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Sample records for aerosol chemical ionization

  1. High-Resolution Desorption Electrospray Ionization Mass Spectrometry for Chemical Characterization of Organic Aerosols

    SciTech Connect

    Laskin, Julia; Laskin, Alexander; Roach, Patrick J.; Slysz, Gordon W.; Anderson, Gordon A.; Nizkorodov, Serguei; Bones, David L.; Nguyen, Lucas

    2010-03-01

    Characterization of the chemical composition and chemical transformations of secondary organic aerosol (SOA) is both a major challenge and the area of greatest uncertainty in current aerosol research. This study presents the first application of desorption electrospray ionization combined with high-resolution mass spectrometry (DESI-MS) for detailed chemical characterization and studies of chemical aging of OA collected on Teflon substrates. DESI-MS offers unique advantages both for detailed characterization of chemically labile components in OA that cannot be detected using more traditional electrospray ionization mass spectrometry (ESI-MS) and for studying chemical aging of OA. DESI-MS enables rapid characterization of OA samples collected on substrates by eliminating the sample preparation stage. In addition, it enables detection and structural characterization of chemically labile molecules in OA samples by minimizing the residence time of analyte in the solvent. SOA produced by the ozonolysis of limonene (LSOA) was allowed to react with gaseous ammonia. Chemical aging resulted in measurable changes in the optical properties of LSOA observed using UV- visible spectroscopy. DESI-MS combined with tandem mass spectrometry experiments (MS/MS) enabled identification of species in aged LSOA responsible for absorption of the visible light. Detailed analysis of the experimental data allowed us to identify chemical changes induced by reactions of LSOA constituents with ammonia and distinguish between different mechanisms of chemical aging.

  2. Real-Time Chemical Analysis of E-Cigarette Aerosols By Means Of Secondary Electrospray Ionization Mass Spectrometry.

    PubMed

    García-Gómez, Diego; Gaisl, Thomas; Barrios-Collado, César; Vidal-de-Miguel, Guillermo; Kohler, Malcolm; Zenobi, Renato

    2016-02-12

    Chemical analysis of aerosols collected from electronic cigarettes (ECs) has shown that these devices produce vapors that contain harmful and potentially harmful compounds. Conventional analytical methods used for the analysis of electronic cigarettes do not reflect the actual composition of the aerosols generated because they usually neglect the changes in the chemical composition that occur during the aerosol generation process and after collection. The aim of this work was to develop and apply a method for the real-time analysis of electronic cigarette aerosols, based on the secondary electrospray ionization technique coupled to high-resolution mass spectrometry, by mimicking the "vaping" process. Electronic cigarette aerosols were successfully analyzed and quantitative differences were found between the liquids and aerosols. Thanks to the high sensitivity shown by this method, more than 250 chemical substances were detected in the aerosols, some of them showing a high correlation with the operating power of the electronic cigarettes. The method also allows proper quantification of several chemical components such as alkaloids and flavor compounds.

  3. Chemical Analysis of Organic Aerosols Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Laskin, A.; Laskin, J.; Nizkorodov, S.

    2013-12-01

    Nanospray Desorption Electrospray Ionization (nano-DESI) technique integrated with high resolution mass spectrometry (HR-MS) enables molecular level analysis of organic aerosol (OA) samples. In nano-DESI, analyte is desorbed into a small volume solvent bridge formed between two capillaries positioned in contact with analyte and enables fast and efficient characterization of OA collected on substrates without sample preparation. We report applications of the nano-DESI/HR-MS approach in a number of our recent studies focused on molecular identification of organic compounds in laboratory and in field collected OA samples. Reactive nano-DESI approach where selected reagent is added to the solvent is used for examining the presence of individual species containing specific functional groups and for their quantification within complex mixtures of OA. Specifically, we use the Girard's reagent T (GT) to probe and quantify carbonyl compounds in the SOA mixtures. We estimate for the first time the amounts of dimers and trimers in the SOA mixtures. We found that the most abundant dimer in limonene/O3 SOA was detected at the ˜0.5 pg level and the total amount of dimers and trimers in the analyzed sample was ˜11 pg. Understanding of the OA composition at the molecular level allowed us to identify key aging reactions, including the transformation of carbonyls to imines and carbonyl-imine oligomerization, that may contribute to the formation of brown carbon in the atmosphere.

  4. Chemical compositions of black carbon particle cores and coatings via soot particle aerosol mass spectrometry with photoionization and electron ionization.

    PubMed

    Canagaratna, Manjula R; Massoli, Paola; Browne, Eleanor C; Franklin, Jonathan P; Wilson, Kevin R; Onasch, Timothy B; Kirchstetter, Thomas W; Fortner, Edward C; Kolb, Charles E; Jayne, John T; Kroll, Jesse H; Worsnop, Douglas R

    2015-05-14

    Black carbon is an important constituent of atmospheric aerosol particle matter (PM) with significant effects on the global radiation budget and on human health. The soot particle aerosol mass spectrometer (SP-AMS) has been developed and deployed for real-time ambient measurements of refractory carbon particles. In the SP-AMS, black carbon or metallic particles are vaporized through absorption of 1064 nm light from a CW Nd:YAG laser. This scheme allows for continuous "soft" vaporization of both core and coating materials. The main focus of this work is to characterize the extent to which this vaporization scheme provides enhanced chemical composition information about aerosol particles. This information is difficult to extract from standard SP-AMS mass spectra because they are complicated by extensive fragmentation from the harsh 70 eV EI ionization scheme that is typically used in these instruments. Thus, in this work synchotron-generated vacuum ultraviolet (VUV) light in the 8-14 eV range is used to measure VUV-SP-AMS spectra with minimal fragmentation. VUV-SP-AMS spectra of commercially available carbon black, fullerene black, and laboratory generated flame soots were obtained. Small carbon cluster cations (C(+)-C5(+)) were found to dominate the VUV-SP-AMS spectra of all the samples, indicating that the corresponding neutral clusters are key products of the SP vaporization process. Intercomparisons of carbon cluster ratios observed in VUV-SP-AMS and SP-AMS spectra are used to confirm spectral features that could be used to distinguish between different types of refractory carbon particles. VUV-SP-AMS spectra of oxidized organic species adsorbed on absorbing cores are also examined and found to display less thermally induced decomposition and fragmentation than spectra obtained with thermal vaporization at 200 °C (the minimum temperature needed to quantitatively vaporize ambient oxidized organic aerosol with a continuously heated surface). The particle cores

  5. Chemical compositions of black carbon particle cores and coatings via soot particle aerosol mass spectrometry with photoionization and electron ionization.

    PubMed

    Canagaratna, Manjula R; Massoli, Paola; Browne, Eleanor C; Franklin, Jonathan P; Wilson, Kevin R; Onasch, Timothy B; Kirchstetter, Thomas W; Fortner, Edward C; Kolb, Charles E; Jayne, John T; Kroll, Jesse H; Worsnop, Douglas R

    2015-05-14

    Black carbon is an important constituent of atmospheric aerosol particle matter (PM) with significant effects on the global radiation budget and on human health. The soot particle aerosol mass spectrometer (SP-AMS) has been developed and deployed for real-time ambient measurements of refractory carbon particles. In the SP-AMS, black carbon or metallic particles are vaporized through absorption of 1064 nm light from a CW Nd:YAG laser. This scheme allows for continuous "soft" vaporization of both core and coating materials. The main focus of this work is to characterize the extent to which this vaporization scheme provides enhanced chemical composition information about aerosol particles. This information is difficult to extract from standard SP-AMS mass spectra because they are complicated by extensive fragmentation from the harsh 70 eV EI ionization scheme that is typically used in these instruments. Thus, in this work synchotron-generated vacuum ultraviolet (VUV) light in the 8-14 eV range is used to measure VUV-SP-AMS spectra with minimal fragmentation. VUV-SP-AMS spectra of commercially available carbon black, fullerene black, and laboratory generated flame soots were obtained. Small carbon cluster cations (C(+)-C5(+)) were found to dominate the VUV-SP-AMS spectra of all the samples, indicating that the corresponding neutral clusters are key products of the SP vaporization process. Intercomparisons of carbon cluster ratios observed in VUV-SP-AMS and SP-AMS spectra are used to confirm spectral features that could be used to distinguish between different types of refractory carbon particles. VUV-SP-AMS spectra of oxidized organic species adsorbed on absorbing cores are also examined and found to display less thermally induced decomposition and fragmentation than spectra obtained with thermal vaporization at 200 °C (the minimum temperature needed to quantitatively vaporize ambient oxidized organic aerosol with a continuously heated surface). The particle cores

  6. Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, X.; Underwood, J. S.; Xing, J.-H.; Mang, S. A.; Nizkorodov, S. A.

    2009-06-01

    Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone (0.1-300 ppm) and D-limonene (0.02-3 ppm) concentrations used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA prepared in these experiments. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.

  7. Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, X.; Underwood, J. S.; Xing, J.-H.; Mang, S. A.; Nizkorodov, S. A.

    2009-02-01

    Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone and D-limonene concentrations (0.1-300 ppm) used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA material. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.

  8. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2012-08-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was increased by a factor of 7.5 to 11 (e.g. ~40 ng m-3 for pinonic acid) by using the miniature Versatile Aerosol Concentration Enrichment System (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total sub-micron organic aerosol mass was estimated to be about 60%. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene) cannot account for all of the measured fragments, which illustrates the complexity of ambient aerosol and possibly indicates unidentified or underestimated biogenic SOA precursor in the boreal forest.

  9. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2013-02-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft-ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was improved by a factor of 7.5 to 11 (e.g. ∼40 ng m3 for pinonic acid) by using the miniature versatile aerosol concentration enrichment system (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total submicron organic aerosol mass was estimated to be about 60%, based on the response of pinic acid. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft-ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene) cannot account for all of the measured fragments. Possible explanations for those unaccounted fragments are the presence of unidentified or underestimated biogenic SOA precursors, or that different products are formed by a different oxidant

  10. Characterization of Organic Nitrate Formation in Limonene Secondary Organic Aerosol using High-Resolution Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Faxon, Cameron; Hammes, Julia; Peng, Jianfei; Hallquist, Mattias; Pathak, Ravi

    2016-04-01

    Previous work has shown that organic nitrates (RONO2) are prevalent in the boundary layer, and can contribute significantly to secondary organic aerosol formation. Monoterpenes, including limonene, have been shown to be precursors for the formation of these organic nitrates. Limonene has two double bonds, either of which may be oxidized by NO3 or O3. This leads to the generation of products that can subsequently condense or partition into the particle phase, producing secondary organic aerosol. In order to further elucidate the particle and gas phase product distribution of organic nitrates forming from the reactions of limonene and the nitrate radical (NO3), a series of experiments were performed in the Gothenburg Flow Reactor for Oxidation Studies at Low Temperatures (G-FROST), described by previous work. N2O5 was used as the source for NO3 and NO2, and a characterized diffusion source was used to introduce limonene into the flow reactor. All experiments were conducted in the absence of light, and the concentration of limonene was increased step-wise throughout each experiment to modify the ratio of N2O5to limonene. The experiments were conducted such that both limonene- and N2O5-limited regimes were present. Gas and particle phase products were measured using an iodide High-Resolution Time-of-Flight Mass Spectrometer (HR-ToF-CIMS) coupled to a Filter Inlet for Gases and AEROsols (FIGAERO, and particle size and SOA mass concentrations were derived using a Scanning Mobility Particle Sizer (SMPS). CIMS measurement techniques have previously been employed for the measurement of organic nitrate products of such compounds using multiple reagent ions. The use of this instrumentation allowed for the identification of chemical formulas for gas and particle phase species. The findings from the experiments will be presented in terms of the relative gas-particle partitioning of major products and the effects of N2O5/limonene ratios on product distributions. Additionally, a

  11. Analysis of organic aerosols using a micro-orifice volatilization impactor coupled to an atmospheric-pressure chemical ionization mass spectrometer.

    PubMed

    Brüggemann, Martin; Vogel, Alexander Lucas; Hoffmann, Thorsten

    2014-01-01

    We present the development and characterization of a combination of a micro-orifice volatilization impactor (MOVI) and an ion trap mass spectrometer (IT/MS) with an atmospheric-pressure chemical ionization (APCI) source. The MOVI is a multi-jet impactor with 100 nozzles, allowing the collection of aerosol particles by inertial impaction on a deposition plate. The pressure drop behind the nozzles is approximately 5%, resulting in a pressure of 96kPa on the collection surface for ambient pressures of 101.3 kPa. The cut-point diameter (diameter of 50% collection efficiency) is at 0.13 microm for a sampling flow rate of 10 L min(-1). After the collection step, aerosol particles are evaporated by heating the impaction surface and transferred into the APCI-IT/MS for detection of the analytes. APCI was used in the negative ion mode to detect predominantly mono- and dicarboxylic acids, which are major oxidation products of biogenic terpenes. The MOVI-APCI-IT/MS instrument was used for the analysis of laboratory-generated secondary organic aerosol (SOA), which was generated by ozonolysis of alpha-pinene in a 100 L continuous-flow reactor under dark and dry conditions. The combination of the MOVI with an APCI-IT/MS improved the detection Limits for small dicarboxylic acids, such as pinic acid, compared to online measurements by APCI-IT/MS. The Limits of detection and quantification for pinic acid were determined by external calibration to 4.4 ng and 13.2 ng, respectively. During a field campaign in the southern Rocky Mountains (USA) in summer 2011 (BEACHON-RoMBAS), the MOVI-APCI-IT/MS was applied for the analysis of ambient organic aerosols and the quantification of individual biogenic SOA marker compounds. Based on a measurement frequency of approximately 5 h, a diurnal cycle for pinic acid in the sampled aerosol particles was found with maximum concentrations at night (median: 10.1 ngm(-3)) and minimum concentrations during the day (median: 8.2 ng m(-3)), which is likely

  12. Ionization detection system for aerosols

    DOEpatents

    Jacobs, Martin E.

    1977-01-01

    This invention relates to an improved smoke-detection system of the ionization-chamber type. In the preferred embodiment, the system utilizes a conventional detector head comprising a measuring ionization chamber, a reference ionization chamber, and a normally non-conductive gas triode for discharging when a threshold concentration of airborne particulates is present in the measuring chamber. The improved system utilizes a measuring ionization chamber which is modified to minimize false alarms and reductions in sensitivity resulting from changes in ambient temperature. In the preferred form of the modification, an annular radiation shield is mounted about the usual radiation source provided to effect ionization in the measuring chamber. The shield is supported by a bimetallic strip which flexes in response to changes in ambient temperature, moving the shield relative to the source so as to vary the radiative area of the source in a manner offsetting temperature-induced variations in the sensitivity of the chamber.

