane and cyclohexane. The organic phase was concentrated and injected onto a short octyl-silica column (30 mm x 4.6 mm I.D.) for separation of methandrostenolone and 17-epimethandrostenolone. The effluent from the column was connected to a Sciex TAGA 6000E triple quadrupole mass spectrometer equipped with an atmospheric pressure ion source for sampling of ions generated by a heated pneumatic nebulizer with corona discharge ionization. This ion source produced abundant [M + H]+ ions and a weak fragment ion due to loss of water. The protonated molecular ions at m/z 301 and 304 for methandrostenolone, 17-epimethandrostenolone and the internal standard were transmitted to the second quadrupole for collision-induced dissociation. Quantification was obtained by selected reaction monitoring of three daughter ions. Methandrostenolone and 17-epimethandrostenolone were separated by liquid chromatography, but gave identical mass spectra. The method detection limit by injection of a urine extract corresponding to 2.8 ml urine was 180 pg/ml at the 99% confidence level. The precision (relative standard deviation) was 3% at the 16 ng/ml level and the linear dynamic range was at least 3 orders of magnitude. Screening for unknown metabolites in urine after administration of methandrostenolone to horses and humans was accomplished by a parent ion scan of m/z 121, a fragment corresponding to the intact A-ring of the steroids.

  13. Exposure of human lung cells to inhalable substances: a novel test strategy involving clean air exposure periods using whole diluted cigarette mainstream smoke.

    PubMed

    Ritter, Detlef; Knebel, Jan W; Aufderheide, Michaela

    2003-01-01

    An experimental approach was established for the validation of an in vitro test system for complex environmental test atmospheres consisting of both gaseous substances and particulates. Smoke from two different cigarette types (generated by an automatic cigarette-smoking machine) was employed to assess both the sensitivity and the specificity of the system. The smoke was diluted with synthetic air and used to expose human lung cells grown on microporous membranes. Cells were exposed alternately to diluted cigarette smoke and pure synthetic air. The effect of diluted smoke was assessed without humidification, addition of CO2, or any other physical or chemical modification of the smoke. The experimental setup included online monitoring of the gas phase (by analysis of CO concentration) and particulate phase (by light-scattering photometry). Replicate experiments confirmed a reproducible generation and dilution of the smoke and a smoke age of about 7 s at the time it came into contact with the cells. Experiments using human lung cells revealed that smoke from the two different cigarette types induced different levels of dose-dependent toxicity. A cell exposure of 6 min using 6 alternating smoke and synthetic air periods was sufficient to cause different effects as measured by intracellular glutathione content. The fact that the system could differentiate between two different types of cigarette smoke demonstrated its high sensitivity and specificity. The system offers new ways to test native complex gaseous and aerosol mixtures in vitro using short exposure times and very small amounts of test substances.

  14. Analysis of acrylamide in water using a coevaporation preparative step and isotope dilution liquid chromatography tandem mass spectrometry.

    PubMed

    Chu, Shaogang; Metcalfe, Chris D

    2007-07-01

    Acrylamide is a probable human carcinogen, and the drinking water quality guideline for this compound is 0.5 mg/L. However, analysis of this compound in water is difficult because of its very high water solubility, which limits the efficiency of sample preconcentration prior to analysis. We developed a robust and sensitive analytical method for the determination of trace quantities of acrylamide in samples of water using a novel preparative technique and isotope dilution liquid chromatography tandem mass spectrometry with atmospheric pressure chemical ionization as the ion source (LC-APCI-MS/MS). The preparative method involves coevaporation of acrylamide with water at pH 10 using a rotary evaporator, followed by acidification to pH 3.0 and concentration of the sample prior to analysis by LC-APCI-MS/MS. To compensate for the loss of the analyte during sample preparation and signal suppression due to interference from the sample matrix, isotope dilution with acrylamide-d3 was used for quantitation. Using this method, analyte recoveries ranged from 74 to 103% for acrylamide spiked into water at a concentration of 0.4 ng/mL. The limit of detection and limit of quantification (LOQ) for acrylamide in water were 0.02 and 0.06 ng/mL, respectively. This method was successfully applied to determine trace levels of acrylamide in samples of river water and in runoff from an agricultural field to which municipal biosolids (i.e., sludge) had been applied. Concentrations of acrylamide in these samples ranged from

  15. Determination of mercury in coal by isotope dilution cold-vapor generation inductively coupled plasma mass spectrometry.

    PubMed

    Long, Stephen E; Kelly, W Robert

    2002-04-01

    A method based on isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICPMS) has been developed for high-accuracy determinations of mercury in bituminous and sub-bituminous coals. A closed-system digestion process employing a Carius tube is used to completely oxidize the coal matrix and chemically equilibrate the mercury in the sample with a 201Hg isotopic spike. The digestates are diluted with high-purity quartz-distilled water, and the mercury is released as a vapor by reduction with tin(II) chloride. Measurements of 201Hg/202Hg isotope ratios are made using a quadrupole ICPMS system in time-resolved analysis mode. The new method has some significant advantages over existing methods. The instrument detection limit is less than 1 pg/mL. The average blank (n = 17) is 30 pg, which is roughly 1 order of magnitude lower than the equivalent microwave digestion procedure. The detection limit in coal is blank limited and is approximately 40 pg/g. Memory effects are very low. The relative reproducibility of the analytical measurements is approximately 0.5% for mercury concentrations in the range 10-150 ng/g. The method has been used to measure mercury concentrations in six coal reference materials, SRM 1632b (77.4 ng/g), SRM 1632c (94.3 ng/g), BCR 40 (433.2 ng/g), BCR 180 (125.0 ng/g), BCR 181 (135.8 ng/g), and SARM 20 (252.6 ng/g), as well as a coal fly ash, SRM 1633b (143.1 ng/g). The method is equally applicable to other types of fossil fuels including both crude and refined oils.

  16. Ions in oceanic and continental air masses

    SciTech Connect

    Tanner, D.J.; Eisele, F.L. )

    1991-01-20

    Measurements of tropospheric ions and several trace atmospheric neutral species have been performed at Cheeka Peak Research Station and at Mauna Loa Observatory. Two new positive ion species at masses 114 and 102 have been identified as protonated caprolactam and a saturated 6-carbon primary amine, respectively. In the negative ion spectrum, methane sulfonic acid (MSA) has been identified as the parent species responsible for an ion commonly observed at mass 95 during these two studies. The diurnal variations of gas phase H{sub 2}SO{sub 4} and MSA were also measured at Cheeka Peak and have typically been found to be present in the sub-ppt range. Ion assisted measurements at Mauna Loa Observatory of pyridine and ammonia indicate concentrations of 2.5 and 70 ppt, respectively, with at least a factor of 2 uncertainty. Interesting variations and potential sources of several of the observed ions are also discussed.

  17. 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.

  18. Quantification of saxitoxin and neosaxitoxin in human urine utilizing isotope dilution tandem mass spectrometry.

    PubMed

    Johnson, Rudolph C; Zhou, Yingtao; Statler, Kristen; Thomas, Jerry; Cox, Frederick; Hall, Sherwood; Barr, John R

    2009-01-01

    Saxitoxin and neosaxitoxin are potent neurotoxins that can cause paralytic shellfish poisoning when consumed. A new assay is presented here to quantify saxitoxin (STX) and neosaxitoxin (NEO) in human urine samples. Sample preparation of 500-microL samples included the use of weak-cation-exchange solid-phase extraction in a multiplexed 96-well format. Extracts were preconcentrated and analyzed via 10-min hydrophilic interaction liquid chromatography followed by electrospray ionization. Protonated molecular ions were quantified via multiple reaction monitoring mode in a Qtrap mass spectrometer. The method uses novel 15N7-isotopically enriched STX and NEO internal standards. Method validation included the characterization of two enriched urine pools. The lowest reportable limits for STX and NEO were 4.80 and 10.1 ng/mL, respectively, using both quantification and confirmation ions. These two toxins were not detected in a reference range of humans who consumed seafood in the preceding 72 h, suggesting that few false positives would occur when trying to identify people exposed to STX or NEO.

  19. 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

  20. 40 CFR 89.424 - Dilute emission sampling calculations.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... emission level (HC, CO, CO2, PM, or NOX) in g/kW-hr. gi = Mass flow in grams per hour, = grams measured...CO× (COconc/106) (4) Carbon dioxide mass: CO2mass= Vmix× DensityCO2 × (CO2conc/102) (c) The mass of... the dilute air as measured, in ppm. (3) For carbon monoxide equations: CO mass=Carbon...

  1. 40 CFR 89.424 - Dilute emission sampling calculations.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... emission level (HC, CO, CO2, PM, or NOX) in g/kW-hr. gi = Mass flow in grams per hour, = grams measured...CO× (COconc/106) (4) Carbon dioxide mass: CO2mass= Vmix× DensityCO2 × (CO2conc/102) (c) The mass of... the dilute air as measured, in ppm. (3) For carbon monoxide equations: CO mass=Carbon...

  2. 40 CFR 89.424 - Dilute emission sampling calculations.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... emission level (HC, CO, CO2, PM, or NOX) in g/kW-hr. gi = Mass flow in grams per hour, = grams measured...CO× (COconc/106) (4) Carbon dioxide mass: CO2mass= Vmix× DensityCO2 × (CO2conc/102) (c) The mass of... the dilute air as measured, in ppm. (3) For carbon monoxide equations: CO mass=Carbon...

  3. Contents of selected B vitamins in NIST SRM 3280 multivitamin/multielement tablets by liquid chromatography isotope dilution mass spectrometry.

    PubMed

    Chen, Pei; Ozcan, Mustafa; Wolf, Wayne R

    2007-09-01

    There is increased interest in accurately assessing the total dietary intake of vitamins from all sources, including foods and dietary supplements. Consequently, a Dietary Supplement Ingredient Database (DSID), based upon analytical values, is being established by USDA with support of the Office of Dietary Supplements (ODS), NIH. The DSID necessitated the development of a new SRM, 3280--Multivitamin/Multimineral Tablets, by the National Institute of Standards and Technology (NIST), with support from the ODS. As a continuation of a long-term project to develop and validate new methods of determining water-soluble B vitamins in foods and dietary supplements, and as part of a collaborative effort with NIST to characterize SRM 3280, values for the vitamin contents of SRM 3280 have been generated by a liquid chromatographic isotope dilution mass spectrometric (LC/IDMS) method. Isotope-labeled ((13)C and/or (2)H) B vitamins (B1-thiamine, B6-pyridoxine, B3-nicotinamide, and B5-pantothenic acid) were obtained from commercial sources, with the support of the ODS/NIH. Our LC/IDMS method uses a C18 reversed phase column, an Agilent 1100 HPLC system, and a Quattro Micro triple-quad mass spectrometer (MS). B vitamin determination was achieved using a gradient LC profile combined with MS/MS detection in multiple reaction monitoring mode. Stock solutions of the isotope-labeled vitamins were calibrated against USP standard solutions. The SRM tablets, with added amounts of the four isotope-labeled B vitamins, were extracted and the vitamins simultaneously determined in a single LC run, in contrast with the single-component determinations performed via IDMS. Unknown vitamin concentrations were calculated by comparing the ratios of the integrated LC peaks at the different masses of the unlabeled and labeled vitamins.

  4. Diagnosis of inborn errors of metabolism using filter paper urine, urease treatment, isotope dilution and gas chromatography-mass spectrometry.

    PubMed

    Kuhara, T

    2001-07-05

    This review will be concerned primarily with a practical yet comprehensive diagnostic procedure for the diagnosis or even mass screening of a variety of metabolic disorders. This rapid, highly sensitive procedure offers possibilities for clinical chemistry laboratories to extend their diagnostic capacity to new areas of metabolic disorders. The diagnostic procedure consists of the use of urine or filter paper urine, preincubation of urine with urease, stable isotope dilution, and gas chromatography-mass spectrometry. Sample preparation from urine or filter paper urine, creatinine determination, stable isotope-labeled compounds used, and GC-MS measurement conditions are described. Not only organic acids or polar ones but also amino acids, sugars, polyols, purines, pyrimidines and other compounds are simultaneously analyzed and quantified. In this review, a pilot study for screening of 22 target diseases in newborns we are conducting in Japan is described. A neonate with presymptomatic propionic acidemia was detected among 10,000 neonates in the pilot study. The metabolic profiles of patients with ornithine carbamoyl transferase deficiency, fructose-1,6-bisphosphatase deficiency or succinic semialdehyde dehydrogenase deficiency obtained by this method are presented as examples. They were compared to those obtained by the conventional solvent extraction methods or by the tandem mass spectrometric method currently done with dried filter blood spots. The highly sensitive, specific and comprehensive features of our procedure are also demonstrated by its use in establishing the chemical diagnosis of pyrimidine degradation defects in order to prevent side effects of pyrimidine analogs such as 5-flurouracil, and the differential diagnosis of three types of homocystinuria, orotic aciduria, uraciluria and other urea cycle disorders. Evaluation of the effects of liver transplantation or nutritional conditions such as folate deficiency in patients with inborn errors of

  5. Relationships between submicrometer particulate air pollution and air mass history in Beijing, China, 2004 2006

    NASA Astrophysics Data System (ADS)

    Wehner, B.; Birmili, W.; Ditas, F.; Wu, Z.; Hu, M.; Liu, X.; Mao, J.; Sugimoto, N.; Wiedensohler, A.

    2008-10-01

    The Chinese capital Beijing is one of the global megacities where the effects of rapid economic growth have led to complex air pollution problems that are not well understood. In this study, ambient particle number size distributions in Beijing between 2004 and 2006 are analysed as a function of regional meteorological transport. An essential result is that the particle size distribution in Beijing depends to large extent on the history of the synoptic scale air masses. A first approach based on manual back trajectory classification yielded differences in particulate matter mass concentration by a factor of two between four different air mass categories, including three main wind directions plus the case of stagnant air masses. A back trajectory cluster analysis refined these results, yielding a total of six trajectory clusters. Besides the large scale wind direction, the transportation speed of an air mass was found to play an essential role on the PM concentrations in Beijing. Slow-moving air masses were shown to be associated with an effective accumulation of surface-based anthropogenic emissions due to both, an increased residence time over densely populated land, and their higher degree of vertical stability. For the six back trajectory clusters, differences in PM1 mass concentrations by a factor of 3.5, in the mean air mass speed by a factor of 6, and in atmospheric visibility by a factor of 4 were found. The main conclusion is that the air quality in Beijing is not only degraded by anthropogenic aerosol sources from within the megacity, but also by sources across the entire Northwest China plain depending on the meteorological situation.

  6. Relationships between submicrometer particulate air pollution and air mass history in Beijing, China, 2004-2006

    NASA Astrophysics Data System (ADS)

    Wehner, B.; Birmili, W.; Ditas, F.; Wu, Z.; Hu, M.; Liu, X.; Mao, J.; Sugimoto, N.; Wiedensohler, A.

    2008-06-01

    The Chinese capital Beijing is one of the global megacities where the effects of rapid economic growth have led to complex air pollution problems that are not well understood. In this study, ambient particle number size distributions in Beijing between 2004 and 2006 are analysed as a function of regional meteorological transport. An essential result is that the particle size distribution in Beijing depends to large extent on the history of the synoptic scale air masses. A first approach based on manual back trajectory classification yielded differences in particulate matter mass concentration (PM1 and PM10) by a factor of two between four different air mass categories, including three main wind directions plus the case of stagnant air masses. A back trajectory cluster analysis refined these results, yielding a total of six trajectory clusters. Besides the large scale wind direction, the transportation speed of an air mass was found to play an essential role on the PM concentrations in Beijing. Slow-moving air masses were shown to be associated with an effective accumulation of surface-based anthropogenic emissions due to both, an increased residence time over densely populated land, and their higher degree of vertical stability. For the six back trajectory clusters, differences in PM1 mass concentrations by a factor of 3.5, in the mean air mass speed by a factor of 6, and in atmospheric visibility by a factor of 4 were found. The main conclusion is that the air quality in Beijing is not only degraded by anthropogenic aerosol sources from within the megacity, but also by sources across the entire Northwest China plain depending on the meteorological situation.

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

    PubMed

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

    2016-01-01

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

  8. 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.; ...

    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

  9. Quantitative measurement of dihydrouridine in RNA using isotope dilution liquid chromatography-mass spectrometry (LC/MS).

    PubMed Central

    Dalluge, J J; Hashizume, T; McCloskey, J A

    1996-01-01

    A method has been developed for the microscale determination of 5,6-dihydrouridine, the most common post-transcriptional modification in bacterial and eukaryotic tRNA. The method is based on stable isotope dilution liquid chromatography-mass spectrometry (LC/MS) using [1,3-15N2]dihydrouridine and [1,3-15N2]uridine as internal standards. RNA samples were enzymatically digested to nucleosides before addition of the internal standards and subsequently analyzed by LC/MS with selected ion monitoring of protonated molecular ions of the labeled and unlabeled nucleosides. Sample quantities of approximately 1 pmol tRNA and 5 pmol 23S rRNA were analyzed for mole% dihydrouridine. Dihydrouridine content of Escherichia coli tRNASer(VGA) and tRNAThr(GGU) as controls were measured as 2.03 and 2.84 residues/tRNA molecule, representing accuracies of 98 and 95%. Overall precision values for the analyses of E. coli tRNASer(VGA) and E. coli tRNAThr(GGU), unfractionated tRNA from E. coli and 23S rRNA from E. coli were within the range 0.43-2.4%. The mole% dihydrouridine in unfractionated tRNA and 23S rRNA from E. coli were determined as 1.79 and 0.0396%, corresponding to 1.4 and 1.1 residues/RNA molecule respectively. PMID:8774907

  10. Isotope dilution/mass spectrometry of serum cholesterol with (3,4-/sup 13/C)cholesterol: proposed definitive method

    SciTech Connect

    Pelletier, O.; Wright, L.A.; Breckenridge, W.C.

    1987-08-01

    We describe a new gas-chromatographic/mass-spectrometric (GC/MS) isotope-dilution method for determination of serum cholesterol. The method has been fully optimized and documented to provide the high accuracy and precision expected for a Definitive Method. In the presence of (3,4-/sup 13/C)cholesterol, cholesteryl esters in serum are hydrolyzed under optimum conditions and the entire cholesterol pool is extracted and derivatized to silyl ethers. The cholesterol derivatives are resolved from other sterols by gas-liquid chromatography on a fused silica column, and selected ions characteristic of cholesterol and the (3,4-/sup 13/C)cholesterol are monitored with a GC/MS quandrupole system. We estimated the cholesterol content of samples by bracketing each sample with standards of comparable cholesterol concentration that also contained the (3,4-/sup 13/C)cholesterol. The procedure was highly reproducible (CV less than 0.5%), better accuracy and precision being obtained with (3,4-/sup 13/C)cholesterol than with heptadeuterated cholesterol. Mean values per gram of dry serum for one serum pool assayed by this method and that of the National Bureau of Standards differed by 0.5%. We conclude that the method satisfies the criteria for a Definitive Method.

  11. 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.

  12. 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,

  13. Radioimmunoassay and liquid-chromatographic analysis for free cortisol in urine compared with isotope dilution-mass spectrometry

    SciTech Connect

    Lantto, O.

    1982-05-01

    Three different routine methods for analysis for urinary cortisol with those by a highly specific reference method based on isotope dilution-mass spectrometry (I) were compared. A ''high-performance'' liquid-chromatographic method (II) gave the most comparable results (regression coefficient 0.86, intercept 9 nmol/L). For some urines much lower values were obtained by I than by II. Two radioimmunoassay (III) methods, one involving direct assay and one involving extraction, gave less-accurate results (regression coefficients of 1.87 and 1.52 and intercepts of 86 and 12 nmol/L, respectively), although values obtained by III and by I correlated well (r = 0.95-0.99), indicating a relation between the free cortisol and the compounds interfering in III. The apparent accuracy for the extraction method was improved by using as calibration standards urine samples previously assayed by I (regression coefficient 0.90, intercept 6 nmol/L). All four methods investigated showed a statistically significant sex-related difference in 24-h urinary cortisol excretion; evidently such a finding should be a prerequisite in any such method proposed for routine use.

  14. 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.

  15. 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.

  16. 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

    2013-02-05

    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).

  17. Determination of Cd and Zn by isotope dilution-thermal ionisation mass spectrometry using a sequential analysis procedure.

    PubMed

    Ayoub, Ahmed S; McGaw, Brian A; Midwood, Andrew J

    2002-05-16

    Isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) was used to examine the certified Cd and Zn content of 4 Certified Reference Materials (CRMs); 2 soils: GBW07401 and GBW07405, 1 plant CRM060 and an animal tissue SRM1566a. The CRMs were chosen to be of contrasting origin and Cd:Zn content. Three digestion procedures were compared: (i) an open tube aqua regia procedure (ii) microwave digestion using Teflon bombs and (iii) hydrofluoric acid (HF) digestion using PTFE bombs. The Cd and Zn levels obtained using ID-TIMS all fell within the published certified range for the CRMs. This was the case regardless of the digestion procedure used, although HF digestion tended to yield marginally higher levels than the other procedures and in one instance, Cd in GBW07401, was significantly different (P<0.05) from the certified range. A filament loading procedure was developed, to allow sequential analysis of Cd and Zn on the same single filament during thermal ionisation mass spectrometry analysis. The sequential analysis technique was evaluated to ensure that Zn did not fractionate during Cd analysis and there was no inter-element interference. No marked difference in the precision and accuracy of the isotope ratio measurements were obtained from sequential element analyses on the same filament when compared to individual element analyses for a range of standard solutions or for sample digests. The most efficient procedure in terms of costs and productivity for future work of this kind would be a combination of microwave digestion and sequential analysis of Cd and Zn on the same filament.

  18. 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.

  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. 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.

  1. Quantification of Influenza Neuraminidase Activity by Ultra-High Performance Liquid Chromatography and Isotope Dilution Mass Spectrometry.

    PubMed

    Solano, Maria I; Woolfitt, Adrian R; Williams, Tracie L; Pierce, Carrie L; Gubareva, Larisa V; Mishin, Vasiliy; Barr, John R

    2017-03-07

    Mounting evidence suggests that neuraminidase's functionality extends beyond its classical role in influenza virus infection and that antineuraminidase antibodies offer protective immunity. Therefore, a renewed interest in the development of neuraminidase (NA)-specific methods to characterize the glycoprotein and evaluate potential advantages for NA standardization in influenza vaccines has emerged. NA displays sialidase activity by cleaving off the terminal N-acetylneuraminic acid on α-2,3 or α-2,6 sialic acid containing receptors of host cells. The type and distribution of these sialic acid containing receptors is considered to be an important factor in transmission efficiency of influenza viruses between and among host species. Changes in hemagglutinin (HA) binding and NA specificity in reassortant viruses may be related to the emergence of new and potentially dangerous strains of influenza. Current methods to investigate neuraminidase activity use small derivatized sugars that are poor models for natural glycoprotein receptors and do not provide information on the linkage specificity. Here, a novel approach for rapid and accurate quantification of influenza neuraminidase activity is achieved utilizing ultra-high performance liquid chromatography (UPLC) and isotope dilution mass spectrometry (IDMS). Direct LC-MS/MS quantification of NA-released sialic acid provides precise measurement of influenza neuraminidase activity over a range of substrates. The method provides exceptional sensitivity and specificity with a limit of detection of 0.38 μM for sialic acid and the capacity to obtain accurate measurements of specific enzyme activity preference toward α-2,3-sialyllactose linkages, α-2,6-sialyllactose linkages, or whole glycosylated proteins such as fetuin.

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

    PubMed

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

    2008-01-01

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

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

    PubMed

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

    2015-12-18

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

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

    PubMed Central

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

    2012-01-01

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

  5. 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.

  6. 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.

  7. Where do the air masses between double tropopauses come from?

    NASA Astrophysics Data System (ADS)

    Parracho, A. C.; Marques, C. A. F.; Castanheira, J. M.

    2014-01-01

    An analysis of the origin of air masses that end up between double tropopauses (DT) in the subtropics and midlatitudes is presented. The double tropopauses were diagnosed in the ERA-Interim reanalysis (1979-2010), and the origin of air masses was analysed using the Lagrangian model FLEXPART. Different processes for the formation of double tropopauses (DT) have been suggested in the literature. Some studies have suggested that double tropopauses may occur as a response to the vertical profile of adiabatic heating, due to the residual meridional circulation, while others have put forward contradicting explanations. Whereas some studies have suggested that double tropopauses result from poleward excursions of the tropical tropopause over the extratropical one, others have argued that DTs develop in baroclinic unstable processes involving transport of air from high latitudes. In some regions, the DT structure has a semipermanent character which cannot be explained by excursions of the tropical tropopause alone. However, the results presented in this paper confirm that processes involving excursions of the tropical tropopause over the extratropical tropopause, which are therefore accompanied by intrusions of air from the tropical troposphere into the lower extratropical stratosphere, make a significant contribution for the occurrence of DTs in the subtropics and midlatitudes. Specifically, it is shown that the air between double tropopauses comes from equatorward regions, and has a higher percentage of tropospheric particles and a lower mean potential vorticity.

  8. 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.

  9. 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.

  10. 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.

  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. Effect of sample dilution on matrix effects in pesticide analysis of several matrices by liquid chromatography-high-resolution mass spectrometry.

    PubMed

    Yang, Paul; Chang, James S; Wong, Jon W; Zhang, Kai; Krynitsky, Alexander J; Bromirski, Maciej; Wang, Jian

    2015-06-03

    This study used two LC columns of different adsorbents and liquid chromatography-electrospray ionization-high-resolution mass spectrometry to study the relationship between matrix effects (ME), the LC separations, and elution patterns of pesticides and those of matrix components. Using calibration standards of 381 pesticides at three dilution levels of 1×, 1/10×, and 1/100×, 108 samples were prepared in solvent and five different sample matrices for the study. Results obtained from principal component analysis and slope ratios of calibration curves provided measurements of the ME and showed the 1/100× sample dilution could minimize suppression ME for most pesticides analyzed. Should a pesticide coeluting with matrix components have a peak intensity of 25 times or higher, the suppression for that pesticide would persist even at 1/100× dilution. The number of pesticides had enhancement ME increased with increasing dilution from 1× to 1/100×, with those early eluting, hydrophilic pesticides affected the most.

  13. Odor as an aid to chemical safety: odor thresholds compared with threshold limit values and volatilities for 214 industrial chemicals in air and water dilution.

    PubMed

    Amoore, J E; Hautala, E

    1983-12-01

    The body of information in this paper is directed to specialists in industrial health and safety, and air and water pollution, who need quantitative data on the odor thresholds of potentially hazardous chemical vapors and gases. The literature, largely unorganized, has been reviewed for 214 compounds and condensed into tables based on consistent units. Data on the volatility, solubility, ionization and water-air distribution ratio at 25 degrees C are included. From the currently recommended threshold limit value (TLV), a safe dilution factor and an odor safety factor are calculated for each compound. The equivalent data are presented for both air and water dilutions of the chemicals. Available data are summarized on the variability of odor sensitivities in the population, and the increased odor concentrations that are required to elicit responses from persons whose attention is distracted, or who are sleeping. This information is reduced to calibration charts that may be used to estimate the relative detectability, warning potential and rousing capacity of the odorous vapors. Each compound has been assigned a letter classification, from A to E, to indicate the margin of safety, if any, that may be afforded by the odor of the compound as a warning that its threshold limit value is being exceeded.

  14. Determination of trace sulfur in biodiesel and diesel standard reference materials by isotope dilution sector field inductively coupled plasma mass spectrometry.

    PubMed

    Amais, Renata S; Long, Stephen E; Nóbrega, Joaquim A; Christopher, Steven J

    2014-01-02

    A method is described for quantification of sulfur at low concentrations on the order of mgkg(-1) in biodiesel and diesel fuels using isotope dilution and sector field inductively coupled plasma mass spectrometry (ID-SF-ICP-MS). Closed vessel microwave-assisted digestion was employed using a diluted nitric acid and hydrogen peroxide decomposition medium to reduce sample dilution volumes. Medium resolution mode was employed to eliminate isobaric interferences at (32)S and (34)S related to polyatomic phosphorus and oxygen species, and sulfur hydride species. The method outlined yielded respective limits of detection (LOD) and limits of quantification (LOQ) of 0.7 mg kg(-1) S and 2.5 mg kg(-1) S (in the sample). The LOD was constrained by instrument background counts at (32)S but was sufficient to facilitate value assignment of total S mass fraction in NIST SRM 2723b Sulfur in Diesel Fuel Oil at 9.06±0.13 mg kg(-1). No statistically significant difference at a 95% confidence level was observed between the measured and certified values for certified reference materials NIST SRM 2773 B100 Biodiesel (Animal-Based), CENAM DRM 272b and NIST SRM 2723a Sulfur in Diesel Fuel Oil, validating method accuracy.

  15. Quantitation of metabolites of the nerve agents sarin, soman, cyclohexylsarin, VX, and Russian VX in human urine using isotope-dilution gas chromatography-tandem mass spectrometry.

    PubMed

    Barr, John R; Driskell, W J; Aston, Linda S; Martinez, Rodolfo A

    2004-01-01

    Organophosphorus nerve agents are among the most toxic organic compounds known and continue to be a threat for both military and terrorist use. We have developed an isotope-dilution gas chromatography-tandem mass spectrometric (GC-MS-MS) method for quantitating the urinary metabolites of the organophosphorus nerve agents sarin (GB), soman (GD), VX, Russian VX (RVX), and cyclohexylsarin (GF). Urine samples were acidified, extracted into ether-acetonitrile, derivatized by methylation with diazomethane, and analyzed by GC-MS-MS. The limits of detection were less than 1 micro g/L for all analytes.

  16. Modelling heat and mass transfer in a membrane-based air-to-air enthalpy exchanger

    NASA Astrophysics Data System (ADS)

    Dugaria, S.; Moro, L.; Del, D., Col

    2015-11-01

    The diffusion of total energy recovery systems could lead to a significant reduction in the energy demand for building air-conditioning. With these devices, sensible heat and humidity can be recovered in winter from the exhaust airstream, while, in summer, the incoming air stream can be cooled and dehumidified by transferring the excess heat and moisture to the exhaust air stream. Membrane based enthalpy exchangers are composed by different channels separated by semi-permeable membranes. The membrane allows moisture transfer under vapour pressure difference, or water concentration difference, between the two sides and, at the same time, it is ideally impermeable to air and other contaminants present in exhaust air. Heat transfer between the airstreams occurs through the membrane due to the temperature gradient. The aim of this work is to develop a detailed model of the coupled heat and mass transfer mechanisms through the membrane between the two airstreams. After a review of the most relevant models published in the scientific literature, the governing equations are presented and some simplifying assumptions are analysed and discussed. As a result, a steady-state, two-dimensional finite difference numerical model is setup. The developed model is able to predict temperature and humidity evolution inside the channels. Sensible and latent heat transfer rate, as well as moisture transfer rate, are determined. A sensitive analysis is conducted in order to determine the more influential parameters on the thermal and vapour transfer.

  17. 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

    2015-04-07

    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

  18. 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.

  19. 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.

  20. Air Mass Frequency during Precipitation Events in the United States Northern Plains

    NASA Astrophysics Data System (ADS)

    Loveless, D. M.; Sharr, N. J.; Baum, A.; Contract, J. S.; DePasquale, R.; Godek, M. L.

    2013-12-01

    Since 1980, numerous billion-dollar disasters have affected the Northern Plains of the United States, including nine droughts and four floods. Given the region's large agricultural sector, the ability to accurately forecast the frequency and quantity of precipitation events here is imperative as it has a major impact on the economy of states in the region. The atmospheric environment present during precipitation events can largely be described by the presiding air mass conditions since air masses characterize a multitude of meteorological variables at one time over a large region. Therefore, understanding the relationship between air masses and rainfall episodes can contribute to improved precipitation forecasts. The goal of this research is to add knowledge to current understandings of the factors responsible for precipitation in the Northern Plains through an assessment of synoptic air mass conditions. The Spatial Synoptic Classification is used to categorize 30 years of daily air mass types across the region and daily precipitation is acquired from the United States Historical Climatological Network at stations in close proximity. Air mass frequencies are then analyzed for all regional precipitation events and rainfall categories are developed based on precipitation quantity. Both annual and seasonal air mass frequencies are assessed at the time of precipitation events. Additionally, air mass frequencies are obtained for positive and negative phases of the Pacific/North American Pattern to examine the influence of a teleconnection forcing factor on the air mass types responsible for producing precipitation quantities. Results indicate that the Transitional (TR) air mass, associated with changing air mass conditions commonly related to passing fronts, is not the leading producer of rainfall in the region. The TR is generally responsible for only 10-20% of regional precipitation, which often is classed in a heavy rainfall category. All moist air mass varieties are

  1. 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

  2. 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.

  3. A determination of character and frequency changes in air masses using a spatial synoptic classification

    NASA Astrophysics Data System (ADS)

    Kalkstein, Laurence S.; Sheridan, Scott C.; Graybeal, Daniel Y.

    1998-09-01

    Of the numerous climate change studies which have been performed, few of these have analyzed recent trends using an air mass-based approach. The air mass approach is superior to simple trend analysis, as it can identify patterns which may be too subtle to influence the entire climate record. The recently-developed spatial synoptic classification (SSC) is thus used to identify trends over the contiguous United States for summer and winter seasons from 1948 to 1993. Both trends in air mass frequency and character have been assessed.The most noteworthy trend in frequency is a decline in air mass transitional days (TR) during both seasons. In winter, decreases of up to 1% per decade are noted in parts of the central U.S. Other notable trends include a decrease in moist tropical (MT) air in winter, and an increase in MT in summer over the southeastern states.Numerous national and local air mass character changes have been uncovered. A large overall upward trend in cloudiness is noted in summer. All air masses feature an overnight increase, yet afternoon cloudiness increases are generally limited to the three dry air masses. Also in summer, a significant warming and increase in dew point of MT air has occurred at many locales. The most profound winter trend is a large decrease in dew point (up to 1.5°C per decade) in the dry polar (DP) air mass over much of the eastern states.

  4. 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…

  5. 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

    2013-07-03

    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.

  6. 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.

  7. 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

  8. Comparison of isotope dilution mass spectrometry methods for the determination of total homocysteine in plasma and serum.

    PubMed

    Satterfield, Mary B; Sniegoski, Lorna T; Welch, Michael J; Nelson, Bryant C; Pfeiffer, Christine M

    2003-09-01

    Two independent methods have been critically evaluated and applied to the measurement of total homocysteine in serum and plasma: solid-phase anion extraction (SPAE) gas chromatography/mass spectrometry (GC/MS) and protein precipitation liquid chromatography/tandem mass spectrometry (LC/MS/MS). In addition, analysis of samples prepared by SPAE was accomplished by liquid chromatography/mass spectrometry (LC/MS) and LC/MS/MS. These methods have been used to determine total homocysteine levels in several existing serum-based Standard Reference Materials (SRMs) from the National Institute of Standards and Technology and in patient plasma samples provided by the Centers for Disease Control and Prevention. The precision of the homocysteine measurements in serum and plasma was critically evaluated, and method comparisons were carried out using Bland-Altman plots and bias analysis. On the basis of the excellent precision and close agreement of the mass spectrometric (MS) methods, the MS-based methods will be used for certification of a serum-based SRM for homocysteine and folates.

  9. ISOTOPE DILUTION ANALYSIS OF BROMATE IN DRINKING WATER MATRIXES BY ION CHROMATOGRAPHY WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

    EPA Science Inventory

    Bromate is a disinfection byproduct in drinking water which is formed during the ozonation of source water containing bromide. This paper described the analysis of bromate via ion chromatography-inductively coupled plasma mass spectrometry. The separation of bromate from interfer...

  10. Accuracy in the isotope dilution mass spectrometry of uranium in rubidium uranium sulphate Rb[sub 2]U(SO[sub 4])[sub 3

    SciTech Connect

    Ramakumar, K.L.; Jeyakumar, S.; Raman, V.A.; Gnanayyan, L.; Rao, R.; Saxena, M.K.; Kavimandan, V.D.; Jain, H.C. )

    1993-05-01

    Problems encountered in the determination of uranium in rubidium uranium sulphate (Rb[sub 2]U(SO[sub 4])[sub 3]) employing isotope dilution thermal ionization mass spectrometry (ID-TIMS) are discussed. The positive bias of 0.2 to 0.3% in the determination of uranium in Rb[sub 2]U(SO[sub 4])[sub 3] by ID-TIMS with respect to the stoichiometric composition has been resolved by modifying the chemical exchange procedures. The concentration of uranium in Rb[sub 2]U(SO[sub 4])[sub 3] could be determined with an accuracy better than 0.1% employing the HClO[sub 4] treatment for proper isotopic exchange between the spike and sample isotopes. 12 refs., 1 fig., 5 tabs.

  11. Analysis of nitroaromatic compounds in complex samples using solid-phase microextraction and isotope dilution quantification gas chromatography-electron-capture negative ionisation mass spectrometry.

    PubMed

    Jönsson, S; Gustavsson, L; van Bavel, B

    2007-09-14

    A solid-phase microextraction (SPME) method using gas chromatography-electron-capture negative ionisation mass spectrometry (GC-ECNI-MS) and isotope dilution quantification for the analysis of nitroaromatic compounds in complex, water based samples has been optimised. For ionisation, ECNI was the most sensitive and selective method. SPME was compared to solid-phase extraction (SPE) and found to be more sensitive for these small volume samples. LODs were in the range 0.02-38ngL(-1) for SPME and 6-184ngL(-1) for SPE, respectively. The SPME method was applied on samples in the ngL(-1) level from artificial reed beds treated with sludge containing residues from explosives and pharmaceuticals.

  12. On the heat and mass transfer analogy for natural convection of non-dilute binary mixtures of ideal gases in cavities

    NASA Astrophysics Data System (ADS)

    Sun, Hua; Lauriat, Guy

    2009-03-01

    An extension of a slightly compressible flow model to double-diffusive convection of a binary mixture of ideal gases enclosed in a cavity is presented. The problem formulation is based on a low Mach number approximation and the impermeable surface assumption is not invoked. The main objectives of this paper are the statement of a new problem formulation, and the analysis of some significant results showing the influence of density variations on transient solutions for pure thermal or pure solutal convection. At steady-state, it is shown that the heat and mass transfer analogy may be applied for non-dilute mixtures at parameter ranges larger than those usually considered. To cite this article: H. Sun, G. Lauriat, C. R. Mecanique 337 (2009).

  13. Modifications to the NIST reference measurement procedure (RMP) for the determination of serum glucose by isotope dilution gas chromatography/mass spectrometry.

    PubMed

    Prendergast, Jocelyn L; Sniegoski, Lorna T; Welch, Michael J; Phinney, Karen W

    2010-07-01

    The definitive method (DM), now known as the reference measurement procedure (RMP), for the analysis of glucose in serum was originally published in 1982 by the National Institute of Standards and Technology (NIST). Over the years the method has been subject to a number of modifications to adapt to newer technologies and simplify sample preparation. We discuss here an adaptation of the method associated with serum glucose measurements using a modified isotope dilution gas chromatography/mass spectrometry (ID-GC/MS) method. NIST has used this modified method to certify the concentrations of glucose in SRM 965b, Glucose in Frozen Human Serum, and SRM 1950, Metabolites in Human Plasma. Comparison of results from the revised method with certified values for existing Standard Reference Materials (SRMs) demonstrated that these modifications have not affected the quality of the measurements, giving both good precision and accuracy, while reducing the sample preparation time by a day and a half.

  14. A novel sample decomposition technique at atmospheric pressure for the determination of Os abundances in iron meteorites using isotope dilution inductively coupled plasma-mass spectrometry.

    PubMed

    Hattori, M; Hirata, T

    2001-06-01

    A safe and reliable analytical technique for the determination of Os abundances in ten iron meteorites of various chemical groups was developed using isotope dilution inductively coupled plasma-mass spectrometry coupled with a sample decomposition technique. A major advantage of the sample decomposition technique developed here is that the pressure inside the reaction flask is not increased through the decomposition reaction because the flask is a fully opened system, obviating the risk of explosion of the glass apparatus. Another advantage is that there is no restriction in the sample size being decomposed. In this study, about 2 g of metallic sample were decomposed safely, and this sample size, > 10 times larger than that typically used for the Carius tube technique, allows one to obtain more reliable Os data for heterogeneous samples. The metallic samples were decomposed in a glass flask purged with Ar. Since the O2 was purged from the reaction flask, Os was not oxidised to volatile OsO4, thereby preventing significant evaporation loss of Os. The typical recovery of Os throughout the sample decomposition and separation processes was > 80%, and the total Os blank through the decomposition of a 1 g amount of sample was less than 20 pg. Os abundances were determined by means of stable isotope dilution mass spectrometry using a 190Os-enriched isotopic tracer. Except for Sikhote-Alin, the measured Os abundances in almost all the iron meteorites exhibited a good agreement with the previously published Os abundance data, within the analytical uncertainty achieved in this study (2-5%). For the Sikhote-Alin meteorite, on the basis of a better correlation between Os and Ir abundances, we believe that our Os abundance data should be more reliable. The Os abundance data obtained in this work clearly demonstrated the suitability of the newly developed sample decomposition procedure for low level Os determinations.

  15. Liquid chromatography/tandem mass spectrometry sensitivity enhancement via online sample dilution and trapping: applications in microdosing and dried blood spot (DBS) bioanalysis.

    PubMed

    Li, Fumin; Zulkoski, John P; Ding, Jie; Brown, Wes; Addison, Tom

    2010-09-15

    A simple online sample dilution, enrichment, and cleanup technique was developed for sensitive microdosing and dried blood spot (DBS) liquid chromatography/tandem mass spectrometric (LC/MS/MS) bioanalysis. Samples are diluted online with water and enriched in a trap column which is subsequently switched inline with the analytical column. Excellent lansoprazole (in acetonitrile) peak shape is maintained even with an 80-microL injection. In comparison, similar chromatographic peaks were observed only when a small volume of the same solution, i.e., 1 microL, was injected on a regular high-performance liquid chromatography (HPLC) system, where an injection of 5 microL resulted in severe peak fronting. A substantial enhancement in sensitivity is realized in the trapping mode using large injection volumes. The trap column is washed at the beginning and at the end of each injection with aqueous and organic solvent respectively to remove matrix components. This ultimately leads to reduction of matrix effects and mass spectrometer noise, thus facilitating the utilization of protein precipitation as the sample preparation for plasma samples. A lower limit of quantitation (LLOQ) of 0.5 pg/mL was demonstrated for lansoprazole in human plasma with a signal-to-noise (S/N) ratio of 13 using a 100 microL injection. Excellent intra-day precision and accuracy were established for lansoprazole in human plasma with good linearity (R(2) > 0.999) from 0.5 to 500 pg/mL. This level of LLOQ makes LC/MS/MS a practical alternative for microdosing bioanalysis, where the dose is typically 100 times lower than the therapeutic dose. The same technique was applied to quantitate lansoprazole in human whole blood employing DBS technology. With a single 3-mm punch, i.e. approximately 2 microL of whole blood or approximately 1 microL plasma, a LLOQ of 0.1 ng/mL showed sufficient S/N ratio (40) for lansoprazole when 75 microL of extract was injected. In all, the online sample dilution, cleanup, and

  16. Preparation of a sewage sludge laboratory quality control material for butyltin compounds and their determination by isotope-dilution mass spectrometry.

    PubMed

    Zuliani, Tea; Milačič, Radmila; Ščančar, Janez

    2012-05-01

    The characterisation of a laboratory quality control material (QCM) for dibutyltin (DBT) and tributyltin (TBT) in sewage sludge is described. The reference values were determined by the use of two different types of isotope-dilution mass spectrometry: gas chromatography-mass spectrometry and gas chromatography-inductively coupled plasma mass spectrometry. To avoid possible analytical errors such as non-quantitative extraction and species degradation during sample preparation, different extraction methods were tested (microwave- and ultrasound-assisted extraction and mechanical stirring). The reference values were based on the unweighted means of results from the homogenisation and characterisation studies. The reference values obtained were 1,553 ± 87 and 534 ± 38 ng Sn g(-1) for DBT and TBT, respectively. In the uncertainty budget estimation, the sample inhomogeneity and between-method imprecision were taken into account. The concentrations of DBT and TBT in QCM are similar to those in the harbour sediment certified reference material PACS-2. Likewise, the levels of DBT and TBT are in the range of these compounds normally present in sewage sludge worldwide. In the future, the QCM will be used for an intercomparison study on DBT and TBT in sewage sludge, and as a day-to-day QCM during studies concerning the application of sewage sludge as an additive to artificial soil or as a raw material in civil engineering construction.

  17. 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.

  18. 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.

  19. 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...

  20. International system of units traceable results of Hg mass concentration at saturation in air from a newly developed measurement procedure.

    PubMed

    Quétel, Christophe R; Zampella, Mariavittoria; Brown, Richard J C; Ent, Hugo; Horvat, Milena; Paredes, Eduardo; Tunc, Murat

    2014-08-05

    Data most commonly used at present to calibrate measurements of mercury vapor concentrations in air come from a relationship known as the "Dumarey equation". It uses a fitting relationship to experimental results obtained nearly 30 years ago. The way these results relate to the international system of units (SI) is not known. This has caused difficulties for the specification and enforcement of limit values for mercury concentrations in air and in emissions to air as part of national or international legislation. Furthermore, there is a significant discrepancy (around 7% at room temperature) between the Dumarey data and data calculated from results of mercury vapor pressure measurements in the presence of only liquid mercury. As an attempt to solve some of these problems, a new measurement procedure is described for SI traceable results of gaseous Hg concentrations at saturation in milliliter samples of air. The aim was to propose a scheme as immune as possible to analytical biases. It was based on isotope dilution (ID) in the liquid phase with the (202)Hg enriched certified reference material ERM-AE640 and measurements of the mercury isotope ratios in ID blends, subsequent to a cold vapor generation step, by inductively coupled plasma mass spectrometry. The process developed involved a combination of interconnected valves and syringes operated by computer controlled pumps and ensured continuity under closed circuit conditions from the air sampling stage onward. Quantitative trapping of the gaseous mercury in the liquid phase was achieved with 11.5 μM KMnO4 in 2% HNO3. Mass concentrations at saturation found from five measurements under room temperature conditions were significantly higher (5.8% on average) than data calculated from the Dumarey equation, but in agreement (-1.2% lower on average) with data based on mercury vapor pressure measurement results. Relative expanded combined uncertainties were estimated following a model based approach. They ranged from 2

  1. Analysis of triclosan and triclocarban in human nails using isotopic dilution liquid chromatography-tandem mass spectrometry.

    PubMed

    Shi, Ying; Liu, Xiangjun; Zhang, Jing; Shao, Bing

    2013-09-01

    In this study, we were able to develop a simple analytical procedure to assay the presence of two antimicrobial agents, triclosan (TCS) and triclocarban (TCC), in human nails. Samples were digested using sodium hydroxide (NaOH), extracted using dichloromethane, and analyzed using ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry operating in the negative ion mode. Mean recoveries were performed at three fortification levels ranging from 98.1% to 106.3% with relative standard deviations between 1.8% and 18.1% (n=6). The limits of quantification (LOQ) for the method were 2.0 and 0.2μg/kg for TCS and TCC, respectively. Both compounds were ubiquitously found in all real samples (n=20) with concentrations ranging from μg/kg to several mg/kg.

  2. 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.

  3. Surface-activated chemical ionization ion trap mass spectrometry in the analysis of amphetamines in diluted urine samples.

    PubMed

    Cristoni, Simone; Bernardi, Luigi Rossi; Gerthoux, Piermario; Gonella, Elisabetta; Mocarelli, Paolo

    2004-01-01

    A new ionization method, named surface-activated chemical ionization (SACI), was employed for the analysis of five amphetamines (3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyethylamphetamine (MDE), amphetamine and methamphetamine) by ion trap mass spectrometry. The results so obtained have been compared with those achieved by using atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) using the same instrument, clearly showing that SACI is the most sensitive of the three. The limit of detection and linearity range for SACI were compared with those obtained using APCI and ESI, showing that the new SACI approach provides the best results for both criteria. SACI was used to analyze MDA, MDMA MDE, amphetamine and methamphetamine in four urine samples, and the quantitation results are compared with those achieved using ESI.

  4. On-line liquid chromatography-mass spectrometry with dilution line to achieve large volume urine injection for the improvement of sensitivity.

    PubMed

    Liu, Min; Yan, Wei; Lin, Jin-Ming; Hashi, Yuki; Liu, Li-Bin; Wei, Yanlin

    2008-07-11

    A unique automated on-line high-performance liquid chromatography-mass spectrometry (LC-MS) method was developed allowing injection of a large volume of urine for the improvement of sensitivity using estrogens as analytes. The urine sample was precipitated by acetonitrile (sample:acetonitrile, 1:2, v/v) to remove most proteins. Then the supernatant was directly delivered at 0.3 mL/min by a pump, which broke through the limit of autosampler with fixed loop. Then the sample was loaded onto a restricted access media (RAM) pre-column after on-line dilution with NH(4)Ac solution which was delivered by another pump under high flow-rate. After the addition of on-line dilution line, the content of organic solvent in the sample aliquot was sharply decreased so that the analytes were effectively trapped by pre-column. In addition, another 6-port valve was added to selectively deliver the effluent containing analytes into MS, which minimized the pollution of the MS and matrix effect. After optimization of the condition of extraction method, 3 mL sample (containing 1 mL urine) could be successfully enriched. The injection volume increased 10 times compared with conventional on-line LC-MS methods for biofluid analysis, significantly improving sensitivity. Moreover, no obvious increase of column pressure was observed after 300 injections. The method was validated by spiking urine. Linearity was determined by sample which was in the range of 1-500 ng/mL. The process efficiency ranged from 70.2 to 106% with RSDs less than 15% with the exception of a few analytes. The limit of detection (LOD) and quantification (LOQ) ranged from 0.3 to 2 ng/mL and 1 to 8 ng/mL, respectively, corresponding a decrease of 1-2 orders of magnitude compared with those of off-line and on-line methods.

  5. Quantification of carcinogenic 4- to 6-ring polycyclic aromatic hydrocarbons in human urine by solid-phase microextraction gas chromatography-isotope dilution mass spectrometry.

    PubMed

    Campo, Laura; Fustinoni, Silvia; Bertazzi, Pieralberto

    2011-08-01

    Polycyclic aromatic hydrocarbons (PAHs) are pollutants found in living and working environments. The aim of this study was to develop a solid-phase microextraction (SPME) gas chromatography (GC)-isotope dilution mass spectrometry method for the quantification of 10 four- to six-ring PAHs in urine samples. Seven of the selected PAHs have been classified as carcinogenic. Under the final conditions, analytes were sampled with a 100-μm polydimethylsiloxane SPME fibre for 60 min at 80 °C and desorbed in the injection port of the GC at 270 °C. Fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene were separated using a highly arylene-modified phase capillary column and quantified by MS using eight deuterated PAHs as surrogate internal standards. Limits of quantification (LOQ) were in the 0.5- to 2.2-ng/L range. Validation showed linear dynamic ranges up to 340 ng/L, inter- and intra-run precisions <20%, and accuracies within 20% of spiked concentrations. Matrix effect evaluation and the use of control charts to monitor process performances showed that the isotope dilution approach allowed for the control of bias sources. Urinary PAHs were above or equal to LOQ, depending on different compounds, in 58-100% (min-max), 40-100% and 5-39% of samples from coke oven workers (n = 12), asphalt workers (n = 10) and individuals not occupationally exposed to PAHs (n = 18), respectively. Chrysene was the most abundant PAH determined with median levels of 62.6, 6.9 and <0.6 ng/L, respectively. These results show that the method is suitable for quantifying carcinogenic PAHs in specimens from individuals with different levels of PAH exposure.

  6. Analysis of hydrazine in drinking water by isotope dilution gas chromatography/tandem mass spectrometry with derivatization and liquid-liquid extraction.

    PubMed

    Davis, William E; Li, Yongtao

    2008-07-15

    A new isotope dilution gas chromatography/chemical ionization/tandem mass spectrometric method was developed for the analysis of carcinogenic hydrazine in drinking water. The sample preparation was performed by using the optimized derivatization and multiple liquid-liquid extraction techniques. Using the direct aqueous-phase derivatization with acetone, hydrazine and isotopically labeled hydrazine-(15)N2 used as the surrogate standard formed acetone azine and acetone azine-(15)N2, respectively. These derivatives were then extracted with dichloromethane. Prior to analysis using methanol as the chemical ionization reagent gas, the extract was dried with anhydrous sodium sulfate, concentrated through evaporation, and then fortified with isotopically labeled N-nitrosodimethylamine-d6 used as the internal standard to quantify the extracted acetone azine-(15)N2. The extracted acetone azine was quantified against the extracted acetone azine-(15)N2. The isotope dilution standard calibration curve resulted in a linear regression correlation coefficient (R) of 0.999. The obtained method detection limit was 0.70 ng/L for hydrazine in reagent water samples, fortified at a concentration of 1.0 ng/L. For reagent water samples fortified at a concentration of 20.0 ng/L, the mean recoveries were 102% with a relative standard deviation of 13.7% for hydrazine and 106% with a relative standard deviation of 12.5% for hydrazine-(15)N2. Hydrazine at 0.5-2.6 ng/L was detected in 7 out of 13 chloraminated drinking water samples but was not detected in the rest of the chloraminated drinking water samples and the studied chlorinated drinking water sample.

  7. Determination of selenium in biological samples by slurry sampling-electrothermal vaporization-in situ fusion-isotope dilution-microwave-induced nitrogen plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kawano, Takafumi; Nishide, Akifumi; Okutsu, Kentaro; Minami, Hirotsugu; Zhang, Qiangbin; Inoue, Sadanobu; Atsuya, Ikuo

    2005-03-01

    Determination of selenium in certified reference biological materials by slurry sampling electrothermal vaporization (ETV)-isotope dilution (ID)-microwave-induced nitrogen plasma mass spectrometry (MIP-MS) was performed. Several parameters such as the heating conditions were studied in order to obtain optimal conditions. A special heating stage called the in situ fusion stage was applied just before the pyrolysis stage in the electrothermal vaporization process in order to fuse the biological sample and to achieve selenium isotope-equilibration between selenium in the sample and the 78Se spike solution. The slurry sample containing an appropriate amount of biological sample, 78Se spike solution, and sodium hydroxide as an alkaline flux was injected into the electrothermal vaporization unit. The slurry sample was in situ fused, pyrolyzed, and then vaporized. The ion counts at m/ z=78 and 80, the spike and reference isotopes, respectively, could be measured accurately without interference caused by argon since nitrogen plasma was used. The analytical utility of the proposed slurry sampling-electrothermal vaporization-in situ fusion-microwave-induced nitrogen plasma mass spectrometry was evaluated by determining the selenium concentration in certified reference biological materials, and the analytical results obtained were in good agreement with the certified values. The limit of detection for selenium was 90 ng g -1. The relative standard deviation of the determination of selenium was 8-15% with a high sample throughput (less than 30 min per sample including a slurry preparation.)

  8. Quantification of 16 polycyclic aromatic hydrocarbons in cigarette smoke condensate using stable isotope dilution liquid chromatography with atmospheric-pressure photoionization tandem mass spectrometry.

    PubMed

    Zhang, Xiaotao; Hou, Hongwei; Chen, Huan; Liu, Yong; Wang, An; Hu, Qingyuan

    2015-09-17

    A stable isotope dilution liquid chromatography with tandem mass spectrometry method for the analysis of 16 polycyclic aromatic hydrocarbons in cigarette smoke condensate was developed and validated. Compared with previously reported methods, this method has lower limits of detection (0.04-1.35 ng/cig). Additionally, the proposed method saves time, reduces the number of separation steps, and reduces the quantity of solvent needed. The new method was applied to evaluate polycyclic aromatic hydrocarbon content in 213 commercially available cigarettes in China, under the International Standardization Organization smoking regime and the Health Canadian intense smoking regime. The results showed that the total polycyclic aromatic hydrocarbon content was more than two times higher in samples from the Health Canadian intense smoking regime than in samples from the International Standardization Organization smoking regime (1189.23 vs. 2859.50 ng/cig, p<0.05). Meanwhile, the concentration of individual polycyclic aromatic hydrocarbons (and total polycyclic aromatic hydrocarbons) increased with labeled tar content in both of the tested smoking regimes. There was a positive correlation between total polycyclic aromatic hydrocarbons under the International Standardization Organization smoking regime with that under the Health Canadian intense smoking regime. The proposed liquid chromatography with tandem mass spectrometry method is satisfactory for the rapid, sensitive, and accurately quantitative evaluation of polycyclic aromatic hydrocarbon content in cigarette smoke condensate, and it can be applied to assess potential health risks from smoking. This article is protected by copyright. All rights reserved.

  9. Molar mass, radius of gyration and second virial coefficient from new static light scattering equations for dilute solutions: application to 21 (macro)molecules.

    PubMed

    Illien, Bertrand; Ying, Ruifeng

    2009-05-11

    New static light scattering (SLS) equations for dilute binary solutions are derived. Contrarily to the usual SLS equations [Carr-Zimm (CZ)], the new equations have no need for the experimental absolute Rayleigh ratio of a reference liquid and solely rely on the ratio of scattered intensities of solutions and solvent. The new equations, which are based on polarizability equations, take into account the usual refractive index increment partial differential n/partial differential rho(2) complemented by the solvent specific polarizability and a term proportional to the slope of the solution density rho versus the solute mass concentration rho(2) (density increment). Then all the equations are applied to 21 (macro)molecules with a wide range of molar mass (0.2500 kg mol(-1)), for which the scattered intensity is no longer independent of the scattering angle, the new equations give the same value of the radius of gyration as the CZ equation and consistent values of the second virial coefficient.

  10. 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.

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

    SciTech Connect

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

    1984-05-01

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

  12. 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

    2015-09-04

    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.

  13. 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

  14. Determination of cyclophosphamide and ifosfamide in sewage effluent by stable isotope-dilution liquid chromatography-tandem mass spectrometry.

    PubMed

    Llewellyn, N; Lloyd, P; Jürgens, M D; Johnson, A C

    2011-11-25

    A reliable and specific method was developed for the determination of the cytotoxic drugs cyclophosphamide and ifosfamide in sewage effluent. The most successful combination was found to be Strata-X solid-phase extraction followed by Florisil® clean-up with analysis by liquid chromatography-tandem mass spectrometry. Quantification by internal standardisation was achieved using custom synthesised d4-cyclophophosphamide. The mass spectrometer was operated in highly selective reaction monitoring (HSRM) mode, which significantly reduced matrix noise and improved sensitivity. Although it suffered from some ionisation suppression, electrospray ionisation (ESI) was found to give an order of magnitude better sensitivity in terms of limit of detection than atmospheric pressure chemical ionisation (APCI). Using final effluent from two different sewage treatment plants, the method was validated following official European guidelines and shown to be a high performance tool for routine analysis at the sub-nanogram per litre level. Depending on the matrix, the limit of detection for cyclophosphamide was between 0.03 ng/L and 0.12 ng/L and for ifosfamide between 0.05 ng/L and 0.09 ng/L. For cyclophosphamide the accuracy and precision, tested at 1.7 ng/L, were 98-109% and ≤ 13%, CV respectively. For ifosfamide the accuracy and precision, tested at 1.1 ng/L, were 98-113% and ≤ 15% CV, respectively. Depending on the sample matrix the absolute recovery of the internal standard was between 57% and 70%. The method was tested by analysis of spot samples taken from the final effluent discharges of two sewage treatment plants; the first using a conventional trickling filter treatment process and second employing activated sludge followed by ultra violet treatment. Cyclophosphamide was detected at 0.19 ng/L at the first plant and at the second detected at 3.7 ng/L and 3.5 ng/L, before and after the UV treatment process; ifosfamide was not detectable at either plant.

  15. 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.

  16. 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.

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

    PubMed Central

    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.

    2016-01-01

    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. PMID:25576235

  18. 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.

  19. Quantitative analysis of menthol in human urine using solid phase microextraction and stable isotope dilution gas chromatography-mass spectrometry.

    PubMed

    Huang, Wenlin; Blount, Benjamin C; Watson, Clifford H; Watson, Christina; Chambers, David M

    2017-02-15

    To accurately measure menthol levels in human urine, we developed a method using gas chromatography/electron ionization mass spectrometry with menthol-d4 stable isotope internal standardization. We used solid phase microextraction (SPME) headspace sampling for collection, preconcentration and automation. Conjugated forms of menthol were released using β-glucuronidase/sulfatase to allow for measuring total menthol. Additionally, we processed the specimens without using β-glucuronidase/sulfatase to quantify the levels of unconjugated (free) menthol in urine. This method was developed to verify mentholated cigarette smoking status to study the influence of menthol on smoking behaviour and exposure. This objective was accomplished with this method, which has no carryover or memory from the SPME fiber assembly, a method detection limit of 0.0017μg/mL, a broad linear range of 0.002-0.5μg/mL for free menthol and 0.01-10μg/mL for total menthol, a 7.6% precision and 88.5% accuracy, and an analysis runtime of 17min. We applied this method in analysis of urine specimens collected from cigarette smokers who smoke either mentholated or non-mentholated cigarettes. Among these smokers, the average total urinary menthol levels was three-fold higher (p<0.001) among mentholated cigarette smokers compared with non-mentholated cigarette smokers.

  20. Establishing ion ratio thresholds based on absolute peak area for absolute protein quantification using protein cleavage isotope dilution mass spectrometry.

    PubMed

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

    2014-11-07

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

  1. 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.

  2. [Preparation and certification of mussel reference material for organochlorine pesticides and polychlorinated biphenyls using isotope dilution-high resolution mass spectrometry].

    PubMed

    Lu, Xianbo; Chen, Jiping; Wang, Shuqiu; Zou, Lili; Tian, Yuzeng; Ni, Yuwen; Su, Fan

    2012-09-01

    A method for the preparation and certification of the reference material of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in mussel tissue is described. The mussel tissue from Dalian Bay was frozen-dried, comminuted, sieved, homogenized, packaged, and sterilized by 60Co radiation sterilization in turn. The certified values for 18 OCPs and 16 PCBs were determined by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) using isotope dilution and internal standard quantitation techniques. The certified values were validated and given based on seven accredited laboratories, and these values are traceable to the SI (international system of units) through gravimetrically prepared standards of established purity and measurement intercomparisons. The certified values of PCBs and OCPs in mussel span 4 orders of magnitude with a relative uncertainty of about 10%. This material is a natural biological material with confirmed good homogeneity and stability, and it was approved as the grade "primary reference material" (GBW10069) in June 2012 in China. This reference material provided necessary quality control products for our country to implement the Stockholm Treaty on the monitoring of persistent organic pollutants (POPs). The material is intended to be used for the method validation and quality control in the determination of OCPs and PCBs in biota samples.

  3. 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.

  4. 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.

  5. Development of isotope dilution cold vapor inductively coupled plasma mass spectrometry and its application to the certification of mercury in NIST standard reference materials.

    PubMed

    Christopher, S J; Long, S E; Rearick, M S; Fassett, J D

    2001-05-15

    An isotope dilution cold vapor inductively coupled plasma mass spectrometry (ID-CV-ICPMS) method featuring gaseous introduction of mercury via tin chloride reduction has been developed and applied to the quantification and certification of mercury in various NIST standard reference materials: SRM 966 Toxic Metals in Bovine Blood (30 ng x mL(-1)); SRM 1641d Mercury in Water (1.6 microg x mL(-1)); and SRM 1946 Lake Superior Fish Tissue (436 ng x g(-1)). Complementary mercury data were generated for SRMs and NIST quality control standards using cold vapor atomic absorption spectroscopy (CVAAS). Certification results for the determination of mercury in SRM 1641d using two independent methods (ID-CV-ICPMS and CVAAS) showed a degree of agreement of 0.3% between the methods. Gaseous introduction of mercury into the ICPMS resulted in a single isotope sensitivity of 2 x 10(6) counts x s(-1)/ng x g(-1) for 201Hg and significantly reduced the memory and washout effects traditionally encountered in solution nebulization ICPMS. Figures of merit for isotope ratio accuracy and precision were evaluated at dwell times of 10, 20, 40, 80, and 160 ms using SRM 3133 Mercury Spectrometric Solution. The optimum dwell time of 80 ms yielded a measured 201Hg/202Hg isotope ratio within 0.13% of the theoretical natural value and a measurement precision of 0.34%, on the basis of three replicate injections of SRM 3133.

  6. Determination of nerve agent metabolites in human urine by isotope-dilution gas chromatography-tandem mass spectrometry after solid phase supported derivatization.

    PubMed

    Lin, Ying; Chen, Jia; Yan, Long; Guo, Lei; Wu, Bidong; Li, Chunzheng; Feng, Jianlin; Liu, Qin; Xie, Jianwei

    2014-08-01

    A simple and sensitive method has been developed and validated for determining ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA), isobutyl methylphosphonic acid (iBuMPA), and pinacolyl methylphosphonic acid (PMPA) in human urine using gas chromatography-tandem mass spectrometry (GC-MS/MS) coupled with solid phase derivatization (SPD). These four alkyl methylphosphonic acids (AMPAs) are specific hydrolysis products and biomarkers of exposure to classic organophosphorus (OP) nerve agents VX, sarin, RVX, and soman. The AMPAs in urine samples were directly derivatized with pentafluorobenzyl bromide on a solid support and then extracted by liquid-liquid extraction. The analytes were quantified with isotope-dilution by negative chemical ionization (NCI) GC-MS/MS in a selected reaction monitoring (SRM) mode. This method is highly sensitive, with the limits of detection of 0.02 ng/mL for each compound in a 0.2 mL sample of human urine, and an excellent linearity from 0.1 to 50 ng/mL. It is proven to be very suitable for the qualitative and quantitative analyses of degradation markers of OP nerve agents in biomedical samples.

  7. Quantification of 13 priority polycyclic aromatic hydrocarbons in human urine by headspace solid-phase microextraction gas chromatography-isotope dilution mass spectrometry.