  13. Aerosol Analysis via Electrostatic Precipitation-Electrospray Ionization Mass Spectrometry.

    PubMed

    He, Siqin; Li, Lin; Duan, Hongxu; Naqwi, Amir; Hogan, Christopher J

    2015-07-01

    Electrospray ionization (ESI) is the preferred mode of ion generation for mass analysis of many organic species, as alternative ionization techniques can lead to appreciable analyte fragmentation. For this reason, ESI is an ideal method for the analysis of species within aerosol particles. However, because of their low concentrations (∼10 μg/m(3)) in most environments, ESI has been applied sparingly in aerosol particle analysis; aerosol mass spectrometers typically employ analyte volatilization followed by electron ionization or chemical ionization, which can lead to a considerable degree of analyte fragmentation. Here, we describe an approach to apply ESI to submicrometer and nanometer scale aerosol particles, which utilizes unipolar ionization to charge particles, electrostatic precipitation to collect particles on the tip of a Tungsten rod, and subsequently, by flowing liquid over the rod, ESI and mass analysis of the species composing collected particles. This technique, which we term electrostatic precipitation-ESI-MS (EP-ESI-MS), is shown to enable analysis of nanogram quantities of collected particles (from aerosol phase concentrations as low as 10(2) ng m(-3)) composed of cesium iodide, levoglucosan, and levoglucosan within a carbon nanoparticle matrix. With EP-ESI-MS, the integrated mass spectrometric signals are found to be a monotonic function of the mass concentration of analyte in the aerosol phase. We additionally show that EP-ESI-MS has a dynamic range of close to 5 orders of magnitude in mass, making it suitable for molecular analysis of aerosol particles in laboratory settings with upstream particle size classification, as well as analysis of PM 2.5 particles in ambient air. PMID:26024017

  14. Chemistry of α-pinene and naphthalene oxidation products generated in a Potential Aerosol Mass (PAM) chamber as measured by acetate chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chhabra, P. S.; Lambe, A. T.; Canagaratna, M. R.; Stark, H.; Jayne, J. T.; Onasch, T. B.; Davidovits, P.; Kimmel, J. R.; Worsnop, D. R.

    2014-07-01

    Recent developments in high resolution, time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made possible the direct detection of atmospheric organic compounds in real-time with high sensitivity and with little or no fragmentation, including low volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, for the first time, we examine gas-phase O3 and OH oxidation products of α-pinene and naphthalene formed in the PAM flow reactor with an HR-ToF-CIMS using acetate reagent ion chemistry. Integrated OH exposures ranged from 1.2 × 1011 to 9.7 × 1011 molec cm-3 s, corresponding to approximately 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. We present a method that estimates vapor pressures of organic molecules using the measured O/C ratio, H/C ratio, and carbon number for each compound detected by the CIMS. The predicted condensed-phase SOA average acid yields and O/C and H/C ratios agree within uncertainties with previous AMS measurements and ambient CIMS results. While acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.

  15. Chemistry of α-pinene and naphthalene oxidation products generated in a Potential Aerosol Mass (PAM) chamber as measured by acetate chemical ionization mass spectrometry

    DOE PAGES

    Chhabra, P. S.; Lambe, A. T.; Canagaratna, M. R.; Stark, H.; Jayne, J. T.; Onasch, T. B.; Davidovits, P.; Kimmel, J. R.; Worsnop, D. R.

    2014-07-01

    Recent developments in high resolution, time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made possible the direct detection of atmospheric organic compounds in real-time with high sensitivity and with little or no fragmentation, including low volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, for the first time, we examine gas-phase O3 and OH oxidation products of α-pinene and naphthalene formed in the PAM flow reactor with an HR-ToF-CIMS using acetate reagent ion chemistry. Integrated OH exposures ranged from 1.2 × 1011 to 9.7 × 1011 molec cm−3 s, corresponding to approximately 1.0 to 7.5 daysmore » of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. We present a method that estimates vapor pressures of organic molecules using the measured O/C ratio, H/C ratio, and carbon number for each compound detected by the CIMS. The predicted condensed-phase SOA average acid yields and O/C and H/C ratios agree within uncertainties with previous AMS measurements and ambient CIMS results. While acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.« less

  16. Identification of oxidized organic atmospheric species during the Southern Oxidant and Aerosol Study (SOAS) using a novel Ion Mobility Time-of-Flight Chemical Ionization Mass Spectrometer (IMS-ToF-CIMS)

    NASA Astrophysics Data System (ADS)

    Krechmer, J.; Canagaratna, M.; Kimmel, J.; Junninen, H.; Knochenmuss, R.; Cubison, M.; Massoli, P.; Stark, H.; Jayne, J. T.; Surratt, J. D.; Jimenez, J. L.; Worsnop, D. R.

    2013-12-01

    We present results from the field deployment of a novel Ion Mobility Time-of-flight Chemical Ionization Mass Spectrometer (CI-IMS-TOF) during the Southern Oxidant and Aerosol Study (SOAS). IMS-TOF is a 2-dimensional analysis method, which separates gas-phase ions by mobility prior to determination of mass-to-charge ratio by mass spectrometry. Ion mobility is a unique physical property that is determined by the collisional cross section of an ion. Because mobility depends on size and shape, the IMS measurement is able to resolve isomers and isobaric compounds. Additionally, trends in IMS-TOF data space can be used to identify relationships between ions, such as common functionality or polymeric series. During SOAS we interfaced the IMS-TOF to a nitrate ion (NO3-) chemical ionization source that enables the selective ionization of highly oxidized gas phase species (those having a high O:C ratio) through clustering with the reagent ion. Highly oxidized products of terpenes and isoprene are important secondary organic aerosol precursors (SOA) that play an uncertain but important role in particle-phase chemistry. We present several case studies of atmospheric events during SOAS that exhibited elevated concentrations of sulfuric acid and/or organics. These events exhibited a rise in particle number and provide an opportunity to examine the role that organic species may have in local atmospheric new particle formation events. We also present the results from the field deployment and subsequent laboratory studies utilizing a Potential Aerosol Mass (PAM) flow reactor as the inlet for the CI-IMS-TOF. The reactor draws in ambient air and exposes it to high concentrations of the OH radical, created by photolysis O3 in the presence of water. The highly oxidized products are then sampled directly by the CI-IMS-TOF. We performed several experiments including placing pine and deciduous plants directly in front of the reactor opening and observed large increases in the number and

  17. Development of a new corona discharge based ion source for high resolution time-of-flight chemical ionization mass spectrometer to measure gaseous H2SO4 and aerosol sulfate

    NASA Astrophysics Data System (ADS)

    Zheng, Jun; Yang, Dongsen; Ma, Yan; Chen, Mindong; Cheng, Jin; Li, Shizheng; Wang, Ming

    2015-10-01

    A new corona discharge (CD) based ion source was developed for a commercial high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) (Aerodyne Research Inc.) to measure both gaseous sulfuric acid (H2SO4) and aerosol sulfate after thermal desorption. Nitrate core ions (NO3-) were used as reagent ions and were generated by a negative discharge in zero air followed by addition of excess nitrogen dioxide (NO2) to convert primary ions and hydroxyl radicals (OH) into NO3- ions and nitric acid (HNO3). The CD-HRToF-CIMS showed no detectable interference from hundreds parts per billion by volume (ppbv) of sulfur dioxide (SO2). Unlike the atmospheric pressure ionization (API) ToF-CIMS, the CD ion source was integrated onto the ion-molecule reaction (IMR) chamber and which made it possible to measure aerosol sulfate by coupling to a filter inlet for gases and aerosols (FIGAERO). Moreover, compared with a quadrupole-based mass spectrometer, the desired HSO4- signal was detected by its exact mass of m/z 96.960, which was well resolved from the potential interferences of HCO3-ṡ(H2O)2 (m/z 97.014) and O-ṡH2OṡHNO3 (m/z 97.002). In this work, using laboratory-generated standards the CD-HRToF-CIMS was demonstrated to be able to detect as low as 3.1 × 105 molecules cm-3 gaseous H2SO4 and 0.5 μg m-3 ammonium sulfate based on 10-s integration time and two times of the baseline noise. The CD ion source had the advantages of low cost and a simple but robust structure. Since the system was non-radioactive and did not require corrosive HNO3 gas, it can be readily field deployed. The CD-HRToF-CIMS can be a powerful tool for both field and laboratory studies of aerosol formation mechanism and the chemical processes that were critical to understand the evolution of aerosols in the atmosphere.

  18. Chemical characterization of secondary organic aerosol constituents from isoprene ozonolysis in the presence of acidic aerosol

    NASA Astrophysics Data System (ADS)

    Riva, Matthieu; Budisulistiorini, Sri Hapsari; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.

    2016-04-01

    Isoprene is the most abundant non-methane hydrocarbon emitted into Earth's atmosphere and is predominantly derived from terrestrial vegetation. Prior studies have focused largely on the hydroxyl (OH) radical-initiated oxidation of isoprene and have demonstrated that highly oxidized compounds, such as isoprene-derived epoxides, enhance the formation of secondary organic aerosol (SOA) through heterogeneous (multiphase) reactions on acidified sulfate aerosol. However, studies on the impact of acidified sulfate aerosol on SOA formation from isoprene ozonolysis are lacking and the current work systematically examines this reaction. SOA was generated in an indoor smog chamber from isoprene ozonolysis under dark conditions in the presence of non-acidified or acidified sulfate seed aerosol. The effect of OH radicals on SOA chemical composition was investigated using diethyl ether as an OH radical scavenger. Aerosols were collected and chemically characterized by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). Analysis revealed the formation of highly oxidized compounds, including organosulfates (OSs) and 2-methylterols, which were significantly enhanced in the presence of acidified sulfate seed aerosol. OSs identified in the chamber experiments were also observed and quantified in summertime fine aerosol collected from two rural locations in the southeastern United States during the 2013 Southern Oxidant and Aerosol Study (SOAS).

  19. Chemical Properties of Combustion Aerosols: An Overview

    EPA Science Inventory

    A wide variety of pyrogenic and anthropogenic sources emit fine aerosols to the atmosphere. The physical and chemical properties of these aerosols are of interest due to their influence on climate, human health, and visibility. Aerosol chemical composition is remarkably complex. ...

  20. Detection of chemical agent aerosols

    NASA Astrophysics Data System (ADS)

    Fox, Jay A.; Ahl, Jeffrey L.; D'Amico, Francis M.; Vanderbeek, Richard G.; Moon, Raphael; Swim, Cynthia R.

    1999-05-01

    One of the major threats presented by a chemical agent attack is that of a munition exploding overhead and 'raining' aerosols which can contaminate surfaces when they impact. Since contact with these surfaces can be fatal, it is imperative to know when such an attack has taken place and the likely threat density and location. We present the results of an experiment designed to show the utility of a CO2 lidar in detecting such an attack. Testing occurred at Dugway Proving Grounds, Utah and involved the simulation of an explosive airburst chemical attack. Explosions occurred at a height of 30 m and liquid droplets from two chemicals, PEG-200 (polyethylene glycol 200) and TEP (triethylphosphate), were expelled and fell to the ground. The munition was the U.S. Army M9 Simulator, Projectile, Airburst, Liquid (SPAL) system that is designed for chemical warfare training exercises. The instrument that was used to detect the presence of the aerosols was the Laser Standoff Chemical Detector (LSCD) which is a light detection and ranging (LIDAR) system that utilizes a rapidly tunable, pulsed CO2 laser. The LIDAR scanned a horizontal path approximately 5 - 8 m above the ground in order to measure the concentration of liquid deposition. The LIDAR data were later correlated with card data to determine how well the system could predict the location and quantity of liquid deposition on the ground.

  1. Development of Soft Ionization for Particulate Organic Detection with the Aerodyne Aerosol Mass Spectrometer

    SciTech Connect

    Trimborn, A; Williams, L R; Jayne, J T; Worsnop, D R

    2008-06-19

    During this DOE SBIR Phase II project, we have successfully developed several soft ionization techniques, i.e., ionization schemes which involve less fragmentation of the ions, for use with the Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS). Vacuum ultraviolet single photon ionization was demonstrated in the laboratory and deployed in field campaigns. Vacuum ultraviolet single photon ionization allows better identification of organic species in aerosol particles as shown in laboratory experiments on single component particles, and in field measurements on complex multi-component particles. Dissociative electron attachment with lower energy electrons (less than 30 eV) was demonstrated in the measurement of particulate organics in chamber experiments in Switzerland, and is now a routine approach with AMS systems configured for bipolar, negative ion detection. This technique is particularly powerful for detection of acidic and other highly oxygenated secondary organic aerosol (SOA) chemical functionality. Low energy electron ionization (10 to 12 eV) is also a softer ionization approach routinely available to AMS users. Finally, Lithium ion attachment has been shown to be sensitive to more alkyl-like chemical functionality in SOA. Results from Mexico City are particularly exciting in observing changes in SOA molecular composition under different photochemical/meteorological conditions. More recent results detecting biomass burns at the Montana fire lab have demonstrated quantitative and selective detection of levoglucosan. These soft ionization techniques provide the ToF-AMS with better capability for identifying organic species in ambient atmospheric aerosol particles. This, in turn, will allow more detailed study of the sources, transformations and fate of organic-containing aerosol.

  2. Applications of online high resolution time of flight chemical ionization mass spectrometry (HRToF-CIMS): opportunities and challenges for aircraft measurements, atmosphere-ecosystem exchange, and organic aerosol composition

    NASA Astrophysics Data System (ADS)

    Thornton, J. A.; Lopez-Hilfiker, F.; Lee, B. H.; D'Ambro, E.; Mohr, C.; Gaston, C.; Schobesberger, S.

    2015-12-01

    Over the past five years, field deployable high resolution time of flight chemical ionization mass spectrometers (HRToF-CIMS) have been developed and deployed for a range of problems relevant to atmospheric chemistry. The inherent duty cycle, dynamic range, mass accuracy, and resolving power of these instruments provide transformative capabilities for deriving new insights into atmospheric composition. We present examples of these capabilities from the deployments of the University of Washington HRToF-CIMS aboard research aircraft, an eddy flux tower in a boreal forest, and to measure organic aerosol composition upon temperature-programmed thermal desorption in field and chamber experiments. Specific examples include measurements of reactive halogens with all relevant isotopes simultaneously resolved from potential interferences, the opportunity for discovery, after the fact, of previously unmeasured or unexpected compounds with acquisition of the full mass spectrum, and providing a broad survey of the 100s of organic compounds that desorb from complex isoprene and monoterpene derived secondary organic aerosol matrices. While there are unique opportunities, there are also significant technical challenges to realizing the full analytical potential these instruments can provide. Many of these challenges are common to any analytical technique, but perhaps seemingly more demanding for HRToF-CIMS, such as the presumed need to calibrate 100s of molecular ion signals routinely detected in each spectrum. We detail some of the more pressing challenges and our approach towards addressing them.

  3. LASER DESORPTION IONIZATION OF ULTRAFINE AEROSOL PARTICLES. (R823980)

    EPA Science Inventory

    On-line analysis of ultrafine aerosol particle in the 12 to 150 nm size range is performed by
    laser desorption/ionization. Particles are size selected with a differential mobility analyzer and then
    sent into a linear time-of-flight mass spectrometer where they are ablated w...

  4. Measurements of aerosol chemical composition in boreal forest summer conditions

    NASA Astrophysics Data System (ADS)

    ńijälä, M.; Junninen, H.; Ehn, M.; Petäjä, T.; Vogel, A.; Hoffmann, T.; Corrigan, A.; Russell, L.; Makkonen, U.; Virkkula, A.; Mäntykenttä, J.; Kulmala, M.; Worsnop, D.

    2012-04-01

    Boreal forests are an important biome, covering vast areas of the northern hemisphere and affecting the global climate change via various feedbacks [1]. Despite having relatively few anthropogenic primary aerosol sources, they always contain a non-negligible aerosol population [2]. This study describes aerosol chemical composition measurements using Aerodyne Aerosol Mass Spectrometer (C-ToF AMS, [3]), carried out at a boreal forest area in Hyytiälä, Southern Finland. The site, Helsinki University SMEAR II measurement station [4], is situated at a homogeneous Scots pine (Pinus sylvestris) forest stand. In addition to the station's permanent aerosol, gas phase and meteorological instruments, during the HUMPPA (Hyytiälä United Measurements of Photochemistry and Particles in Air) campaign in July 2010, a very comprehensive set of atmospheric chemistry measurement instrumentation was provided by the Max Planck Institute for chemistry, Johannes Gutenberg-University, University of California and the Finnish Meteorological institute. In this study aerosol chemical composition measurements from the campaign are presented. The dominant aerosol chemical species during the campaign were the organics, although periods with elevated amounts of particulate sulfates were also seen. The overall AMS measured particle mass concentrations varied from near zero to 27 μg/m observed during a forest fire smoke episode. The AMS measured aerosol mass loadings were found to agree well with DMPS derived mass concentrations (r2=0.998). The AMS data was also compared with three other aerosol instruments. The Marga instrument [5] was used to provide a quantitative semi-online measurement of inorganic chemical compounds in particle phase. Fourier Transform Infrared Spectroscopy (FTIR) analysis was performed on daily filter samples, enabling the identification and quantification of organic aerosol subspecies. Finally an Atmospheric Pressure Chemical Ionization Ion Trap Mass Spectrometer (APCI

  5. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

    SciTech Connect

    University of California; ERC, Incorporated, Edwards Air Force Base; Air Force Research Laboratory, Edwards Air Force Base; National Synchrotron Radiation Research Center; Institute of Chemistry, Hebrew University; Koh, Christine J.; Liu, Chen-Lin; Harmon, Christopher W.; Strasser, Daniel; Golan, Amir; Kostko, Oleg; Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; Leone, Stephen R.

    2011-07-19

    Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N?]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca?]), are generated by vaporizing ionic liquid submicron aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Photoionization efficiency curves in the near threshold ionization region of isolated ion pairs of [Emim+][Tf2N?]ionic liquid vapor are compared for an aerosol source and an effusive source, revealing changes in the appearance energy due to the amount of internal energy in the ion pairs. The aerosol source has a shift to higher threshold energy (~;;0.3 eV), attributed to reduced internal energy of the isolated ion pairs. The method of ionic liquid submicron aerosol particle vaporization, for reactive ionic liquids such as hypergolic species, is a convenient, thermally ?cooler? source of isolated intact ion pairs in the gas phase compared to effusive sources.

  6. Soft Ionization of Thermally Evaporated Hypergolic Ionic Liquid Aerosols

    SciTech Connect

    Koh, Christine J.; Liu, Chen-Lin; Harmon, Christopher W.; Strasser, Daniel; Golan, Amir; Kostko, Oleg; Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; Leone, Stephen R.

    2011-04-20

    Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N–]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca–]), are generated by vaporizing ionic liquid submicrometer aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Also, hotoionization efficiency curves in the near threshold ionization region of isolated ion pairs of [Emim+][Tf2N] ionic liquid vapor are compared for an aerosol source and an effusive source, revealing changes in the appearance energy due to the amount of internal energy in the ion pairs. The aerosol source has a shift to higher threshold energy (~0.3 eV), attributed to reduced internal energy of the isolated ion pairs. Lastly, the method of ionic liquid submicrometer aerosol particle vaporization, for reactive ionic liquids such as hypergolic species, is a convenient, thermally “cooler” source of isolated intact ion pairs in the gas phase compared to effusive sources.

  7. CHEMICAL ANALYSIS METHODS FOR ATMOSPHERIC AEROSOL COMPONENTS

    EPA Science Inventory

    This chapter surveys the analytical techniques used to determine the concentrations of aerosol mass and its chemical components. The techniques surveyed include mass, major ions (sulfate, nitrate, ammonium), organic carbon, elemental carbon, and trace elements. As reported in...

  8. Atmospheric aerosols as prebiotic chemical reactors

    PubMed Central

    Dobson, Christopher M.; Ellison, G. Barney; Tuck, Adrian F.; Vaida, Veronica

    2000-01-01

    Aerosol particles in the atmosphere have recently been found to contain a large number of chemical elements and a high content of organic material. The latter property is explicable by an inverted micelle model. The aerosol sizes with significant atmospheric lifetimes are the same as those of single-celled organisms, and they are predicted by the interplay of aerodynamic drag, surface tension, and gravity. We propose that large populations of such aerosols could have afforded an environment, by means of their ability to concentrate molecules in a wide variety of physical conditions, for key chemical transformations in the prebiotic world. We also suggest that aerosols could have been precursors to life, since it is generally agreed that the common ancestor of terrestrial life was a single-celled organism. The early steps in some of these initial transformations should be accessible to experimental investigation. PMID:11035775

  9. Atmospheric aerosols as prebiotic chemical reactors

    NASA Astrophysics Data System (ADS)

    Dobson, Christopher M.; Ellison, G. Barney; Tuck, Adrian F.; Vaida, Veronica

    2000-10-01

    Aerosol particles in the atmosphere have recently been found to contain a large number of chemical elements and a high content of organic material. The latter property is explicable by an inverted micelle model. The aerosol sizes with significant atmospheric lifetimes are the same as those of single-celled organisms, and they are predicted by the interplay of aerodynamic drag, surface tension, and gravity. We propose that large populations of such aerosols could have afforded an environment, by means of their ability to concentrate molecules in a wide variety of physical conditions, for key chemical transformations in the prebiotic world. We also suggest that aerosols could have been precursors to life, since it is generally agreed that the common ancestor of terrestrial life was a single-celled organism. The early steps in some of these initial transformations should be accessible to experimental investigation.

  10. Microphysical and Chemical Properties of Agricultural Aerosols

    NASA Astrophysics Data System (ADS)

    Brooks, S. D.; Moon, S.; Littleton, R.; Auvermann, B.

    2005-12-01

    Due to significant atmospheric loadings of agricultural dust aerosols, the aerosol's ability to contribute significantly to climate forcing on a regional to global level has been a topic of recent interest. Efforts have been made to quantify both the aerosol extinction of the total aerosol population and the hygroscopic and chemical properties of individual particles at a cattle feedyard near Canyon, Texas. Measurements of aerosol extinction are made using open-path transmissometry. Our results show that extinction varies significantly with relative humidity. To further explore the hygroscopic nature of the particles, size-resolved aerosol samples are collected using a cascade impactor system (7 stages ranging from 0.6 micron to 16 micron diameter) and hygroscopicity measurements are conducted on these using an Environmental Scanning Electron Microscope (ESEM). Complimentary determination of the elemental composition of individual particles is performed using Energy Dispersive X-ray Spectroscopy. Results of the optical properties, hygroscopicity and chemical composition of aerosols will be presented and atmospheric implications discussed.

  11. Physical and Chemical Properties of Anthropogenic Aerosols: An Overview

    EPA Science Inventory

    Aerosol chemical composition is complex. Combustion aerosols can comprise tens of thousands of organic compounds, refractory brown and black carbon, heavy metals, cations, anions, salts, and other inorganic phases. Aerosol organic matter normally contains semivolatile material th...

  12. Physical and Chemical Properties of Anthropogenic Aerosols: An overview

    EPA Science Inventory

    A wide variety of anthropogenic sources emit fine aerosols to the atmosphere. The physical and chemical properties of these aerosols are of interest due to their influence on climate, human health, and visibility. Aerosol chemical composition is complex. Combustion aerosols can c...

  13. ON-LINE ANALYSIS OF AQUEOUS AEROSOLS BY LASER DESORPTION IONIZATION. (R823980)

    EPA Science Inventory

    In this work the effects of water on the laser desorption ionization mass spectra of single aerosol particles are explored. Aqueous aerosols are produced by passing dry particles through a humid environment so that they undergo deliquescent growth. Laser desorption ionization is ...

  14. Miniature Dual-Corona Ionizer for Bipolar Charging of Aerosol

    PubMed Central

    Qi, Chaolong; Kulkarni, Pramod

    2015-01-01

    A corona-based bipolar charger has been developed for use in compact, field-portable mobility size spectrometers. The charger employs an aerosol flow cavity exposed to two corona ionizers producing ions of opposite polarity. Each corona ionizer houses two electrodes in parallel needle-mesh configuration and is operated at the same magnitude of corona current. Experimental measurement of detailed charge distribution of near-monodisperse particles of different diameter in the submicrometer size range showed that the charger is capable of producing well-defined, consistent bipolar charge distributions for flow rates up to 1.5 L/min and aerosol concentration up to 107 per cm3. For particles with preexisting charge of +1, 0, and −1, the measured charge distributions agreed well with the theoretical distributions within the range of experimental and theoretical uncertainties. The transmission efficiency of the charger was measured to be 80% for 10 nm particles (at 0.3 L/min and 5 μA corona current) and increased with increasing diameter beyond this size. Measurement of uncharged fractions at various combinations of positive and negative corona currents showed the charger performance to be insensitive to fluctuations in corona current. Ion concentrations under positive and negative unipolar operation were estimated to be 8.2 × 107 and 3.37 × 108 cm−3 for positive and negative ions; the n·t product value under positive corona operation was independently estimated to be 8.5 × 105 s/cm3. The ion concentration estimates indicate the charger to be capable of “neutralizing” typical atmospheric and industrial aerosols in most measurement applications. The miniature size, simple and robust operation makes the charger suitable for portable mobility spectrometers. PMID:26512158

  15. Complete chemical analysis of aerosol particles in real-time

    SciTech Connect

    Yang, Mo; Reilly, P.T.A.; Gieray, R.A.; Whitten, W.B.; Ramsey, J.M.

    1996-12-31

    Real-time mass spectrometry of individual aerosol particles using an ion trap mass spectrometer is described. The microparticles are sampled directly from the air by a particle inlet system into the vacuum chamber. An incoming particle is detected as it passes through two CW laser beams and a pulsed laser is triggered to intercept the particle for laser ablation ionization at the center of the ion trap. The produced ions are analyzed by the ion trap mass spectrometer. Ions of interest are selected and dissociated through collision with buffer gas atoms for further fragmentation analysis. Real-time chemical analyses of inorganic, organic, and bacterial aerosol articles have been demonstrated. It has been confirmed that the velocity and the size of the incoming particles highly correlate to each other. The performance of the inlet system, particle detection, and preliminary results are discussed.

  16. The Development of Electrostatic Precipitation-Electrospray Ionization Mass Spectrometry (EP-ESI-MS) for Atmospheric Aerosol Analysis

    NASA Astrophysics Data System (ADS)

    He, S.; Hogan, C. J., Jr.; Naqwi, A.; Gross, D. S.; Li, L.; Duan, H.; Jiang, L.; Flowers, J.; Grubb, E.; Au, L.

    2015-12-01

    Chemical composition analysis of atmospheric aerosols is of considerable interest and has been facilitated by mass spectrometry. Electrospray ionization (ESI) is a suitable mode of ion generation of many organic species comprising aerosol particles, as it leads to minimal analyte fragmentation. However, particles exist in the atmosphere at mass concentrations of the order 10 μg/m3 or less in many environments and are highly heterogeneous; low concentrations and chemical complexity have limited ESI application in aerosol analysis. In this presentation, the development of an approach to apply ESI to molecules within submicrometer and nanometer scale aerosol particles is discussed. The technique, which we term electrostatic precipitation-ESI-MS (EP-ESI-MS), utilizes unipolar ionization to charge particles, electrostatic precipitation to collect particles on the tip of a tungsten rod, and subsequently, by flowing liquid over the rod, ESI and mass analysis of dissolved species originating from the collected particles. EP-ESI-MS is shown to enable analysis of nanogram quantities of collected inorganic and organic components. Furthermore, it is coupled with a tandem mass spectrometry and challenged with oxidation products of α-pinene to investigate its capability of enabling structure analysis of complex organic compounds in aerosol particles. With EP-ESI-MS, the identification of chemical components in aerosol particles is realized and the integrated mass spectrometric signals are found to be a monotonic function of the analyte mass concentration in the aerosol phase. Additionally, it is shown to have a dynamic range of 5 orders of magnitude in mass, making it suitable for molecular analysis of aerosol particles in laboratory settings, as well as analysis of atmospheric aerosols in ambient air.

  17. Chemical protection against ionizing radiation. Final report

    SciTech Connect

    Livesey, J.C.; Reed, D.J.; Adamson, L.F.

    1984-08-01

    The scientific literature on radiation-protective drugs is reviewed. Emphasis is placed on the mechanisms involved in determining the sensitivity of biological material to ionizing radiation and mechanisms of chemical radioprotection. In Section I, the types of radiation are described and the effects of ionizing radiation on biological systems are reviewed. The effects of ionizing radiation are briefly contrasted with the effects of non-ionizing radiation. Section II reviews the contributions of various natural factors which influence the inherent radiosensitivity of biological systems. Inlcuded in the list of these factors are water, oxygen, thiols, vitamins and antioxidants. Brief attention is given to the model describing competition between oxygen and natural radioprotective substances (principally, thiols) in determining the net cellular radiosensitivity. Several theories of the mechanism(s) of action of radioprotective drugs are described in Section III. These mechanisms include the production of hypoxia, detoxication of radiochemical reactive species, stabilization of the radiobiological target and the enhancement of damage repair processes. Section IV describes the current strategies for the treatment of radiation injury. Likely areas in which fruitful research might be performed are described in Section V. 495 references.