    PubMed

    Campo, Laura; Mercadante, Rosa; Rossella, Federica; Fustinoni, Silvia

    2009-01-12

    Polycyclic aromatic hydrocarbons (PAHs) are common environmental pollutants in both living and working environments. The aim of this study was the development of a headspace solid-phase microextraction gas chromatography-isotope dilution mass spectrometry (HS-SPME/GC-IDMS) method for the simultaneous quantification of 13 PAHs in urine samples. Different parameters affecting PAHs extraction by HS-SPME were considered and optimized: type/thickness of fiber coatings, extraction temperature/time, desorption temperature/time, ionic strength and sample agitation. The stability of spiked PAHs solutions and of real urine samples stored up to 90 days in containers of different materials was evaluated. In the optimized method, analytes were absorbed for 60min at 80 degrees C in the sample headspace with a 100mum polydimethylsiloxane fiber. The method is very specific, with linear range from the limit of quantification to 8.67 x 10(3)ngL(-1), a within-run precision of <20% and a between-run precision of <20% for 2-, 3- and 4-ring compounds and of <30% for 5-ring compounds, trueness within 20% of the spiked concentration, and limit of quantification in the 2.28-2.28 x 10(1)ngL(-1) range. An application of the proposed method using 15 urine samples from subjects exposed to PAHs at different environmental levels is shown.

  8. Rapid determination of trace dicyandiamide in mussels from Zhejiang coast by ultra-fast liquid chromatography-tandem mass spectrometry with isotope internal standard dilution technique.

    PubMed

    Zhang, Yun; Gong, Wen-Jie; Zhao, Yong-Gang; Zhou, Hua

    2014-12-01

    In this study, a rapid and accurate ultra-fast liquid chromatography-tandem quadrupole mass spectrometry (UFLC-MS/MS) method coupled with the isotope internal standard dilution technique was established and validated to determine trace dicyandiamide (DCD) in mussels. The sample was extracted by acetonitrile, and chromatographic separations were performed on an Acquity UPLC BEH Amide column by using water-acetonitrile (9:91, v/v) as the mobile phase within 3 min. DCD was determined by using DCD-(15)N4 as an internal standard. The results showed that the recoveries were between 96.2 and 103 % with relative standard deviations (RSDs) in the range of 0.6-6.0 %. The limit of quantification (LOQ) was 0.05 μg/kg. This method can be applied to the routine analysis for the rapid and sensitive determination of trace DCD in mussels. Overall, the data reiterate the importance of investigating the presence of DCD in marine biological samples, which can act as food quality controls for human health.

  9. Quantification of 2-acetyl-1-pyrroline in rice by stable isotope dilution assay through headspace solid-phase microextraction coupled to gas chromatography-tandem mass spectrometry.

    PubMed

    Maraval, Isabelle; Sen, Kemal; Agrebi, Abdelhamid; Menut, Chantal; Morere, Alain; Boulanger, Renaud; Gay, Frédéric; Mestres, Christian; Gunata, Ziya

    2010-08-24

    A new and convenient synthesis of 2-acetyl-1-pyrroline (2AP), a potent flavor compound in rice, and its ring-deuterated analog, 2-acetyl-1-d(2)-pyrroline (2AP-d(2)), was reported. A stable isotope dilution assay (SIDA), involving headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-positive chemical ionization-ion trap-tandem mass spectrometry (GC-PCI-IT-MS-MS), was developed for 2AP quantification. A divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was used for HS-SPME procedure and parameters affecting analytes recovery, such as extraction time and temperature, pH and salt, were studied. The repeatability of the method (n=10) expressed as relative standard deviation (RSD) was 11.6%. A good linearity was observed from 5.9 to 779 ng of 2AP (r(2)=0.9989). Limits of detection (LOD) and quantification (LOQ) for 2AP were 0.1 and 0.4 ng g(-1) of rice, respectively. The recovery of spiked 2AP from rice matrix was almost complete. The developed method was applied to the quantification of 2AP in aerial parts and grains of scented and non-scented rice cultivars.

  10. 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.

  11. Isotope dilution high-resolution gas chromatography/high-resolution mass spectrometry method for analysis of selected acidic herbicides in surface water.

    PubMed

    Woudneh, Million B; Sekela, Mark; Tuominen, Taina; Gledhill, Melissa

    2006-11-10

    In this work, an isotope dilution method for determination of selected acidic herbicides by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was developed for surface water samples. Average percent recoveries of native analytes were observed to be between 70.8 and 93.5% and average recoveries of labeled quantification standards [(13)C(6)]2,4-D and [(13)C(6)]2,4,5-T were 85.5 and 101%, respectively. Using this method, detection limits of 0.05 ng/L for dicamba, MCPA, MCPP, and triclopyr, and 0.5 ng/L for 2,4-D were routinely achieved. The method was applied to measuring the concentration of these analytes in surface water samples collected from five sampling locations in the Lower Fraser Valley region of British Columbia, Canada. All of the herbicides monitored were detected at varying levels in the surface water samples collected. The highest concentrations detected for each analyte were 345 ng/L for 2,4-D, 317 ng/L for MCPA, 271 ng/L for MCPP, 15.7 ng/L for dicamba, and 2.18 ng/L for triclopyr. Average detection frequencies of the herbicides were 95% for MCPA, 80% for MCPP, 70% for dicamba, 65% for 2,4-D, and 46% for triclopyr. Seasonal variations of herbicide levels are also discussed.

  12. 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.

  13. 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.

  14. Simultaneous determination of Δ9-tetrahydrocannabinol and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol in oral fluid using isotope dilution liquid chromatography tandem mass spectrometry.

    PubMed

    Lee, Pin Duo; Chang, Yuan-Jhe; Lin, Keh-Liang; Chang, Yan-Zin

    2012-01-01

    The detection and confirmation of cannabinoids in oral fluid are important in forensic toxicology. Currently, the presence of Δ(9)-tetrahydrocannabinol (THC) is used for the detection of cannabis in oral fluid. A low concentration of 11-nor-9-carboxy-Δ(9)-tetrahydrocannabinol (THC-COOH) is found in oral fluid, which suggested a convenient and low-sensitivity confirmation assay can be used in a routine forensic laboratory. In this study, a highly sensitive isotope dilution liquid chromatography-tandem mass spectrometry method following dansylation was successfully developed for simultaneous determination of THC and THC-COOH in oral fluid. The dansylated derivatives dramatically demonstrated and enhanced the sensitivity of THC and THC-COOH. To avoid signal influenced by the matrix, a 5-min liquid chromatography gradient program was evaluated and optimized, which reduced the sample diffusion and caused sharp peaks (less than 12 s) and thus helped to achieve detection at a low level. The sensitivity, accuracy, and precision were also evaluated, and high quantitative accuracy and precision were obtained. The limit of quantitation of this approach was 25 pg/mL for THC and 10 pg/mL for THC-COOH in oral fluid. Finally, the method was successfully applied to eight suspected cannabis users. Among them, in six oral fluid samples THC-COOH was determined at a concentration from 13.1 to 47.2 pg/mL.

  15. [Determination of 18 pesticide residues in red wine by ultra high performance liquid chromatography-high resolution mass spectrometry with isotope dilution technique].

    PubMed

    Chen, Dawei; Lü, Bing; Ding, Hao; Zou, Jianhong; Yang, Xin; Zhao, Yunfeng; Miao, Hong

    2014-05-01

    A method for the simultaneous determination of 18 pesticide residues in red wine was developed using ultra high performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) with isotope dilution technique. The red wine samples were extracted with acetonitrile, and the extracts were cleaned up with dispersive solid phase extraction (dSPE) using the mixture of N-propyl ethylene diamine (PSA) and C18 powder as sorbent. The extracted components were separated on a BEH C18 column by gradient elution. The qualitative and quantitative analyses were operated under full scan/data dependent MS/MS (ddms2) and targeted selective ion monitoring (tSIM) by high resolution mass spectrometry, respectively. Carbendazim-D4, chlorpyrifos-D10, imidacloprid-D4, methoxyfenozide-D9, pyrimethanil-D5 and tebuconazole-D6 were used as the internal standards to reduce the matrix effects. The response of each pesticide showed a good linearity in the range of 0.5-50 microg/kg with the correlation coefficient more than 0.999. The limits of detection and quantification for the 18 pesticides in the spiked blank red wine were 0.5 microg/kg and 1.0 microg/kg, respectively. The recovery results with spiked blank red wine samples at the levels of 1 to 40 microg/kg were satisfactory with average recoveries of 85.4% - 117.9% and the RSDs of 0.5%-6.1%. The method was applied for the determination of the red wine real samples from the market. Carbendazim, imidacloprid, pyrimethanil, tebuconazole and triadimenol were detected in the samples. The results show that the method is suitable for the rapid screening and quantitative analysis of pesticide residues in red wine.

  16. Simultaneous speciation of selenoproteins and selenometabolites in plasma and serum by dual size exclusion-affinity chromatography with online isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    García-Sevillano, M A; García-Barrera, T; Gómez-Ariza, J L

    2014-04-01

    A method for the simultaneous speciation of selenoproteins and selenometabolites in mouse plasma has been developed based on in series two-dimensional size exclusion and affinity high-performance liquid chromatography (2D/SE-AF-HPLC), using two columns of each type, and hyphenation to inductively coupled plasma-(quadrupole) mass spectrometry (ICP-QMS). The method allows the quantitative determination of selenoprotein P (SeP), extracellular glutathione peroxidase (eGPx), selenoalbumin (SeAlb), and selenometabolites in mouse plasma using species-unspecific isotope dilution (SUID). The 2D chromatographic separation is proposed to remove typical spectral interferences in plasma from chloride and bromide on (77)Se ((40)Ar(37)Cl) and (82)Se ((81)Br(1)H). In addition, the approach increases chromatographic resolution allowing the separation of eGPx from Se metabolites of low molecular mass. The method is robust, reliable, and fast with a typical chromatographic runtime less than 20 min. Precision in terms of relative standard deviation (n = 5) is in the order of 4 %, and detection limits are in the range of 0.2 to 1.0 ng Se g(-1). Method accuracy for determination of total protein bound to Se was assessed by analyzing human serum reference material (BCR-637) certified for total Se content, and latterly applied to mouse plasma (Mus musculus). In summary, a reliable speciation method for the analysis of eGPx, selenometabolites, SeP, and SeAlb in plasma/serum samples is proposed for the first time and is applicable to the evaluation of Se status in human in clinical studies and other mammals for environmental or toxicological assessment.

  17. 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)

  18. On the evaluation of air mass factors for atmospheric near-ultraviolet and visible absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Perliski, Lori M.; Solomon, Susan

    1993-01-01

    The interpretation of UV-visible twilight absorption measurements of atmospheric chemical constituents is dependent on how well the optical path, or air mass factor, of light collected by the spectrometer is understood. A simple single scattering model and a Monte Carlo radiative transfer scheme have been developed to study the effects of multiple scattering, aerosol scattering, surface albedo and refraction on air mass factors for scattered light observations. At fairly short visible wavelengths (less than about 450 nm), stratospheric air mass factors are found to be relatively insensitive to multiple scattering, surface albedo and refraction, as well as aerosol scattering by background aerosols. Longer wavelengths display greater sensitivity to refraction and aerosol scattering. Tropospheric air mass factors are found to be highly dependent on aerosol scattering, surface albedo and, at long visible wavelengths (about 650 nm), refraction. Absorption measurements of NO2 and O4 are shown to support these conclusions.

  19. 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.

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

    PubMed

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

    2014-11-28

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

  1. 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

    2013-07-03

    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

  2. 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)

  3. 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...

  4. Aerosol properties and radiative forcing for three air masses transported in Summer 2011 to Sopot, Poland

    NASA Astrophysics Data System (ADS)

    Rozwadowska, Anna; Stachlewska, Iwona S.; Makuch, P.; Markowicz, K. M.; Petelski, T.; Strzałkowska, A.; Zieliński, T.

    2013-05-01

    Properties of atmospheric aerosols and solar radiation reaching the Earth's surface were measured during Summer 2011 in Sopot, Poland. Three cloudless days, characterized by different directions of incoming air-flows, which are typical transport pathways to Sopot, were used to estimate a radiative forcing due to aerosols present in each air mass.

  5. 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.

  6. 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.

  7. Erroneous mass transit system and its tended relationship with motor vehicular air pollution (An integrated approach for reduction of urban air pollution in Lahore).

    PubMed

    Aziz, Amer; Bajwa, Ihsan Ullah

    2008-02-01

    Air pollution is threat to the lives of people living in big cities of Pakistan. In Lahore 1,250 people die annually because of air pollution. Mass transit system that can be put forth as solution to urban air pollution is contingent with right choice of system and its affiliation with motorized vehicles and nature of urban air pollution. Existing mass transit system in Lahore due to untrue operation causes surfeit discharge of motor vehicular carbon monoxide. Tended relationships of mass transit system with motorized vehicles and urban air pollution are quite noteworthy. The growing motor vehicles (a consequence of flawed public mass transit system) are potential source of urban air pollution. This paper attempts to highlight correlations and regression curves of existing mass transit system. Further it recommends a two facet approach for reduction of motor vehicular air pollution in Lahore.

  8. 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

  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. 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.

  11. Simultaneous determination of amphetamine and methamphetamine enantiomers in urine by simultaneous liquid-liquid extraction and diastereomeric derivatization followed by gas chromatographic-isotope dilution mass spectrometry.

    PubMed

    Wang, Sheng-Meng; Wang, Ting-Cheng; Giang, Yun-Seng

    2005-02-25

    A simple, rapid, reliable, and economic analytical scheme starting with in situ liquid-liquid extraction and asymmetric (or diastereomeric) chemical derivatization (ChD) followed by gas chromatography (GC)-isotope dilution mass spectrometry (MS) is described for the simultaneous determination of D- and L-amphetamine (AP) and methamphetamine (MA) in urine which could have resulted from the administration of various forms of questioned amphetamines or amphetamines-generating drugs. By using L-N-trifluoroacetyl-1-prolyl chloride (L-TPC) as chiral derivatizing agent, resolutions of 2.2 and 2.0 were achieved for the separation of AP and MA enantiomeric pairs, respectively, on an ordinary HP-5MS capillary column. The GC-MS quantitation was carried out in the selected ion monitoring (SIM) mode using m/z 237 and 251 as the quantifier ions for the respective diastereomeric pairs of AP-L-TPC and MA-L-TPC. The calibration curves plotted for the two pairs of analytes stretch with good linearity down to 45 ng/mL, and the limits of detection and quantitation determined were as low as 40 and 45 ng/mL, respectively. Also, a comparative study using 10 real-case urine specimens previously screened as positive for MA administration showed mostly tolerable biases between the two sums (of concentration) of D- and L-MA obtained via an asymmetric L-TPC-ChD approach and via an ordinary pentafluoropropionylation (PFPA-ChD) approach, respectively, as well as between the two sums of D- and L-AP obtained thereupon, thus validating the proposed analytical scheme as a promising forensic protocol for the detailed analysis of enantiomeric amphetamines in urine.

  12. 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.

  13. 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.

  14. 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.

  15. Application of the reference method isotope dilution gas chromatography mass spectrometry (ID/GC/MS) to establish metrological traceability for calibration and control of blood glucose test systems.

    PubMed

    Andreis, Elisabeth; Küllmer, Kai; Appel, Matthias

    2014-05-01

    Self-monitoring of blood glucose (BG) by means of handheld BG systems is a cornerstone in diabetes therapy. The aim of this article is to describe a procedure with proven traceability for calibration and evaluation of BG systems to guarantee reliable BG measurements. Isotope dilution gas chromatography mass spectrometry (ID/GC/MS) is a method that fulfills all requirements to be used in a higher-order reference measurement procedure. However, this method is not applicable for routine measurements because of the time-consuming sample preparation. A hexokinase method with perchloric acid (PCA) sample pretreatment is used in a measurement procedure for such purposes. This method is directly linked to the ID/GC/MS method by calibration with a glucose solution that has an ID/GC/MS-determined target value. BG systems are calibrated with whole blood samples. The glucose levels in such samples are analyzed by this ID/GC/MS-linked hexokinase method to establish traceability to higher-order reference material. For method comparison, the glucose concentrations in 577 whole blood samples were measured using the PCA-hexokinase method and the ID/GC/MS method; this resulted in a mean deviation of 0.1%. The mean deviation between BG levels measured in >500 valid whole blood samples with BG systems and the ID/GC/MS was 1.1%. BG systems allow a reliable glucose measurement if a true reference measurement procedure, with a noninterrupted traceability chain using ID/GC/MS linked hexokinase method for calibration of BG systems, is implemented. Systems should be calibrated by means of a traceable and defined measurement procedure to avoid bias.

  16. 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.

  17. Simultaneous determination of four sulfur mustard-DNA adducts in rabbit urine after dermal exposure by isotope-dilution liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhang, Yajiao; Yue, Lijun; Nie, Zhiyong; Chen, Jia; Guo, Lei; Wu, Bidong; Feng, Jianlin; Liu, Qin; Xie, Jianwei

    2014-06-15

    Sulfur mustard (SM) is a classic vesicant agent, which has been greatly employed in several wars or military conflicts. The most lesion mechanism is its strong alkylation of DNAs in vivo. Until now there are four specific DNA adducts of SM identified for further retrospective detection, i.e., N(7)-(2-hydroxyethylthioethyl)-2'-guanine (N(7)-HETEG), bis(2-ethyl-N(7)-guanine)thioether (Bis-G), N(3)-(2-hydroxyethylthioethyl)-2'-adenine (N(3)-HETEA) and O(6)-(2-hydroxyethylthioethyl)-2'-guanine (O(6)-HETEG), respectively. Here, a novel and sensitive method of isotope-dilution ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) combining with solid phase extraction was reported for the simultaneous determination of four SM-DNA adducts. A lower limit of detection of 2-5ngL(-1), and a lower limit of quantitation of 5-10ngL(-1) were achieved, respectively, and the recoveries ranged from 87% to 116%. We applied this method in the determination of four SM-DNA adducts in rabbit urine after dermal exposure by SM in three dose levels (2, 5, 15mgkg(-1)), so as to investigate the related metabolic behavior in vivo. For the first time, in SM exposed rabbit urine, our results revealed the relative accumulation abundance of four SM-DNA adducts, i.e., 67.4% for N(7)-HETEG, 22.7% for Bis-G, 9.8% for N(3)-HETEA, 0.1% for O(6)-HETEG, and significant dose and time dependent responses of these SM-DNA adducts. The four adducts were detectable after 8h, afterwards, their contents continuously increased, achieved maximum in the first two or three days and then gradually decreased till the end of one month. Meanwhile, the amounts of SM-DNA adducts were positively correlated with the exposure doses.

  18. Monolithic mass sensor fabricated using a conventional technology with attogram resolution in air conditions

    NASA Astrophysics Data System (ADS)

    Verd, J.; Uranga, A.; Abadal, G.; Teva, J.; Torres, F.; Pérez-Murano, F.; Fraxedas, J.; Esteve, J.; Barniol, N.

    2007-07-01

    Monolithic mass sensors for ultrasensitive mass detection in air conditions have been fabricated using a conventional 0.35μm complementary metal-oxide-semiconductor (CMOS) process. The mass sensors are based on electrostatically excited submicrometer scale cantilevers integrated with CMOS electronics. The devices have been calibrated obtaining an experimental sensitivity of 6×10-11g/cm2Hz equivalent to 0.9ag/Hz for locally deposited mass. Results from time-resolved mass measurements are also presented. An evaluation of the mass resolution have been performed obtaining a value of 2.4×10-17g in air conditions, resulting in an improvement of these devices from previous works in terms of sensitivity, resolution, and fabrication process complexity.

  19. Peroxy radicals and ozone photochemistry in air masses undergoing long-range transport

    NASA Astrophysics Data System (ADS)

    Parker, A. E.; Monks, P. S.; Jacob, M. J.; Penkett, S. A.; Lewis, A. C.; Stewart, D. J.; Whalley, L. K.; Methven, J.; Stohl, A.

    2009-09-01

    Concentrations of peroxy radicals (HO2+ΣiRiO2) in addition to other trace gases were measured onboard the UK Meteorological Office/Natural Environment Research Council British Aerospace 146-300 atmospheric research aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) campaign based at Horta Airport, Faial, Azores (38.58° N, 28.72° W) in July/August 2004. The overall peroxy radical altitude profile displays an increase with altitude that is likely to have been impacted by the effects of long-range transport. The peroxy radical altitude profile for air classified as of marine origin shows no discernable altitude profile. A range of air-masses were intercepted with varying source signatures, including those with aged American and Asian signatures, air-masses of biomass burning origin, and those that originated from the east coast of the United States. Enhanced peroxy radical concentrations have been observed within this range of air-masses indicating that long-range transported air-masses traversing the Atlantic show significant photochemical activity. The net ozone production at clear sky limit is in general negative, and as such the summer mid-Atlantic troposphere is at limit net ozone destructive. However, there is clear evidence of positive ozone production even at clear sky limit within air masses undergoing long-range transport, and during ITOP especially between 5 and 5.5 km, which in the main corresponds to a flight that extensively sampled air with a biomass burning signature. Ozone production was NOx limited throughout ITOP, as evidenced by a good correlation (r2=0.72) between P(O3) and NO. Strong positive net ozone production has also been seen in varying source signature air-masses undergoing long-range transport, including but not limited to low-level export events, and export from the east coast of the United States.

  20. A candidate reference measurement procedure for quantifying serum concentrations of 25-hydroxyvitamin D₃ and 25-hydroxyvitamin D₂ using isotope-dilution liquid chromatography-tandem mass spectrometry.

    PubMed

    Mineva, Ekaterina M; Schleicher, Rosemary L; Chaudhary-Webb, Madhulika; Maw, Khin L; Botelho, Julianne C; Vesper, Hubert W; Pfeiffer, Christine M

    2015-07-01

    The inaccuracy of routine serum 25-hydroxyvitamin D measurements hampers the interpretation of data in patient care and public health research. We developed and validated a candidate reference measurement procedure (RMP) for highly accurate quantitation of two clinically important 25-hydroxyvitamin D metabolites in serum, 25-hydroxyvitamin D2 [25(OH)D2] and 25-hydroxyvitamin D3 [25(OH)D3]. The two compounds of interest together with spiked deuterium-labeled internal standards [d 3-25(OH)D2 and d 6-25(OH)D3] were extracted from serum via liquid-liquid extraction. The featured isotope-dilution LC-MS/MS method used reversed-phase chromatography and atmospheric pressure chemical ionization in positive ion mode. A pentafluorophenylpropyl-packed UHPLC column together with isocratic elution allowed for complete baseline resolution of 25(OH)D2 and 25(OH)D3 from their structural C-3 isomers within 12 min. We evaluated method trueness, precision, potential interferences, matrix effects, limits of quantitation, and measurement uncertainty. Calibration materials were, or were traceable to, NIST Standard Reference Materials 2972. Within-day and total imprecision (CV) averaged 1.9 and 2.0% for 25(OH)D3, respectively, and 2.4 and 3.5% for 25(OH)D2, respectively. Mean trueness was 100.3% for 25(OH)D3 and 25(OH)D2. The limits of quantitation/limits of detection were 4.61/1.38 nmol/L for 25(OH)D3 and 1.46/0.13 nmol/L for 25(OH)D2. When we compared our RMP results to an established RMP using 40 serum samples, we found a nonsignificant mean bias of 0.2% for total 25(OH)D. This candidate RMP for 25(OH)D metabolites meets predefined method performance specifications (≤5% total CV and ≤1.7% bias) and provides sufficient sample throughput to meet the needs of the Centers for Disease Control and Prevention Vitamin D Standardization Certification Program. Graphical abstract Bias assessment using NIST standard reference materials. Legend CDC mean mass fractions (ng/g) ± U 95 (6

  1. 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.…

  2. A Synoptic Air Mass Approach to Defining Southwest U.S. Summer Duration and Change

    NASA Astrophysics Data System (ADS)

    Morrill, C.; Wachtel, C. J.; Godek, M. L.

    2015-12-01

    As the past decade was the warmest in the 110-year active record, and future Southwest warming is expected to be most intense in the summer season, it is important to have an updated atmospheric definition of what constitutes a Southwest summer. This is particularly true given the intensity of current drought conditions and that summers may be changing. Using weather-type data from the Spatial Synoptic Classification, this research aims to synoptically define the summer season in the Southwest since 1950. The Southwest is spatially described here by sub-region and 28 air mass stations within are chosen for air mass analysis. Daily air mass frequencies are examined to determine the dominant and less prevalent types annually and seasonally, from May to September. Then, frequencies in the middle of summer are compared to those in the seasonal fringe months to explore the possibility of a synoptic shift in the timing of the region's summer season. Finally, to further scrutinize how regional air mass frequencies have changed with time, the data are subdivided and evaluated for the 'Early record' (years prior to 1975) and 'Modern record' (post 1975). Frequency departures are tested for practical and statistical significance to characterize the strength of summer season variability. Results indicate that Dry Moderate air masses are the most common annually and in summer. Moist and transitional air masses tend to less frequent throughout the Southwest; however, frequencies vary greatly by sub-region. Wet and dry conditions are observed in accordance with the monsoon in some sub-regions, but not throughout the region. Significant changes in sub-regional air mass tendencies are identified that show the Early record experienced cooler air mass conditions (fewer tropical types and more moderate and cool types) than the Modern record. From a long-term synoptic air mass perspective, typical Southwest summers likely last from May to August. However, in the Modern record May

  3. Monitoring urinary metabolites resulting from sulfur mustard exposure in rabbits, using highly sensitive isotope-dilution gas chromatography-mass spectrometry.

    PubMed

    Nie, Zhiyong; Zhang, Yajiao; Chen, Jia; Lin, Ying; Wu, Bidong; Dong, Yuan; Feng, Jianlin; Liu, Qin; Xie, Jianwei

    2014-08-01

    A highly sensitive method for the determination of sulfur mustard (SM) metabolites thiodiglycol (TDG) and thiodiglycol sulfoxide (TDGO) in urine was established and validated using isotope-dilution negative-ion chemical ionization (NICI) gas chromatography-mass spectrometry (GC-MS). TDGO in the samples was reduced with TiCl3, and then determined together with TDG as a single analyte. The sample preparation procedures, including two solid-phase-extraction (SPE) clean-up steps, were optimized to improve the sensitivity of the method. The limits of detection (LOD) for both TDG and TDG plus TDGO (TDG + TDGO) were 0.1 ng mL(-1), and the limits of quantitation (LOQ) for both were 0.3 ng mL(-1). The method was used in a rabbit cutaneous SM exposure model. Domestic rabbits were exposed to neat liquid SM at three dosage levels (0.02, 0.05, and 0.15 LD50), and the urinary excretion of four species of hydrolysis metabolites, namely free TDG, free plus conjugated TDG (total TDG), free TDG + TDGO, and free plus conjugated TDG + TDGO (total TDG + TDGO), was evaluated to investigate the metabolic processes. The total urinary excretion profiles of the metabolites, including the peak time, time window, and dose-response and time-response relationships, were clarified. The results revealed that the concentrations of TDG and TDG + TDGO in the urine increased quickly and then decreased rapidly in the first two days after SM exposure. The cumulative amount of total TDG + TDGO excreted in urine during the first five days accounted for 0.5-1% of the applied dose of SM. It is also concluded that TDG and TDGO in urine existed mainly in free form, the levels of glucuronide and of sulfate conjugates of TDG or TDGO were very low, and most hydrolysis metabolites were present in the oxidized form (TDGO). The study indicates that the abnormal increase of TDG and TDGO excretion levels can be used as a diagnostic indicator and establishes a reference time-window for retrospective analysis and

  4. Simple and accurate measurement of carbamazepine in surface water by use of porous membrane-protected micro-solid-phase extraction coupled with isotope dilution mass spectrometry.

    PubMed

    Teo, Hui Ling; Wong, Lingkai; Liu, Qinde; Teo, Tang Lin; Lee, Tong Kooi; Lee, Hian Kee

    2016-03-17

    To achieve fast and accurate analysis of carbamazepine in surface water, we developed a novel porous membrane-protected micro-solid-phase extraction (μ-SPE) method, followed by liquid chromatography-isotope dilution tandem mass spectrometry (LC-IDMS/MS) analysis. The μ-SPE device (∼0.8 × 1 cm) was fabricated by heat-sealing edges of a polypropylene membrane sheet to devise a bag enclosing the sorbent. The analytes (both carbamazepine and isotope-labelled carbamazepine) were first extracted by μ-SPE device in the sample (10 mL) via agitation, then desorbed in an organic solvent (1 mL) via ultrasonication. Several parameters such as organic solvent for pre-conditioning of μ-SPE device, amount of sorbent, adsorption time, and desorption solvent and time were investigated to optimize the μ-SPE efficiency. The optimized method has limits of detection and quantitation estimated to be 0.5 ng L(-1) and 1.6 ng L(-1), respectively. Surface water samples spiked with different amounts of carbamazepine (close to 20, 500, and 1600 ng L(-1), respectively) were analysed for the validation of method precision and accuracy. Good precision was obtained as demonstrated by relative standard deviations of 0.7% for the samples with concentrations of 500 and 1600 ng kg(-1), and 5.8% for the sample with concentration of 20 ng kg(-1). Good accuracy was also demonstrated by the relative recoveries in the range of 96.7%-103.5% for all samples with uncertainties of 1.1%-5.4%. Owing to the same chemical properties of carbamazepine and isotope-labelled carbamazepine, the isotope ratio in the μ-SPE procedure was accurately controlled. The use of μ-SPE coupled with IDMS analysis significantly facilitated the fast and accurate measurement of carbamazepine in surface water.

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

    PubMed

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

    2002-08-01

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

  6. Discovery and microassay of a nitrite-dependent carbonic anhydrase activity by stable-isotope dilution gas chromatography-mass spectrometry.

    PubMed

    Zinke, Maximilian; Hanff, Erik; Böhmer, Anke; Supuran, Claudiu T; Tsikas, Dimitrios

    2016-01-01

    The intrinsic activity of carbonic anhydrase (CA) is the hydration of CO2 to carbonic acid and its dehydration to CO2. CA may also function as esterase and phosphatase. Recently, we demonstrated that renal CA is mainly responsible for the reabsorption of nitrite (NO2(-)) which is the most abundant reservoir of the biologically highly potent nitric oxide (NO). By means of a stable-isotope dilution GC-MS method, we discovered a novel CA activity which strictly depends upon nitrite. We found that bovine erythrocytic CAII (beCAII) catalyses the incorporation of (18)O from H2 (18)O into nitrite at pH 7.4. After derivatization with pentafluorobenzyl bromide, gas chromatographic separation and mass spectrometric analysis, we detected ions at m/z 48 for singly (18)O-labelled nitrite ((16)O=N-(18)O(-)/(18)O=N-(16)O(-)) and at m/z 50 for doubly (18)O-labelled nitrite ((18)O=N-(18)O(-)) in addition to m/z 46 for unlabelled nitrite. Using (15)N-labelled nitrite ((15)NO2 (-), m/z 47) as an internal standard and selected-ion monitoring of m/z 46, m/z 48, m/z 50 and m/z 47, we developed a GC-MS microassay for the quantitative determination of the nitrite-dependent beCAII activity. The CA inhibitors acetazolamide and FC5 207A did not alter beCAII-catalysed formation of singly and doubly (18)O-labelled nitrite. Cysteine and the experimental CA inhibitor DIDS (a diisothiocyanate) increased several fold the beCAII-catalysed formation of the (18)O-labelled nitrite species. Cysteine, acetazolamide, FC5 207A, and DIDS by themselves had no effect on the incorporation of (18)O from H2 (18)O into nitrite. We conclude that erythrocytic CA possesses a nitrite-dependent activity which can only be detected when nitrite is used as the substrate and the reaction is performed in buffers of neutral pH values prepared in H2 (18)O. This novel CA activity, i.e., the nitrous acid anhydrase activity, represents a bioactivation of nitrite and may have both beneficial (via S-nitrosylation and subsequent

  7. 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

  8. 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.

  9. Total-reflection X-ray fluorescence — a tool to obtain information about different air masses and air pollution

    NASA Astrophysics Data System (ADS)

    Schmeling, Martina

    2001-11-01

    Atmospheric aerosols are solid particles dissolved in air and change their chemical composition frequently depending on various parameters. In order to identify regional air circulation atmospheric aerosol filter samples were taken at Loyola University Chicago's Lake Shore Campus during the months of July and August 2000 with sampling times ranging between 1 and 2 h. The samples were digested in a microwave oven and analyzed by total-reflection X-ray fluorescence (TXRF) spectrometry. One diurnal variation comprising five consecutive sampling events was selected and discussed as well as 4 days experiencing different meteorology were compared to exemplify the variation in trace elemental concentration according to air mass movements and highlight the capability of total-reflection X-ray fluorescence analysis. It was found that due to changes in meteorological conditions particularly wind direction and wind speed, trace elemental compositions varied rapidly and could be used to distinguish between 'Lake Michigan air' and 'metropolitan Chicago air' on such short-term time scale like one hour. Back trajectory analysis was applied to support and corroborate the results. The outcome of this study clearly shows that total-reflection X-ray fluorescence is an optimal tool for analysis of atmospheric aerosols.

  10. 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.

  11. Technical note: Air compared to nitrogen as nebulizing and drying gases for electrospray ionization mass spectrometry.