  18. Molecular Characterization of Organic Aerosols Using Nanospray Desorption/Electrospray Ionization-Mass Spectrometry

    SciTech Connect

    Roach, Patrick J.; Laskin, Julia; Laskin, Alexander

    2010-10-01

    Nanospray desorption electrospray ionization (Nano-DESI) combined with high-resolution mass spectrometry (HR/MS) is a promising approach for detailed chemical characterization of atmospheric organic aerosol (OA) collected in laboratory and field experiments. In Nano-DESI analyte is desorbed into a solvent bridge formed between two capillaries and the analysis surface, which enables fast and efficient characterization of OA collected on substrates without special sample preparation. Stable signals achieved using Nano-DESI make it possible to obtain high-quality HR/MS data using only a small amount of material (<10 ng). Furthermore, Nano-DESI enables efficient detection of chemically labile compounds in OA, which is important for understanding chemical aging phenomena.

  19. Improving Molecular Level Chemical Speciation of Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Worton, D. R.; Decker, M.; Isaacman, G. A.; Chan, A.; Wilson, K. R.; Goldstein, A. H.

    2013-12-01

    A substantial fraction of fine mode aerosols are organic with the majority formed in the atmosphere through oxidation of gas phase compounds emitted from a variety of natural and man-made sources. As a result, organic aerosols are comprised of thousands of individual organic species whose complexity increases exponentially with carbon number and degree of atmospheric oxidation. Chemical characterization of individual compounds present in this complex mixture provides information on sources and transformation processes that are critical for apportioning organic carbon from an often convoluted mixture of sources and to constrain oxidation mechanisms needed for atmospheric models. These compounds also affect the physical and optical properties of the aerosol but the vast majority remain unidentified and missing from published mass spectral libraries because of difficulties in separating and identifying them. We have developed improved methodologies for chemical identification in order to better understand complex environmental mixtures. Our approach has been to combine two-dimensional gas chromatography with high resolution time of flight mass spectrometry (GC×GC-HRTOFMS) and both traditional electron ionization (EI) and vacuum ultraviolet (VUV) photoionization. GC×GC provides improved separation of individual compounds over traditional one dimensional GC and minimizes co-elution of peaks resulting in mass spectra that are virtually free of interferences. VUV ionization is a ';soft' ionization technique that reduces fragmentation and enhances the abundance of the parent or molecular ion, which when combined with high resolution mass spectrometry can provide molecular formulas for chromatographic peaks. We demonstrate our methodology by applying it to identify more than 500 individual compounds in aerosol filter samples collected at Blodgett Forest, a rural site in the Sierra Nevada Mountains. Using the EI NIST mass spectral library and molecular formulas determined

  20. Comparison of Aerosol Mass Spectrometer and Aerosol Chemical Speciation Monitor Measurements of Secondary Organic Aerosol Formation in Smog Chamber Studies

    NASA Astrophysics Data System (ADS)

    Croteau, P. L.; Hunter, J. F.; Daumit, K. E.; Carrasquillo, A. J.; Cross, E. S.; Canagaratna, M.; Jayne, J.; Worsnop, D. R.; Kroll, J. H.

    2012-12-01

    Thermal vaporization-electron impact ionization (TV-EI) mass spectrometry is a powerful tool for understanding the chemistry of secondary organic aerosol (SOA) formation and atmospheric aging. The Aerodyne Aerosol Mass Spectrometer (AMS) and recently developed Aerosol Chemical Speciation Monitor (ACSM) are two instruments that utilize the same TV-EI technique. The ACSM trades the particle sizing capability, sensitivity, speed, and resolution of the AMS for simplicity, affordability, and ease of operation - enabling stand-alone continuous sampling for extended periods of time. Here we present results of an intercomparison between a high-resolution AMS and an ACSM. Three well-studied SOA formation chamber experiments were conducted: isoprene photooxidation under high NOx conditions, m-xylene photooxidation under high NOx conditions, and α-pinene ozonolysis under low NOx conditions. Comparisons between time-series and mass spectra from these experiments, along with positive matrix factorization analysis results demonstrate that the ACSM, while it does not provide the same level of detail as an AMS, is a suitable tool for exploring the chemistry of SOA formation in chamber studies.

  1. Elucidating the Chemical Complexity of Organic Aerosol Constituents Measured During the Southeastern Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Yee, L.; Isaacman, G. A.; Spielman, S. R.; Worton, D. R.; Zhang, H.; Kreisberg, N. M.; Wilson, K. R.; Hering, S. V.; Goldstein, A. H.

    2013-12-01

    Thousands of volatile organic compounds are uniquely created in the atmosphere, many of which undergo chemical transformations that result in more highly-oxidized and often lower vapor pressure species. These species can contribute to secondary organic aerosol, a complex mixture of organic compounds that is still not chemically well-resolved. Organic aerosol collected on filters taken during the Southeastern Oxidant and Aerosol Study (SOAS) constitute hundreds of unique chemical compounds. Some of these include known anthropogenic and biogenic tracers characterized using standardized analytical techniques (e.g. GC-MS, UPLC, LC-MS), but the majority of the chemical diversity has yet to be explored. By employing analytical techniques involving sample derivatization and comprehensive two-dimensional gas chromatography (GC x GC) with high-resolution-time-of-flight mass spectrometry (HR-ToF-MS), we elucidate the chemical complexity of the organic aerosol matrix along the volatility and polarity grids. Further, by utilizing both electron impact (EI) and novel soft vacuum ultraviolet (VUV) ionization mass spectrometry, a greater fraction of the organic mass is fully speciated. The GC x GC-HR-ToF-MS with EI/VUV technique efficiently provides an unprecedented level of speciation for complex ambient samples. We present an extensive chemical characterization and quantification of organic species that goes beyond typical atmospheric tracers in the SOAS samples. We further demonstrate that complex organic mixtures can be chemically deconvoluted by elucidation of chemical formulae, volatility, functionality, and polarity. These parameters provide insight into the sources (anthropogenic vs. biogenic), chemical processes (oxidation pathways), and environmental factors (temperature, humidity), controlling organic aerosol growth in the Southeastern United States.

  2. Aerosol matrix-assisted laser desorption ionization for liquid chromatography/time-of-flight mass spectrometry

    SciTech Connect

    Murray, K.K.; Lewis, T.M.; Beeson, M.D.; Russell, D.H. )

    1994-05-15

    We report the application of aerosol matrix-assisted laser desorption ionization (MALDI) to liquid chromatography/mass spectrometry (LC/MS). The aerosol MALDI experiment uses aerosol liquid introduction in conjunction with pulsed UV laser ionization to form ions from large biomolecules in solution. Mass analysis is achieved in a time-of-flight mass spectrometer. In the LC/MALDI-MS experiment, the matrix solution is combined with the column effluent in a mixing tee, LC/MALDI-MS is demonstrated for the separation of bradykinin, gramicidin S, and myoglobin. 32 refs., 8 figs., 1 tab.

  3. Apparatus for rapid measurement of aerosol bulk chemical composition

    DOEpatents

    Lee, Yin-Nan E.; Weber, Rodney J.

    2003-01-01

    An apparatus and method for continuous on-line measurement of chemical composition of aerosol particles with a fast time resolution are provided. The apparatus includes a modified particle size magnifier for producing activated aerosol particles and a collection device which collects the activated aerosol particles into a liquid stream for quantitative analysis by analytical methods. The method provided for on-line measurement of chemical composition of aerosol particles includes exposing aerosol carrying sample air to hot saturated steam thereby forming activated aerosol particles; collecting the activated aerosol particles by a collection device for delivery as a jet stream onto an impaction surface; flushing off the activated aerosol particles from the impaction surface into a liquid stream for delivery of the collected liquid stream to an analytical instrument for quantitative measurement.

  4. Apparatus for rapid measurement of aerosol bulk chemical composition

    DOEpatents

    Lee, Yin-Nan E.; Weber, Rodney J.; Orsini, Douglas

    2006-04-18

    An apparatus for continuous on-line measurement of chemical composition of aerosol particles with a fast time resolution is provided. The apparatus includes an enhanced particle size magnifier for producing activated aerosol particles and an enhanced collection device which collects the activated aerosol particles into a liquid stream for quantitative analysis by analytical means. Methods for on-line measurement of chemical composition of aerosol particles are also provided, the method including exposing aerosol carrying sample air to hot saturated steam thereby forming activated aerosol particles; collecting the activated aerosol particles by a collection device for delivery as a jet stream onto an impaction surface; and flushing off the activated aerosol particles from the impaction surface into a liquid stream for delivery of the collected liquid stream to an analytical instrument for quantitative measurement.

  5. The Effect of Solvent on the Analysis of Secondary Organic Aerosol Using Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Bateman, Adam P.; Walser, Maggie L.; Dessiaterik, Yury; Laskin, Julia; Laskin, Alexander; Nizkorodov, Serguei

    2008-08-29

    Solvent-analyte reactions in organic aerosol (OA) extracts prepared for analysis by electrospray ionization mass spectrometry (ESI-MS) were examined. Secondary organic aerosol (SOA) produced by ozonation of d-limonene as well as several test organic chemicals with functional groups typical for OA constituents were dissolved and stored in methanol, d3-methanol, acetonitrile, and d3-acetonitrile to investigate the extent and relative rates of reactions between analyte and solvent. High resolution ESI-MS showed that reactions of carbonyls with methanol produce significant amounts of hemiacetals and acetals on time scales ranging from several minutes to several days, with the reaction rates increasing in acidified solutions. Carboxylic acid groups were observed to react with methanol resulting in the formation of esters. In contrast, acetonitrile extracts showed no evidence of reactions with analyte molecules, suggesting that acetonitrile is the preferred solvent for SOA extraction. The use of solvent-analyte reactivity as an analytical chemistry tool for the improved characterization of functional groups in complex organic mixtures was also demonstrated. Direct comparison between ESI mass spectra of the same SOA samples extracted in reactive (methanol) versus non-reactive (acetonitrile) solvents was used to estimate the relative fractions of ketones (≥38%), aldehydes (≥6%), and carboxylic acids (≥55%) in d-limonene SOA.

  6. Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    St. Clair, J. M.; Spencer, K. M.; Beaver, M. R.; Crounse, J. D.; Paulot, F.; Wennberg, P. O.

    2014-04-01

    Chemical ionization mass spectrometry (CIMS) enables online, rapid, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are generally capable of the measurement of hydroxyacetone, an analyte with known but minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. The single quadrupole CIMS measurement of glycolaldehyde was demonstrated during the ARCTAS-CARB (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites - California Air Resources Board) 2008 campaign, while triple quadrupole CIMS measurements of glycolaldehyde and hydroxyacetone were demonstrated during the BEARPEX (Biosphere Effects on Aerosols and Photochemistry Experiment) 2009 campaign. Enhancement ratios of glycolaldehyde in ambient biomass-burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.

  7. Intercomparison of an Aerosol Chemical Speciation Monitor (ACSM) with ambient fine aerosol measurements in downtown Atlanta, Georgia

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Canagaratna, M. R.; Croteau, P. L.; Baumann, K.; Edgerton, E. S.; Kollman, M. S.; Ng, N. L.; Verma, V.; Shaw, S. L.; Knipping, E. M.; Worsnop, D. R.; Jayne, J. T.; Weber, R. J.; Surratt, J. D.

    2014-07-01

    Currently, there are a limited number of field studies that evaluate the long-term performance of the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011-2012. Intercomparison of two collocated ACSMs resulted in strong correlations (r2 > 0.8) for all chemical species, except chloride (r2 = 0.21) indicating that ACSM instruments are capable of stable and reproducible operation. In general, speciated ACSM mass concentrations correlate well (r2 > 0.7) with the filter-adjusted continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Correlations of the ACSM NR-PM1 (non-refractory particulate matter with aerodynamic diameter less than or equal to 1 μm) plus elemental carbon (EC) with tapered element oscillating microbalance (TEOM) PM2.5 and Federal Reference Method (FRM) PM1 mass are strong with r2 > 0.7 and r2 > 0.8, respectively. Discrepancies might be attributed to evaporative losses of semi-volatile species from the filter measurements used to adjust the collocated continuous measurements. This suggests that adjusting the ambient aerosol continuous measurements with results from filter analysis introduced additional bias to the measurements. We also recommend to calibrate the ambient aerosol monitoring instruments using aerosol standards rather than gas-phase standards. The fitting approach for ACSM relative ionization for sulfate was shown to improve the comparisons between ACSM and collocated measurements in the absence of calibrated values, suggesting the importance of adding sulfate calibration into the ACSM calibration routine.

  8. Electron Impact Ionization of SOx, NOx and H2 SO4 - The Aerosol Relevance

    NASA Astrophysics Data System (ADS)

    Vaishnav, B. G.; Patel, U. R.; Joshipura, K. N.; Pandya, S. H.

    2016-05-01

    This paper reports our theoretical studies on electron impact ionization of reactive molecules SOx, NOx (x = 1-3) and H2 SO4, at incident energies from threshold to 2000 eV. Motivation for this work derives from the relevance of these molecules in connection with atmospheric aerosols analysis through mass spectrometric studies and quantification of mass concentrations amongst the aerosol species. The ionization efficiency of a molecule is directly proportional to ionization cross section, which represents the efficiency on a per-molecule basis. Study of electron impact ionization cross sections of molecules, like H2 SO4, versus number of electrons in the molecule can lead to information about mass concentrations of aerosol species. We have employed in this work, the well-known spherical complex potential formalism (SCOP), which provides total elastic as well as inelastic cross sections, wherein the latter includes ionization cross sections. We have developed a method to extract ionization cross section from calculated inelastic cross section by introducing a ratio function, in a semi-empirical formalism known as CSP-ic method. For SOx and NOx targets single-centre scattering calculations are performed, while for H2 SO4, the additivity rule augmented with overlap or screening corrections, has been employed. The calculated cross sections are examined as functions of incident electron energy along with comparisons (theoretical or experimental) as available.

  9. LASER DESORPTION/IONIZATION OF SINGLE ULTRAFINE MULTICOMPONENT AEROSOLS. (R823980)

    EPA Science Inventory

    Laser desorption/ionization characteristics of single
    ultrafine multicomponent aerosols have been investigated.
    The results confirm earlier findings that (a) the negative
    ion spectra are dominated by free electrons and (b) the ion
    yield-to-mass ratio is higher for ...

  10. Development of a Metastable Atom Bombardment (MAB) Source for Penning Ionization Time-of-flight Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Robinson, C. B.; Kimmel, J. R.; David, D.; Jayne, J. T.; Trimborn, A.; Worsnop, D. R.; Jimenez, J. L.

    2009-12-01

    The Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS) utilizes thermal vaporization followed by electron ionization (EI) to convert aerosol components to gas-phase ions. The method enables quantification of chemical classes, but the extensive fragmentation caused by EI limits the specificity of both chemical analysis and source identification by factor analysis. To better identify the molecular components of aerosols, we have constructed a metastable atom bombardment (MAB) ionization source that can be interfaced to standard ToF-AMS hardware. A beam of metastable rare gas atoms is produced by a low-voltage DC discharge and focused toward the vaporization plume, yielding Penning Ionization of the analyte molecules. By changing gases, the excited energies of the metastables can be adjusted between 20.61 eV (He) and 9.92 eV (Kr). Source parameters, including pressures, current, geometry, and materials, were optimized for He, Ar, and Kr. Instrument sensitivity and induced fragmentation was characterized for each using lab-generated oleic acid particles. The demonstrated sensitivities are 0.1% of EI (3% of the SNR of EI in the V-mode, comparable to the Q-AMS SNR), which is sufficient for ambient monitoring. A metastable flux of 2.6e14 sr-1sec-1 has been achieved. The MAB-AMS has been deployed to the FLAME-3 campaign at the USDA Fire Sciences Laboratory in Missoula, MT, and used to sample smoke from open burning of different biomass samples. Preliminary results from FLAME-3 will be presented.

  11. Parameterization of Aerosol Sinks in Chemical Transport Models

    NASA Technical Reports Server (NTRS)

    Colarco, Peter

    2012-01-01

    The modelers point of view is that the aerosol problem is one of sources, evolution, and sinks. Relative to evolution and sink processes, enormous attention is given to the problem of aerosols sources, whether inventory based (e.g., fossil fuel emissions) or dynamic (e.g., dust, sea salt, biomass burning). On the other hand, aerosol losses in models are a major factor in controlling the aerosol distribution and lifetime. Here we shine some light on how aerosol sinks are treated in modern chemical transport models. We discuss the mechanisms of dry and wet loss processes and the parameterizations for those processes in a single model (GEOS-5). We survey the literature of other modeling studies. We additionally compare the budgets of aerosol losses in several of the ICAP models.

  12. Chemical distribution in high-solids paint overspray aerosols.

    PubMed

    D'Arcy, J B; Chan, T L

    1990-03-01

    The chemical composition of high-solids basecoat paint overspray aerosols was determined as a function of particle size. Detailed information on the chemical composition of the overspray aerosols is important in health hazard evaluation since the composition and distribution within the airborne particles may differ significantly from the bulk paint material. This study was conducted in a typical down-draft paint booth equipped with air-atomized spray painting equipment. A fixed paint target was used to simulate typical overspray generation conditions and the aerosols were collected isokinetically with a seven-stage cascade impactor for size-fractionated analysis. The overspray aerosol from six paints consisted of organic paint binders with varying amounts of inorganic species as pigments or luster enhancers. These overspray aerosols had mass median aerodynamic diameters (MMAD) ranging from 2.9 to 9.7 microns. The size-fractionated paint samples collected on the impaction stages were analyzed by energy dispersive X-ray spectrometry on a scanning electron microscope (SEM-EDXRS) to identify the metallic elements. Atomic absorption spectrometry was used to determine the mass distribution of aluminum and iron as indicators of nonuniform distribution. Three of the aerosols containing aluminum were found to have bimodal distributions with most aluminum distributions having cumulative MMADs larger than the total aerosol. Iron in the aerosols was bimodal for three of the paints with all samples having an overall iron MMAD less than or equal to the overspray aerosol MMAD. Analysis using ultraviolet spectrometry revealed that the organic compounds present in the size-fractionated particulate samples consisted of a single, polydispersed mode with an MMAD similar to that of the total overspray aerosol.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2327324

  13. Chemical distribution in high-solids paint overspray aerosols

    SciTech Connect

    D'Arcy, J.B.; Chan, T.L. )

    1990-03-01

    The chemical composition of high-solids basecoat paint overspray aerosols was determined as a function of particle size. Detailed information on the chemical composition of the overspray aerosols is important in health hazard evaluation since the composition and distribution within the airborne particles may differ significantly from the bulk paint material. This study was conducted in a typical down-draft paint booth equipped with air-atomized spray painting equipment. A fixed paint target was used to simulate typical overspray generation conditions and the aerosols were collected isokinetically with a seven-stage cascade impactor for size-fractionated analysis. The overspray aerosol from six paints consisted of organic paint binders with varying amounts of inorganic species as pigments or luster enhancers. These overspray aerosols had mass median aerodynamic diameters (MMAD) ranging from 2.9 to 9.7 microns. The size-fractionated paint samples collected on the impaction stages were analyzed by energy dispersive X-ray spectrometry on a scanning electron microscope (SEM-EDXRS) to identify the metallic elements. Atomic absorption spectrometry was used to determine the mass distribution of aluminum and iron as indicators of nonuniform distribution. Three of the aerosols containing aluminum were found to have bimodal distributions with most aluminum distributions having cumulative MMADs larger than the total aerosol. Iron in the aerosols was bimodal for three of the paints with all samples having an overall iron MMAD less than or equal to the overspray aerosol MMAD. Analysis using ultraviolet spectrometry revealed that the organic compounds present in the size-fractionated particulate samples consisted of a single, polydispersed mode with an MMAD similar to that of the total overspray aerosol.

  14. Atmospheric pressure chemical ionization source. 1. Ionization of compounds in the gas phase.

    PubMed

    Andrade, Francisco J; Shelley, Jacob T; Wetzel, William C; Webb, Michael R; Gamez, Gerardo; Ray, Steven J; Hieftje, Gary M

    2008-04-15

    A novel chemical ionization source for organic mass spectrometry is introduced. This new source uses a glow discharge in the flowing afterglow mode for the generation of excited species and ions. The direct-current gas discharge is operated in helium at atmospheric pressure; typical operating voltages and currents are around 500 V and 25 mA, respectively. The species generated by this atmospheric pressure glow discharge are mixed with ambient air to generate reagent ions (mostly ionized water clusters and NO+), which are then used for the ionization of gaseous organic compounds. A wide variety of substances, both polar and nonpolar, can be ionized. The resulting mass spectra generally show the parent molecular ion (M+ or MH+) with little or no fragmentation. Proton transfer from ionized water clusters has been identified as the main ionization pathway. However, the presence of radical molecular ions (M+) for some compounds indicates that other ionization mechanisms are also involved. The analytical capabilities of this source were evaluated with a time-of-flight mass spectrometer, and preliminary characterization shows very good stability, linearity, and sensitivity. Limits of detection in the single to tens of femtomole range are reported for selected compounds. PMID:18345693

  15. Analysis of the chemical and physical properties of combustion aerosols: Properties overview

    EPA Science Inventory

    Aerosol chemical composition is remarkably complex. Combustion aerosols can comprise tens of thousands of organic compounds and fragments, refractory carbon, metals, cations, anions, salts, and other inorganic phases and substituents [Hays et al., 2004]. Aerosol organic matter no...

  16. Physical and Chemical Characterization of Carbonaceous Aerosols in Korea

    NASA Astrophysics Data System (ADS)

    Choung, S.; Jin, J. S.; Hwang, G. S.; Jang, K. S.; Han, W. S.; OH, J.; Kwon, Y.

    2014-12-01

    Atmospheric aerosols have been recently paid attention more in environmental research due to their negative effects on air quality, public health, and climate change. The aerosols contain approximately >20-50% carbonaceous components such as organic carbon (OC) and black carbon (BC) (or elemental carbon [EC]) derived from organic compounds, biomass burning, and incomplete combustion of fossil fuels. The physical, chemical, and biological properties of atmospheric aerosols are strongly dependent on the carbonaceous components. In particular, the BC could significantly affect the regional air quality in the northeastern Asia, because China is one of the foremost BC emission country in the world. Previous studies have mainly focused on the quantification and source identification for carbonaceous aerosols. However, understanding of physical and chemical properties for the carbonaceous aerosols related to environmental contamination and toxicity was still incomplete due to analytical difficulties. This study is addressed to evaluate the contribution of carbonaceous aerosols to air pollution through the surface, mass spectroscopic, and electron microscopic analyses, and determination of chemical composition and structure using the air particulate matter (PM2.5 and >PM2.5) samples.

  17. Intercomparison of an Aerosol Chemical Speciation Monitor (ACSM) with ambient fine aerosol measurements in Downtown Atlanta, Georgia

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Canagaratna, M. R.; Croteau, P. L.; Baumann, K.; Edgerton, E. S.; Kollman, M. S.; Ng, N. L.; Verma, V.; Shaw, S. L.; Knipping, E. M.; Worsnop, D. R.; Jayne, J. T.; Weber, R. J.; Surratt, J. D.

    2013-12-01

    The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was recently developed to provide long-term real-time continuous measurements of ambient non-refractory (i.e., organic, sulfate, ammonium, nitrate, and chloride) submicron particulate matter (NR-PM1). Currently, there are a limited number of field studies that evaluate the long-term performance of the ACSM against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011-2012. The collocated measurements included a second ACSM, continuous and integrated sulfate, nitrate, and ammonium measurements, as well as a semi-continuous Sunset organic carbon/elemental carbon (OC/EC) analyzer, continuous tapered element oscillating microbalance (TEOM), 24 h integrated Federal Reference Method (FRM) filters, and continuous scanning electrical mobility system-mixing condensation particle counter (SEMS-MCPC). Intercomparison of the two collocated ACSMs resulted in strong correlations (r2 > 0.8) for all chemical species, except chloride (r2 = 0.21); mass concentration for all chemical species agreed within ±27%, indicating that ACSM instruments are capable of stable and reproducible operation. Chemical constituents measured by the ACSM are also compared with those obtained from the continuous measurements from JST. Since the continuous measurement concentrations are adjusted to match the integrated filter measurements, these comparisons reflect the combined uncertainties of the ACSM, continuous, and filter measurements. In general, speciated ACSM mass concentrations correlate well (r2 > 0.7) with the continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Differences between ACSM mass concentrations and the filter-adjusted JST continuous data are 5-27%, 4

  18. UPTAKE OF IONIZABLE ORGANIC CHEMICALS AT FISH GILLS

    EPA Science Inventory

    Uptake of organic acids by fish, and their toxicity, generally decrease with increasing pH above the pK, presumably due to neutral forms of such chemicals being more readily adsorbed than their ionized forms. However, uptake usually exceeds that expected based just on the concent...

  19. Chemical characterizations of soluble aerosols in southern China.

    PubMed

    Wu, Dui; Tie, Xuexi; Deng, Xuejiao

    2006-07-01

    Soluble aerosols are measured at Guangdong and Hainan Provinces of southern China. The measured chemical composition of aerosols includes F-, Cl-, NO3-, SO4=, Na+, NH4+, K+, Ca2+, and Mg2+. The locations of measurements include a mega city (Guangzhou), a medium city along the coastline (Haiko), a small city along the coastline (Shanya), and a remote island site in the South China Sea (Yongxing island). The results reveal that aerosols in this region are complex and heterogeneous. Sulfate aerosol (SO4=) has the highest concentrations in Guangzhou (approximately 41% of total soluble aerosol mass), suggesting that anthropogenic activities (e.g., coal burning) play important roles in controlling aerosol concentrations in Guangzhou. By contrast, the concentrations of chlorine (Cl-) and sodium (Na+) are higher in Yongxing than in Guangzhou, indicating that the sea salt is the dominant aerosol in this marine environment site. In the medium (Haiko) and small (Shanya) city sites, the effects of anthropogenic and marine activities on aerosols fall in between the values in the mega city and the remote island site. The measured ratio of Cl-/Na+ shows that the ratio is less than 1.16 in all observation sites. The ratio in the Guangzhou city, the Haiko city, the Shanya city, and the Yongxing island is 0.52, 0.91, 0.24, and 0.53, respectively, indicating that significantly heterogeneous chemical reactions occur on sea salt particles. Unlike those in Europe and North America, there are high concentrations of calcium (Ca+) in all observation sites. The percentage of calcium mass to the measured total soluble aerosols mass is 21, 32, 34, and 30 at Guangzhou, Haiko, Sanya, and Yongxing, respectively. The calculations show that calcium plays an important role in neutralizing aerosols. The calculated "cation/anion" (summation operator[ion+]/summation operator[ion-]) ratio is 2.5, 2.5, 3.2, and 2.1, at Guangzhou, Haiko, Shanya, and Yongxing, respectively. The high "cation/anion" ratios

  20. Identification and quantification of individual chemical compounds in biogenic secondary organic aerosols using GCxGC-VUV/EI-HRTOFMS

    NASA Astrophysics Data System (ADS)

    Decker, M.; Worton, D. R.; Isaacman, G. A.; Chan, A. W.; Ruehl, C.; Zhao, Y.; Wilson, K. R.; Goldstein, A. H.

    2012-12-01

    Atmospheric aerosols have adverse effects on human health and air quality and affect radiative forcing and thus climate. While the organic fraction of aerosols is substantial, the sources and chemistry leading to the formation of secondary organic aerosols are very poorly understood. Characterizing individual compounds present in organic aerosol provides insights into the sources, formation mechanisms and oxidative transformations that have taken place. Fifteen aerosol samples collected over a 5 day period at the Blodgett Forest Research Station in the Sierra Nevada Mountains, part of the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) in July 2009, were analyzed using comprehensive two dimensional gas chromatography with high resolution time of flight mass spectrometry (GCxGC-HRTOFMS). Approximately 600 compounds were observed in each sample as significant peaks in the chromatogram. Of these, around a third were identified by matching the unique electron ionization (EI) mass spectrum of each compound to the NIST library of characteristic fragmentation patterns. One filter sample was also analyzed using vacuum ultraviolet ionization (VUV) instead of EI. This 'soft' ionization technique results in much less fragmentation yielding the molecular ion of each compound, from which the exact mass was determined. If the formula of the EI library matched compound equaled the high mass resolution VUV molecular weight within a certain tolerance (< 30 ppm), then the library match was considered confirmed; 226 compounds were identified in this way. Using the VUV technique 234 additional compounds that were not in the EI mass spectral database were assigned chemical formulas based on the observed molecular weights. The chemical formulas in conjunction with the location of the compound in the GCxGC chromatogram were used to provide further classification of these compounds based on their likely functionalization. The broad array of observed oxygenated

  1. Molecular corridors represent the multiphase chemical evolution of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Berkemeier, T.; Schilling-Fahnestock, K. A.; Seinfeld, J. H.; Pöschl, U.