    PubMed

    Mielczarek, P; Silberring, J; Smoluch, M

    2016-01-01

    In the present study we tested the application of compressed air instead of pure nitrogen as the nebulizing and drying gas, and its influence on the quality of electrospray ionization (ESI) mass spectra. The intensities of the signals corresponding to protonated molecules were significantly (twice) higher when air was used. Inspection of signal-to-noise (S/N) ratios revealed that, in both cases, sensitivity was comparable. A higher ion abundance after the application of compressed air was followed by a higher background. Another potential risk of using air in the ESI source is the possibility for sample oxidation due to the presence of oxygen. To test this, we selected five easily oxidizing compounds to verify their susceptibility to oxidation. In particular, the presence of methionine was of interest. For all the compounds studied, no oxidation was observed. Amodiaquine oxidizes spontaneously in water solutions and its oxidized form can be detected a few hours after preparation. Direct comparison of the spectra where nitrogen was used with the corresponding spectra obtained when air was applied did not show significant differences. The only distinction was slightly different patterns of adducts when air was used. The difference concerns acetonitrile, which forms higher signals when air is the nebulizing gas. It is also important that the replacement of nitrogen with air does not affect quantitative data. The prepared calibration curves also visualize an intensity twice as high (independent of concentration within tested range) of the signal where air was applied. We have used our system continuously for three months with air as the nebulizing and drying gas and have not noticed any unexpected signal deterioration caused by additional source contamination from the air. Moreover, compressed air is much cheaper and easily available using oil-free compressors or pumps.

  12. Remote mass spectrometric sampling of electrospray- and desorption electrospray-generated ions using an air ejector.

    PubMed

    Dixon, R Brent; Bereman, Michael S; Muddiman, David C; Hawkridge, Adam M

    2007-10-01

    A commercial air ejector was coupled to an electrospray ionization linear ion trap mass spectrometer (LTQ) to transport remotely generated ions from both electrospray (ESI) and desorption electrospray ionization (DESI) sources. We demonstrate the remote analysis of a series of analyte ions that range from small molecules and polymers to polypeptides using the AE-LTQ interface. The details of the ESI-AE-LTQ and DESI-AE-LTQ experimental configurations are described and preliminary mass spectrometric data are presented.

  13. Dilutions Made Easy.

    ERIC Educational Resources Information Center

    Kamin, Lawrence

    1996-01-01

    Presents problems appropriate for high school and college students that highlight dilution methods. Promotes an understanding of dilution methods in order to prevent the unnecessary waste of chemicals and glassware in biology laboratories. (JRH)

  14. 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.

  15. Detection of Hydrazine in Air Using Electron Transfer Ionization Mass Spectrometry.

    DTIC Science & Technology

    1981-02-15

    is in tI qualitative agreement with American Petroleum Institute (API) 6 data. Unequivocal identification and monitoring of N2H4 fuels at the launch...N2H4 in air. At even lower concentrations, the delay time 61ndex of Mass Spectral Data, American Petroleum Institute , Research Project 44, NBS

  16. Toward a better understanding of the impact of mass transit air pollutants on human health

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Modern mass transit systems, based on roads, rail, water, and air, generate toxic airborne pollutants throughout the developed world. This has become one of the leading concerns about the use of modern transportation, particularly in densely-populated urban areas where their use is enormous and inc...

  17. Low-CCN concentration air masses over the eastern North Atlantic: Seasonality, meteorology, and drivers

    NASA Astrophysics Data System (ADS)

    Wood, Robert; Stemmler, Jayson D.; Rémillard, Jasmine; Jefferson, Anne

    2017-01-01

    A 20 month cloud condensation nucleus concentration (NCCN) data set from Graciosa Island (39°N, 28°W) in the remote North Atlantic is used to characterize air masses with low cloud condensation nuclei (CCN) concentrations. Low-CCN events are defined as 6 h periods with mean NCCN<20 cm-3 (0.1% supersaturation). A total of 47 low-CCN events are identified. Surface, satellite, and reanalysis data are used to explore the meteorological and cloud context for low-CCN air masses. Low-CCN events occur in all seasons, but their frequency was 3 times higher in December-May than during June-November. Composites show that many of the low-CCN events had a common meteorological basis that involves southerly low-level flow and rather low wind speeds at Graciosa. Anomalously low pressure is situated to the west of Graciosa during these events, but back trajectories and lagged SLP composites indicate that low-CCN air masses often originate as cold air outbreaks to the north and west of Graciosa. Low-CCN events were associated with low cloud droplet concentrations (Nd) at Graciosa, but liquid water path (LWP) during low-CCN events was not systematically different from that at other times. Satellite Nd and LWP estimates from MODIS collocated with Lagrangian back trajectories show systematically lower Nd and higher LWP several days prior to arrival at Graciosa, consistent with the hypothesis that observed low-CCN air masses are often formed by coalescence scavenging in thick warm clouds, often in cold air outbreaks.

  18. Low Fractal Dimension Cluster-Dilute Soot Aggregates from a Premixed Flame

    NASA Astrophysics Data System (ADS)

    Chakrabarty, Rajan K.; Moosmüller, Hans; Arnott, W. Patrick; Garro, Mark A.; Tian, Guoxun; Slowik, Jay G.; Cross, Eben S.; Han, Jeong-Ho; Davidovits, Paul; Onasch, Timothy B.; Worsnop, Douglas R.

    2009-06-01

    Using a novel morphology segregation technique, we observed minority populations (≈3%) of submicron-sized, cluster-dilute fractal-like aggregates, formed in the soot-formation window (fuel-to-air equivalence ratio of 2.0-3.5) of a premixed flame, to have mass fractal dimensions between 1.2 and 1.51. Our observations disagree with previous observations of a universal mass fractal dimension of ≈1.8 for fractal-like aerosol aggregates formed in the dilute-limit via three-dimensional diffusion-limited cluster aggregation processes. A hypothesis is presented to explain this observation. Subject to verification of this hypothesis, it may be possible to control the fractal dimension and associated properties of aggregates in the cluster-dilute limit through application of a static electric field during the aggregation process.

  19. 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.

  20. 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.

  1. 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

  2. Certification of butyltins and phenyltins in marine sediment certified reference material by species-specific isotope-dilution mass spectrometric analysis using synthesized 118Sn-enriched organotin compounds

    PubMed Central

    Takatsu, Akiko; Watanabe, Takuro; Aoyagi, Yoshie; Yarita, Takashi; Okamoto, Kensaku; Chiba, Koichi

    2006-01-01

    A new marine sediment certified reference material, NMIJ CRM 7306-a, for butyltin and phenyltin analysis has been prepared and certified by the National Metrological Institute of Japan at the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Candidate sediment material was collected at a bay near industrial activity in Japan. After air-drying, sieving, and mixing the material was sterilized with γ-ray irradiation. The material was re-mixed and packaged into 250 glass bottles (15 g each) and these were stored in a freezer at −30 °C. Certification was performed by use of three different types of species-specific isotope-dilution mass spectrometry (SSID–MS)—SSID–GC–ICP–MS, SSID–GC–MS, and SSID–LC–ICP–MS, with 118Sn-enriched organotin compounds synthesized from 118Sn-enriched metal used as a spike. The 118Sn-enriched mono-butyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were synthesized as a mixture whereas the 118Sn-enriched di-phenyltin (DPhT) and triphenyltin (TPhT) were synthesized individually. Four different extraction methods, mechanical shaking, ultrasonic, microwave-assisted, and pressurized liquid extraction, were adopted to avoid possible analytical bias caused by non-quantitative extraction and degradation or inter-conversion of analytes in sample preparations. Tropolone was used as chelating agent in all the extraction methods. Certified values are given for TBT 44±3 μg kg−1 as Sn, DBT 51 ± 2 μg kg−1 as Sn, MBT 67 ± 3 μg kg−1 as Sn, TPhT 6.9 ± 1.2 μg kg−1 as Sn, and DPhT 3.4 ± 1.2 μg kg−1 as Sn. These levels are lower than in other sediment CRMs currently available for analysis of organotin compounds. PMID:16874473

  3. Volatile release from aqueous solutions under dynamic headspace dilution conditions.

    PubMed

    Marin, M; Baek, I; Taylor, A J

    1999-11-01

    Static equilibrium was established between the gas phase (headspace) and an unstirred aqueous phase in a sealed vessel. The headspace was then diluted with air to mimic the situation when a container of food is opened and the volatiles are diluted by the surrounding air. Because this first volatile signal can influence overall flavor perception, the parameters controlling volatile release under these conditions are of interest. A mechanistic model was developed and validated experimentally. Release of compounds depended on the air-water partition coefficient (K(aw)) and the mass transport in both phases. For compounds with K(aw) values <10(-)(3), K(aw) was the factor determining release rate. When K(aw) was >10(-)(3), mass transport in the gas phase became significant and the Reynolds number played a role. Because release from packaged foods occurs at low Reynolds numbers, whereas most experiments are conducted at medium to high Reynolds numbers, the experimentally defined profile may not reflect the real situation.

  4. 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.

  5. 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.

  6. 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

  7. Source areas and trajectories of nucleating air masses within and near the Carpathian Basin

    NASA Astrophysics Data System (ADS)

    Németh, Z.; Salma, I.

    2014-04-01

    Particle number size distributions were measured by differential mobility particle sizer in the diameter range of 6-1000 nm in the near-city background and city centre of Budapest continuously for two years. The city is situated in the middle part of the Carpathian Basin, which is a topographically discrete unit in the southeast Central Europe. Yearly mean nucleation frequencies and uncertainties for the near-city background and city centre were (28+6/-4) % and (27+9/-4) %, respectively. Total numbers of days with continuous and uninterrupted growth process were 43 and 31, respectively. These events and their properties were utilised to investigate if there are any specific tracks and/or separable source regions for the nucleating air masses within or near the basin. Local wind speed and direction data indicated that there seem to be differences between the nucleation and growth intervals and non-nucleation days. For further analysis, backward trajectories were generated by a simple air parcel trajectory model. Start and end time parameters of the nucleation, and end time parameter of the particle growth were derived by a standardized procedure based on examining the channel contents of the contour plots. These parameters were used to specify a segment on each air mass trajectory that is associated with the track of the nucleating air mass. The results indicated that the nucleation events happened in the continental boundary layer mostly within the Carpathian Basin but the most distant trajectories originated outside of the basin. The tracks of the nucleating air masses were predominantly associated with NW and SE geographical fields, while the source areas that could be separated were frequently situated in the NW and NE quarters. Many of them were within or close to large forested territories. The results also emphasize that the new particle formation and growth phenomenon that occurs in the region influences larger territories than the Carpathian Basin.

  8. Seasonal air and water mass redistribution effects on LAGEOS and Starlette

    NASA Technical Reports Server (NTRS)

    Gutierrez, Roberto; Wilson, Clark R.

    1987-01-01

    Zonal geopotential coefficients have been computed from average seasonal variations in global air and water mass distribution. These coefficients are used to predict the seasonal variations of LAGEOS' and Starlette's orbital node, the node residual, and the seasonal variation in the 3rd degree zonal coefficient for Starlette. A comparison of these predictions with the observed values indicates that air pressure and, to a lesser extent, water storage may be responsible for a large portion of the currently unmodeled variation in the earth's gravity field.

  9. Improving Hydrological Models by Applying Air Mass Boundary Identification in a Precipitation Phase Determination Scheme

    NASA Astrophysics Data System (ADS)

    Feiccabrino, James; Lundberg, Angela; Sandström, Nils

    2013-04-01

    Many hydrological models determine precipitation phase using surface weather station data. However, there are a declining number of augmented weather stations reporting manually observed precipitation phases, and a large number of automated observing systems (AOS) which do not report precipitation phase. Automated precipitation phase determination suffers from low accuracy in the precipitation phase transition zone (PPTZ), i.e. temperature range -1° C to 5° C where rain, snow and mixed precipitation is possible. Therefore, it is valuable to revisit surface based precipitation phase determination schemes (PPDS) while manual verification is still widely available. Hydrological and meteorological approaches to PPDS are vastly different. Most hydrological models apply surface meteorological data into one of two main PPDS approaches. The first is a single rain/snow threshold temperature (TRS), the second uses a formula to describe how mixed precipitation phase changes between the threshold temperatures TS (below this temperature all precipitation is considered snow) and TR (above this temperature all precipitation is considered rain). However, both approaches ignore the effect of lower tropospheric conditions on surface precipitation phase. An alternative could be to apply a meteorological approach in a hydrological model. Many meteorological approaches rely on weather balloon data to determine initial precipitation phase, and latent heat transfer for the melting or freezing of precipitation falling through the lower troposphere. These approaches can improve hydrological PPDS, but would require additional input data. Therefore, it would be beneficial to link expected lower tropospheric conditions to AOS data already used by the model. In a single air mass, rising air can be assumed to cool at a steady rate due to a decrease in atmospheric pressure. When two air masses meet, warm air is forced to ascend the more dense cold air. This causes a thin sharp warming (frontal

  10. 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 ...

  11. Mixing of stratospheric and tropospheric air-masses detected with CRISTA-NF during AMMA

    NASA Astrophysics Data System (ADS)

    Weigel, K.; Guenther, G.; Hoffmann, L.; Konopka, P.; Riese, M.

    2009-04-01

    CRISTA-NF (CRyogenic Infrared Spectrometers and Telescopes for the Atmosphere - New Frontiers) is an infrared limb sounding instrument installed onbord the high-flying research aircraft M55-Geophysica and took part in the AMMA-SCOUT measurement campaign in Summer 2006. During the test flight on 29th of July 2006, CRISTA-NF detected a sharp boundary between ozone rich air over northernItaly and ozone poor air over southern Italy and the Mediterranean Sea. The structure is also clearly visible in the HNO3 distribution. The air mass boundary extends from about 10km altitude to the thermal tropopause at about 16km altitude with indication for mixing in the lower part of this altitude range. This is supported by enhanced values of PAN and water vapour found. The observed structure is also visible in the CLaMS (Chemical Lagrangian Model of the Stratosphere) ozone distribution but hardly resolved in ECMWF forecast data. Backward trajectories show that the ozone rich air is originated westwards, between 40 and 60oN while the ozone poor air is coming from the south-east, at about 0-20oN and has a younger age of air. In the presentation details of the CRISTA-NF measurements and retrieval procedures as well as the origin of the trace gas structures will be discussed.

  12. Microfluidic serial dilution ladder.

    PubMed

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

    2014-01-07

    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).

  13. 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.

  14. 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.; Sellegri, K.; Burkhart, J. F.; Stohl, A.; Gomes, L.; Quennehen, B.; Roberts, G.; Weigel, R.; Roger, J. C.; Villani, P.; Pichon, J. M.; Bourrianne, T.; Laj, P.

    2012-04-01

    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 in order to study aerosol physical, chemical and optical properties, as well as cloud microphysics. During the campaign, continental air masses from Eastern and Western Europe were encountered, along with polar and Scandinavian air masses. 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 which allows for a qualitative evaluation of emission influence on the respective air parcel. In the polluted boundary layer (BL), typical concentrations of particles with diameters larger than 10 nm (N10) are of the order of 5000-6000 cm-3, whereas N10 concentrations of clean air masses were lower than 1300 cm-3. The detection of the largest particle number concentrations occurred in air masses coming from Polar and Scandinavian regions for which an elevated number of nucleation mode (25-28 nm) particles was observed and attributed to new particle formation over open sea. In the free troposphere (FT), typical observed N10 are of the order of 900 cm-3 in polluted air masses and 400-600 cm-3 in clean air masses, respectively. In both layers, the chemical composition of submicron aerosol particles is dominated by organic matter and nitrate in polluted air masses, while, sulphate and ammonium followed by organics dominate the submicron aerosols in clean air masses. The highest CCN/CN ratios were observed within the polar air masses while the CCN concentration values are the highest within the polluted air masses. Within the five air mass sectors defined and the two layers (BL and FT), observations have been distinguished into anticyclonic (first half of May 2008) and cyclonic

  15. Enhancement of acidic gases in biomass burning impacted air masses over Canada

    NASA Technical Reports Server (NTRS)

    Lefer, B. L.; Talbot, R. W.; Harriss, R. C.; Bradshaw, J. D.; Sandholm, S. T.; Olson, J. O.; Sachse, G. W.; Collins, J.; Shipham, M. A.; Blake, D. R.

    1994-01-01

    Biomass-burning impacted air masses sampled over central and eastern Canada during the summer of 1990 as part of ABLE 3B contained enhanced mixing ratios of gaseous HNO3, HCOOH, CH3COOH, and what appears to be (COOH)2. These aircraft-based samples were collected from a variety of fresh burning plumes and more aged haze layers from different source regions. Values of the enhancement factor, delta X/delta CO, where X represents an acidic gas, for combustion-impacted air masses sampled both near and farther away from the fires, were relatively uniform. However, comparison of carboxylic acid emission ratios measured in laboratory fires to field plume enhancement factors indicates significant in-plume production of HCOOH. Biomass-burning appears to be an important source of HNO3, HCOOH, and CH3COOH to the troposphere over subarctic Canada.

  16. Ozone and Trace Gas Trends in the UK and Links to Changing Air Mass Pathways

    NASA Astrophysics Data System (ADS)

    Fleming, Z.; Monks, P. S.; Reeves, C.; Bohnenstengel, S.

    2014-12-01

    Trace gas measurements from UK measurement sites on the North Sea coast and in central London reveal a complicated relationship between NO2, CO, hydrocarbons and ozone. Due to the location of the sites, they receive air masses from the UK, Europe, the North sea, Scandinavia and the Arctic and Atlantic Seas and any seasonality is hard to discern. The transport pathway of air masses that can change on an hourly timescale clearly influences the trace gas levels. Investigations into how the transport pathways have changed over the years, using the NAME dispersion model try to elucidate whether it is the 'where' (transport pathway) or the 'what' (trace gas emissions) that is leading to the ozone trends recorded over the past few years.

  17. Toward a better understanding of the impact of mass transit air pollutants on human health.

    PubMed

    Kim, Ki-Hyun; Kumar, Pawan; Szulejko, Jan E; Adelodun, Adedeji A; Junaid, Muhammad Faisal; Uchimiya, Minori; Chambers, Scott

    2017-05-01

    Globally, modern mass transport systems whether by road, rail, water, or air generate airborne pollutants in both developing and developed nations. Air pollution is the primary human health concern originating from modern transportation, particularly in densely-populated urban areas. This review will specifically focus on the origin and the health impacts of carbonaceous traffic-related air pollutants (TRAP), including particulate matter (PM), volatile organic compounds (VOCs), and elemental carbon (EC). We conclude that the greatest current challenge regarding urban TRAP is understanding and evaluating the human health impacts well enough to set appropriate pollution control measures. Furthermore, we provide a detailed discussion regarding the effects of TRAP on local environments and pedestrian health in low and high traffic-density environments.

  18. 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.

  19. 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).

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. Influence of air mass origin on aerosol properties at a remote Michigan forest site

    NASA Astrophysics Data System (ADS)

    VanReken, T. M.; Mwaniki, G. R.; Wallace, H. W.; Pressley, S. N.; Erickson, M. H.; Jobson, B. T.; Lamb, B. K.

    2015-04-01

    The northern Great Lakes region of North America is a large, relatively pristine area. To date, there has only been limited study of the atmospheric aerosol in this region. During summer 2009, a detailed characterization of the atmospheric aerosol was conducted at the University of Michigan Biological Station (UMBS) as part of the Community Atmosphere-Biosphere Interactions Experiment (CABINEX). Measurements included particle size distribution, water-soluble composition, and CCN activity. Aerosol properties were strongly dependent on the origin of the air masses reaching the site. For ∼60% of the study period, air was transported from sparsely populated regions to the northwest. During these times aerosol loadings were low, with mean number and volume concentrations of 1630 cm-3 and 1.91 μm3 cm-3, respectively. The aerosol during clean periods was dominated by organics, and exhibited low hygroscopicities (mean κ = 0.18 at s = 0.3%). When air was from more populated regions to the east and south (∼29% of the time), aerosol properties reflected a stronger anthropogenic influence, with 85% greater particle number concentrations, 2.5 times greater aerosol volume, six times more sulfate mass, and increased hygroscopicity (mean k = 0.24 at s = 0.3%). These trends are have the potential to influence forest-atmosphere interactions and should be targeted for future study.

  9. 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).

  10. 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.

  11. Calibration of Dissolved Noble Gas Mass Spectrometric Measurements by an Air-Water Equilibration System

    NASA Astrophysics Data System (ADS)

    Hillegonds, Darren; Matsumoto, Takuya; Jaklitsch, Manfred; Han, Liang-Feng; Klaus, Philipp; Wassenaar, Leonard; Aggarwal, Pradeep

    2013-04-01

    Precise measurements by mass spectrometry of dissolved noble gases (He, Ar, Ne, Kr, Xe) in water samples require careful calibration against laboratory standards with known concentrations. Currently, air pipettes are used for day-to-day calibrations, making estimation of overall analytical uncertainties for dissolved noble gas measurements in water difficult. Air equilibrated water (AEW) is often used as a matrix-equivalent laboratory standard for dissolved gases in groundwater, because of the well-known and constant fractions of noble gases in the atmosphere. AEW standards, however, are only useful if the temperature and pressure of the gas-water equilibrium can be controlled and measured precisely (i.e., to better than 0.5%); contamination and partial sample degassing must also be prevented during sampling. Here we present the details of a new custom air-water equilibration system which consists of an insulated 600 liter tank filled with deionized water, held isothermally at a precise target temperature (<0.05 °C) through the use of a heat exchanger. The temperature and total dissolved gas of the water in the tank are monitored continually, as are atmospheric pressure and air temperature in the laboratory. Different noble gas concentration standards can be reliably produced by accurately controlling the water temperature of the equilibration system. Equilibration characteristics and reproducibility of this system for production of copper tubes containing known amounts of noble gases will be presented.

  12. Determination of the effect of transfer between vacuum and air on mass standards of platinum-iridium and stainless steel

    NASA Astrophysics Data System (ADS)

    Davidson, Stuart

    2010-08-01

    This paper reports work undertaken to assess the change in the mass values of stainless steel and platinum-iridium weights transferred between air and vacuum and to determine the repeatability of this change. Sets of kilogram transfer standards, manufactured from stainless steel and platinum-iridium and with different surface areas, were used to determine the effect of transfer between air and vacuum on the values of the mass standards. The SI unit of mass is the only unit of the seven base SI quantities which is still defined in terms of an artefact rather than by relation to a fundamental physical constant. Work is underway to identify a means of deriving the SI unit of mass from fundamental constants and at present the two principal approaches are the International Avogadro Coordination and the watt balance projects. Both of these approaches involve realizing a kilogram in vacuum and therefore the traceability from a kilogram realized in vacuum to mass standards in air is crucial to the effective dissemination of the mass scale. The work reported here characterizes the changes in mass values of standards on transfer between air and vacuum and thus will enable traceability to be established for an in-air mass scale based on a definition of the unit in vacuum.

  13. Effect of the relative optical air mass and the clearness index on solar erythemal UV irradiance.

    PubMed

    Moreno, J C; Serrano, M A; Cañada, J; Gurrea, G; Utrillas, M P

    2014-09-05

    This paper analyses the effects of the clearness index (Kt) and the relative optical air mass (mr) on erythemal UV irradiance (UVER). The UVER measurements were made in Valencia (Spain) from 6:00 am to 6:00 pm between June 2003 and December 2012 and (140,000 data points). Firstly, two models were used to calculate values for the erythemal ultraviolet irradiance clearness index (KtUVER) as a function of the global irradiance clearness index (Kt). Secondly, a potential regression model to measure the KtUVER as a function of the relative optical air mass was studied. The coefficients of this regression were evaluated for clear and cloudy days, as well as for days with high and low ozone levels. Thirdly, an analysis was made of the relationship between the two effects in the experimental database, with it being found that the highest degree of agreement, or the joint highest frequencies, are located in the optical mass range mr∈[1.0, 1.2] and the clearness index range of Kt∈[0.8, 1.0]. This is useful for establishing the ranges of parameters where models are more efficient. Simple equations have been tested that can provide additional information for the engineering projects concerning thermal installations. Fourthly, a high dispersion of radiation data was observed for intermediate values of the clearness for UV and UVER.

  14. Visual Steering and Verification of Mass Spectrometry Data Factorization in Air Quality Research.

    PubMed

    Engel, D; Greff, K; Garth, C; Bein, K; Wexler, A; Hamann, B; Hagen, H

    2012-12-01

    The study of aerosol composition for air quality research involves the analysis of high-dimensional single particle mass spectrometry data. We describe, apply, and evaluate a novel interactive visual framework for dimensionality reduction of such data. Our framework is based on non-negative matrix factorization with specifically defined regularization terms that aid in resolving mass spectrum ambiguity. Thereby, visualization assumes a key role in providing insight into and allowing to actively control a heretofore elusive data processing step, and thus enabling rapid analysis meaningful to domain scientists. In extending existing black box schemes, we explore design choices for visualizing, interacting with, and steering the factorization process to produce physically meaningful results. A domain-expert evaluation of our system performed by the air quality research experts involved in this effort has shown that our method and prototype admits the finding of unambiguous and physically correct lower-dimensional basis transformations of mass spectrometry data at significantly increased speed and a higher degree of ease.

  15. 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).

  16. Air-mass flux measurement system using Doppler-shifted filtered Rayleigh scattering

    NASA Technical Reports Server (NTRS)

    Shirley, John A.; Winter, Michael

    1993-01-01

    An optical system has been investigated to measure mass flux distributions in the inlet of a high speed air-breathing propulsion system. Rayleigh scattered light from air is proportional to the number density of molecules and hence can be used to ascertain the gas density in a calibrated system. Velocity field measurements are achieved by spectrally filtering the elastically-scattered Doppler-shifted light with an absorbing molecular filter. A novel anamorphic optical collection system is used which allows optical rays from different scattering angles, that have different Doppler shifts, to be recorded separately. This is shown to obviate the need to tune the laser through the absorption to determine velocities, while retaining the ability to make spatially-resolved measurements along a line. By properly selecting the laser tuning and filter parameters, simultaneous density measurements can be made. These properties are discussed in the paper and experiments demonstrating the velocimetry capability are described.

  17. Ozone Modulation/Membrane Introduction Mass Spectrometry for Analysis of Hydrocarbon Pollutants in Air

    NASA Astrophysics Data System (ADS)

    Atkinson, D. B.

    2001-12-01

    Modulation of volatile hydrocarbons in two-component mixtures is demonstrated using an ozonolysis pretreatment with membrane introduction mass spectrometry (MIMS). The MIMS technique allows selective introduction of volatile and semivolatile analytes into a mass spectrometer via processes known collectively as pervaporation [Kotiaho and Cooks, 1992]. A semipermeable polymer membrane acts as an interface between the sample (vapor or solution) and the vacuum of the mass spectrometer. This technique has been demonstrated to allow for sensitive analysis of hydrocarbons and other non-polar volatile organic compounds (VOC`s) in air samples[Cisper et al., 1995] . The methodology has the advantages of no sample pretreatment and short analysis time, which are promising for online monitoring applications but the chief disadvantage of lack of a separation step for the different analytes in a mixture. Several approaches have been investigated to overcome this problem including use of selective chemical ionization [Bier and Cooks, 1987] and multivariate calibration techniques[Ketola et al., 1999] . A new approach is reported for the quantitative measurement of VOCs in complex matrices. The method seeks to reduce the complexity of mass spectra observed in hydrocarbon mixture analysis by selective pretreatment of the analyte mixture. In the current investigation, the rapid reaction of ozone with alkenes is used, producing oxygenated compounds which are suppressed by the MIMS system. This has the effect of removing signals due to unsaturated analytes from the compound mass spectra, and comparison of the spectra before and after the ozone treatment reveals the nature of the parent compounds. In preliminary investigations, ozone reacted completely with cyclohexene from a mixture of cylohexene and cyclohexane, and with β -pinene from a mixture of toluene and β -pinene, suppressing the ion signals from the olefins. A slight attenuation of the cyclohexane and toluene in those

  18. 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.

  19. Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography-high resolution mass spectrometry.

    PubMed

    Takasuga, Takumi; Senthilkumar, Kurunthachalam; Matsumura, Tohru; Shiozaki, Ken; Sakai, Shin-ichi

    2006-01-01

    Special polychlorinated biphenyls (PCBs) standards (native and isotope labeled) were analyzed by isotope dilution method using HRGC-HRMS. Multiple analysis of special PCBs standards by three different laboratories produced the relative response factors (RRFs) and relative standard deviations (RSDs %) was in the average of 0.979 and 3.86, respectively. Additionally, inter-laboratory analysis of various forms of transformer oil revealed the PCBs concentrations were in the following order; PCBs fortified transformer oil (940-1300 ng/g)>PCB polluted transformer oil (490-680 ng/g)>chemically degraded-transformer oil (480-490 ng/g) and PCBs free oil (ND-17 ng/g). Chemical degradation resulted in an order of magnitude decrease in the PCB concentrations. Specifically, higher chlorinated PCBs degraded into lower chlorinated PCBs. Also, composition of PCBs have been determined in PCB formulations from Japan (Kanechlor), Germany (Clophen), USA (Aroclor), Russia (Sovol) and Poland (Chlorofen). Major PCBs (24-PCB congeners) contributed 54-67%, 55-68%, 16-69%, 71% and 72% in Kanechlor, Clophen, Aroclor, Sovol and Chlorofen, respectively to total PCBs. The homologue pattern of Kanechlor, Aroclor and Clophen in technical fromulation was similar (e.g., Kanechlor-300 resembled to those of Clophen A-30 and Aroclor-1242). Furthermore, congener-specific distributions of major PCBs/dioxin-like PCBs and toxic equivalency quantities (TEQ) were calculated. Based on our tentative assumption calculations, cumulative production of five different technical PCB formulations, WHO-TEQ emission was estimated to be approximately 16.05 tons.

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

    PubMed

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

    2015-12-01

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

  1. VOC Composition of Air Masses Transported from Asia to the U.S. West Coast

    NASA Astrophysics Data System (ADS)

    de Gouw, J.; Warneke, C.; Kuster, B.; Parrish, D.; Holloway, J.; Huebler, G.; Fehsenfeld, F.

    2002-12-01

    Airborne measurements of volatile organic compounds (VOCs) were performed using a proton-transfer-reaction mass spectrometer (PTR-MS) operated onboard a NOAA WP-3 aircraft during the Intercontinental Transport and Chemical Transformation (ITCT) experiment in 2002. Enhancements of acetone (CH3COCH3), methanol (CH3OH), acetonitrile (CH3CN) and in some cases benzene were observed in air masses that were impacted by outflow from Asia. The enhancement ratios with respect to carbon monoxide are compared to emission factors for fossil fuel combustion and biomass burning, which gives some insight into the sources responsible for the pollution. The observed mixing ratios for acetone, methanol and in particular acetonitrile were generally reduced in the marine boundary layer, suggesting the presence of an ocean uptake sink. The ocean uptake of acetonitrile was found to be particularly efficient in a zone with upwelling water off of the U.S. west coast. Reduced mixing ratios of acetone and methanol were observed in a stratospheric intrusion. This observation gives some information about the lifetime of these VOCs in the stratosphere. Enhanced concentrations of aromatic hydrocarbons were observed in air masses that were impacted by urban sources in California. The ratio between the concentrations of benzene, toluene and higher aromatics indicated the degree of photochemical oxidation. PTR-MS only gives information about the mass of the ions produced by proton-transfer reactions between H3O+ and VOCs in the instrument. The identification of VOCs was confirmed by coupling a gas-chromatographic (GC) column to the instrument and post-flight GC-PTR-MS analyses of canister samples collected during the flights.

  2. Infiltration as Ventilation: Weather-Induced Dilution

    SciTech Connect

    Sherman, Max H.; Turner, William J.N.; Walker, Iain S.

    2011-06-01

    The purpose of outdoor air ventilation is to dilute or remove indoor contaminants to which occupants are exposed. It can be provided by mechanical or natural means. In most homes, especially older homes, weather-driven infiltration provides the dominant fraction of the total ventilation. As we seek to provide good indoor air quality at minimum energy cost, it is important to neither over-ventilate nor under-ventilate. Thus, it becomes critically important to evaluate correctly the contribution infiltration makes to the total outdoor air ventilation rate. Because weather-driven infiltration is dependent on building air leakage and weather-induced pressure differences, a given amount of air leakage will provide different amounts of infiltration. Varying rates of infiltration will provide different levels of contaminant dilution and hence effective ventilation. This paper derives these interactions and then calculates the impact of weather-driven infiltration for different climates. A new “N-factor” is introduced to provide a convenient method for calculating the ventilation contribution of infiltration for over 1,000 locations across North America. The results of this work could be used in indoor air quality standards (specifically ASHRAE 62.2) to account for the contribution of weather-driven infiltration towards the dilution of indoor pollutants.

  3. Accumulation of intact sulfur mustard in adipose tissue and toxicokinetics by chemical conversion and isotope-dilution liquid chromatography-tandem mass spectrometry.