    2014-03-01

    The dominant component of atmospheric organic aerosol is that derived from the oxidation of volatile organic compounds (VOCs), so-called secondary organic aerosol (SOA). SOA consists of a multitude of organic compounds, only a small fraction of which has historically been identified. Formation and evolution of SOA is a complex process involving coupled chemical reaction and mass transport in the gas and particle phases. Current SOA models do not embody the full spectrum of reaction and transport processes nor do they identify the dominant rate-limiting steps in SOA formation. The recent advent of soft ionization mass spectrometry methods now facilitates a more complete molecular identification of SOA than heretofore possible. Based on such novel measurements, we show here that the chemical evolution of SOA from a variety of VOC precursors adheres to characteristic "molecular corridors" with a tight inverse correlation between volatility and molar mass. Sequential and parallel reaction oxidation and dimerization pathways progress along these corridors through characteristic regimes of reaction-, diffusion-, or accommodation-limited multiphase chemical kinetics that can be classified according to reaction location, degree of saturation, and extent of heterogeneity of gas and particle phases. These molecular corridors constrain the properties of unidentified products and reaction pathways and rates of SOA evolution, thereby facilitating the further development of aerosol models for air quality and climate.

  2. Lake Spray Aerosol: A Chemical Signature from Individual Ambient Particles.

    PubMed

    Axson, Jessica L; May, Nathaniel W; Colón-Bernal, Isabel D; Pratt, Kerri A; Ault, Andrew P

    2016-09-20

    Aerosol production from wave breaking on freshwater lakes, including the Laurentian Great Lakes, is poorly understood in comparison to sea spray aerosol (SSA). Aerosols from freshwater have the potential to impact regional climate and public health. Herein, lake spray aerosol (LSA) is defined as aerosol generated from freshwater through bubble bursting, analogous to SSA from seawater. A chemical signature for LSA was determined from measurements of ambient particles collected on the southeastern shore of Lake Michigan during an event (July 6-8, 2015) with wave heights up to 3.1 m. For comparison, surface freshwater was collected, and LSA were generated in the laboratory. Single particle microscopy and mass spectrometry analysis of field and laboratory-generated samples show that LSA particles are primarily calcium (carbonate) with lower concentrations of other inorganic ions and organic material. Laboratory number size distributions show ultrafine and accumulation modes at 53 (±1) and 276 (±8) nm, respectively. This study provides the first chemical signature for LSA. LSA composition is shown to be coupled to Great Lakes water chemistry (Ca(2+) > Mg(2+) > Na(+) > K(+)) and distinct from SSA. Understanding LSA physicochemical properties will improve assessment of LSA impacts on regional air quality, climate, and health. PMID:27548099

  3. Lake Spray Aerosol: A Chemical Signature from Individual Ambient Particles.

    PubMed

    Axson, Jessica L; May, Nathaniel W; Colón-Bernal, Isabel D; Pratt, Kerri A; Ault, Andrew P

    2016-09-20

    Aerosol production from wave breaking on freshwater lakes, including the Laurentian Great Lakes, is poorly understood in comparison to sea spray aerosol (SSA). Aerosols from freshwater have the potential to impact regional climate and public health. Herein, lake spray aerosol (LSA) is defined as aerosol generated from freshwater through bubble bursting, analogous to SSA from seawater. A chemical signature for LSA was determined from measurements of ambient particles collected on the southeastern shore of Lake Michigan during an event (July 6-8, 2015) with wave heights up to 3.1 m. For comparison, surface freshwater was collected, and LSA were generated in the laboratory. Single particle microscopy and mass spectrometry analysis of field and laboratory-generated samples show that LSA particles are primarily calcium (carbonate) with lower concentrations of other inorganic ions and organic material. Laboratory number size distributions show ultrafine and accumulation modes at 53 (±1) and 276 (±8) nm, respectively. This study provides the first chemical signature for LSA. LSA composition is shown to be coupled to Great Lakes water chemistry (Ca(2+) > Mg(2+) > Na(+) > K(+)) and distinct from SSA. Understanding LSA physicochemical properties will improve assessment of LSA impacts on regional air quality, climate, and health.

  4. Measurements of the aerosol chemical composition and mixing state in the Po Valley using multiple spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Decesari, S.; Allan, J.; Plass-Duelmer, C.; Williams, B. J.; Paglione, M.; Facchini, M. C.; O'Dowd, C.; Harrison, R. M.; Gietl, J. K.; Coe, H.; Giulianelli, L.; Gobbi, G. P.; Lanconelli, C.; Carbone, C.; Worsnop, D.; Lambe, A. T.; Ahern, A. T.; Moretti, F.; Tagliavini, E.; Elste, T.; Gilde, S.; Zhang, Y.; Dall'Osto, M.

    2014-04-01

    The use of co-located multiple spectroscopic techniques can provide detailed information on the atmospheric processes regulating aerosol chemical composition and mixing state. So far, field campaigns heavily equipped with aerosol mass spectrometers have been carried out mainly in large conurbations and in areas directly affected by their outflow, whereas lesser efforts have been dedicated to continental areas characterized by a less dense urbanization. We present here the results obtained in San Pietro Capofiume, which is located in a sparsely inhabited sector of the Po Valley, Italy. The experiment was carried out in summer 2009 in the framework of the EUCAARI project ("European Integrated Project on Aerosol, Cloud Climate Aerosol Interaction"). For the first time in Europe, six state-of-the-art techniques were used in parallel: (1) on-line TSI aerosol time-of-flight mass spectrometer (ATOFMS), (2) on-line Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS), (3) soot particle aerosol mass spectrometer (SP-AMS), (4) on-line high resolution time-of-flight mass spectrometer-thermal desorption aerosol gas chromatograph (HR-ToFMS-TAG), (5) off-line twelve-hour resolution proton nuclear magnetic resonance (H-NMR) spectroscopy, and (6) chemical ionization mass spectrometry (CIMS) for the analysis of gas-phase precursors of secondary aerosol. Data from each aerosol spectroscopic method were analysed individually following ad-hoc tools (i.e. PMF for AMS, Art-2a for ATOFMS). The results obtained from each techniques are herein presented and compared. This allows us to clearly link the modifications in aerosol chemical composition to transitions in air mass origin and meteorological regimes. Under stagnant conditions, atmospheric stratification at night and early morning hours led to the accumulation of aerosols produced by anthropogenic sources distributed over the Po Valley plain. Such aerosols include primary components such as black carbon (BC

  5. Aerosol chemical composition in cloud events by high resolution time-of-flight aerosol mass spectrometry.

    PubMed

    Hao, Liqing; Romakkaniemi, Sami; Kortelainen, Aki; Jaatinen, Antti; Portin, Harri; Miettinen, Pasi; Komppula, Mika; Leskinen, Ari; Virtanen, Annele; Smith, James N; Sueper, Donna; Worsnop, Douglas R; Lehtinen, Kari E J; Laaksonen, Ari

    2013-03-19

    This study presents results of direct observations of aerosol chemical composition in clouds. A high-resolution time-of-flight aerosol mass spectrometer was used to make measurements of cloud interstitial particles (INT) and mixed cloud interstitial and droplet residual particles (TOT). The differences between these two are the cloud droplet residuals (RES). Positive matrix factorization analysis of high-resolution mass spectral data sets and theoretical calculations were performed to yield distributions of chemical composition of the INT and RES particles. We observed that less oxidized hydrocarbon-like organic aerosols (HOA) were mainly distributed into the INT particles, whereas more oxidized low-volatile oxygenated OA (LVOOA) mainly in the RES particles. Nitrates existed as organic nitrate and in chemical form of NH(4)NO(3). Organic nitrates accounted for 45% of total nitrates in the INT particles, in clear contrast to 26% in the RES particles. Meanwhile, sulfates coexist in forms of acidic NH(4)HSO(4) and neutralized (NH(4))(2)SO(4). Acidic sulfate made up 64.8% of total sulfates in the INT particles, much higher than 10.7% in the RES particles. The results indicate a possible joint effect of activation ability of aerosol particles, cloud processing, and particle size effects on cloud formation.

  6. Self-consistent chemical model of partially ionized plasmas

    SciTech Connect

    Arkhipov, Yu. V.; Baimbetov, F. B.; Davletov, A. E.

    2011-01-15

    A simple renormalization theory of plasma particle interactions is proposed. It primarily stems from generic properties of equilibrium distribution functions and allows one to obtain the so-called generalized Poisson-Boltzmann equation for an effective interaction potential of two chosen particles in the presence of a third one. The same equation is then strictly derived from the Bogolyubov-Born-Green-Kirkwood-Yvon (BBGKY) hierarchy for equilibrium distribution functions in the pair correlation approximation. This enables one to construct a self-consistent chemical model of partially ionized plasmas, correctly accounting for the close interrelation of charged and neutral components thereof. Minimization of the system free energy provides ionization equilibrium and, thus, permits one to study the plasma composition in a wide range of its parameters. Unlike standard chemical models, the proposed one allows one to study the system correlation functions and thereby to obtain an equation of state which agrees well with exact results of quantum-mechanical activity expansions. It is shown that the plasma and neutral components are strongly interrelated, which results in the short-range order formation in the corresponding subsystem. The mathematical form of the results obtained enables one to both firmly establish this fact and to determine a characteristic length of the structure formation. Since the cornerstone of the proposed self-consistent chemical model of partially ionized plasmas is an effective pairwise interaction potential, it immediately provides quite an efficient calculation scheme not only for thermodynamical functions but for transport coefficients as well.

  7. Sarychev Volcanic Aerosol and Chemical measurements over Eureka, Canada

    NASA Astrophysics Data System (ADS)

    Perro, C. W.; Duck, T. J.; Bitar, L.; Nott, G. J.; Lesins, G. B.; O'Neill, N. T.; Eloranta, E.; Strong, K.; Carn, S. A.; Lindenmaier, R.; Batchelor, R.; Saha, A.; Pike-Thackray, C.; Drummond, J. R.

    2010-12-01

    On July 01, 2009, lidar measurements from Eureka, Canada (80°N, 85°W) detected unusually high amounts of aerosol in the lower stratosphere which are believed to have originated from the Sarychev Eruption on the Kuril Islands in Russia (48°N,153°E). The suite of instruments that are part of the Canadian Network for the Detection of Atmospheric Change (CANDAC) have been used to measure the optical and chemical properties of the volcanic plume over Eureka. Lidar measurements show significant structure in the stratospheric aerosol that reaches altitudes of approximately 17 km. Initially there were several layers of aerosol in the lower stratosphere, which began to mix vertically so that by the end of August the aerosol was mixed into one homogeneous layer in the lower stratosphere. Lidar and sun photometer measurements are used to track the change in the integrated volume backscatter cross section from July 2009, with an initial peak value of 0.007 sr-1 until March 2010 when values have returned to background levels. Lidar measurements also show the plume descending over time. Satellite data from OMI and CALIPSO are used to track the SO2 and aerosols in the plume as it travels from the Kuril Islands to Eureka. Ground based measurements from a UV-VIS Spectrophotometer detected SO2 that correlated with OMI measurements over Eureka on July 01. A fourier transform spectrometer was used to monitor a number of chemical species in the UTLS region with HCL for example spiking during the same period. Effects of the stratospheric aerosols on the incoming short wave radiation during the summer months are also examined.

  8. In situ submicron organic aerosol characterization at a boreal forest research station during HUMPPA-COPEC 2010 using soft and hard ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Corrigan, A. L.; Junninen, H.; Ehn, M.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Russell, L. M.; Williams, J.; Hoffmann, T.

    2013-11-01

    The chemical composition of submicron aerosol during the comprehensive field campaign HUMPPA-COPEC 2010 at Hyytiälä, Finland, is presented. The focus lies on online measurements of organic acids, which were achieved by using atmospheric pressure chemical ionization (APCI) ion trap mass spectrometry (IT-MS). These measurements were accompanied by aerosol mass spectrometry (AMS) measurements and Fourier transform infrared spectroscopy (FTIR) of filter samples, all showing a high degree of correlation. The soft ionization mass spectrometer alternated between gas-phase measurements solely and measuring the sum of gas and particle phase. The AMS measurements of C, H and O elemental composition show that the aerosol during the campaign was highly oxidized, which appears reasonable due to high and prolonged radiation during the boreal summer measurement period as well as the long transport times of some of the aerosol. In order to contrast ambient and laboratory aerosol, an average organic acid pattern, measured by APCI-IT-MS during the campaign, was compared to terpene ozonolysis products in a laboratory reaction chamber. Identification of single organic acid species remains a major challenge due to the complexity of the boreal forest aerosol. Unambiguous online species identification was attempted by the combinatorial approach of identifying unique fragments in the MS2 mode of standards, and then comparing these results with MS2 field spectra. During the campaign, unique fragments of limonene-derived organic acids (limonic acid and ketolimononic acid) and of the biomass burning tracer vanillic acid were detected. Other specific fragments (neutral loss of 28 Da) in the MS2 suggest the occurrence of semialdehydes. Furthermore, an approach to determine the average molecular weight of the aerosol is presented. The campaign average organic molecular weight was determined to be 300 g mol-1. However, a plume of aged biomass burning aerosol, arriving at Hyytiälä from Russia

  9. In-situ submicron organic aerosol characterization at a boreal forest research station during HUMPPA-COPEC 2010 using soft and hard ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Corrigan, A. L.; Junninen, H.; Ehn, M.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Russell, L. M.; Williams, J.; Hoffmann, T.

    2013-07-01

    The chemical composition of submicron aerosol during the comprehensive field campaign HUMPPA-COPEC 2010 at Hyytiälä, Finland is presented. The focus lies on online measurements of organic acids, which was achieved by using atmospheric pressure chemical ionization (APCI) ion trap mass spectrometry (IT-MS). These measurements were accompanied by Aerosol Mass Spectrometry (AMS) measurements and Fourier-Transform Infrared Spectroscopy (FTIR) of filter samples, all showing a high degree of correlation. The soft ionization mass spectrometer alternated between gas phase measurements solely and measuring the sum of gas- and particle-phase. The AMS measurements of C, H and O elemental composition show that the aerosol during the campaign was highly oxidized, which appears reasonable due to high and prolonged radiation during the boreal summer measurement period as well as the long transport times of some of the aerosol. In order to contrast ambient and laboratory aerosol, an average organic acid pattern, measured by APCI-IT-MS during the campaign, was compared to terpene ozonolysis products in a laboratory reaction chamber. Identification of single organic acid species remains a major challenge due to the complexity of the boreal forest aerosol. Unambiguous online species identification was attempted by the combinatorial approach of identifying unique fragments in the MS2-mode of standards, and then comparing these results with MS2 field spectra. During the campaign, unique fragments of limonene derived organic acids (limonic acid and ketolimononic acid) and of the biomass burning tracer vanillic acid were detected. Other specific fragments (neutral loss of 28 Da) in the MS2 suggest the occurrence of semialdehydes. Furthermore, an approach to determine the average molecular weight of the aerosol is presented. The campaign average organic molecular weight was determined to be 300 g mol-1. However, a plume of aged biomass burning aerosol, arriving at Hyytiälä from Russia

  10. Quantification of aerosol chemical composition using continuous single particle measurements

    NASA Astrophysics Data System (ADS)

    Jeong, C.-H.; McGuire, M. L.; Godri, K. J.; Slowik, J. G.; Rehbein, P. J. G.; Evans, G. J.