    PubMed

    Xu, Bin; Zong, Cheng; Zhang, Yajiao; Zhang, Tianhong; Wang, Xiaoying; Qi, Meiling; Wu, Jianfeng; Guo, Lei; Wang, Peng; Chen, Jia; Liu, Qin; Xu, Hua; Xie, Jianwei; Zhang, Zhenqing

    2017-02-01

    Sulfur mustard (SM) is a powerful vesicant and one of the most harmful chemical warfare agents. Although having been studied for a long time, it is still difficult to fully elucidate the mechanisms of SM poisoning, and there is no effective antidote or specific treatment for SM injury. The investigations on toxicokinetics and tissue distribution of SM will help to understand its toxicity and provide a theoretical basis for pretreatment and therapy of SM poisoning. But the metabolic trajectory or fate of intact SM in vivo remains unclear, and there are insufficient experimental data to elucidate, due to its high reactivity and difficulty in biomedical sample analysis. In this paper, a sensitive method for the detection and quantification of intact SM in blood or tissues using isotope-dilution LC-MS/MS coupled with chemical conversion was developed. By transforming highly reactive SM into stable derivative product, the real concentration of intact SM in biological samples was obtained accurately. The toxicokinetics and tissue distribution studies of intact SM in rats were successfully profiled by the novel method after intravenous (10 mg/kg) or cutaneous administration (1, 3 and 10 mg/kg). The SM level in blood with peak time at 30-60 min determined in cutaneous exposure experiment was found much higher than previously reported, and the mean residence time in blood extended to 1-1.5 h. A significant accumulation of intact SM was observed in adipose tissues, including the perirenal fat, epididymal fat, subcutaneous fat and brown fat, in which the concentrations of SM were at least 15 times greater than those in non-adipose tissues in cutaneous exposed rats. The recovery of SM in body fat was calculated as 3.3 % of bioavailable SM (the bioavailability after cutaneous exposure was evaluated as 16 %). Thus, the adipose tissue was important for SM distribution and toxicity, which may pioneer a new model for both the prevention and treatment of SM exposure.

  4. Candidate Reference Measurement Procedure for the Determination of (24R),25-Dihydroxyvitamin D3 in Human Serum Using Isotope-Dilution Liquid Chromatography-Tandem Mass Spectrometry.

    PubMed

    Tai, Susan S-C; Nelson, Michael A

    2015-08-04

    The two major forms of vitamin D, vitamin D3 and vitamin D2, are metabolized in the liver through hydroxylation to 25-hydroxyvitamin D species, and then further hydroxylated in the kidney to various dihydroxyvitamin D species. (24R),25-Dihydroxyvitamin D3 ((24R),25(OH)2D3) is a major catabolite of 25-hydroxyvitamin D metabolism and is an important vitamin D metabolite used as a catabolism marker and indicator of kidney disease. The National Institute of Standards and Technology has recently developed a reference measurement procedure for the determination of (24R),25(OH)2D3 in human serum using isotope-dilution LC-MS/MS. The (24R),25(OH)2D3 and added deuterated labeled internal standard (24R),25(OH)2D3-d6 were extracted from serum matrix using liquid-liquid extraction prior to LC-MS/MS analysis. Chromatographic separation was performed using a fused-core C18 column. Atmospheric pressure chemical ionization in the positive ion mode and multiple reaction monitoring were used for LC-MS/MS. The accuracy of the measurement of (24R),25(OH)2D3 was evaluated by recovery studies of measuring (24R),25(OH)2D3 in gravimetrically prepared spiked samples of human serum with known (24R),25(OH)2D3 levels. The recoveries of the added (24R),25(OH)2D3 averaged 99.0% (0.8% SD), and the extraction efficiencies averaged 95% (2% SD). Excellent repeatability was demonstrated with CVs of ∼1%. The limit of quantitation at a signal-to-noise ratio of ∼10 was 0.2 ng/g. Potential isomeric interferences from other endogenous species and from impurity components of the reference standard were investigated. LC baseline resolution of (24R),25(OH)2D3 from these isomers was achieved within 35 min. This method was used for value assignment of (24R),25(OH)2D3 in Standard Reference Materials of Vitamin D Metabolites in Human Serum, which can serve as an accuracy base for routine methods used in clinical laboratories.

  5. Air mass characterization during the DAURE field campaign by PTR-TOF

    NASA Astrophysics Data System (ADS)

    Metzger, Axel; Schallhart, Simon; Müller, Markus; Hansel, Armin

    2010-05-01

    Volatile organic compounds (VOCs) are emitted into the atmosphere from a wide variety of biogenic and anthropogenic sources. Although some of the sources are well characterized, many uncertainties remain about the fate of these compounds in the atmosphere and their role in organic aerosol formation. Here we present measurements using Proton Transfer Reaction Time-of-Flight (PTR-TOF) Mass Spectrometry during the DAURE field campaign ("Determination of the sources of atmospheric Aerosols in Urban and Rural Environments in the western Mediterranean") obtained during February and March 2009. Measurements were performed at a rural mountain site located in the Montseny Natural Park 40 km to the NNE of the city of Barcelona, and 25 km from the Mediterranean coast. Volatile organic compounds where identified and quantified using PTR-TOF with 1 minute time resolution. The instruments mass resolving power of 4000 - 5000 and a mass accuracy of 5 ppm allows for the unambiguous sum-formula identification of e.g. hydrocarbons (HCs) or oxygenated VOCs (OVOCs). The high time resolution allows separating out on site pollution events. Air masses impacted by biomass-burning, urban, marine and vegetation emissions are characterized using tracers like acetonitrile, aromatics, dimethyl sulfide or biogenic compounds (terpenoids) and the degree of photochemical processing is inferred from the data.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. The impact of air mass advection on aerosol optical properties over Gotland (Baltic Sea)

    NASA Astrophysics Data System (ADS)

    Zdun, Agnieszka; Rozwadowska, Anna; Kratzer, Susanne

    2016-12-01

    In the present paper, measurements of aerosol optical properties from the Gotland station of the AERONET network, combined with a two-stage cluster analysis of back trajectories of air masses moving over Gotland, were used to identify the main paths of air mass advection to the Baltic Sea and to relate them to aerosol optical properties, i.e. the aerosol optical thickness at the wavelength λ = 500 nm, AOT (500) and the Ångström exponent for the spectral range from 440 to 870 nm, α(440,870). One- to six-day long back trajectories ending at 300, 500 and 3000 m above the station were computed using the HYSPLIT model. The study shows that in the Gotland region, variability in aerosol optical thickness AOT(500) is more strongly related to advections in the boundary layer than to those in the free troposphere. The observed variability in AOT(500) was best explained by the advection speeds and directions given by clustering of 4-day backward trajectories of air arriving in the boundary layer at 500 m above the station. 17 clusters of 4-day trajectories arriving at altitude 500 m above the Gotland station (sea level) derived using two-stage cluster analysis differ from each other with respect to trajectory length, the speed of air mass movement and the direction of advection. They also show different cluster means of AOT(500) and α(440,870). The cluster mean AOT(500) ranges from 0.342 ± 0.012 for the continental clusters M2 (east-southeast advection with moderate speed) and 0.294 ± 0.025 for S5 (slow south-southeast advection) to 0.064 ± 0.002 and 0.069 ± 0.002 for the respective marine clusters L3 (fast west-northwest advection) and M3 (north-northwest advection with moderate speed). The cluster mean α(440,870) varies from 1.65-1.70 for the short-trajectory clusters to 0.98 ± 0.03 and 1.06 ± 0.03 for the Arctic marine cluster L4 (fast inflow from the north) and marine cluster L5 (fast inflow from the west) respectively.

  11. Accounting for an isobaric interference allows correct determination of folate vitamers in serum by isotope dilution-liquid chromatography-tandem mass spectrometry1, 2, 3

    PubMed Central

    Fazili, Zia; Pfeiffer, Christine M.

    2017-01-01

    Mild and prolonged oxidative degradation of 5-methyltetrahydrofolate (5-methylTHF) leads to the biologically inactive pyrazino-s-triazine derivative of 4α-hydroxy-5-methylTHF (MeFox). MeFox and the biologically active 5-formyltetrahydrofolate (5-formylTHF) are isobaric compounds that behave similarly during chromatographic and mass separation, making coelution and misidentification likely. Our published routine LC-MS/MS method did not discern between 5-formylTHF and MeFox, measuring the sum of these compounds at mass/charge ratio [m/z] 474→327 as 5-formylTHF. We modified this method to separate MeFox and 5-formylTHF either by chromatography or by unique mass transitions and then applied the two methods to serum specimens to determine typical concentrations of these compounds. The two unique transitions (m/z: 5-formylTHF 474→299; MeFox 474→284) showed good sensitivity (LOD [nmol/L]: 5-formylTHF 0.21; MeFox 0.34), selectivity (no interfering peaks), spiking recovery (mean±SD: 5-formylTHF 103%±3.4%; MeFox 94%±10%), and low imprecision (CV: 5-formylTHF 3.9% at 2.4 nmol/L; MeFox 5.1% at 2.9 nmol/L). The mass separation method detected 5-formylTHF in the same specimens as the chromatographic separation method. Analysis of several thousand serum specimens showed that the majority (~85%) contained MeFox at <3 nmol/L, but no detectable 5-formylTHF concentrations; some (~14%) contained 5-formylTHF at <0.5 nmol/L; a few specimens contained 5-formylTHF at >1 nmol/L and MeFox at >10 nmol/L. In summary, serum can contain 5-formylTHF high enough to contribute to total folate and contains MeFox that will bias total folate if not separated appropriately. Including measurements of MeFox and 5-formylTHF along with the other folate vitamers will enhance assessments of the association between biologically active folate and health effects. PMID:23173171

  12. Use of stable lead isotopes and trace metals to characterize air mass sources into the eastern North Atlantic

    NASA Astrophysics Data System (ADS)

    VéRon, Alain J.; Church, Thomas M.

    1997-12-01

    Stable lead isotopes (204Pb, 206Pb, 207Pb, 208Pb) and trace metals (Mn, Al, Fe, Ni, Cu, Cd, Zn, Pb) have been analyzed in aerosol collected during the Atlantic Stratocumulus Transition Experiment-Marine Aerosol and Gas Exchange (ASTEX-MAGE) cruise that transited between Miami and the Azores from May to July 1992. Our goal was to define the continental signatures of the air masses encountered between the Azores and the subtropical regions. The combination of air mass trajectories, trace metal concentrations and stable lead isotopes allowed us to characterize the anthropogenic character of encountered air masses. The average 206Pb/207Pb ratio was 1.148±0.021 and corresponded to a mixing between well defined European (such as Great Britain with 1.115<206Pb/207Pb<1.125 and France with 206Pb/207Pb=1.141±0.000) and North American sources (with 206Pb/207Pb=1.184±0.000). On the basis of air mass trajectories and trace metal concentrations, the background isotopic signature associated with the trade winds (206Pb/207Pb=1.161±0.004) is consistent with previous reports by Church et al. [1990] such as 206Pb/207Pb=1.154±0.004 in 1988, (Véron et al., 1993), 206Pb/207Pb=1.155±0.004 in 1989, and Hamelin et al. [1996] (206Pb/207Pb=1.158±0.006) in 1991. Short-term variations of continental air mass sources was particularly investigated by considering the anthropogenic character of aerosols collected during two Lagrangian experiments conducted as part of the ASTEX-MAGE cruise. We demonstrated the utility of stable lead isotopes to assign a "continental source signature" (or mixture thereof) to air masses beyond that normally possible by conventional air mass trajectory analysis in remote oceanic regions.

  13. 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.

  14. Microfluidic serial dilution circuit.

    PubMed

    Paegel, Brian M; Grover, William H; Skelley, Alison M; Mathies, Richard A; Joyce, Gerald F

    2006-11-01

    In vitro evolution of RNA molecules requires a method for executing many consecutive serial dilutions. To solve this problem, a microfluidic circuit has been fabricated in a three-layer glass-PDMS-glass device. The 400-nL serial dilution circuit contains five integrated membrane valves: three two-way valves arranged in a loop to drive cyclic mixing of the diluent and carryover, and two bus valves to control fluidic access to the circuit through input and output channels. By varying the valve placement in the circuit, carryover fractions from 0.04 to 0.2 were obtained. Each dilution process, which is composed of a diluent flush cycle followed by a mixing cycle, is carried out with no pipeting, and a sample volume of 400 nL is sufficient for conducting an arbitrary number of serial dilutions. Mixing is precisely controlled by changing the cyclic pumping rate, with a minimum mixing time of 22 s. This microfluidic circuit is generally applicable for integrating automated serial dilution and sample preparation in almost any microfluidic architecture.

  15. 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.

  16. Aerosols in polluted versus nonpolluted air masses Long-range transport and effects on clouds

    NASA Technical Reports Server (NTRS)

    Pueschel, R. F.; Van Valin, C. C.; Castillo, R. C.; Kadlecek, J. A.; Ganor, E.

    1986-01-01

    To assess the influence of anthropogenic aerosols on the physics and chemistry of clouds in the northeastern United States, 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, NY, 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 of 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. (2) A significant fraction of anthropogenic sulfur appears to act as cloud condensation nuclei (CCN) to affect the cloud drop concentration. (3) 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. (4) 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.

  17. 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.

  18. An effective indicator of continental scale cold air outbreaks in northern winter: the intensity variation of the meridional mass circulation

    NASA Astrophysics Data System (ADS)

    Ren, R.; Yu, Y.; Cai, M.

    2015-12-01

    This study reports that the intensity variation of the meridional mass circulation can be an effective leading indicator of cold air outbreaks (CAOs) over midlatitudes in northern winter. It is found that continental-scale coldness by cold air outbreaks (CAOs) tend to preferentially occur within a week after stronger mass circulation events defined as the peak time when the net mass transport across 60°N in the upper warm or the lower cold air branch exceeds ~88×109 kg s-1. During weaker mass circulation events when the net mass transport across 60°N is below ~71.6×109 kg s-1, most areas of the mid-latitudes are generally in mild condition except the northern part of Western Europe. Composite pattern of circulation anomalies during stronger mass circulation events greatly resemble that of the winter-mean, with the two main routes of anomalous cold air outbreaks being along the climatological routes of polar cold air, namely, via East Asia and North America. The Siberian High shifts westward during stronger mass circulation events, opening up a third route of cold air outbreaks through Eastern Europe. The relationship of CAOs with Arctic Oscillation (AO) is less robust because temporal changes of AO are resulted from a small imbalance between the poleward and equatorward branches of the mass circulation. Only when the poleward branch leads the equatorward branch (44% of all cases), CAOs tend to take place within a week after a negative phase of AO. The daily ERA-Interim reanalysis data set for the 32 winters in 1979-2011 were used in this study.

  19. 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.

  20. Decomposition of dilute trichloroethylene by nonthermal plasma

    SciTech Connect

    Oda, Tetsuji; Takahashi, Tadashi; Tada, Keiko

    1999-03-01

    Decomposition performance of a dilute toxic organic compound, trichloroethylene (TCE), in air by using nonthermal plasma processing was studied extensively. The nonthermal plasma was generated by the high-frequency (2 kHz) or commercial-frequency (50 Hz) barrier discharge in a fused silica tube. Three types of reactors, bolt type, rod type (both are barrier-discharge type), and coil type (surface-discharge type), were tested. Analysis of byproducts, residual materials, and end products generated by the plasma process was performed by a gas chromatography mass spectrometer of gas chromatography. Most organic byproducts decrease with an increase of the electric discharge power, but only toxic phosgene increases with the increase of the discharge power. As a post process, NaOH solution was used to test effluent from the plasma reactor. The solution was found effective in phosgene absorption. Comparison between nonthermal plasma and UV irradiation for TCE decomposition was also made. In regard to the energy efficiency of the TCE decomposition, UV irradiation is found much better than discharge plasma.

  1. High-throughput screening for various classes of doping agents using a new 'dilute-and-shoot' liquid chromatography-tandem mass spectrometry multi-target approach.

    PubMed

    Guddat, S; Solymos, E; Orlovius, A; Thomas, A; Sigmund, G; Geyer, H; Thevis, M; Schänzer, W

    2011-01-01

    A new multi-target approach based on liquid chromatography--electrospray ionization tandem mass spectrometry (LC-(ESI)-MS/MS) is presented to screen for various classes of prohibited substances using direct injection of urine specimens. With a highly sensitive new generation hybrid mass spectrometer classic groups of drugs--for example, diuretics, beta2-agonists--stimulants and narcotics are detectable at concentration levels far below the required limits. Additionally, more challenging and various new target compounds could be implemented. Model compounds of stimulant conjugates were studied to investigate a possible screening without complex sample preparation. As a main achievement, the integration of the plasma volume expanders dextran and hydroxyethyl starch (HES), commonly analyzed in time-consuming, stand-alone procedures, is accomplished. To screen for relatively new prohibited compounds, a common metabolite of the selective androgen receptor modulator (SARMs) andarine, a metabolite of growth hormone releasing peptide (GHRP-2), and 5-amino-4-imidazolecarboxyamide ribonucleoside (AICAR) are analyzed. Following a completely new approach, conjugates of di(2-ethylhexyl) phthalate (DEHP) metabolites are monitored to detect abnormally high levels of plasticizers indicating for illicit blood transfusion. The assay was fully validated for qualitative purposes considering the parameters specificity, intra- (3.2-16.6%) and inter-day precision (0.4-19.9%) at low, medium and high concentration, robustness, limit of detection (1-70 ng/ml, dextran: 30 µg/ml, HES: 10 µg/ml) and ion suppression/enhancement effects. The analyses of post-administration and routine doping control samples demonstrates the applicability of the method for sports drug testing. This straightforward and reliable approach accomplishes the combination of different screening procedures resulting in a high-throughput method that increases the efficiency of the labs daily work.

  2. Air mass modification over Europe: EARLINET aerosol observations from Wales to Belarus

    NASA Astrophysics Data System (ADS)

    Wandinger, Ulla; Mattis, Ina; Tesche, Matthias; Ansmann, Albert; BöSenberg, Jens; Chaikovski, Anatoly; Freudenthaler, Volker; Komguem, Leonce; Linné, Holger; Matthias, Volker; Pelon, Jacques; Sauvage, Laurent; Sobolewski, Piotr; Vaughan, Geraint; Wiegner, Matthias

    2004-12-01

    For the first time, the vertically resolved aerosol optical properties of western and central/eastern European haze are investigated as a function of air mass transport. Special emphasis is put on clean maritime air masses that cross the European continent from the west and become increasingly polluted on their way into the continent. The study is based on observations at seven lidar stations (Aberystwyth, Paris, Hamburg, Munich, Leipzig, Belsk, and Minsk) of the European Aerosol Research Lidar Network (EARLINET) and on backward trajectory analysis. For the first time, a lidar network monitored continent-scale haze air masses for several years (since 2000). Height profiles of the particle backscatter coefficient and the particle optical depth of the planetary boundary layer (PBL) at 355-nm wavelength are analyzed for the period from May 2000 to November 2002. From the observations at Aberystwyth, Wales, the aerosol reference profile for air entering Europe from pristine environments was determined. A mean 355-nm optical depth of 0.05 and a mean PBL height of 1.5 km was found for clean maritime summer conditions. The particle optical depth and PBL height increased with increasing distance from the North Atlantic. Mean summer PBL heights were 1.9-2.8 km at the continental sites of Leipzig, Belsk, and Minsk. Winter mean PBL heights were mostly between 0.7 and 1.3 km over the seven EARLINET sites. Summer mean 355-nm optical depths increased from 0.17 (Hamburg, northwesterly airflow from the North Sea) and 0.21 (Paris, westerly flow from the Atlantic) over 0.33 (Hamburg, westerly flow) and 0.35 (Leipzig, westerly flow) to 0.59 (Belsk, westerly flow), and decreased again to 0.37 (westerly flow) at Minsk. Winter mean optical depths were, on average, 10-30% lower than the respective summer values. PBL-mean extinction coefficients were of the order of 200 Mm-1 at 355 nm at Hamburg and Leipzig, Germany, and close to 600 Mm-1 at Belsk, Poland, in winter for westerly flows

  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. 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. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Dilution Zone Mixing

    NASA Technical Reports Server (NTRS)

    Holdeman, J. D.

    1983-01-01

    Studies to characterize dilution zone mixing; experiments on the effects of free-stream turbulence on a jet in crossflow; and the development of an interactive computer code for the analysis of the mixing of jets with a confined crossflow are reviewed.

  13. 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.…

  14. Quantification of the major urinary metabolite of 15-F2t-isoprostane (8-iso-PGF2alpha) by a stable isotope dilution mass spectrometric assay.

    PubMed

    Morrow, J D; Zackert, W E; Yang, J P; Kurhts, E H; Callewaert, D; Dworski, R; Kanai, K; Taber, D; Moore, K; Oates, J A; Roberts, L J

    1999-05-01

    The isoprostanes (IsoPs) are a series of novel prostaglandin (PG)-like compounds generated from the free radical-catalyzed peroxidation of arachidonic acid. The first series of IsoPs characterized contained F-type prostane rings analogous to PGF2alpha. One F-ring IsoP, 15-F2t-IsoP (8-iso-PGF2alpha) has been shown to be formed in abundance in vivo and to exert potent biological activity. As a means to assess the endogenous production of this compound, we developed a method to quantify the major urinary metabolite of 15-F2t-IsoP, 2,3-dinor-5,6-dihydro-15-F2t-IsoP (2,3-dinor-5, 6-dihydro-8-iso-PGF2alpha), by gas chromotography/negative ion chemical ionization mass spectrometry. This metabolite was chemically synthesized and converted to an 18O2-labeled derivative for use as an internal standard. After purification, the compound was analyzed as a pentafluorobenzyl ester trimethylsilyl ether. Precision of the assay is +/-4% and accuracy is 97%. The lower limit of sensitivity is approximately 20 pg. Levels of the urinary excretion of this metabolite in 10 normal adults were found to be 0. 39 +/- 0.18 ng/mg creatinine (mean +/- 2 SD). Substantial elevations in the urinary excretion of the metabolite were found in situations in which IsoP generation is increased and antioxidants effectively suppressed metabolite excretion. Levels of 2,3-dinor-5, 6-dihydro-15-F2t-IsoP were not affected by cyclooxygenase inhibitors. Thus, this assay provides a sensitive and accurate method to assess endogenous production of 15-F2t-IsoP as a means to explore the pathophysiological role of this compound in human disease.

  15. Analysis of organochlorines in harbor seal (Phoca vitulina) tissue samples from Alaska using gas chromatography/ion trap mass spectrometry by an isotopic dilution technique.

    PubMed

    Wang, Dongli; Atkinson, Shannon; Hoover-Miller, Anne; Li, Qing X

    2005-01-01

    A gas chromatography/ion trap mass spectrometry (GC/ITMS) method was developed for the determination of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in harbor seal (Phoca vitulina) tissues. Tissue samples were homogenized, lyophilized and fortified with (13)C-PCBs 28, 123, 169 and 170, and then extracted with an accelerated solvent extractor with a mixture of hexane and methylene chloride (1:1, v/v). After lipid removal using a 40% H(2)SO(4)-modified silica gel column, all organochlorines were collected in one fraction and further fractionated with an activated carbon/silica gel (1:20) column into a first fraction containing OCPs, non-coplanar PCBs and (13)C-PCBs 28, 123 and 170, and a second containing PCNs, coplanar PCBs and (13)C-PCB 169. Prior to GC/MS/MS analysis, (13)C-PCB 169 was added into the first fraction as an injection standard and (13)C-PCB 170 into the second fraction to calibrate the recoveries of the fortified internal standards. This method can effectively eliminate matrix interferences, and has high selectivity and sensitivity. Recoveries averaged 45-86% for OCPs with relative standard deviations (RSDs) of 2-14%, 52-137% for PCBs with RSDs of 3-29% and 36-152% for PCNs with RSDs of 7-29% from lard and chicken heart samples, which were used as alternative matrices to harbor seal samples in recovery studies. The limits of detection for OCPs, PCBs and PCNs were 0.7-1.9, 1.5-8.9 and 0.5-10 pg/g dry weight, respectively. This method can be used to analyze OCPs, PCBs and PCNs in harbor seal blubber, liver and kidney samples.

  16. The influence of polarization on box air mass factors for UV/vis nadir satellite observations

    NASA Astrophysics Data System (ADS)

    Hilboll, Andreas; Richter, Andreas; Rozanov, Vladimir V.; Burrows, John P.

    2015-04-01

    Tropospheric abundances of pollutant trace gases like, e.g., NO2, are often derived by applying the differential optical absorption spectroscopy (DOAS) method to space-borne measurements of back-scattered and reflected solar radiation. The resulting quantity, the slant column density (SCD), subsequently has to be converted to more easily interpretable vertical column densities by means of the so-called box air mass factor (BAMF). The BAMF describes the ratio of SCD and VCD within one atmospheric layer and is calculated by a radiative transfer model. Current operational and scientific data products of satellite-derived trace gas VCDs do not include the effect of polarization in their radiative transfer models. However, the various scattering processes in the atmosphere do lead to a distinctive polarization pattern of the observed Earthshine spectra. This study investigates the influence of these polarization patterns on box air mass factors for satellite nadir DOAS measurements of NO2 in the UV/vis wavelength region. NO2 BAMFs have been simulated for a multitude of viewing geometries, surface albedos, and surface altitudes, using the radiative transfer model SCIATRAN. The results show a potentially large influence of polarization on the BAMF, which can reach 10% and more close to the surface. A simple correction for this effect seems not to be feasible, as it strongly depends on the specific measurement scenario and can lead to both high and low biases of the resulting NO2 VCD. We therefore conclude that all data products of NO2 VCDs derived from space-borne DOAS measurements should include polarization effects in their radiative transfer model calculations, or at least include the errors introduced by using linear models in their uncertainty estimates.

  17. 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.

  18. A Comparison of Two Methods for Initiating Air Mass Back Trajectories

    NASA Astrophysics Data System (ADS)

    Putman, A.; Posmentier, E. S.; Faiia, A. M.; Sonder, L. J.; Feng, X.

    2014-12-01

    Lagrangian air mass tracking programs in back cast mode are a powerful tool for estimating the water vapor source of precipitation events. The altitudes above the precipitation site where particle's back trajectories begin influences the source estimation. We assume that precipitation comes from water vapor in condensing regions of the air column, so particles are placed in proportion to an estimated condensation profile. We compare two methods for estimating where condensation occurs and the resulting evaporation sites for 63 events at Barrow, AK. The first method (M1) uses measurements from a 35 GHz vertically resolved cloud radar (MMCR), and algorithms developed by Zhao and Garrett1 to calculate precipitation rate. The second method (M2) uses the Global Data Assimilation System reanalysis data in a lofting model. We assess how accurately M2, developed for global coverage, will perform in absence of direct cloud observations. Results from the two methods are statistically similar. The mean particle height estimated by M2 is, on average, 695 m (s.d. = 1800 m) higher than M1. The corresponding average vapor source estimated by M2 is 1.5⁰ (s.d. = 5.4⁰) south of M1. In addition, vapor sources for M2 relative to M1 have ocean surface temperatures averaging 1.1⁰C (s.d. = 3.5⁰C) warmer, and reported ocean surface relative humidities 0.31% (s.d. = 6.1%) drier. All biases except the latter are statistically significant (p = 0.02 for each). Results were skewed by events where M2 estimated very high altitudes of condensation. When M2 produced an average particle height less than 5000 m (89% of events), M2 estimated mean particle heights 76 m (s.d. = 741 m) higher than M1, corresponding to a vapor source 0.54⁰ (s.d. = 4.2⁰) south of M1. The ocean surface at the vapor source was an average of 0.35⁰C (s.d. = 2.35⁰C) warmer and ocean surface relative humidities were 0.02% (s.d. = 5.5%) wetter. None of the biases was statistically significant. If the vapor source

  19. 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.

  20. Large-scale transport of a CO-enhanced air mass from Europe to the Middle East

    NASA Technical Reports Server (NTRS)

    Connors, V. S.; Miles, T.; Reichle, H. G., Jr.

    1989-01-01

    On November 14, 1981, the shuttle-borne Measurement of Air Pollution from Satellites (MAPS) experiment observed a carbon monoxide (CO) enhanced air mass in the middle troposphere over the Middle East. The primary source of this polluted air was estimated by constructing adiabatic isentropic trajectories backwards from the MAPS measurement location over a 36 h period. The isentropic diagnostics indicate that CO-enhanced air was transported southeastward over the Mediterranean from an organized synoptic-scale weather regime, albeit of moderate intensity, influencing central Europe on November 12. Examination of the evolving synoptic scale vertical velocity and precipitation patterns during this period, in conjuction with Meteosat visible, infrared, and water vapor imagery, suggests that the presence of this disturbed weather system over Europe may have created upward transport of CO-enhanced air between the boundary-layer and midtropospheric levels, and subsequent entrainment in the large-scale northwesterly jet stream flow over Europe and the Mediterranean.

  1. Numerical Simulation of Air Mass Modification Over the East China Sea during the Winter Season

    NASA Astrophysics Data System (ADS)

    Hsu, Wu-Ron

    Air mass modification over the East China Sea during cold air outbreaks in the winter season was simulated by utilizing a high-resolution numerical model. The model includes most of the major physical processes, such as, surface exchange of heat and moisture between water and air; condensation and evaporation; and vertical turbulent transfer of heat, moisture, and momentum. The simulated convective boundary layer (CBL) consists of a surface layer, a subcloud layer, and a cloud layer. It is capped by an inversion with strong temperature and moisture gradients. Mesoscale cellular convection (MCC) embedded within the convective layer moves along with the mean wind. The average aspect ratio of the cells is 17.5, which agrees with observed aspect ratios for convective cells over the East China Sea. The upward convective motion correlates very well with the appearance of clouds, higher temperature, and higher moisture content in the CBL. The effects of diabatic heating were found to be very important in driving the thermal convection. Without the release of latent heat, the convective layer would be very shallow, and the convective motion would be greatly suppressed. Even though the formulation and dissipation of a cloud is associated with the movement of the resolvable scale MCC, the vertical transport of heat and moisture is achieved mainly by the unresolvable turbulent eddies. The distribution of specific humidity during the passage of the surface front reveals the moisture being pushed upward along the frontal surface as observed. The cold and dry air behind the cold front is quickly modified by strong convection over the warm water surface, especially over the Kuroshio Current. A cloud-free region exists near the coast where the CBL is too shallow for clouds to develop. A layer of stratocumulus forms downstream from the cloud-free region. The depth of the CBL increases toward the Kuroshio Current due to strong heat and moisture fluxes from the water surface. The CBL

  2. 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.

  3. Air/water subchannel measurements of the equilibrium quality and mass-flux distribution in a rod bundle. [BWR

    SciTech Connect

    Sterner, R.W.; Lahey, R.T. Jr.

    1983-07-01

    Subchannel measurements were performed in order to determine the equilibrium quality and mass flux distribution in a four rod bundle, using air/water flow. An isokinetic technique was used to sample the flow in the center, side and corner subchannels of this test section. Flow rates of the air and water in each sampled subchannel were measured. Experiments were performed for two test-section-average mass fluxes (0.333x10/sup 6/ and 0.666x10/sup 6/ lb/sub m//h-ft/sup 2/), and the test-section-average quality was varied from 0% to 0.54% for each mass flux. Single-phase liquid, bubbly, slug and churn-turbulent two-phase flow regimes were achieved. The observed data trends agreed with previous diabatic measurements in which the center subchannel had the highest quality and mass flux, while the corner subchannel had the lowest.

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

    PubMed

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

    2015-04-01

    This paper presents the certification of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in a candidate tea certified reference material (code: GLHK-11-03) according to the requirements of the ISO Guide 30 series. Certification of GLHK-11-03 was based on an analytical method purposely developed for the accurate measurement of the mass fraction of the target analytes in the material. An isotope dilution mass spectrometry (IDMS) method involving determination by (i) gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS) and (ii) gas chromatography-electron ionization-high-resolution mass spectrometry (GC-EI-HRMS) techniques was employed. The performance of the described method was demonstrated through participation in the key comparison CCQM-K95 "Mid-Polarity Analytes in Food Matrix: Mid-Polarity Pesticides in Tea" organized by the Consultative Committee for Amount of Substance-Metrology in Chemistry in 2012, where the study material was the same as the certified reference material (CRM). The values reported by using the developed method were in good agreement with the key comparison reference value (KCRV) assigned for beta-endosulfan (727 ± 14 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 %).

  5. Click chemistry mediated Eu-tagging: activity-based specific quantification and simultaneous activity evaluation of CYP3A4 using 153Eu species-unspecific isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Liang, Yong; Yan, Xiaowen; Li, Zhaoxin; Yang, Limin; Zhang, Bo; Wang, Qiuquan

    2014-04-15

    P450 3A4 (CYP3A4) is one of the most important isoforms in the human cytochrome P450 superfamily. It was used as an example in this proof-of-concept study in order to demonstrate an activity-based labeling and then click chemistry (CC) mediated element-tagging strategy for simultaneously specific quantification and activity measurement of an enzyme using species-unspecific isotope dilution inductively coupled plasma mass spectrometry (SUID ICPMS). A dual functional hexynylated 17α-ethynylestradiol activity-based probe was synthesized for specifically labeling CYP3A4 and then CC-mediated Eu-tagging with an azido-DOTA-Eu complex for CYP3A4 quantification and activity measurement in human liver microsome and serum samples using (153)Eu SUID ICPMS. The LOD (3σ) of CYP3A4 reached 20.3 fmol when monitoring (151/153)Eu ICPMS signals, in addition to the merits of specificity and simultaneous activity measurement achieved. We believe that this activity-based CC-mediated element-tagging strategy will liberate more potential advantages of ICPMS in bioanalysis.

  6. 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.

  7. Quantitation of the DNA Adduct of Semicarbazide in Organs of Semicarbazide-Treated Rats by Isotope-Dilution Liquid Chromatography-Tandem Mass Spectrometry: A Comparative Study with the RNA Adduct.

    PubMed

    Wang, Yinan; Wong, Tin-Yan; Chan, Wan

    2016-09-19

    Semicarbazide is a widespread food contaminant that is produced by multiple pathways. However, the toxicity of semicarbazide to human health remains unclear. Using a highly accurate and sensitive isotope-dilution liquid chromatography-tandem mass spectrometry method, we identified and quantitated in this study for the first time the DNA and RNA adduct of semicarbazide in DNA/RNA isolated from the internal organs of semicarbazide-exposed rats. The analysis revealed a dose-dependent formation of the adducts in the internal organs of the semicarbazide-dosed rats and with the highest adduct levels identified in the stomach and small intestine. Furthermore, results showed significantly higher levels of the RNA adduct (4.1-7.0 times) than that of the DNA adducts. By analyzing DNA/RNA samples isolated from rat organs in semicarbazide-dosed rats at different time points postdosing, the adduct stability in vivo was also investigated. These findings suggest that semicarbazide could have exerted its toxicity by affecting both the transcription and translation processes of the cell.

  8. Preparation, certification and validation of a stable solid spike of uranium and plutonium coated with a cellulose derivative for the measurement of uranium and plutonium content in dissolved nuclear fuel by isotope dilution mass spectrometry.

    PubMed

    Surugaya, Naoki; Hiyama, Toshiaki; Verbruggen, André; Wellum, Roger

    2008-02-01

    A stable solid spike for the measurement of uranium and plutonium content in nitric acid solutions of spent nuclear fuel by isotope dilution mass spectrometry has been prepared at the European Commission Institute for Reference Materials and Measurements in Belgium. The spike contains about 50 mg of uranium with a 19.838% (235)U enrichment and 2 mg of plutonium with a 97.766% (239)Pu abundance in each individual ampoule. The dried materials were covered with a thin film of cellulose acetate butyrate as a protective organic stabilizer to resist shocks encountered during transportation and to eliminate flaking-off during long-term storage. It was found that the cellulose acetate butyrate has good characteristics, maintaining a thin film for a long time, but readily dissolving on heating with nitric acid solution. The solid spike containing cellulose acetate butyrate was certified as a reference material with certified quantities: (235)U and (239)Pu amounts and uranium and plutonium amount ratios, and was validated by analyzing spent fuel dissolver solutions of the Tokai reprocessing plant in Japan. This paper describes the preparation, certification and validation of the solid spike coated with a cellulose derivative.

  9. Separation and quantification of silver nanoparticles and silver ions using reversed phase high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry in combination with isotope dilution analysis.

    PubMed

    Sötebier, Carina A; Weidner, Steffen M; Jakubowski, Norbert; Panne, Ulrich; Bettmer, Jörg

    2016-10-14

    A reversed phase high performance liquid chromatography coupled to an inductively coupled plasma mass spectrometer (HPLC-ICP-MS) approach in combination with isotope dilution analysis (IDA) for the separation and parallel quantification of nanostructured and ionic silver (Ag) is presented. The main focus of this work was the determination of the ionic Ag concentration. For a sufficient stabilization of the ions without dissolving the nanoparticles (NPs), the eluent had to be initially optimized. The determined Ag ion concentration was in a good agreement with results obtained using ultrafiltration. Further, the mechanism of the NP separation in the HPLC column was investigated. Typical size exclusion effects were found by comparing results from columns with different pore sizes. Since the recovery rates decreased with increasing Ag NP size and large Ag NPs did not elute from the column, additional interactions of the particles with the stationary phase were assumed. Our results reveal that the presented method is not only applicable to Ag NPs, but also to gold and polystyrene NPs. Finally, IDA-HPLC-ICP-MS experiments in single particle mode were performed to determine the particle cut-off size. The comparison with conventional spICP-MS experiments resulted in a similar diameter and particle size distribution.

  10. Detection of 1,N(2)-propano-2'-deoxyguanosine adducts in genomic DNA by ultrahigh performance liquid chromatography-electrospray ionization-tandem mass spectrometry in combination with stable isotope dilution.

    PubMed

    Zhang, Ning; Song, Yuanyuan; Wu, Danni; Xu, Tian; Lu, Meiling; Zhang, Weibing; Wang, Hailin

    2016-06-10

    Crotonaldehyde (Cro) is one of widespread and genotoxic α,β-unsaturated aldehydes and can react with the exocyclic amino group of 2'-deoxyguanosine (dG) in genomic DNA to form 1,N(2)-propano-2'-deoxyguanosine (ProdG) adducts. In this study, two diastereomers of high purity were prepared, including non-isotope and stable isotope labeled ProdG adducts, and exploited stable isotope dilution-based calibration method. By taking advantage of synthesized ProdG standards, we developed a sensitive ultrahigh performance liquid chromatography-electrospray ionization-tandem mass spectrometry (UHPLC-ESI-MS/MS) method for accurate quantification of two diastereomers of ProdG adducts. In addition to optimization of the UHPLC separation, ammonium bicarbonate (NH4HCO3) was used as additive in the mobile phase for enhancing the ionization efficiency to ProdG adducts and facilitating MS detection. The limits of detection (LODs, S/N=3) and the limits of quantification (LOQs, S/N=10) are estimated about 50 amol and 150 amol, respectively. By the use of the developed method, both diastereomers of ProdG adducts can be detected in untreated human MRC5 cells with a frequency of 2.4-3.5 adducts per 10(8) nucleotides. Crotonaldehyde treatment dramatically increases the levels of ProdG adducts in human MRC5 in a concentration-dependent manner.

  11. 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)).

  12. 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.

  13. "Dilute-and-inject" multi-target screening assay for highly polar doping agents using hydrophilic interaction liquid chromatography high resolution/high accuracy mass spectrometry for sports drug testing.

    PubMed

    Görgens, Christian; Guddat, Sven; Orlovius, Anne-Katrin; Sigmund, Gerd; Thomas, Andreas; Thevis, Mario; Schänzer, Wilhelm

    2015-07-01

    In the field of LC-MS, reversed phase liquid chromatography is the predominant method of choice for the separation of prohibited substances from various classes in sports drug testing. However, highly polar and charged compounds still represent a challenging task in liquid chromatography due to their difficult chromatographic behavior using reversed phase materials. A very promising approach for the separation of hydrophilic compounds is hydrophilic interaction liquid chromatography (HILIC). Despite its great potential and versatile advantages for the separation of highly polar compounds, HILIC is up to now not very common in doping analysis, although most manufacturers offer a variety of HILIC columns in their portfolio. In this study, a novel multi-target approach based on HILIC high resolution/high accuracy mass spectrometry is presented to screen for various polar stimulants, stimulant sulfo-conjugates, glycerol, AICAR, ethyl glucuronide, morphine-3-glucuronide, and myo-inositol trispyrophosphate after direct injection of diluted urine specimens. The usage of an effective online sample cleanup and a zwitterionic HILIC analytical column in combination with a new generation Hybrid Quadrupol-Orbitrap® mass spectrometer enabled the detection of highly polar analytes without any time-consuming hydrolysis or further purification steps, far below the required detection limits. The methodology was fully validated for qualitative and quantitative (AICAR, glycerol) purposes considering the parameters specificity; robustness (rRT < 2.0%); linearity (R > 0.99); intra- and inter-day precision at low, medium, and high concentration levels (CV < 20%); limit of detection (stimulants and stimulant sulfo-conjugates < 10 ng/mL; norfenefrine; octopamine < 30 ng/mL; AICAR < 10 ng/mL; glycerol 100 μg/mL; ETG < 100 ng/mL); accuracy (AICAR 103.8-105.5%, glycerol 85.1-98.3% at three concentration levels) and ion suppression/enhancement effects.

  14. Accurate, Direct, and High-Throughput Analyses of a Broad Spectrum of Endogenously Generated DNA Base Modifications with Isotope-Dilution Two-Dimensional Ultraperformance Liquid Chromatography with Tandem Mass Spectrometry: Possible Clinical Implication.

    PubMed

    Gackowski, Daniel; Starczak, Marta; Zarakowska, Ewelina; Modrzejewska, Martyna; Szpila, Anna; Banaszkiewicz, Zbigniew; Olinski, Ryszard

    2016-12-20

    Our hereby presented methodology is suitable for reliable assessment of the most common unavoidable DNA modifications which arise as a product of fundamental metabolic processes. 8-Oxoguanine, one of the oxidatively modified DNA bases, is a typical biomarker of oxidative stress. A noncanonical base, uracil, may be also present in small quantities in DNA. A set of ten-eleven translocation (TET) proteins are involved in oxidation of 5-methylcytosine to 5-hydroxymethylcytosine which can be further oxidized to 5-formylcytosine and 5-carboxycytosine. 5-Hydroxymethyluracil may be formed in deamination reaction of 5-hydroxymethylcytosine or can be also generated by TET enzymes. All of the aforementioned modifications seem to play some regulatory roles. We applied isotope-dilution automated online two-dimensional ultraperformance liquid chromatography with tandem mass spectrometry (2D-UPLC-MS/MS) for direct measurement of the 5-methyl-2'-deoxycytidine, 5-(hydroxymethyl)-2'-deoxycytidine, 5-formyl-2'-deoxycytidine, 5-carboxy-2'-deoxycytidine, 5-(hydroxymethyl)-2'-deoxyuridine, 2'-deoxyuridine, and 8-oxo-2'-deoxyguanosine. Analyses of DNA extracted from matched human samples showed that the 5-(hydroxymethyl)-2'-deoxycytidine level was 5-fold lower in colorectal carcinoma tumor in comparison with the normal one from the tumor's margin; also 5-formyl-2'-deoxycytidine and 5-carboxy-2'-deoxycytidine were lower in colorectal carcinoma tissue (ca. 2.5- and 3.5-fold, respectively). No such differences was found for 2'-deoxyuridine and 5-(hydroxymethyl)-2'-deoxyuridine. The presented methodology is suitable for fast, accurate, and complex evaluation of an array of endogenously generated DNA deoxynucleosides modifications. This novel technique could be used for monitoring of cancer and other diseases related to oxidative stress, aberrant metabolism, and environmental exposure. Furthermore, the fully automated two-dimensional separation is extremely useful for analysis of material

  15. 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.

  16. Optimization of solar cells for air mass zero operation and a study of solar cells at high temperatures, phase 3

    NASA Technical Reports Server (NTRS)

    Blakeslee, A. E.; Hovel, H. J.; Woodall, J. M.

    1977-01-01

    The etch-back epitaxy process is described for producing thin, graded composition GaAlAs layers. The palladium-aluminum contact system is discussed along with its associated problems. Recent solar cell results under simulated air mass zero light and at elevated temperatures are reported and the growth of thin polycrystalline GaAs films on foreign substrates is developed.

  17. On the association between daily mortality and air mass types in Athens, Greece during winter and summer.

    PubMed

    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.

  18. 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.

  19. 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.

  20. Northern East Asian Monsoon Precipitation Revealed by Air Mass Variability and Its Prediction

    NASA Astrophysics Data System (ADS)

    Son, J. H.; Seo, K. H.

    2015-12-01

    This work provides a new perspective on the major factors controlling the East Asian summer monsoon (EASM) in July, and a promising physical-statistical forecasting of the EASM ahead of summer. Dominant modes of the EASM are revealed from the variability of large-scale air masses discerned by equivalent potential temperature, and are found to be dynamically connected with the anomalous sea surface temperatures (SSTs) over the three major oceans of the world and their counterparts of prevailing atmospheric oscillation or teleconnection patterns. Precipitation over Northeast Asia (NEA) during July is enhanced by the tropical central Indian Ocean warming and central Pacific El Niño-related SST warming, the northwestern Pacific cooling off the coast of NEA, and the North Atlantic Ocean warming. Using these factors and data from the preceding spring seasons, the authors build a multiple linear regression model for seasonal forecasting. The cross-validated correlation skill predicted for the period 1994 to 2012 is up to 0.84, which far exceeds the skill level of contemporary climate models.

  1. Inverse Estimation of SO2 Emissions over China with Local Air Mass Factor Applied

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Wang, J.; Xu, X.; Henze, D. K.

    2015-12-01

    Sulfur dioxide (SO2) has significant impacts on human health as it forms sulfate aerosols in the atmosphere. Widespread uncertainty in the magnitude of SO2 emissions hinders efforts to address this issue. In this work we use Ozone Monitoring Instrument (OMI) slant column SO2 observations as constraints to conduct inversion of SO2 emissions over China for April 2008. Local air mass factors are formulated as the integral of the relative vertical distribution of SO2 simulated from GEOS-Chem, weighted by scattering weights computed from VLIDORT. They are applied to convert slant column to vertical column GEOS-Chem SO2. After data assimilation SO2 emissions decrease in Sichuan Basin, South China, and most areas of North China. The posterior SO2 emissions are evaluated with in situ SO2 observation. Besides, we apply the posterior SO2 emissions of April 2008 to April 2009, and it leads to improved agreement of modeled SO2 to the OMI observations. This offers potential to update SO2 emissions in real time.

  2. 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

  3. Automatic diluter for bacteriological samples.

    PubMed Central

    Trinel, P A; Bleuze, P; Leroy, G; Moschetto, Y; Leclerc, H

    1983-01-01

    The described apparatus, carrying 190 tubes, allows automatic and aseptic dilution of liquid or suspended-solid samples. Serial 10-fold dilutions are programmable from 10(-1) to 10(-9) and are carried out in glass tubes with screw caps and split silicone septa. Dilution assays performed with strains of Escherichia coli and Bacillus stearothermophilus permitted efficient conditions for sterilization of the needle to be defined and showed that the automatic dilutions were as accurate and as reproducible as the most rigorous conventional dilutions. Images PMID:6338826

  4. On-line solid phase extraction-high performance liquid chromatography-isotope dilution-tandem mass spectrometry approach to quantify N,N-diethyl-m-toluamide and oxidative metabolites in urine.

    PubMed

    Kuklenyik, Peter; Baker, Samuel E; Bishop, Amanda M; Morales-A, Pilar; Calafat, Antonia M

    2013-07-17

    Human exposure to N,N-diethyl-m-toluamide (DEET) occurs because of the widespread use of DEET as an active ingredient in insect repellents. However, information on the extent of such exposure is rather limited. Therefore, we developed a fast on-line solid phase extraction-high performance liquid chromatography-isotope dilution tandem mass spectrometry (HPLC-MS/MS) method to measure in urine the concentrations of DEET and two of its oxidative metabolites: N,N-diethyl-3-(hydroxymethyl)benzamide and 3-(diethylcarbamoyl)benzoic acid (DCBA). To the best of our knowledge, this is the first HPLC-MS/MS method for the simultaneous quantification of DEET and its select metabolites in human urine. After enzymatic hydrolysis of the conjugated species in 0.1 mL of urine, the target analytes were retained and pre-concentrated on a monolithic column, separated from each other and from other urinary biomolecules on a reversed-phase analytical column, and detected by atmospheric pressure chemical ionization in positive ion mode. The limits of detection ranged from 0.1 ng mL(-1) to 1.0 ng mL(-1), depending on the analyte. Accuracy ranged between 90.4 and 104.9%, and precision ranged between 5.5 and 13.1% RSD, depending on the analyte and the concentration. We tested the usefulness of this method by analyzing 75 urine samples collected anonymously in the Southeastern United States in June 2012 from adults with no known exposure to DEET. Thirty eight samples (51%) tested positive for at least one of the analytes. We detected DCBA most frequently and at the highest concentrations. Our results suggest that this method can be used for the analysis of a large number of samples for epidemiological studies to assess human exposure to DEET.

  5. Development and Validation of a Rapid 13C6-Glucose Isotope Dilution UPLC-MRM Mass Spectrometry Method for Use in Determining System Accuracy and Performance of Blood Glucose Monitoring Devices

    PubMed Central

    Matsunami, Risë K.; Angelides, Kimon; Engler, David A.

    2015-01-01

    Background: There is currently considerable discussion about the accuracy of blood glucose concentrations determined by personal blood glucose monitoring systems (BGMS). To date, the FDA has allowed new BGMS to demonstrate accuracy in reference to other glucose measurement systems that use the same or similar enzymatic-based methods to determine glucose concentration. These types of reference measurement procedures are only comparative in nature and are subject to the same potential sources of error in measurement and system perturbations as the device under evaluation. It would be ideal to have a completely orthogonal primary method that could serve as a true standard reference measurement procedure for establishing the accuracy of new BGMS. Methods: An isotope-dilution liquid chromatography/mass spectrometry (ID-UPLC-MRM) assay was developed using 13C6-glucose as a stable isotope analogue to specifically measure glucose concentration in human plasma, and validated for use against NIST standard reference materials, and against fresh isolates of whole blood and plasma into which exogenous glucose had been spiked. Assay performance was quantified to NIST-traceable dry weight measures for both glucose and 13C6-glucose. Results: The newly developed assay method was shown to be rapid, highly specific, sensitive, accurate, and precise for measuring plasma glucose levels. The assay displayed sufficient dynamic range and linearity to measure across the range of both normal and diabetic blood glucose levels. Assay performance was measured to within the same uncertainty levels (<1%) as the NIST definitive method for glucose measurement in human serum. Conclusions: The newly developed ID UPLC-MRM assay can serve as a validated reference measurement procedure to which new BGMS can be assessed for glucose measurement performance. PMID:25986627

  6. High-accuracy determination of iron in seawater by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using nitrilotriacetic acid chelating resin for pre-concentration and matrix separation.

    PubMed

    de Jong, Jeroen; Schoemann, Véronique; Lannuzel, Delphine; Tison, Jean-Louis; Mattielli, Nadine

    2008-08-15

    In the present paper we describe a robust and simple method to measure dissolved iron (DFe) concentrations in seawater down to <0.1 nmol L(-1) level, by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using a (54)Fe spike and measuring the (57)Fe/(54)Fe ratio. The method provides for a pre-concentration step (100:1) by micro-columns filled with the resin NTA Superflow of 50 mL seawater samples acidified to pH 1.9. NTA Superflow is demonstrated to quantitatively extract Fe from acidified seawater samples at this pH. Blanks are kept low (grand mean 0.045+/-0.020 nmol L(-1), n=21, 3 x S.D. limit of detection per session 0.020-0.069 nmol L(-1) range), as no buffer is required to adjust the sample pH for optimal extraction, and no other reagents are needed than ultrapure nitric acid, 12 mM H(2)O(2), and acidified (pH 1.9) ultra-high purity (UHP) water. We measured SAFe (sampling and analysis of Fe) reference seawater samples Surface-1 (0.097+/-0.043 nmol L(-1)) and Deep-2 (0.91+/-0.17 nmol L(-1)) and obtained results that were in excellent agreement with their DFe consensus values: 0.118+/-0.028 nmol L(-1) (n=7) for Surface-1 and 0.932+/-0.059 nmol L(-1) (n=9) for Deep-2. We also present a vertical DFe profile from the western Weddell Sea collected during the Ice Station Polarstern (ISPOL) ice drift experiment (ANT XXII-2, RV Polarstern) in November 2004-January 2005. The profile shows near-surface DFe concentrations of approximately 0.6 nmol L(-1) and bottom water enrichment up to 23 nmol L(-1) DFe.

  7. 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.

  8. Planning a serial dilution test with multiple dilutions.

    PubMed

    Blodgett, Robert J

    2009-06-01

    The dilutions used in a serial dilution test determine which concentrations it can estimate well. Two criteria help to select how many and which dilutions to use. The first criterion is a low probability of outcomes with either all growth or all non-growth tubes at the concentrations of interest. The second criterion considers how far the estimated concentration (MPN) is likely to be from the actual concentration.

  9. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    SciTech Connect

    Morrison, Glenn Charles

    1999-12-01

    -7, 10-5, and 10-5 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 10-5, 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.

  10. Change of microbial communities in glaciers along a transition of air masses in western China

    NASA Astrophysics Data System (ADS)

    Xiang, Shu-Rong; Chen, Yong; Shang, Tian-Cui; Jing, Ze-Fan; Wu, Guangjian

    2010-12-01

    Microbial community dynamics across glaciers in different climatic zones provide important information about the sources, transportation pathways, and deposition of microorganisms. To better understand the possible driving forces of microbial community shifts in glacier ice at a large spatial scale, 16S rRNA gene amplification was used to establish clone libraries containing 95 bacterial sequences from three different habitats in the Qiangyong Gacier in 2005. The libraries were used in phylogenetic comparison with 149 previously reported sequences from the surface samples collected from the Kuytun 51, and East Rongbuk glaciers in the same year. The results showed the presence of cosmopolitan and endemic species, and displayed a tendency of zonal distribution of bacterial communities at genera and community levels, corresponding to the geographic placement of the three glaciers. Data also showed a significant difference in the proportion of dominant phylogenetic groups in the three glaciers. Comamonadaceae/Polaromonas (Betaproteobacteria) and Flexibacteraceae (Bacteroidetes) were dominant in the Qiangyong Glacier, Cyanobacteria, Comamonadaceae/Polaromonas, and Rhodoferax (Betaproteobacteria) were dominant in the Kuytun 51 Glacier, and Acinetobacteria (Gammaproteobacteria) were dominant in the Rongbuk Glacier. In conclusion, the current study provides evidence of microbial biogeography in glacier ice at both the fine lineage and whole community levels. The biogeographical patterns were generally associated with the hydrological transition over the glaciers in the northern periphery and southern part of the Tibetan plateau. This supports our hypothesis of air mass behavior being one of the main drivers determining the zonal distribution of microbial communities across the mountain glaciers in western China.

  11. Climatology of wintertime long-distance transport of surface-layer air masses arriving urban Beijing in 2001-2012

    NASA Astrophysics Data System (ADS)

    Chen, Bin; Xiang-De, XU

    2017-02-01

    In this study, the FLEXPART-WRF coupled modeling system is used to conduct 12-year Lagrangian modeling over Beijing, China, for the winters of 2001-2012. Based on large trajectory tracking ensembles, the long-range air transport properties, in terms of geographic source regions within the atmospheric planetary boundary layer (PBL) and large-scale ventilation, and its association with air quality levels were quantified from a climatological perspective. The results show the following: (1) The air masses residing in the near-surface layer over Beijing potentially originate from broader atmospheric boundary-layer regions, which cover vast areas with the backward tracking time elapsed. However, atmospheric transport from northeastern China and, to a lesser extent, from the surrounding regions of Beijing is important. (2) The evolution of air quality over Beijing is negatively correlated with large-scale ventilation conditions, particularly at a synoptic timescale. Thus, the simple but robust backward-trajectory ventilation (BV) index defined in this study could facilitate operational forecasting of severe air pollution events. (3) By comparison, the relatively short-range transport occurring over transport timescales of less than 3 days from southern and southeastern Beijing and its surrounding areas plays a vital role in the formation of severe air pollution events during the wintertime. (4) Additionally, an interannual trend analysis suggests that the geographic sources and ventilation conditions also changed, at least over the last decade, corresponding to the strength variability of the winter East Asian monsoon.

  12. 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.

  13. Study of the Tropospheric Aerosol Structure Under Changing of the Air Mass Type from Lidar Observations in Tomsk

    NASA Astrophysics Data System (ADS)

    Samoilova, S. V.; Balin, Yu. S.; Kokhanenko, G. P.; Penner, I. É.

    2016-04-01

    The aerosol optical characteristics in the main tropospheric layers are investigated based on joint interpretation of data of multi-frequency lidar sensing (110 sessions) and results of modeling of back air mass trajectories. Methodical problems for separating layers with different scattering properties and estimating their vertical boundaries are considered. Three optical criteria are simultaneously used to distinguish aerosol layers from cloud formations, including the gradient of the backscattering coefficient, optical depth, and the depolarization ratio. High values of the lidar ratio (66 sr) and of the Angstrom exponent (1.62) in the shortwavelength spectral range are observed in the boundary layer for Arctic transport. At the same time, low values of these optical parameters are characteristic for Asian transport: the lidar ratio is 54 sr and the Angstrom exponent is 1.1, which is explained by different relative contributions of the coarse and fine aerosol fractions to the air mass.

  14. Simultaneous determination of aliphatic and aromatic amines in ambient air and airborne particulate matters by gas chromatography-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Akyüz, Mehmet

    2008-05-01

    A gas chromatography-mass spectrometry (GC-MS) method has been proposed for the simultaneous determination of aliphatic and aromatic amines in ambient air and airborne particulate matters (PMs). The method includes collection of the particulate matters (PM2.5 and PM10) using dichotomous Partisol 2025 sampler followed by extraction of the compounds into acidic solution, and pre-concentration of the compounds by percolating the air samples through the acidic solution, then ion-pair extraction of amines with bis-2-ethylhexylphosphate and derivatisation with isobutyl chloroformate prior to their GC-MS analysis in both electron impact and positive and negative ion chemical ionisation mode as their isobutyloxycarbonyl (isoBOC) derivatives. In the present study, ambient air and airborne particulate samples collected in Zonguldak province during summer and winter times of 2006-2007 were analysed for aliphatic and aromatic amines by the proposed method and the method was shown to be suitable for the simultaneous determination of these compounds at the levels of pg m-3 in air and airborne particulate samples. The seasonal distributions of bioactive amines in concentrations in ambient air and airborne PMs were evaluated as they are significant for the estimation of their effects on the environment and human health. The concentration levels of water soluble amines fluctuate significantly within a year with higher means and peak concentrations, probably due to the increased emissions from coal-fired domestic and central heating, in the winter times compared to the summer times. The results indicated that the relative amine content in particulates modulates with molecular mass and time of the year and the relative amine content especially in fine fractions of inhalable airborne particulates increases with the molecular mass of species but decreases with temperature.

  15. Calculations of relative optical air masses for various aerosol types and minor gases in Arctic and Antarctic atmospheres

    NASA Astrophysics Data System (ADS)

    Tomasi, Claudio; Petkov, Boyan H.

    2014-02-01

    The dependence functions of relative optical air mass on apparent solar zenith angle θ have been calculated over the θ < 87° range for the vertical profiles of wet-air molecular number density in the Arctic and Antarctic atmospheres, extinction coefficients of different aerosol types, and molecular number density of water vapor, ozone, nitrogen dioxide, and oxygen dimer. The calculations were made using as weight functions the seasonal average vertical profiles of (i) pressure and temperature derived from multiyear sets of radiosounding measurements performed at Ny-Ålesund, Alert, Mario Zucchelli, and Neumayer stations; (ii) volume extinction coefficients of background summer aerosol, Arctic haze, and Kasatochi and Pinatubo volcanic aerosol measured with lidars or balloon-borne samplings; and (iii) molecular number concentrations of the above minor gases, derived from radiosonde, ozonesonde, and satellite-based observations. The air mass values were determined using a formula based on a realistic atmospheric air-refraction model. They were systematically checked by comparing their mutual differences with the uncertainties arising from the seasonal and daily variations in pressure and temperature conditions within the various ranges, where aerosol and gases attenuate the solar radiation most efficiently. The results provide evidence that secant-approximated and midlatitude air mass values are inappropriate for analyzing the Sun photometer measurements performed at polar sites. They indicate that the present evaluations can be reliably used to estimate the aerosol optical depth from the Arctic and Antarctic measurements of total optical depth, after appropriate corrections for the Rayleigh scattering and gaseous absorption optical depths.

  16. Screening for sarin in air and water by solid-phase microextraction-gas chromatography-mass spectrometry.

    PubMed

    Schneider, J F; Boparai, A S; Reed, L L

    2001-10-01

    A method of screening air and water samples for the chemical-warfare agent Sarin is developed using solid-phase microextraction (SPME)-gas chromatography (GC)-mass spectrometry (MS). The SPME field kit sampler is ideal for collecting air and water samples in the field and transporting samples safely to the laboratory. The sampler also allows the sample to be introduced into the GC-MS system without further sample preparation. Results of the tests with Sarin using the SPME technique indicate that a sample collection time of 5 min is sufficient to detect 100 ng/L of Sarin in air. For water samples, Sarin is detected at a concentration of 12 microg/mL or higher. This method is ideal for screening samples for quick response situations.

  17. Screening for sarin in air and water by solid-phase microextraction-gas chromatography/mass spectrometry.

    SciTech Connect

    Schneider, J. F.; Boparai, A. S.; Reed, L. L.

    2001-10-01

    A method of screening air and water samples for the chemical-warfare agent Sarin is developed using solid-phase microextraction (SPME)-gas chromatography (GC)-mass spectrometry (MS). The SPME field kit sampler is ideal for collecting air and water samples in the field and transporting samples safely to the laboratory. The sampler also allows the sample to be introduced into the GC-MS system without further sample preparation. Results of the tests with Sarin using the SPME technique indicate that a sample collection time of 5 min is sufficient to detect 100 ng/L of Sarin in air. For water samples, Sarin is detected at a concentration of 12 {mu}g/mL or higher. This method is ideal for screening samples for quick response situations.

  18. 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.

  19. 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

  20. 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

  1. 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

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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 Astrophysics Data System (ADS)

    Bell, Shaun W.; Hansell, Richard A.; Chow, Judith C.; Tsay, Si-Chee; Hsu, N. Christina; Lin, Neng-Huei; Wang, Sheng-Hsiang; Ji, Qiang; Li, Can; Watson, John G.; Khlystov, Andrey

    2013-10-01

    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 (λ = 550 nm) 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 sulfate, nitrate, and elemental carbon. Achieving full optical closure is hampered by limitations in accounting for the role of water vapor in the system, uncertainties in the instruments and the need for further knowledge in the source apportionment of the model's major chemical components. Nonetheless, 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 sulfate 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. Consistency between the measured and modeled optical parameters serves as an

  7. 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

  8. New air Cherenkov light detectors to study mass composition of cosmic rays with energies above knee region

    NASA Astrophysics Data System (ADS)

    Tsunesada, Yoshiki; Katsuya, Ryoichi; Mitsumori, Yu; Nakayama, Keisuke; Kakimoto, Fumio; Tokuno, Hisao; Tajima, Norio; Miranda, Pedro; Salinas, Juan; Tavera, Wilfredo

    2014-11-01

    We have installed a hybrid detection system for air showers generated by cosmic rays with energies greater than 3 ×1015 eV at Mount Chacaltaya (5200 m above the sea level), in order to study the mass composition of cosmic rays above the knee region. This detection system comprises an air shower array with 49 scintillation counters in an area of 500 m×650 m, and seven new Cherenkov light detectors installed in a radial direction from the center of the air shower array with a separation of 50 m. It is known that the longitudinal development of a particle cascade in the atmosphere strongly depends on the type of the primary nucleus, and an air shower initiated by a heavier nucleus develops faster than that by a lighter primary of the same energy, because of the differences in the interaction cross-section and the energy per nucleon. This can be measured by detecting the Cherenkov radiation emitted from charged particles in air showers at higher altitudes. In this paper we describe the design and performance of our new non-imaging Cherenkov light detectors at Mount Chacaltaya that are operated in conjunction with the air shower array. The arrival directions and energies of air showers are determined by the shower array, and information about the primary masses is obtained from the Cherenkov light data including the time profiles and lateral distributions. The detector consists of photomultiplier tube (PMT), high-speed ADCs, other control modules, and data storage device. The Cherenkov light signals from an air shower are typically 10-100 ns long, and the waveforms are digitized with a sampling frequency of 1 GHz and recorded in situ without long-distance analog signal transfers. All the Cherenkov light detectors record their time-series data by receiving a triggering signal transmitted from the trigger module of the air shower array, which is fired by a coincidence of shower signals in four neighboring scintillation counters. The optical characteristics of the

  9. Linear and cyclic methylsiloxanes in air by concurrent solvent recondensation-large volume injection-gas chromatography-mass spectrometry.

    PubMed

    Companioni-Damas, E Y; Santos, F J; Galceran, M T

    2014-01-01

    In the present work, a simple and fast method for the analysis of linear and cyclic methylsiloxanes in ambient air based on active sampling combined with gas chromatography - mass spectrometry (GC-MS) was developed. The retention efficiency of five sampling sorbents (activated coconut charcoal, Carbopack B, Cromosorb 102, Cromosorb 106 and Isolute ENV+) was evaluated and Isolute ENV+ was found to be the most effective. A volume of 2700 L of air can be sampled without significant losses of the most volatile methylsiloxanes. To improve the sensitivity of the GC-MS method, concurrent solvent recondensation - large volume injection (CSR-LVI), using volumes up to 30 µl of sample extract, is proposed and limits of quantification down to 0.03-0.45 ng m(-3), good linearity (r>0.999) and precision (RSD %<9%) were obtained. The developed method was applied to the analysis of ambient air. Concentrations of linear and cyclic methylsiloxanes in indoor air ranging from 3.9 to 319 ng m(-3) and between 48 and 292668 ng m(-3), were obtained, respectively, while levels from 6 to 22 ng m(-3) for linear and between 2.2 and 439 ng m(-3) for cyclic methylsiloxanes in outdoor air from Barcelona (Spain), were found.