    2011-01-01

    Mass concentrations of particulate matter (PM) chemical components were determined from data for 0.3 to 3.0 μm particles measured by an Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) data at an urban and rural site. Hourly-averaged concentrations of nitrate, sulphate, ammonium, organic carbon, and elemental carbon, estimated based on scaled ATOFMS peak intensities of corresponding ion marker species, were compared with collocated chemical composition measurements by an Aerosol Mass Spectrometer (AMS), a Gas-Particle Ion Chromatograph (GPIC), and a Sunset Lab field OCEC analyzer. The highest correlation was found for nitrate, with correlation coefficients (Pearson r) of 0.89 and 0.85 at the urban and rural sites, respectively. ATOFMS mass calibration factors, determined for the urban site, were used to calculate mass concentrations of the major PM chemical components at the rural site. Mass reconstruction using this ATOFMS based composition data agreed very well with the total PM mass measured at the rural site. Size distributions of the ten main types of particles were resolved for the rural site and the mass composition of each particle type was determined in terms of sulphate, nitrate, ammonium, organic carbon and elemental carbon. This is the first study to estimate hourly mass concentrations of individual aerosol components and the mass composition of individual particle-types based on ATOFMS single particle measurements.

  11. Chemical and physicochemial properties of submicron aerosol agglomerates

    SciTech Connect

    Scripsick, R.C.; Ehrman, S.; Friedlander, S.K.

    1998-12-31

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory. The formation of nanometer-sized aerosol particles in a premixed methane flame from both solid-phase aerosol precursors and gas-phase precursors was investigated. Techniques were developed to determine the distribution of the individual chemical species as a function of agglomerate size by using inductively coupled plasma atomic emission spectroscopy (ICP-AES). To determine the distribution of chemical species both from particle to particle and within the particles on a nanometer scale, we used the analytical electron microscopy techniques of energy dispersive x-ray spectrometry (EDS) and electron energy loss spectrometry (EELS) coupled with transmission electron microscopy (TEM). The observed distribution of individual chemical species as a function of agglomerate size was linked to the material properties of the solid-phase precursors. For aerosol formed from gas-phase precursors by gas-to-particle conversion, the distribution of species on a manometer scale was found to correspond to the equilibrium phase distribution expected from equilibrium for the system at the flame temperatures.

  12. Chemical evolution of multicomponent aerosol particles during evaporation

    NASA Astrophysics Data System (ADS)

    Zardini, Alessandro; Riipinen, Ilona; Pagels, Joakim; Eriksson, Axel; Worsnop, Douglas; Switieckli, Erik; Kulmala, Markku; Bilde, Merete

    2010-05-01

    Atmospheric aerosol particles have an important but not well quantified effect on climate and human health. Despite the efforts made in the last decades, the formation and evolution of aerosol particles in the atmosphere is still not fully understood. The uncertainty is partly due to the complex chemical composition of the particles which comprise inorganic and organic compounds. Many organics (like dicarboxylic acids) can be present both in the gas and in the condensed phase due to their low vapor pressure. Clearly, an understanding of this partition is crucial to address any other issue in atmospheric physics and chemistry. Moreover, many organics are water soluble, and their influence on the properties of aqueous solution droplets is still poorly characterized. The solid and sub-cooled liquid state vapor pressures of some organic compounds have been previously determined by measuring the evaporation rate of single-compound crystals [1-3] or binary aqueous droplets [4-6]. In this work, we deploy the HTDMA technique (Hygroscopicity Tandem Differential Mobility Analyzer) coupled with a 3.5m laminar flow-tube and an Aerosol Mass Spectrometer (AMS) for determining the chemical evolution during evaporation of ternary droplets made of one dicarboxylic acid (succinic acid, commonly found in atmospheric samples) and one inorganic compound (sodium chloride or ammonium sulfate) in different mixing ratios, in equilibrium with water vapor at a fixed relative humidity. In addition, we investigate the evaporation of multicomponent droplets and crystals made of three organic species (dicarboxylic acids and sugars), of which one or two are semi-volatile. 1. Bilde M. and Pandis, S.N.: Evaporation Rates and Vapor Pressures of Individual Aerosol Species Formed in the Atmospheric Oxidation of alpha- and beta-Pinene. Environmental Science and Technology, 35, 2001. 2. Bilde M., et al.: Even-Odd Alternation of Evaporation Rates and Vapor Pressures of C3-C9 Dicarboxylic Acid Aerosols

  13. Microbiology and atmospheric processes: chemical interactions of primary biological aerosols

    NASA Astrophysics Data System (ADS)

    Deguillaume, L.; Leriche, M.; Amato, P.; Ariya, P. A.; Delort, A.-M.; Pöschl, U.; Chaumerliac, N.; Bauer, H.; Flossmann, A. I.; Morris, C. E.

    2008-07-01

    This paper discusses the influence of primary biological aerosols (PBA) on atmospheric chemistry and vice versa through microbiological and chemical properties and processes. Several studies have shown that PBA represent a significant fraction of air particulate matter and hence affect the microstructure and water uptake of aerosol particles. Moreover, airborne micro-organisms, namely fungal spores and bacteria, can transform chemical constituents of the atmosphere by metabolic activity. Recent studies have emphasized the viability of bacteria and metabolic degradation of organic substances in cloud water. On the other hand, the viability and metabolic activity of airborne micro-organisms depend strongly on physical and chemical atmospheric parameters such as temperature, pressure, radiation, pH value and nutrient concentrations. In spite of recent advances, however, our knowledge of the microbiological and chemical interactions of PBA in the atmosphere is rather limited. Further targeted investigations combining laboratory experiments, field measurements, and modelling studies will be required to characterize the chemical feedbacks, microbiological activities at the air/snow/water interface supplied to the atmosphere.

  14. Aging of Secondary Organic Aerosol from β-Pinene: Changes in Chemical Composition, Density and Morphology

    NASA Astrophysics Data System (ADS)

    Sarrafzadeh, M.; Hastie, D. R.

    2013-12-01

    Biogenic volatile organic compounds (VOC) are emitted in large quantities into the atmosphere. These VOC, which includes β-pinene, can react to produce secondary organic aerosols (SOA), which contribute to a substantial fraction of ambient organic aerosols and are known to adversely affect visibility, climate and health. Despite this, the current knowledge regarding the SOA composition, their physical properties and the chemical aging processes they undergo in the atmosphere is limited. In this study, chemical aging of SOA generated from the photooxidation of β-pinene was investigated in the York University smog chamber. The formation and aging of both gas and particle phase products were analyzed using an atmospheric pressure chemical ionization triple quadrupole mass spectrometer. The density of secondary organic matter was also simultaneously measured over the course of the aging experiments, allowing us to improve our understanding in changes in particle composition that may occur. In addition, particle phase and shape was investigated for generated particles from β-pinene oxidation by scanning electron microscope (SEM). Results of this work, including particle density and morphology will be presented as well as comparisons of gas and particle phase products time profiles during aging.

  15. Optical and Chemical Characterization of Aerosols Produced from Cooked Meats

    NASA Astrophysics Data System (ADS)

    Niedziela, R. F.; Foreman, E.; Blanc, L. E.

    2011-12-01

    Cooking processes can release a variety compounds into the air immediately above a cooking surface. The distribution of compounds will largely depend on the type of food that is being processed and the temperatures at which the food is prepared. High temperatures release compounds from foods like meats and carry them away from the preparation surface into cooler regions where condensation into particles can occur. Aerosols formed in this manner can impact air quality, particularly in urban areas where the amount of food preparation is high. Reported here are the results of laboratory experiments designed to optically and chemically characterize aerosols derived from cooking several types of meats including ground beef, salmon, chicken, and pork both in an inert atmosphere and in synthetic air. The laboratory-generated aerosols are studied using a laminar flow cell that is configured to accommodate simultaneous optical characterization in the mid-infrared and collection of particles for subsequent chemical analysis by gas chromatography. Preliminary optical results in the visible and ultra-violet will also be presented.

  16. Uncertainties of simulated aerosol optical properties induced by assumptions on aerosol physical and chemical properties: an AQMEII-2 perspective

    EPA Science Inventory

    The calculation of aerosol optical properties from aerosol mass is a process subject to uncertainty related to necessary assumptions on the treatment of the chemical species mixing state, density, refractive index, and hygroscopic growth. In the framework of the AQMEII-2 model in...

  17. Multi- year Arctic and Antarctic aerosol chemical characterization

    NASA Astrophysics Data System (ADS)

    Udisti, Roberto; Becagli, Silvia; Caiazzo, Laura; Calzolai, Giulia; Cappelletti, David; Giardi, Fabio; Grotti, Marco; Malandrino, Mery; Nava, Silvia; Severi, Mirko; Traversi, Rita

    2016-04-01

    Long term measurements of aerosol chemical composition in polar region are particularly relevant to investigate potential climatic effects of atmospheric components arising from both natural and anthropogenic emissions. In order to improve our knowledge on the atmospheric load and chemical composition of polar aerosol, several measurements and sampling campaigns were carried out both in Antarctica and in the Arctic since 2005.The main results are here reported. As regard as Antarctica, a continuous all-year-round sampling of size-segregated aerosol was carried from 2005 to 2013 at Dome C (East Antarctica; 75° 60' S, 123° 200' E, 3220 m a.s.l. and 1100 km away from the nearest coast). Aerosol was collected by PM10 and PM2.5 samplers and by multi-stage impactors (Dekati 4-stage impactor). Chemical analysis was carried out by Ion Chromatography (ions composition) and ICP-MS (trace metals). Sea spray showed a sharp seasonal pattern, with winter (Apr-Nov) concentrations about ten times larger than summer (Dec-Mar). Besides, in winter, sea spray particles are mainly sub micrometric, while the summer size-mode is around 1-2 um. Meteorological analysis and air mass back trajectory reconstructions allowed the identification of two major air mass pathways: micrometric fractions for transport from the closer Indian-Pacific sector, and sub-micrometric particles for longer trajectories over the Antarctic Plateau. The markers of oceanic biogenic emission (methanesulfonic acid - MSA, and non-sea-salt sulphate) exhibit a seasonal cycle with summer maxima (Nov-Mar). Their size distributions show two modes (0.4- 0.7 um and 1.1-2.1 um) in early summer and just one sub-micrometric mode in full summer. The two modes are related to different transport pathways. In early summer, air masses came primarily from the Indian Ocean and spent a long time over the continent. The transport of sulphur compounds is related to sea spray aerosols and the resulting condensation of H2SO4 and MSA over

  18. Chemical characterization of aerosol particles by laser Raman spectroscopy. Revision

    SciTech Connect

    Fung, K.H.

    1999-12-01

    The importance of aerosol particles in many branches of science, such as atmospheric chemistry, combustion, interfacial science, and material processing, has been steadily growing during the past decades. One of the unique properties of these particles is the very high surface-to-volume ratios, thus making them readily serve as centers for gas-phase condensation and heterogeneous reactions. These particles must be characterized by size, shape, physical state, and chemical composition. Traditionally, optical elastic scattering has been applied to obtain the physical properties of these particle (e.g., particle size, size distribution, and particle density). These physical properties are particularly important in atmospheric science as they govern the distribution and transport of atmospheric aerosols.

  19. A comparison between the processing of Titan aerosols analogs by ionizing photons and energetic cosmic rays.

    NASA Astrophysics Data System (ADS)

    De Araujo Vasconcelos, Fredson; Pilling, Sergio; Boduch, Philippe; Alexandre Souza Bergantini, M.; Ding, M. Jingjie J.; Rothard, Hermann; Robson Rocha, Will

    Titan, the largest satellite of Saturn, has an atmosphere mainly made of N_{2} and CH_{4} and includes traces of several simple organic compounds. This atmosphere also partly consists of haze and erosol particles which during the last 4.5 gigayears have been processed by electric discharges, ions, and ionizing photons, being slowly deposited over Titańs surface. In this work, we investigate the possible effects produced by ionizing photons (vacuum ultraviolet and soft X-rays) and cosmic ray analogs (15.7 MeV (16) O (+5) ) on Titan aerosol analogs in an attempt to simulate some prebiotic photochemistry. For photons, the experiments have been performed using a high vacuum portable chamber from the Laboratorio de Astroquimica e Astrobiologia (LASA/UNIVAP) coupled to the the Brazilian Synchrotron Light Source (LNLS) in Campinas, Brazil. For ions, the investigation was performed at the Grand Accelerateur National d’Ions Lourds (GANIL) Caen, France. In-situ sample analyses were performed by a Fourier transform infrared spectrometer at different fluences. During the sample processing, the infrared spectra have presented several new organic molecules, including nitriles, HCN and aromatic CN compounds. The processing of the sample by fast ions has enhanced the formation of daughter species in the Titan aerosol sample when compared with the products from the employing VUV and soft X-rays photons. The destruction cross section of the parent species was determined, as well as, the formation cross section for some selected daughter species. Molecular Half-lives were extrapolated to the Titańs environment. This investigation confirms previous results which showed that the organic chemistry on frozen moons inside Solar system can be very complex and extremely rich in prebiotic compounds. Authors would like to tanks the agencies FAPESP (JP-2009/18304-0), CAPES-Cofecub (569/2007), INCT-A and CNPq for the financial support.

  20. Extractive Electrospray Ionization Mass Spectrometry of Heterogeneous Particles: Implications for Applications to Complex Atmospheric Aerosol

    NASA Astrophysics Data System (ADS)

    Longin, T.; Waring-Kidd, C.; Wingen, L. M.; Lyster, K.; Anderson, C.; Kumbhani, S.; Finlayson-Pitts, B. J.

    2015-12-01

    Extractive electrospray ionization mass spectrometry (EESI-MS) is a direct, real time technique for obtaining mass spectra of gases, liquid droplets, solid particles, and aerosols with little sample processing. EESI-MS involves the interaction of charged electrospray droplets with a separate spray containing the analyte of interest, but the exact mechanism by which the solvent droplets extract analyte from the sample is unclear. Possible mechanisms include complete coalescence of the sample particle with the solvent droplet in which all of the analyte is incorporated into the solvent or a more temporary interaction such that only some of the analyte is transferred to the solvent. Previous studies of the mechanism of EESI-MS on homogeneous particles indicate that both mechanisms are possible. We studied the behavior of EESI-MS toward heterogeneous particles created by coating NaCl particles with various thicknesses of organic diacids. Our results indicate that the signal strength depends on the solubility of the organic acid in the electrospray solvent, in agreement with previous studies, and also that the outer 10-15 nm of the particles are most susceptible to extraction into the electrospray droplets. Our results combined with those of previous studies suggest that the mass spectra obtained with EESI will not necessarily reflect the overall particle composition, especially for particles that are spatially inhomogeneous, and hence caution in interpretation of the data is advised for application to complex atmospheric aerosol.