  10. 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

  11. Structural uncertainty in air mass factor calculation for NO2 and HCHO satellite retrievals

    NASA Astrophysics Data System (ADS)

    Lorente, Alba; Folkert Boersma, K.; Yu, Huan; Dörner, Steffen; Hilboll, Andreas; Richter, Andreas; Liu, Mengyao; Lamsal, Lok N.; Barkley, Michael; De Smedt, Isabelle; Van Roozendael, Michel; Wang, Yang; Wagner, Thomas; Beirle, Steffen; Lin, Jin-Tai; Krotkov, Nickolay; Stammes, Piet; Wang, Ping; Eskes, Henk J.; Krol, Maarten

    2017-03-01

    Air mass factor (AMF) calculation is the largest source of uncertainty in NO2 and HCHO satellite retrievals in situations with enhanced trace gas concentrations in the lower troposphere. Structural uncertainty arises when different retrieval methodologies are applied within the scientific community to the same satellite observations. Here, we address the issue of AMF structural uncertainty via a detailed comparison of AMF calculation methods that are structurally different between seven retrieval groups for measurements from the Ozone Monitoring Instrument (OMI). We estimate the escalation of structural uncertainty in every sub-step of the AMF calculation process. This goes beyond the algorithm uncertainty estimates provided in state-of-the-art retrievals, which address the theoretical propagation of uncertainties for one particular retrieval algorithm only. We find that top-of-atmosphere reflectances simulated by four radiative transfer models (RTMs) (DAK, McArtim, SCIATRAN and VLIDORT) agree within 1.5 %. We find that different retrieval groups agree well in the calculations of altitude resolved AMFs from different RTMs (to within 3 %), and in the tropospheric AMFs (to within 6 %) as long as identical ancillary data (surface albedo, terrain height, cloud parameters and trace gas profile) and cloud and aerosol correction procedures are being used. Structural uncertainty increases sharply when retrieval groups use their preference for ancillary data, cloud and aerosol correction. On average, we estimate the AMF structural uncertainty to be 42 % over polluted regions and 31 % over unpolluted regions, mostly driven by substantial differences in the a priori trace gas profiles, surface albedo and cloud parameters. Sensitivity studies for one particular algorithm indicate that different cloud correction approaches result in substantial AMF differences in polluted conditions (5 to 40 % depending on cloud fraction and cloud pressure, and 11 % on average) even for low

  12. Stability of reference masses: VII. Cleaning methods in air and vacuum applied to a platinum mass standard similar to the international and national kilogram prototypes

    NASA Astrophysics Data System (ADS)

    Cumpson, Peter J.; Sano, Naoko; Barlow, Anders J.; Portoles, Jose F.

    2013-10-01

    Mercury contamination and the build-up of carbonaceous contamination are two contributing factors to the instability observed in kilogram prototype masses. The kilogram prototypes that lie at the core of the dissemination of the SI base unit were manufactured in the late 19th century, and have polished surfaces. In papers IV and V of this series we developed a method for cleaning noble metal mass standards in air to remove carbonaceous contamination. At the core of this ‘UVOPS’ protocol is the application of UV light and ozone gas generated in situ in air. The precise nature of the carbonaceous contamination that builds up on such surfaces is difficult to mimic demonstrably or quickly on new test surfaces, yet data from such tests are needed to provide the final confidence to allow UVOPS to be applied to a real 19th century kilogram prototype. Therefore, in the present work we have applied the UVOPS method to clean a platinum avoirdupois pound mass standard, ‘RS2’, manufactured in the mid-19th century. This is thought to have been polished in a similar manner to the kilogram prototypes. To our knowledge this platinum surface has not previously been cleaned by any method. We used x-ray photoelectron spectroscopy to identify organic contamination, and weighing to quantify the mass lost at each application of the UVOPS procedure. The UVOPS procedure is shown to be very effective. It is likely that the redefinition of the kilogram will require mass comparisons in vacuum in the years to come. Therefore, in addition to UVOPS a cleaning method for use in vacuum will also be needed. We introduce and evaluate gas cluster ion-beam (GCIB) treatment as a potential method for cleaning reference masses in vacuum. Again, application of this GCIB cleaning to a real artefact, RS2, allows us to make a realistic evaluation of its performance. While it has some attractive features, we cannot recommend it for cleaning mass standards in its present form.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Effect of humidity and particle hygroscopicity on the mass loading capacity of high efficiency particulate air (HEPA) filters

    SciTech Connect

    Gupta, A.; Biswas, P. ); Monson, P.R. ); Novick, V.J. )

    1993-07-01

    The effect of humidity, particle hygroscopicity, and size on the mass loading capacity of glass fiber high efficiency particulate air filters was studied. Above the deliquescent point, the pressure drop across the filter increased nonlinearly with areal loading density (mass collected/filtration area) of a NaCl aerosol, thus significantly reducing the mass loading capacity of the filter compared to dry hygroscopic or nonhygroscopic particle mass loadings. The specific cake resistance K[sub 2] was computed for different test conditions and used as a measure of the mass loading capacity. K[sub 2] was found to decrease with increasing humidity for nonhygroscopic aluminum oxide particles and for hygroscopic NaCl particles (at humidities below the deliquescent point). It is postulated that an increase in humidity leads to the formation of a more open particulate cake which lowers the pressure drop for a given mass loading. A formula for predicting K[sub 2] for lognormally distributed aerosols (parameters obtained from impactor data) was derived. The resistance factor, R, calculated using this formula was compared to the theoretical R calculated using the Rudnick-Happel expression. For the nonhygroscopic aluminum oxide, the agreement was good but for the hygroscopic sodium chloride, due to large variation in the cake porosity estimates, the agreement was poor. 17 refs., 6 figs., 3 tabs.

  18. Air Superiority at Red Flag: Mass, Technology, and Winning the Next War

    DTIC Science & Technology

    2009-10-01

    improved their estimate. In The Art of Wargaming, Peter Perla suggests that adding exercise analysis could help. He recommends a “continuous cycle...Survey, 44. 45. Ibid., 27–28. 46. “Desert Shield Tactical Air Force Combat Losses, Damage, and Muni- tions Consumption.” 47. Ibid. 48. Perla , Art of...Williamson. Strategy for Defeat: The Luftwaffe, 1933– 1945, 1983. Reprint. Maxwell AFB, AL: Air University Press, 2007. Perla , Peter P. The Art of Wargaming

  19. Federal Air Pollutant Emission Regulations and Preliminary Estimates of Potential-to-Emit from Biorefineries. Pathway #1: Dilute-Acid and Enzymatic Deconstruction of Biomass-to-Sugars and Biological Conversion of Sugars-to-Hydrocarbons

    SciTech Connect

    Zhang, Yimin; Bhatt, Arpit; Heath, Garvin; Thomas, Mae; Renzaglia, Jason

    2016-02-01

    Biorefineries are subject to environmental laws, including complex air quality regulations that aim to protect and improve the quality of the air. These regulations govern the amount of certain types of air pollutants that can be emitted from different types of emission sources. To determine which federal air emission regulations potentially apply to the sugars-to-hydrocarbon (HC) biorefinery, we first identified the types of regulated air pollutants emitted to the ambient environment by the biorefinery or from specific equipment. Once the regulated air pollutants are identified, we review the applicability criteria of each federal air regulation to determine whether the sugars-to-HC biorefinery or specific equipment is subject to it. We then estimate the potential-to-emit of pollutants likely to be emitted from the sugars-to-HC biorefinery to understand the air permitting requirements.

  20. EPA Air Method, Toxic Organics - 15 (TO-15): Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specially-Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS)

    EPA Pesticide Factsheets

    Method T)-15 describes procedures for for preparation and analysis of air samples containing volatile organic compounds collected in specially-prepared canisters, using gas chromatography-mass spectrometry.

  1. 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.

  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. 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.

  4. 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.

  5. Variability of aerosol, gaseous pollutants and meteorological characteristics associated with changes in air mass origin at the SW Atlantic coast of Iberia

    NASA Astrophysics Data System (ADS)

    Diesch, J.-M.; Drewnick, F.; Zorn, S. R.; von der Weiden-Reinmüller, S.-L.; Martinez, M.; Borrmann, S.

    2012-04-01

    Measurements of the ambient aerosol were performed at the Southern coast of Spain, within the framework of the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) project. The field campaign took place from 20 November until 9 December 2008 at the atmospheric research station "El Arenosillo" (37°5'47.76" N, 6°44'6.94" W). As the monitoring station is located at the interface between a natural park, industrial cities (Huelva, Seville) and the Atlantic Ocean, a variety of physical and chemical parameters of aerosols and gas phase could be characterized in dependency on the origin of air masses. Backwards trajectories were examined and compared with local meteorology to classify characteristic air mass types for several source regions. Aerosol number and mass as well as polycyclic aromatic hydrocarbons and black carbon concentrations were measured in PM1 and size distributions were registered covering a size range from 7 nm up to 32 μm. The chemical composition of the non-refractory submicron aerosol (NR-PM1) was measured by means of an Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS). Gas phase analyzers monitored various trace gases (O3, SO2, NO, NO2, CO2) and a weather station provided meteorological parameters. Lowest average submicron particle mass and number concentrations were found in air masses arriving from the Atlantic Ocean with values around 2 μg m-3 and 1000 cm-3. These mass concentrations were about two to four times lower than the values recorded in air masses of continental and urban origins. For some species PM1-fractions in marine air were significantly larger than in air masses originating from Huelva, a closely located city with extensive industrial activities. The largest fraction of sulfate (54%) was detected in marine air masses and was to a high degree not neutralized. In addition, small concentrations of methanesulfonic acid (MSA), a product of biogenic dimethyl sulfate (DMS) emissions, could be identified in the particle phase

  6. 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

  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.

  8. Numerical study of coupled transfer of heat and mass between air and water inside a geothermal water cooling tower

    NASA Astrophysics Data System (ADS)

    Bassem, Mohamed Mehdi; Bourouni, Karim; Thameur Chaibi, Mohamed

    2006-11-01

    In the south of Tunisia, geothermal water is used to irrigate cultures. Since its temperature is very high (70 C), geothermal water is cooled by cooling towers. These towers are sized empirically and present many operating problems such as excessive energy consumption, big loss of vapour and low cooling efficiency. The aim of our work is modelling the coupled heat and mass transfer between air and water inside the cooling tower. The most important results obtained are that the evaporative potential is dominating the convective one in the cooling process. That's why the cooling is more efficient in summer than in hibernal period when humidity of ambient air reaches high values. In other hand, the negative convective phenomenon is illustrated. In fact, at the bottom of the tower, water temperature reaches the air one; the two fluids begin to cooling simultaneously. Air is cooled by convection and water by evaporation. We demonstrate also that there is no point in putting fans in working during cold weather. We studied also the effect of the variation of heat transfer coefficient on the efficiency of cooling.

  9. Petroleum mass removal from low permeability sediment using air sparging/soil vapor extraction: impact of continuous or pulsed operation

    NASA Astrophysics Data System (ADS)

    Kirtland, Brian C.; Aelion, C. Marjorie

    2000-02-01

    Air sparging and soil vapor extraction (AS/SVE) are innovative remediation techniques that utilize volatilization and microbial degradation to remediate petroleum spills from soils and groundwater. This in situ study investigated the use of AS/SVE to remediate a gasoline spill from a leaking underground storage tank (UST) in the low permeability, clayey soil of the Appalachian Piedmont. The objectives of this study were to evaluate AS/SVE in low permeability soils by quantifying petroleum mass removal rates, monitoring vadose zone contaminant levels, and comparing the mass extraction rates of continuous AS/SVE to 8 and 24 h pulsed operation. The objectives were met by collecting AS/SVE exhaust gas samples and vadose zone air from multi-depth soil vapor probes. Samples were analyzed for O 2, CO 2, BTEX (benzene, toluene, ethylbenzene, xylene), and total combustible hydrocarbon (TCH) concentrations using portable hand meters and gas chromatography. Continuous AS/SVE was effective in removing 608 kg of petroleum hydrocarbons from low permeability soil in 44 days (14.3 kg day -1). Mass removal rates ranged from 2.6 times higher to 5.1 times lower than other AS/SVE studies performed in sandy sediments. BTEX levels in the vadose zone were reduced from about 5 ppm to 1 ppm. Ten pulsed AS/SVE tests removed 78 kg in 23 days and the mean mass removal rate (17.6 kg day -1) was significantly higher than the last 15 days of continuous extraction. Pulsed operation may be preferable to continuous operation because of increased mass removal and decreased energy consumption.

  10. Small Barriers Trigger Liftoff of Unconfined Dilute Heated Laboratory Density Currents

    NASA Astrophysics Data System (ADS)

    Fauria, K.; Andrews, B. J.; Manga, M.

    2015-12-01

    Dilute pyroclastic density currents (PDCs) are hot, turbulent, particle-laden flows that propagate because they are denser than air. PDCs can traverse tens to hundreds of kilometers and surmount ridges 100s of m tall, yet the effects of complex topography on PDC liftoff and runout distance are uncertain. Here we used scaled laboratory experiments to explore how barriers affect dilute density current dynamics and the occurrence of liftoff. We created dilute density currents by heating and suspending 20 μm diameter talc in air in an 8.5 x 6.1 x 2.6 m tank. We scaled the currents with respect to Froude, densimetric and thermal Richardson, particle Stokes and Settling numbers such that they were dynamically similar to natural PDCs. While currents were fully turbulent, their Reynolds numbers were not as high as those for natural PDCs. We performed the first set of experiments in a laterally unconfined volume, used laser sheets to illuminate the currents, measured bulk sedimentation rates down the current centerlines, and positioned four to twenty-four cm tall ridge-like barriers in the path of the currents. We found that relatively small barriers (~ half the current height) caused PDC liftoff. By comparison, conservation of kinetic and potential energy predicts that incompressible density currents are able to surmount barriers twice their height. Furthermore, we observed increased sedimentation immediately upstream of barriers and conclude that small barriers initiated buoyancy reversal through a combination of increased air entrainment and sedimentation. We conducted a second set of experiments with the same thermal scaling and mass flux rates but where the currents were laterally confined within a 0.6 m wide channel. We found that small barriers also triggered liftoff of confined currents, but that the body of these currents reattached after liftoff. Those results suggest that lateral confinement inhibits buoyancy reversal by limiting the surface area of the current-air

  11. Ambient air analyses using nonspecific flame ionization and electron capture detection compared to specific detection by mass spectroscopy

    SciTech Connect

    Pleil, J.D.; Oliver, K.D.; McClenny, W.A.

    1988-08-01

    Ambient air samples from various studies were analyzed for a specific set of trace-level volatile organic compounds by using a gas chromatograph (GC) equipped with a flame ionization detector (FID) in parallel with an electron capture detector (ECD). The samples were then reanalyzed on a second GC system equipped with a mass selective detector (MSD). GC-FID/ECD data were compared to the nominally correct GC-MSD data to determine the accuracy of the nonspecific detectors, which often do not differentiate the targeted compound from interfering compounds. Qualitative accuracy (capability for correctly identifying compounds on the basis of retention time only) and quantitative accuracy (capability for correctly measuring the concentration of an identified compound on the basis of peak area) were evaluated. Data are presented on a per-compound basis to provide the combined typical results from air samples collected in three geographic regions: Kanawha Valley, WV; Los Angeles, CA, area; and Houston, TX.

  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.

    2017-01-01

    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. 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.

  14. Identifying tropospheric baseline air masses at Mauna Loa Observatory between 2004 and 2010 using Radon-222 and back trajectories

    NASA Astrophysics Data System (ADS)

    Chambers, Scott D.; Zahorowski, Wlodek; Williams, Alastair G.; Crawford, Jagoda; Griffiths, Alan D.

    2013-01-01

    We use 7 years of hourly radon observations at Mauna Loa Observatory (MLO), together with 10-day back trajectories, to identify baseline air masses at the station. The amplitude of the annual MLO radon cycle, based on monthly means, was 98 mBq m-3 (39 -137 mBq m-3), with maximum values in February (90th percentile 330 mBq m-3) and minimum values in August (10th percentile 8.1 mBq m-3). The composite diurnal radon cycle (amplitude 49 mBq m-3) is discussed with reference to the influences of local flow features affecting the site, and a 3-hour diurnal sampling window (0730-1030 HST) is proposed for observing the least terrestrially influenced tropospheric air masses. A set of 763 baseline events is selected, using the proposed sampling window together with trajectory information, and presented along with measured radon concentrations as a supplement. This data set represents a resource for the selection of baseline events at MLO for use with a range of trace species. A reduced set of 196 "deep baseline" events occurring in the July-September window is also presented and discussed. The distribution (10th/50th/90th percentile) of radon in deep-baseline events (8.7/29.2/66.1 mBq m-3) was considerably lower than that for the overall set of 763 baseline events (12.3/40.8/104.1 mBq m-3). Results from a simple budget calculation, using sonde-derived mixing depths and literature-based estimates of oceanic radon flux and radon concentrations in the marine boundary layer, indicate that the main source of residual radon in the lower troposphere under baseline conditions at MLO is downward mixing from aged terrestrial air masses in the upper troposphere.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 40 CFR 1066.140 - Diluted exhaust flow calibration.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...: (i) The mean flow rate of the reference flow meter, Q ref. This may include several measurements of... v, at measured values of pressure, temperature and air flow. Calibrate the CFV at the lowest... 40 Protection of Environment 33 2014-07-01 2014-07-01 false Diluted exhaust flow calibration....

  1. Dynamics of atmospheres with a non-dilute condensible component.

    PubMed

    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.

  2. 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.

  3. Facility monitoring of chemical warfare agent simulants in air using an automated, field-deployable, miniature mass spectrometer.

    PubMed

    Smith, Jonell N; Noll, Robert J; Cooks, R Graham

    2011-05-30

    Vapors of four chemical warfare agent (CWA) stimulants, 2-chloroethyl ethyl sulfide (CEES), diethyl malonate (DEM), dimethyl methylphosphonate (DMMP), and methyl salicylate (MeS), were detected, identified, and quantitated using a fully automated, field-deployable, miniature mass spectrometer. Samples were ionized using a glow discharge electron ionization (GDEI) source, and ions were mass analyzed with a cylindrical ion trap (CIT) mass analyzer. A dual-tube thermal desorption system was used to trap compounds on 50:50 Tenax TA/Carboxen 569 sorbent before their thermal release. The sample concentrations ranged from low parts per billion [ppb] to two parts per million [ppm]. Limits of detection (LODs) ranged from 0.26 to 5.0 ppb. Receiver operating characteristic (ROC) curves are presented for each analyte. A sample of CEES at low ppb concentration was combined separately with two interferents, bleach (saturated vapor) and diesel fuel exhaust (1%), as a way to explore the capability of detecting the simulant in an environmental matrix. Also investigated was a mixture of the four CWA simulants (at concentrations in air ranging from 270 to 380 ppb). Tandem mass (MS/MS) spectral data were used to identify and quantify the individual components.

  4. 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.

  5. Plasma flame for mass purification of contaminated air with chemical and biological warfare agents

    NASA Astrophysics Data System (ADS)

    Uhm, Han S.; Shin, Dong H.; Hong, Yong C.

    2006-09-01

    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 22cm diameter and 30cm length, purifies an airflow rate of 5000lpm 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.

  6. 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.

  7. Identification of European Air Masses Using an Interactive Computer Technique for Separating Mixed Normal Distributions.

    DTIC Science & Technology

    1982-01-01

    classifying a maritime surface, he refers to the Pacific, Atlantic, or Gulf of Mexico using the general term "maritime" only when the exact origin is...portions of North Atlantic NPA PA air modified over warm North Atlantic TC Southern U.S. and Northern Mexico TG Gulf of Mexico and Caribbean NTG TG...Bergeron, T., 1928: " Uber Die Dreidimensional Verknupfende Wetteranalyse, Teil I." Geofys. Pub!., Vol. 5, No. 6. Berggren, R., 1953: "On Temperature

  8. Properties of individual aerosol particles and their relation to air mass origins in a south China coastal city

    NASA Astrophysics Data System (ADS)

    Shi, Zongbo; He, Kebin; Xue, Zhigang; Yang, Fumo; Chen, Yanju; Ma, Yongliang; Luo, Jiaojiao

    2009-05-01

    Atmospheric particles in urban and rural areas in Shenzhen city were collected in summer and winter 2004. The particles were analyzed using a scanning electron microscope equipped with an energy dispersive X-ray spectrometer. The fine particles (<1 μm) were categorized into chain-like, elongated, rounded, and others on the basis of their morphology. Chain-like particles were likely soot aggregates. In summer and winter, chain-like particles accounted for 43% and 42% of total particles in the urban area, and 22% and 43% in the rural area, respectively. The elongated particles were mixtures of aged sea salts and ammonium sulfate, suggesting an aqueous phase reaction mechanism, i.e., in-cloud sulfate formation. Such particles occupied 12% of total particles in the urban area in the summer and were rarely observed in the wintertime samples. The rounded particles were mainly composed of sulfate and/or carbon. Their number concentration in the urban area was more than three times higher in the winter. In addition, we found that air masses from northern inland contained much higher concentrations of particles than those from the ocean. This was particularly evident in the rural area, where concentrations of chain-like and rounded particles were eight times higher in the continental air masses. These results suggest the strong influence of regional pollution on the particle number concentrations in the coastal city.

  9. 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.

  10. An improved, automated whole air sampler and gas chromatography mass spectrometry analysis system for volatile organic compounds in the atmosphere

    NASA Astrophysics Data System (ADS)

    Lerner, Brian M.; Gilman, Jessica B.; Aikin, Kenneth C.; Atlas, Elliot L.; Goldan, Paul D.; Graus, Martin; Hendershot, Roger; Isaacman-VanWertz, Gabriel A.; Koss, Abigail; Kuster, William C.; Lueb, Richard A.; McLaughlin, Richard J.; Peischl, Jeff; Sueper, Donna; Ryerson, Thomas B.; Tokarek, Travis W.; Warneke, Carsten; Yuan, Bin; de Gouw, Joost A.

    2017-01-01

    Volatile organic compounds were quantified during two aircraft-based field campaigns using highly automated, whole air samplers with expedited post-flight analysis via a new custom-built, field-deployable gas chromatography-mass spectrometry instrument. During flight, air samples were pressurized with a stainless steel bellows compressor into electropolished stainless steel canisters. The air samples were analyzed using a novel gas chromatograph system designed specifically for field use which eliminates the need for liquid nitrogen. Instead, a Stirling cooler is used for cryogenic sample pre-concentration at temperatures as low as -165 °C. The analysis system was fully automated on a 20 min cycle to allow for unattended processing of an entire flight of 72 sample canisters within 30 h, thereby reducing typical sample residence times in the canisters to less than 3 days. The new analytical system is capable of quantifying a wide suite of C2 to C10 organic compounds at part-per-trillion sensitivity. This paper describes the sampling and analysis systems, along with the data analysis procedures which include a new peak-fitting software package for rapid chromatographic data reduction. Instrument sensitivities, uncertainties and system artifacts are presented for 35 trace gas species in canister samples. Comparisons of reported mixing ratios from each field campaign with measurements from other instruments are also presented.

  11. Aerosol properties associated with air masses arriving into the North East Atlantic during the 2008 Mace Head EUCAARI intensive observing period: an overview

    NASA Astrophysics Data System (ADS)

    Dall'Osto, M.; Ceburnis, D.; Martucci, G.; Bialek, J.; Dupuy, R.; Jennings, S. G.; Berresheim, H.; Wenger, J. C.; Sodeau, J. R.; Healy, R. M.; Facchini, M. C.; Rinaldi, M.; Giulianelli, L.; Finessi, E.; Worsnop, D.; O'Dowd, C. D.

    2009-12-01

    As part of the EUCAARI Intensive Observing Period, a 4-week campaign to measure aerosol physical, chemical and optical properties, atmospheric structure, and cloud microphysics was conducted from mid-May to mid-June 2008 at the Mace Head Atmospheric Research Station, located at the interface of Western Europe and the NE Atlantic and centered on the west Irish coastline. During the campaign, continental air masses comprising both young and aged continental plumes were encountered, along with polar, Arctic and tropical air masses. Polluted-continental aerosol concentrations were of the order of 3000 cm-3, while background marine air aerosol concentrations were between 400-600 cm-3. The highest marine air concentrations occurred in polar air masses in which a 15 nm nucleation mode, with concentration of 1100 cm-3, was observed and attributed to open ocean particle formation. Black carbon concentrations in polluted air were between 300-400 ng m-3, and in clean marine air were less than 50 ng m-3. Continental air submicron chemical composition (excluding refractory sea salt) was dominated by organic matter, closely followed by sulphate mass. Although the concentrations and size distribution spectral shape were almost identical for the young and aged continental cases, hygroscopic growth factors (GF) and cloud condensation nuclei (CCN) to total condensation nuclei (CN) concentration ratios were significantly less in the younger pollution plume, indicating a more oxidized organic component to the aged continental plume. The difference in chemical composition and hygroscopic growth factor appear to result in a 40-50% impact on aerosol scattering coefficients and Aerosol Optical Depth, despite almost identical aerosol microphysical properties in both cases, with the higher values been recorded for the more aged case. For the CCN/CN ratio, the highest ratios were seen in the more age plume. In marine air, sulphate mass dominated the sub-micron component, followed by water

  12. Identification of oxidation products of solanesol produced during air sampling for tobacco smoke by electrospray mass spectrometry and HPLC.

    PubMed

    Tucker, Samuel P; Pretty, Jack R

    2005-10-01

    Solanesol, a 45-carbon, trisesquiterpenoid alcohol found in tobacco leaves and tobacco smoke, has been used as a quantitative marker for tobacco smoke for years. However, solanesol appears to be unreliable as a quantitative marker for tobacco smoke during environmental air sampling because it can be degraded substantially when present as a component of tobacco smoke and by as much as 100% when present as pure solanesol on fortified filters during air sampling. Since there is strong evidence that ozone is the agent responsible for the degradation, solanesol appears to be unreliable as a quantitative marker during indoor air sampling when indoor levels of ozone are greater than about 15 ppb. The degree of loss of pure solanesol is directly proportional to the concentration of ozone and the length of the sampling period and depends on the type of 37 mm membrane filter used for air sampling (PTFE or quartz fiber). While the degree of loss of solanesol is inversely proportional to the relative humidity of the air at a sampling rate of 1.7 L min(-1), the degree of loss is virtually independent of relative humidity at a lower sampling rate; i.e., 0.25 L min(-1). A curve of loss of solanesol on a filter versus concentration of ozone from an ozone generator is virtually identical to a curve segment based on atmospheric ozone under the same conditions of air sampling. Oxidation of solanesol by ozone to approximately 25 to 60% completion produces at least three series of products for a total of at least 26 compounds: (1) isoprenoid acetones, (2)omega-hydroxyisoprenoid acetaldehydes, and (3) isoprenoid oxoaldehydes. All products in each series were tentatively identified as their derivatives with 2-(p-aminophenyl)ethanol (APE) by electrospray mass spectrometry (ES-MS). Ten ozonation products were detected as their 2,4-dinitrophenylhydrazine derivatives by HPLC at 360 nm: 4-oxopentanal and nine isoprenoid acetones (acetone, 6-methyl-5-hepten-2-one, geranylacetone

  13. Upper air relaxation in regional climate model improves resolved interannual variability of the surface mass balance of Antarctica

    NASA Astrophysics Data System (ADS)

    van de Berg, Willem Jan; Medley, Brooke; van Meijgaard, Erik

    2015-04-01

    The surface mass balance (SMB) determines the variability of the mass balance of the Antarctic Ice sheet on sub-decadal timescales. Since continent-wide SMB cannot be measured, it must be modeled and regional climate models (RCMs) generally outperform global reanalyses in the representation of total mass flux and the spatial distribution of SMB. However, if RCMs are only forced with reanalysis on their lateral boundaries, the representation of the interannual variability of SMB deteriorates significantly. In this study we show how to improve the resolved interannual variability in RCM modeled SMB. For this purpose we use annual SMB observations in the Thwaites drainage basin in Antarctica derived from airborne radar reflections and the RCM RACMO2. RACMO2, driven by ERA-Interim, better represents the mean spatial SMB pattern in this basin than ERA-Interim. However, without relaxation in the interior, RACMO2 poorly resolves the observed interannual SMB variability. If we gently relax the temperature and wind field in the upper atmosphere in RACMO2 to ERA-Interim, RACMO2 gets the best of both. Upper air relaxation little changes the mean SMB and spatial pattern compared to the original RACMO2 output, but allows RACMO2 to resolve the observed interannual SMB as good as ERA-Interim.

  14. Decomposing the profile of PM in two low polluted German cities--mapping of air mass residence time, focusing on potential long range transport impacts.

    PubMed

    Dimitriou, Konstantinos; Kassomenos, Pavlos

    2014-07-01

    This paper aims to decompose the profile of particulates in Karlsruhe and Potsdam (Germany), focusing on the localization of PM potential transboundary sources. An air mass cluster analysis was implemented, followed by a study of air mass residence time on a grid of a 0.5° × 0.5° resolution. Particulate/gaseous daily air pollution and meteorological data were used to indicate PM local sources. Four Principal Component Analysis (PCA) components were produced: traffic, photochemical, industrial/domestic and particulate. PM2.5/PM10 ratio seasonal trends, indicated production of PMCOARSE (PM10-PM2.5) from secondary sources in Potsdam during warm period (WP). The residing areas of incoming slow moving air masses are potential transboundary PM sources. For Karlsruhe those areas were mainly around the city. An air mass residence time secondary peak was observed over Stuttgart. For Potsdam, areas with increased dwelling time of the arriving air parcels were detected particularly above E/SE Germany.

  15. Biomathematical modeling for diluted drugs.

    PubMed

    Chattopadhyay, S

    2003-07-01

    Several workers have proven that succussed ultra high dilution of a drug molecule in water or alcoholic medium, even exceeding Avogadro number, can bring forth noticeable physiological changes of an organism. Homeopathic drugs are prepared by dissolving such drug ingredients in distilled water and then the solution is centesimally diluted serially by ethanol. A mathematical model has been proposed by the present worker, which explains why the drug does not become non-molecular even in ultra-high dilution. This is due to loss of homogeneity in the solution, caused by increase of dielectric constant of the medium during the process of potentization. Facilitated binding of the drug molecules with minute physiologically important protein factors may be the cause of visible physiological alterations.

  16. Evaluation of two gas-dilution methods for instrument calibration

    NASA Technical Reports Server (NTRS)

    Evans, A., Jr.

    1977-01-01

    Two gas dilution methods were evaluated for use in the calibration of analytical instruments used in air pollution studies. A dual isotope fluorescence carbon monoxide analyzer was used as the transfer standard. The methods are not new but some modifications are described. The rotary injection gas dilution method was found to be more accurate than the closed loop method. Results by the two methods differed by 5 percent. This could not be accounted for by the random errors in the measurements. The methods avoid the problems associated with pressurized cylinders. Both methods have merit and have found a place in instrument calibration work.

  17. 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

  18. Differential optical absorption spectroscopy (DOAS) and air mass factor concept for a multiply scattering vertically inhomogeneous medium: theoretical consideration

    NASA Astrophysics Data System (ADS)

    Rozanov, V. V.; Rozanov, A. V.

    2010-06-01

    The Differential Optical Absorption Spectroscopy (DOAS) technique is widely used to retrieve amounts of atmospheric species from measurements of the direct solar light transmitted through the Earth's atmosphere as well as of the solar light scattered in the atmosphere or reflected from the Earth's surface. For the transmitted direct solar light the theoretical basis of the DOAS technique represented by the Beer-Lambert law is well studied. In contrast, scarcely investigated is the theoretical basis and validity range of the DOAS method for those cases where the contribution of the multiple scattering processes is not negligible. Our study is intended to fill this gap by means of a theoretical investigation of the applicability of the DOAS technique for the retrieval of amounts of atmospheric species from observations of the scattered solar light with a non-negligible contribution of the multiple scattering. Starting from the expansion of the intensity logarithm in the functional Taylor series we formulate the general form of the DOAS equation. The thereby introduced variational derivative of the intensity logarithm with respect to the variation of the gaseous absorption coefficient, which is often referred to as the weighting function, is demonstrated to be closely related to the air mass factor. Employing some approximations we show that the general DOAS equation can be rewritten in the form of the weighting function (WFDOAS), the modified (MDOAS), and the standard DOAS equations. For each of these forms a specific equation for the air mass factor follows which, in general, is not suitable for other forms of the DOAS equation. Furthermore, the validity range of the standard DOAS equation is quantitatively investigated using a suggested criterion of a weak absorption. The results presented in this study are intended to provide a basis for a better understanding of the applicability range of different forms of the DOAS equation as well as of the relationship between

  19. Differential optical absorption spectroscopy (DOAS) and air mass factor concept for a multiply scattering vertically inhomogeneous medium: theoretical consideration

    NASA Astrophysics Data System (ADS)

    Rozanov, V. V.; Rozanov, A. V.

    2010-02-01

    The Differential Optical Absorption Spectroscopy (DOAS) technique is widely used to retrieve amounts of atmospheric species from measurements of the direct solar light transmitted through the Earth's atmosphere as well as of the solar light scattered in the atmosphere or reflected from the Earth's surface. For the transmitted direct solar light the theoretical basis of the DOAS technique represented by the Beer-Lambert law is well studied. In contrast, scarcely investigated is the theoretical basis and validity range of the DOAS method for those cases where the contribution of the multiple scattering processes is not negligible. Our study is intended to fill this gap by means of a theoretical investigation of the applicability of the DOAS technique for the retrieval of amounts of atmospheric species from observations of the scattered solar light with a non-negligible contribution of the multiple scattering. Starting from the expansion of the intensity logarithm in the functional Taylor series we formulate the general form of the DOAS equation. The thereby introduced variational derivative of the intensity logarithm with respect to the variation of the gaseous absorption coefficient, which is often referred to as the weighting function, is demonstrated to be closely related to the air mass factor. Employing some approximations we show that the general DOAS equation can be rewritten in the form of the weighting function (WFDOAS), the modified (MDOAS), and the standard DOAS equations. For each of these forms a specific equation for the air mass factor follows which, in general, is not suitable for other forms of the DOAS equation. Furthermore, the validity range of the standard DOAS equation is quantitatively investigated using a suggested criterion of a weak absorption. The results presented in this study are intended to provide a basis for a better understanding of the applicability range of different forms of the DOAS equation as well as of the relationship between

  20. Aerosol properties associated with air masses arriving into the North East Atlantic during the 2008 Mace Head EUCAARI intensive observing period: an overview

    NASA Astrophysics Data System (ADS)

    Dall'Osto, M.; Ceburnis, D.; Martucci, G.; Bialek, J.; Dupuy, R.; Jennings, S. G.; Berresheim, H.; Wenger, J.; Healy, R.; Facchini, M. C.; Rinaldi, M.; Giulianelli, L.; Finessi, E.; Worsnop, D.; Ehn, M.; Mikkilä, J.; Kulmala, M.; O'Dowd, C. D.

    2010-09-01

    As part of the EUCAARI Intensive Observing Period, a 4-week campaign to measure aerosol physical, chemical and optical properties, atmospheric structure, and cloud microphysics was conducted from mid-May to mid-June, 2008 at the Mace Head Atmospheric Research Station, located at the interface of Western Europe and the N. E. Atlantic and centered on the west Irish coastline. During the campaign, continental air masses comprising both young and aged continental plumes were encountered, along with polar, Arctic and tropical air masses. Polluted-continental aerosol concentrations were of the order of 3000 cm-3, while background marine air aerosol concentrations were between 400-600 cm-3. The highest marine air concentrations occurred in polar air masses in which a 15 nm nucleation mode, with concentration of 1100 cm-3, was observed and attributed to open ocean particle formation. Continental air submicron chemical composition (excluding refractory sea salt) was dominated by organic matter, closely followed by sulphate mass. Although the concentrations and size distribution spectral shape were almost identical for the young and aged continental cases, hygroscopic growth factors (GF) and cloud condensation nuclei (CCN) to total condensation nuclei (CN) concentration ratios were significantly less in the younger pollution plume, indicating a more oxidized organic component to the aged continental plume. The difference in chemical composition and hygroscopic growth factor appear to result in a 40-50% impact on aerosol scattering coefficients and Aerosol Optical Depth, despite almost identical aerosol microphysical properties in both cases, with the higher values been recorded for the more aged case. For the CCN/CN ratio, the highest ratios were seen in the more age plume. In marine air, sulphate mass dominated the sub-micron component, followed by water soluble organic carbon, which, in turn, was dominated by methanesulphonic acid (MSA). Sulphate concentrations were

  1. 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.

  2. 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)

  3. Characterisation of a smartphone image sensor response to direct solar 305nm irradiation at high air masses.

    PubMed

    Igoe, D P; Amar, A; Parisi, A V; Turner, J

    2017-06-01

    This research reports the first time the sensitivity, properties and response of a smartphone image sensor that has been used to characterise the photobiologically important direct UVB solar irradiances at 305nm in clear sky conditions at high air masses. Solar images taken from Autumn to Spring were analysed using a custom Python script, written to develop and apply an adaptive threshold to mitigate the effects of both noise and hot-pixel aberrations in the images. The images were taken in an unobstructed area, observing from a solar zenith angle as high as 84° (air mass=9.6) to local solar maximum (up to a solar zenith angle of 23°) to fully develop the calibration model in temperatures that varied from 2°C to 24°C. The mean ozone thickness throughout all observations was 281±18 DU (to 2 standard deviations). A Langley Plot was used to confirm that there were constant atmospheric conditions throughout the observations. The quadratic calibration model developed has a strong correlation between the red colour channel from the smartphone with the Microtops measurements of the direct sun 305nm UV, with a coefficient of determination of 0.998 and very low standard errors. Validation of the model verified the robustness of the method and the model, with an average discrepancy of only 5% between smartphone derived and Microtops observed direct solar irradiances at 305nm. The results demonstrate the effectiveness of using the smartphone image sensor as a means to measure photobiologically important solar UVB radiation. The use of ubiquitous portable technologies, such as smartphones and laptop computers to perform data collection and analysis of solar UVB observations is an example of how scientific investigations can be performed by citizen science based individuals and groups, communities and schools.

  4. 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.

  5. The collision cross sections of iodide salt cluster ions in air via differential mobility analysis-mass spectrometry.

    PubMed

    Ouyang, Hui; Larriba-Andaluz, Carlos; Oberreit, Derek R; Hogan, Christopher J

    2013-12-01

    To date, most collision cross section (CCS) predictions have invoked gas molecule impingement-reemission rules in which specular and elastic scattering of spherical gas molecules from rigid polyatomic surfaces are assumed. Although such predictions have been shown to agree well with CCSs measured in helium bath gas, a number of studies reveal that these predictions do not agree with CCSs for ions in diatomic gases, namely, air and molecular nitrogen. To further examine the validity of specular-elastic versus diffuse-inelastic scattering models, we measured the CCSs of positively charged metal iodide cluster ions of the form [MI]n[M(+)]z, where M = Na, K, Rb, or Cs, n = 1 - 25, and z = 1 - 2. Measurements were made in air via differential mobility analysis mass spectrometry (DMA-MS). The CCSs measured are compared with specular-elastic as well as diffuse-inelastic scattering model predictions with candidate ion structures determined from density functional theory. It is found that predictions from diffuse-inelastic collision models agree well (within 5%) with measurements from sodium iodide cluster ions, while specular-elastic collision model predictions are in better agreement with cesium iodide cluster ion measurements. The agreement with diffuse-inelastic and specular-elastic predictions decreases and increases, respectively, with increasing cation mass. However, even when diffuse-inelastic cluster ion predictions disagree with measurements, the disagreement is of a near-constant factor for all ions, indicating that a simple linear rescaling collapses predictions to measurements. Conversely, rescaling cannot be used to collapse specular-elastic predictions to measurements; hence, although the precise impingement reemission rules remain ambiguous, they are not specular-elastic.

  6. 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.

  7. The Collision Cross Sections of Iodide Salt Cluster Ions in Air via Differential Mobility Analysis-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ouyang, Hui; Larriba-Andaluz, Carlos; Oberreit, Derek R.; Hogan, Christopher J.

    2013-12-01

    To date, most collision cross section (CCS) predictions have invoked gas molecule impingement-reemission rules in which specular and elastic scattering of spherical gas molecules from rigid polyatomic surfaces are assumed. Although such predictions have been shown to agree well with CCSs measured in helium bath gas, a number of studies reveal that these predictions do not agree with CCSs for ions in diatomic gases, namely, air and molecular nitrogen. To further examine the validity of specular-elastic versus diffuse-inelastic scattering models, we measured the CCSs of positively charged metal iodide cluster ions of the form [MI]n[M+]z, where M = Na, K, Rb, or Cs, n = 1 - 25, and z = 1 - 2. Measurements were made in air via differential mobility analysis mass spectrometry (DMA-MS). The CCSs measured are compared with specular-elastic as well as diffuse-inelastic scattering model predictions with candidate ion structures determined from density functional theory. It is found that predictions from diffuse-inelastic collision models agree well (within 5 %) with measurements from sodium iodide cluster ions, while specular-elastic collision model predictions are in better agreement with cesium iodide cluster ion measurements. The agreement with diffuse-inelastic and specular-elastic predictions decreases and increases, respectively, with increasing cation mass. However, even when diffuse-inelastic cluster ion predictions disagree with measurements, the disagreement is of a near-constant factor for all ions, indicating that a simple linear rescaling collapses predictions to measurements. Conversely, rescaling cannot be used to collapse specular-elastic predictions to measurements; hence, although the precise impingement reemission rules remain ambiguous, they are not specular-elastic.

  8. 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

  9. 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

  10. Development of a thermal desorption-gas chromatography-mass spectrometry method for determining personal care products in air.

    PubMed

    Ramírez, Noelia; Marcé, Rosa Maria; Borrull, Francesc

    2010-06-25

    This study describes the development of a new analytical method for determining 14 personal care products (PCPs) - nine synthetic musks, four parabens and one insect repellent - in air samples. The method is based on active sampling on sorbent tubes and thermal desorption-gas chromatography-mass spectrometry analysis, and is rapid, sensitive and drastically reduces the risk of sample contamination. Three kinds of tubes and traps were tested, those filled with Tenax TA being the most suitable for this study. Method validation showed good repeatability and reproducibility, low detection limits (between 0.03 ng m(-3) for DPMI and 12.5 ng m(-3) for propyl paraben) and good linearity for all compounds. Stability during storage indicated that samples must be kept refrigerated at 4 degrees C and analysed within 1 week of collection. The applicability of the technique to real samples was tested in different indoor and outdoor atmospheres. The total PCP values for indoor air ranged from 135 ng m(-3) in a pharmacy to 2838 ng m(-3) in a hairdresser's, whereas the values for outdoor air ranged from 14 ng m(-3) for a suburban environment to 26 ng m(-3) for an urban environment. In general, the most abundant synthetic musks were galaxolide (5.9-1256 ng m(-3)), musk xylene (1.6-766 ng m(-3)) and tonalide (1.1-138 ng m(-3)). Methyl and ethyl paraben (2.4-313 ng m(-3) and 1.8-117 ng m(-3), respectively) were the most abundant parabens. Although thermal desorption methods have been widely used for determining volatile organic compounds, they are rarely used with semi-volatile compounds. This study thus demonstrates that the thermal desorption method performs well with semi-volatile compounds and, for the first time, that it can be used for determining PCPs.

  11. 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.

  12. 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

    2013-03-05

    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.

  13. Simulation of solid oxide iron-air battery: Effects of heat and mass transfer on charge/discharge characteristics

    NASA Astrophysics Data System (ADS)

    Ohmori, Hiroko; Iwai, Hiroshi

    2015-07-01

    A time-dependent 2-D numerical simulation was performed on a solid oxide iron-air battery (SOIAB) to reveal the fundamental characteristics of this new system. The SOIAB is a rechargeable battery consisting of a solid oxide electrochemical cell (SOEC) and iron as a redox metal. A simple battery configuration was employed assuming a system with a small capacity. A simulation model for a unit element was developed considering heat and mass transfer in the system, taking both electrochemical and redox reactions into account. The numerical results showed the spatial and temporal changes in the temperature field in the charge and discharge operations, which were due to the combined effects of heat generation/absorption by the electrochemical and redox reactions and heat exchange with the air supplied through convective heat transfer. As the reaction rates are functions of the local temperature, the predicted results show the importance of considering the heat transfer phenomena in this system. It was also found that the active reaction region in the redox metal evolves with time. The nonuniform distribution of iron utilization is affected by the effective gas diffusion coefficients in the porous redox metal, and consequently the change in the current density distribution in the SOEC.

  14. 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.

  15. 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.

  16. 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).

  17. 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.

  18. Measurement error models in chemical mass balance analysis of air quality data

    NASA Astrophysics Data System (ADS)

    Christensen, William F.; Gunst, Richard F.

    The chemical mass balance (CMB) equations have been used to apportion observed pollutant concentrations to their various pollution sources. Typical analyses incorporate estimated pollution source profiles, estimated source profile error variances, and error variances associated with the ambient measurement process. Often the CMB model is fit to the data using an iteratively re-weighted least-squares algorithm to obtain the effective variance solution. We consider the chemical mass balance model within the framework of the statistical measurement error model (e.g., Fuller, W.A., Measurement Error Models, Wiley, NewYork, 1987), and we illustrate that the models assumed by each of the approaches to the CMB equations are in fact special cases of a general measurement error model. We compare alternative source contribution estimators with the commonly used effective variance estimator when standard assumptions are valid and when such assumptions are violated. Four approaches for source contribution estimation and inference are compared using computer simulation: weighted least squares (with standard errors adjusted for source profile error), the effective variance approach of Watson et al. (Atmos, Environ., 18, 1984, 1347), the Britt and Luecke (Technometrics, 15, 1973, 233) approach, and a method of moments approach given in Fuller (1987, p. 193). For the scenarios we consider, the simplistic weighted least-squares approach performs as well as the more widely used effective variance solution in most cases, and is slightly superior to the effective variance solution when source profile variability is large. The four estimation approaches are illustrated using real PM 2.5 data from Fresno and the conclusions drawn from the computer simulation are validated.

  19. Chemical composition of air masses transported from Asia to the U.S. West Coast during ITCT 2K2: Fossil fuel combustion versus biomass-burning signatures

    NASA Astrophysics Data System (ADS)

    de Gouw, J. A.; Cooper, O. R.; Warneke, C.; Hudson, P. K.; Fehsenfeld, F. C.; Holloway, J. S.; Hübler, G.; Nicks, D. K., Jr.; Nowak, J. B.; Parrish, D. D.; Ryerson, T. B.; Atlas, E. L.; Donnelly, S. G.; Schauffler, S. M.; Stroud, V.; Johnson, K.; Carmichael, G. R.; Streets, D. G.

    2004-12-01

    As part of the Intercontinental Transport and Chemical Transformation experiment in 2002 (ITCT 2K2), a National Oceanic and Atmospheric Administration (NOAA) WP-3D research aircraft was used to study the long-range transport of Asian air masses toward the west coast of North America. During research flights on 5 and 17 May, strong enhancements of carbon monoxide (CO) and other species were observed in air masses that had been transported from Asia. The hydrocarbon composition of the air masses indicated that the highest CO levels were related to fossil fuel use. During the flights on 5 and 17 May and other days, the levels of several biomass-burning indicators increased with altitude. This was true for acetonitrile (CH3CN), methyl chloride (CH3Cl), the ratio of acetylene (C2H2) to propane (C3H8), and, on May 5, the percentage of particles measured by the particle analysis by laser mass spectrometry (PALMS) instrument that were attributed to biomass burning based on their carbon and potassium content. An ensemble of back-trajectories, calculated from the U.S. west coast over a range of latitudes and altitudes for the entire ITCT 2K2 period, showed that air masses from Southeast Asia and China were generally observed at higher altitudes than air from Japan and Korea. Emission inventories estimate the contribution of biomass burning to the total emissions to be low for Japan and Korea, higher for China, and the highest for Southeast Asia. Combined with the origin of the air masses versus altitude, this qualitatively explains the increase with altitude, averaged over the whole ITCT 2K2 period, of the different biomass-burning indicators.

  20. 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.

  1. Variability of aerosol, gaseous pollutants and meteorological characteristics associated with continental, urban and marine air masses at the SW Atlantic coast of Iberia

    NASA Astrophysics Data System (ADS)

    Diesch, J.-M.; Drewnick, F.; Zorn, S. R.; von der Weiden-Reinmüller, S.-L.; Martinez, M.; Borrmann, S.

    2011-12-01

    Measurements of the ambient aerosol were performed at the Southern coast of Spain, within the framework of the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) project. The field campaign took place from 20 November until 9 December 2008 at the atmospheric research station "El Arenosillo" (37°5'47.76" N, 6°44'6.94" W). As the monitoring station is located at the interface between a natural park, industrial cities (Huelva, Seville) and the Atlantic Ocean a variety of physical and chemical parameters of aerosols and gas phase could be characterized in dependency on the origin of air masses. Backwards trajectories were examined and compared with local meteorology to classify characteristic air mass types for several source regions. Aerosol number and mass as well as polycyclic aromatic hydrocarbons and black carbon concentrations were measured in PM1 and size distributions were registered covering a size range from 7 nm up to 32 μm. The chemical composition of the non-refractory submicron aerosol was measured by means of an Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS). Gas phase analyzers monitored various trace gases (O3, SO2, NO, NO2, CO2) and a weather station provided meteorological parameters. Lowest average submicron particle mass and number concentrations were found in air masses arriving from the Atlantic Ocean with values around 2 μg m-3 and 1000 cm-3. These mass concentrations were about two to four times lower than the values recorded in air masses of continental and urban origins. For some species PM1-fractions in marine air were significantly larger than in air masses originating from Huelva, a closely located city with extensive industrial activities. The largest fraction of sulfate (54%) was detected in marine air masses and was to a high degree not neutralized. In addition small concentrations of methanesulfonic acid (MSA), a product of biogenic dimethyl sulfate (DMS) emissions could be identified in the particle phase. In all

  2. 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

  3. Air mass 1.5 global and direct solar simulation and secondary reference cell calibration using a filtered large area pulsed solar simulator

    NASA Technical Reports Server (NTRS)

    Mueller, Robert L.

    1985-01-01

    Spectral mismatch between a solar simulator and a desired spectrum can result in nearly 20 percent measurement error in the output of photovoltaic devices. This occurs when a crystalline silicon cell monitors the intensity of an unfiltered large area pulsed solar simulator (LAPSS) simulating the ASTM air mass 1.5 direct spectrum and the test device is amorphous silicon. The LAPSS spectral irradiance is modified with readily available glass UV filters to closely match either the ASTM air mass 1.5 direct or global spectrum. Measurement error is reduced to about 1 percent when using either filter if the reference cell and test device are the same general type.

  4. 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.

  5. Polycyclic aromatic hydrocarbons in air on small spatial and temporal scales - II. Mass size distributions and gas-particle partitioning

    NASA Astrophysics Data System (ADS)

    Lammel, Gerhard; Klánová, Jana; Ilić, Predrag; Kohoutek, Jiří; Gasić, Bojan; Kovacić, Igor; Škrdlíková, Lenka

    2010-12-01

    Polycyclic aromatic hydrocarbons (PAHs) were measured together with inorganic air pollutants at two urban sites and one rural background site in the Banja Luka area, Bosnia and Hercegovina, during 72 h in July 2008 using a high time resolution (5 samples per day) with the aim to study gas-particle partitioning, aerosol mass size distributions and to explore the potential of a higher time resolution (4 h-sampling). In the particulate phase the mass median diameters of the PAHs were found almost exclusively in the accumulation mode (0.1-1.0 μm of size). These were larger for semivolatile PAHs than for non-volatile PAHs. Gas-particle partitioning of semivolatile PAHs was strongly influenced by temperature. The results suggest that the Junge-Pankow model is inadequate to explain the inter-species variation and another process must be significant for phase partitioning which is less temperature sensitive than adsorption. Care should be taken when interpreting slopes m of plots of the type log K p = m log p L0 + b based on 24 h means, as these are found sensitive to the time averaging, i.e. tend to be higher than when based on 12 h-mean samples.

  6. 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

  7. 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.

  8. PMF receptor modelling of fine and coarse PM 10 in air masses governing monsoon conditions in Hanoi, northern Vietnam

    NASA Astrophysics Data System (ADS)

    Hien, P. D.; Bac, V. T.; Thinh, N. T. H.

    Fine and coarse PM 10 samples collected in Hanoi in 1999-2001 were analysed for black carbon (BC) and water soluble ions (WSI) and measured data were disaggregated according to three types of back trajectories, namely (1) northerly, over inland China, (2) northeasterly, over East China Sea and, (3) southwesterly over Indochina peninsula. Trajectories of types 1, 2 and 3 prevail in September/October-December, January-March/April and May-August, respectively. A source-receptor modelling was performed for each type of trajectories individually using the Positive Matrix Factorisation (PMF) technique. Six or seven sources were extracted for each trajectory type, including soil dust, primary and secondary emissions from local burning (LB), vehicle/road dust, sea salt, Cl-depleted marine aerosols and long-range transport (LRT). LRT contributes little to the coarse mass, but accounts for 50%, 34% and 33% of the fine mass in trajectories of types 1, 2 and 3, respectively. More than two-thirds of the fine mode sulphate are attributed to LRT and associated with ammonium. The comparison of LRT and LB source profiles suggests that air masses arriving from north-northeasterly trajectories are more polluted than those coming from the southwest. Therefore the contribution of LRT's aerosols further enhances the seasonal contrast in the particulate concentration with maximum in winter and minimum in summer. Various mechanisms of sulphate formation in LRT and LB were suggested based on the concentration ratios of [SO 42-]/[K +], [SO 42-]/[BC] and [NH 4+]/[SO 42-] for the two sources.

  9. 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.

  10. Biomass Burning versus Fossil Fuel Combustion Signatures of Air Masses Transported from Asia to the U.S. West Coast during ITCT2k2

    NASA Astrophysics Data System (ADS)

    de Gouw, J.; Cooper, O.; Warneke, C.; Hudson, P.; Brock, C.; Fehsenfeld, F.; Holloway, J.; Huebler, G.; Murphy, D.; Nowak, J.; Parrish, D.; Ryerson, T.; Trainer, M.; Atlas, E.

    2003-12-01

    The goal of the Intercontinental Transport and Chemical Transformation experiment in 2002 (ITCT2k2) was to study the transport of air pollution from Asia across the Pacific Ocean, and the implications for the background atmospheric composition at the surface in North America. During research flights of the NOAA WP-3 research aircraft on May 5 and 17, strong enhancements of carbon monoxide (CO) and other species were observed in air masses that had been transported from Asia in the free troposphere to North America. The hydrocarbon composition of the air masses indicated that the highest CO levels were related to fossil fuel use. During the flights on May 5, 17 and other days, the levels of several biomass-burning indicators increased with altitude. This was true for acetonitrile (CH3CN), methyl chloride (CH3Cl), the ratio of acetylene (C2H2) versus propane (C3H8), and the percentage of particles measured by the PALMS (particle analysis by laser mass spectrometry) instrument that were attributed to biomass burning based on their carbon and potassium content. An ensemble of back-trajectories, calculated from the U.S. west coast at various latitudes and pressures during the entire ITCT2k2 period, showed that air masses from South-East Asia and China were generally transported at higher altitudes than air from Japan and Korea. Emission inventories estimate the contribution of biomass burning to the total emissions to be low for Japan and Korea, higher for China, and the highest for South-East Asia. Combined with the origin of the air masses versus altitude determined by the back-trajectories, this explains the measured altitude profiles of the biomass burning indicators.

  11. Characterization of key aerosol, trace gas and meteorological properties and particle formation and growth processes dependent on air mass origins in coastal Southern Spain

    NASA Astrophysics Data System (ADS)

    Diesch, J.; Drewnick, F.; Sinha, V.; Williams, J.; Borrmann, S.

    2011-12-01

    The chemical composition and concentration of aerosols at a certain site can vary depending on season, the air mass source region and distance from sources. Regardless of the environment, new particle formation (NPF) events are one of the major sources for ultrafine particles which are potentially hazardous to human health. Grown particles are optically active and efficient CCN resulting in important implications for visibility and climate (Zhang et al., 2004). The study presented here is intended to provide information about various aspects of continental, urban and marine air masses reflected by wind patterns of the air arriving at the measurement site. Additionally we will be focusing on NPF events associated with different types of air masses affecting their emergence and temporal evolution. Measurements of the ambient aerosol, various trace gases and meteorological parameters were performed within the framework of the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) project. The field campaign took place from mid-November to mid-December 2008 at the atmospheric research station "El Arenosillo" located at the interface between a natural park, industrial cities (Huelva, Seville) and the Atlantic Ocean. Number and mass as well as PAH and black carbon concentrations were measured in PM1 and size distribution instruments covered the size range 6 nm up to 32 μm. The chemical composition of the non-refractory submicron aerosol was measured by means of an Aerosol Mass Spectrometer (AMS). In order to evaluate the characteristics of different air masses linking local and regional sources as well as NPF processes, characteristic air mass types were classified dependent on backwards trajectory pathways and local meteorology. Large nuclei mode concentrations in the number size distribution were found within continental and urban influenced air mass types due to frequently occurring NPF events. Exploring individual production and sink variables, sulfuric

  12. Satellite-based identification of tropopause folding signatures along air mass boundaries

    NASA Astrophysics Data System (ADS)

    Wimmers, Anthony James

    Tropopause folding is a significant though frequently underestimated source of mass exchange between the stratosphere and the troposphere. Although tropopause folds are inherently three-dimensional phenomena, empirical evidence shows that certain signature features in two-dimensional satellite products that are sensitive to tropopause height can be used to infer the vertical layering that characterizes tropopause folds. Both Altered Water Vapor (AWV) imagery and Total Ozone Mapping Spectrometer (TOMS) total ozone reveal significant gradients at the "openings" of tropopause folds, and the direction of the gradient indicates the direction of the intrusion. This is demonstrated empirically with a comparison of the satellite imagery to a data set of aircraft-based ozone lidar transects from the Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiment. Using the data set to optimize the parameters of this empirical relationship, a statistical model is developed to predict the location of tropopause folds based solely on the properties of AWV imagery, which operates on a hemispheric-scale domain and at the approximately 10-km resolution of the GOES water vapor channel. Validation of this model with evidence of tropopause folding from operational radiosonde data was only partially successful; the validation was not reliable enough to provide precise confirmation of the model parameter values, but it did provide some confirmation that the model was well calibrated. Application of this model over a February to May, 2000 time period provides a four-month "climatology" of tropopause folding activity around North America. During this time period, tropopause folding activity was strongest over the northeast Pacific and northwest Atlantic, and at a minimum in the high latitudes around Hudson Bay. Over the entire domain (25--63° N, 40--165° W), tropopause folding activity was greatest in March. This result does not prove that downward vertical transport from

  13. Recent trends of persistent organic pollutants in air in central Europe - Air monitoring in combination with air mass trajectory statistics as a tool to study the effectivity of regional chemical policy

    NASA Astrophysics Data System (ADS)

    Dvorská, A.; Lammel, G.; Holoubek, I.

    We use air mass back trajectory analysis of persistent organic pollutant (POP) levels monitored at a regional background site, Košetice, Czech Republic, as a tool to study the effectiveness of emission reduction measures taken in the last decade in the region. The representativity of the chosen trajectory starting height for air sampling near ground was ensured by excluding trajectories starting at time of inversions lower than their starting height. As the relevant pollutant sources are exclusively located in the atmospheric boundary layer, trajectory segments above this layer were also excluded from the analysis. We used a linear time weight to account for the influence of dispersion and deposition on trace components abundances and to quantify the ground source loading, a continuous measure for the influence of surface emissions. Hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), DDT, and two time periods, the years 1997-1999 and 2004-2006, were studied. The pollutant levels transported to Košetice decreased for all substances except HCB. Except for lindane seasonal emissions were insignificant. Increasing emissions of HCB were at least partly linked to the 2002 floods in the Danube basin. Major emissions of 1997-1999 which decreased significantly were in France (lindane), western Poland, Hungary and northern ex-Yugoslavia (technical HCH), and the Czech Republic (DDT). Emissions remaining in 2004-2006 include HCB and DDT in the northern Czech Republic, HCB and PCBs in Germany. Besides changes in emission strength meteorological factors influence the level of transported pollutant concentrations. The prevailing air flow pattern limits the geographic coverage of this analysis to central Europe and parts of western Europe. However, no POP monitoring stations exist in areas suitable for a possible extension of the study area.

  14. A Collaborative Study: Determination of Mycotoxins in Corn, Peanut Butter, and Wheat Flour Using Stable Isotope Dilution Assay (SIDA) and Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS).

    PubMed

    Zhang, Kai; Schaab, Matthew R; Southwood, Gavin; Tor, Elizabeth R; Aston, Linda S; Song, Wenlu; Eitzer, Brian; Majumdar, Sanghamitra; Lapainis, Theodore; Mai, Huy; Tran, Kevin; El-Demerdash, Aref; Vega, Victor; Cai, Yanxuan; Wong, Jon W; Krynitsky, Alexandra J; Begley, Timothy H

    2017-01-03

    A collaborative study was conducted to evaluate stable isotope dilution assay (SIDA) and LC-MS/MS for the simultaneous determination of aflatoxins B1, B2, G1, and G2; deoxynivalenol; fumonisins B1, B2, and B3; ochratoxin A; HT-2 toxin; T-2 toxin; and zearalenone in foods. Samples were fortified with 12 (13)C uniformly labeled mycotoxins ((13)C-IS) corresponding to the native mycotoxins and extracted with acetonitrile/water (50:50 v/v), followed by centrifugation, filtration, and LC-MS/MS analysis. In addition to certified reference materials, the six participating laboratories analyzed corn, peanut butter, and wheat flour fortified with the 12 mycotoxins at concentrations ranging from 1.0 to 1000 ng/g. Using their available LC-MS/MS platform, each laboratory developed in-house instrumental conditions for analysis. The majority of recoveries ranged from 80 to 120% with relative standard derivations (RSDs) <20%. Greater than 90% of the average recoveries of the participating laboratories were in the range of 90-110%, with repeatability RSDr (within laboratory) < 10% and reproducibility RSDR (among laboratory) < 15%. All Z scores of the results of certified reference materials were between -2 and 2. Using (13)C-IS eliminated the need for matrix-matched calibration standards for quantitation, simplified sample preparation, and achieved simultaneous identification and quantitation of multiple mycotoxins in a simple LC-MS/MS procedure.

  15. [Study on drawing aseptic gas in diluting drugs].

    PubMed

    Fan, Z C; Yu, F Y; Zou, F S

    1996-07-01

    In this study, the gas was drawn from sealed aseptic bottles, the blue flame of an alcohol lamp, and the air of the same treatment room. And the gas was put into aseptic solutions of 10% glucose separately and dripped. Then the samples were taken for bacteriaculture at appointed time-points. Meanwhile, the gases were drawn and put into aseptic solutions of 10% glucose separately. Then deactived penicillines were diluted with the solutions separately. Finally, the penicillines were mixed with 10% glucose and dripped. The samples were taken for bacteria-culture in the same way. The results showed that there was no colony existed in the gas from the sealed aseptic bottles and the flame of the alcohol lamp. However, colonies existed in the samples from the air of the treatment room. It is suggested that sealed aseptic gas should be drawn and kept for use in diluting drugs.

  16. Validation and Application of the Mass Balance Model To Determine the Effectiveness of Portable Air Purifiers in Removing Ultrafine and Submicrometer Particles in an Apartment.

    PubMed

    Lee, Wan-Chen; Catalano, Paul J; Yoo, Jun Young; Park, Chan Jung; Koutrakis, Petros

    2015-08-18

    We validated the use of the mass balance model to determine the effectiveness of portable air purifiers in removing ultrafine (<0.10 μm) and submicrometer particles (0.10-0.53 μm) in an apartment. We evaluated two identical portable air purifiers, equipped with high efficiency particulate air filters, for their performance under three different air flow settings and three target air exchange rates: 0.60, 0.90, and 1.20 h(-1). We subsequently used a mixed effects model to estimate the slope between the measured and modeled effectiveness by particle size. Our study showed that effectiveness was highly particle size-dependent. For example, at the lowest target air exchange rate, it ranged from 0.33 to 0.56, 0.51 to 0.75, and 0.60 to 0.81 for the three air purifier flow settings, respectively. Our findings suggested that filtration was the dominant removal mechanism for submicrometer particles, whereas deposition could play a more important role in ultrafine particle removal. We found reasonable agreement between measured and modeled effectiveness with size-resolved slopes ranging from 1.11 ± 0.06 to 1.25 ± 0.07 (mean ± SE), except for particles <35 nm. Our study design can be applied to investigate the performances of other portable air purifiers as well as the influences of various parameters on effectiveness in different residential settings.

  17. Air mass origin signals in δ 18O of tree-ring cellulose revealed by back-trajectory modeling at the monsoonal Tibetan plateau

    NASA Astrophysics Data System (ADS)

    Wernicke, Jakob; Hochreuther, Philipp; Grießinger, Jussi; Zhu, Haifeng; Wang, Lily; Bräuning, Achim

    2016-12-01

    A profound consideration of stable oxygen isotope source water origins is a precondition for an unambiguous palaeoenvironmental interpretation of terrestrial δ 18O archives. To stress the influence of air mass origins on widely used δ 18O tree-ring chronologies, we conducted correlation analyses between six annually resolved δ 18O tree-ring cellulose ( δ ^{18}O_{TC}) chronologies and mean annual air package origins obtained from backward trajectory modeling. This novel approach has been tested for a transect at the southeastern Tibetan plateau (TP), where air masses with different isotopic composition overlap. Detailed examinations of daily precipitation amounts and monthly precipitation δ 18O values ( δ ^{18}OP) were conducted with the ERA Interim and Laboratoire de Météorologie Dynamique General Circulation Model (LMDZiso) data, respectively. Particularly the southernmost study sites are influenced by a distinct amount effect. Here, air package origin δ ^{18}O_{TC} relations are generally weaker in contrast to our northern located study sites. We found that tree-ring isotope signatures at dry sites with less rain days per year tend to be influenced stronger by air mass origin than tree-ring isotope values at semi-humid sites. That implies that the local hydroclimate history inferred from δ ^{18}O_{TC} archives is better recorded at semi-humid sites.