  1. Aerosol chemical vapor deposition of metal oxide films

    DOEpatents

    Ott, Kevin C.; Kodas, Toivo T.

    1994-01-01

    A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said FIELD OF THE INVENTION The present invention relates to the field of film coating deposition techniques, and more particularly to the deposition of multicomponent metal oxide films by aerosol chemical vapor deposition. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

  2. Quantification of aerosol chemical composition using continuous single particle measurements

    NASA Astrophysics Data System (ADS)

    Jeong, C.-H.; McGuire, M. L.; Godri, K. J.; Slowik, J. G.; Rehbein, P. J. G.; Evans, G. J.

    2011-07-01

    Mass concentrations of sulphate, nitrate, ammonium, organic carbon (OC), elemental carbon (EC) were determined from real time single particle data in the size range 0.1-3.0 μm measured by an Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) at urban and rural sites in Canada. To quantify chemical species within individual particles measured by an ATOFMS, ion peak intensity of m/z -97 for sulphate, -62 for nitrate, +18 for ammonium, +43 for OC, and +36 for EC were scaled using the number and size distribution data by an Aerodynamic Particle Sizer (APS) and a Fast Mobility Particle Sizer (FMPS). Hourly quantified chemical species from ATOFMS single-particle analysis were compared with collocated fine particulate matter (aerodynamic diameter < 2.5 μm, PM2.5) chemical composition measurements by an Aerosol Mass Spectrometer (AMS) at a rural site, a Gas-Particle Ion Chromatograph (GPIC) at an urban site, and a Sunset Lab field OCEC analyzer at both sites. The highest correlation was found for nitrate, with correlation coefficients (Pearson r) of 0.89 (ATOFMS vs. GPIC) and 0.85 (ATOFMS vs. AMS). ATOFMS mass calibration factors, determined for the urban site, were used to calculate mass concentrations of the major PM2.5 chemical components at the rural site near the US border in southern Ontario. Mass reconstruction using the ATOFMS mass calibration factors agreed very well with the PM2.5 mass concentrations measured by a Tapered Element Oscillating Microbalance (TEOM, r = 0.86) at the urban site and a light scattering monitor (DustTrak, r = 0.87) at the rural site. In the urban area nitrate was the largest contributor to PM2.5 mass in the winter, while organics and sulphate contributed ~64 % of the summer PM2.5 in the rural area, suggesting a strong influence of regional/trans-boundary pollution. The mass concentrations of five major species in ten size-resolved particle-types and aerosol acidity of each particle-type were determined for the rural site. On a mass basis

  3. Hygroscopic, Morphological, and Chemical Properties of Agricultural Aerosols

    NASA Astrophysics Data System (ADS)

    Hiranuma, N.; Brooks, S. D.; Cheek, L.; Thornton, D. C.; Auvermann, B. W.; Littleton, R.

    2007-12-01

    Agricultural fugitive dust is a significant source of localized air pollution in the semi-arid southern Great Plains. In the Texas Panhandle, daily episodes of ground-level fugitive dust emissions from the cattle feedlots are routinely observed in conjunction with increased cattle activity in the late afternoons and early evenings. We conducted a field study to characterize size-selected agricultural aerosols with respect to hygroscopic, morphological, and chemical properties and to attempt to identify any correlations between these properties. To explore the hygroscopic nature of agricultural particles, we have collected size-resolved aerosol samples using a cascade impactor system at a cattle feedlot in the Texas Panhandle and have used the Environmental Scanning Electron Microscope (ESEM) to determine the water uptake by individual particles in those samples as a function of relative humidity. To characterize the size distribution of agricultural aerosols as a function of time, A GRIMM aerosol spectrometer and Sequential Mobility Particle Sizer and Counter (SMPS) measurements were simultaneously performed in an overall size range of 11 nm to 20 µm diameters at a cattle feedlot. Complementary determination of the elemental composition of individual particles was performed using Energy Dispersive X-ray Spectroscopy (EDS). In addition to the EDS analysis, an ammonia scrubber was used to collect ammonia and ammonium in the gas and particulate phases, respectively. The concentration of these species was quantified offline via UV spectrophotometry at 640 nanometers. The results of this study will provide important particulate emission data from a feedyard, needed to improve our understanding of the role of agricultural particulates in local and regional air quality.

  4. Modeling regional secondary organic aerosol using the Master Chemical Mechanism

    NASA Astrophysics Data System (ADS)

    Li, Jingyi; Cleveland, Meredith; Ziemba, Luke D.; Griffin, Robert J.; Barsanti, Kelley C.; Pankow, James F.; Ying, Qi

    2015-02-01

    A modified near-explicit Master Chemical Mechanism (MCM, version 3.2) with 5727 species and 16,930 reactions and an equilibrium partitioning module was incorporated into the Community Air Quality Model (CMAQ) to predict the regional concentrations of secondary organic aerosol (SOA) from volatile organic compounds (VOCs) in the eastern United States (US). In addition to the semi-volatile SOA from equilibrium partitioning, reactive surface uptake processes were used to simulate SOA formation due to isoprene epoxydiol, glyoxal and methylglyoxal. The CMAQ-MCM-SOA model was applied to simulate SOA formation during a two-week episode from August 28 to September 7, 2006. The southeastern US has the highest SOA, with a maximum episode-averaged concentration of ∼12 μg m-3. Primary organic aerosol (POA) and SOA concentrations predicted by CMAQ-MCM-SOA agree well with AMS-derived hydrocarbon-like organic aerosol (HOA) and oxygenated organic aerosol (OOA) urban concentrations at the Moody Tower at the University of Houston. Predicted molecular properties of SOA (O/C, H/C, N/C and OM/OC ratios) at the site are similar to those reported in other urban areas, and O/C values agree with measured O/C at the same site. Isoprene epoxydiol is predicted to be the largest contributor to total SOA concentration in the southeast US, followed by methylglyoxal and glyoxal. The semi-volatile SOA components are dominated by products from β-caryophyllene oxidation, but the major species and their concentrations are sensitive to errors in saturation vapor pressure estimation. A uniform decrease of saturation vapor pressure by a factor of 100 for all condensable compounds can lead to a 150% increase in total SOA. A sensitivity simulation with UNIFAC-calculated activity coefficients (ignoring phase separation and water molecule partitioning into the organic phase) led to a 10% change in the predicted semi-volatile SOA concentrations.

  5. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Rondo, L.; Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-03-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  6. Characterization of glycosphingolipids by direct inlet chemical ionization mass spectrometry.

    PubMed

    Ariga, T; Murata, T; Oshima, M; Maezawa, M; Miyatake, T

    1980-09-01

    Permethylated derivatives of cerebrosides and ceramide di-, tri-, tetra-, and penta-hexosides were analyzed by the direct inlet ammonia chemical ionization (CI) mass spectrometry. In the CI mass spectra, the fragment ions produced by the loss of methanol from the protonated molecular ion were observed in all of the glycosphingolipids. Other fragment ions due to the cleavage of glycosidic moiety were major ones under the CI conditions. These ions provide information on the molecular species of glycosphingolipids and the sugar sequence of their oligosaccharides. Glycosphingolipids with hydroxy fatty acids could also be differentiated from those with nonhydroxy fatty acids by comparing the intensities of characteristic fragment ions. The CI method should be particularly useful in structural studies of glycosphingolipids from natural sources. PMID:7441059

  7. Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Spencer, K. M.; Beaver, M. R.; St. Clair, J. M.; Crounse, J. D.; Paulot, F.; Wennberg, P. O.

    2011-08-01

    Chemical ionization mass spectrometry (CIMS) enables online, fast, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are capable of the measurement of hydroxyacetone, an analyte with minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. Measurement of hydroxyacetone and glycolaldehyde by these methods was demonstrated during the ARCTAS-CARB 2008 campaign and the BEARPEX 2009 campaign. Enhancement ratios of these compounds in ambient biomass burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.

  8. [Determination of homocysteine by tandem mass spectrometry with chemical ionization].

    PubMed

    Miroshnichenko, I I; Platova, A I; Safarova, T P; Iakovleva, O B

    2014-01-01

    Homocysteine (Hcy) is an intermediate of methionine metabolism. High plasma Hcy concentrations are an independent risk factor for stroke, peripheral vascular disease, deep venous thrombosis, coronary disease, and cognitive deficiency. Apparently, it is a great importance to measure Hcy levels in human blood. A new method for the quantification of Hcy by means of reversed-phase LC/atmospheric pressure chemical ionization mass spectrometry has been developed. The MRM ion transition, m/z 136.0 ® 90.0 was used for Hcy quantification. The limit of detection was 0.4 mM, quantification was performed from 1 mM to 40 mM with coefficient of determination of R2=0,997. The method was applied successfully to Hcy determination in human blood.

  9. Constraining Anthropogenic and Biogenic Emissions Using Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Spencer, Kathleen M.

    Numerous gas-phase anthropogenic and biogenic compounds are emitted into the atmosphere. These gases undergo oxidation to form other gas-phase species and particulate matter. Whether directly or indirectly, primary pollutants, secondary gas-phase products, and particulate matter all pose health and environmental risks. In this work, ambient measurements conducted using chemical ionization mass spectrometry are used as a tool for investigating regional air quality. Ambient measurements of peroxynitric acid (HO2NO2) were conducted in Mexico City. A method of inferring the rate of ozone production, PO3, is developed based on observations of HO2NO 2, NO, and NO2. Comparison of this observationally based PO3 to a highly constrained photochemical box model indicates that regulations aimed at reducing ozone levels in Mexico City by reducing NOx concentrations may be effective at higher NO x levels than predicted using accepted photochemistry. Measurements of SO2 and particulate sulfate were conducted over the Los Angeles basin in 2008 and are compared to measurements made in 2002. A large decrease in SO2 concentration and a change in spatial distribution are observed. Nevertheless, only a modest reduction in sulfate concentration is observed at ground sites within the basin. Possible explanations for these trends are investigated. Two techniques, single and triple quadrupole chemical ionization mass spectrometry, were used to quantify ambient concentrations of biogenic oxidation products, hydroxyacetone and glycolaldehyde. The use of these techniques demonstrates the advantage of triple quadrupole mass spectrometry for separation of mass analogues, provided the collision-induced daughter ions are sufficiently distinct. Enhancement ratios of hydroxyacetone and glycolaldehyde in Californian biomass burning plumes are presented as are concentrations of these compounds at a rural ground site downwind of Sacramento.

  10. Molecular corridors and parameterizations of volatility in the chemical evolution of organic aerosols

    NASA Astrophysics Data System (ADS)

    Li, Ying; Pöschl, Ulrich; Shiraiwa, Manabu

    2016-03-01

    The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the saturation mass concentration of organic compounds containing oxygen, nitrogen, and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less-oxidized indoor OA are constrained to a corridor of low molar mass and high volatility, whereas highly oxygenated compounds in atmospheric water extend to high molar mass and low volatility. Among the nitrogen- and sulfur-containing compounds identified in atmospheric aerosols, amines tend to exhibit low molar mass and high volatility, whereas organonitrates and organosulfates follow high O : C corridors extending to high molar mass and low volatility. We suggest that the consideration of molar mass and molecular corridors can help to constrain volatility and particle-phase state in the modeling of OA particularly for nitrogen- and sulfur-containing compounds.

  11. Gas uptake and chemical aging of semisolid organic aerosol particles.

    PubMed

    Shiraiwa, Manabu; Ammann, Markus; Koop, Thomas; Pöschl, Ulrich

    2011-07-01

    Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate.

  12. Molecular Characterization of Organic Aerosol Using Nanospray Desorption/Electrospray Ionization Mass Spectrometry: CalNex 2010 field study

    SciTech Connect

    O'Brien, Rachel E.; Laskin, Alexander; Laskin, Julia; Liu, Shang; Weber, Robin; Russell, Lynn; Goldstein, Allen H.

    2013-04-01

    Aerosol samples from the CalNex 2010 field study were analyzed using high resolution mass spectrometry (HR-MS) coupled to a nanospray-desorption/electrospray ionization (nano-DESI) source. The samples were collected in Bakersfield, CA on June 22-23, 2010. The chemical formulas of over 1300 unique molecular species were detected in the mass range of 50-800 m/z. Our analysis focused on identification of two main groups: compounds containing only carbon, hydrogen, and oxygen (CHO only), and nitrogen-containing organic compounds (NOC). The NOC accounted for 35% (by number) of the compounds observed in the afternoon, and for 59% in the early morning samples. By comparing plausible reactant-product pairs, we propose that over 50% of the NOC in each sample could have been formed through reactions transforming carbonyls into imines. The CHO only compounds were dominant in the afternoon suggesting a photochemical source. The average O:C ratios of all observed compounds were fairly consistent throughout the day, ranging from 0.34 in the early morning to 0.37 at night. We conclude that both photooxidation and ammonia chemistry play important roles in forming the compounds observed in this mixed urban-rural environment.

  13. Chemical characterization of springtime submicrometer aerosol in Po Valley, Italy

    NASA Astrophysics Data System (ADS)

    Saarikoski, S.; Carbone, S.; Decesari, S.; Giulianelli, L.; Angelini, F.; Canagaratna, M.; Ng, N. L.; Trimborn, A.; Facchini, M. C.; Fuzzi, S.; Hillamo, R.; Worsnop, D.

    2012-09-01

    The chemistry of submicron particles was investigated at San Pietro Capofiume (SPC) measurement station in the Po Valley, Italy, in spring 2008. The measurements were performed by using both off-line and on-line instruments. Organic carbon (OC) and elemental carbon, organic acids and biomass burning tracers were measured off-line by using a 24-h PM1 filter sampling. More detailed particle chemistry was achieved by using a Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and analyzing the data by positive matrix factorization (PMF). Oxalic acid had the highest concentrations of organic acids (campaign-average 97.4 ng m-3) followed by methane sulfonic, formic, malonic, and malic acids. Samples were also analyzed for glyoxylic, succinic, azelaic and maleic acids. In total, the nine acids composed 1.9 and 3.8% of OC and water-soluble OC, respectively (average), in terms of carbon atoms. Levoglucosan concentration varied from 17.7 to 495 ng m-3 with the concentration decreasing in the course of the campaign most likely due to the reduced use of domestic heating with wood. Six factors were found for organic aerosol (OA) at SPC by PMF: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), nitrogen-containing OA (N-OA) and three different oxygenated OAs (OOA-a, OOA-b and OOA-c). Most of the OA mass was composed of OOA-a, HOA and OOA-c (26, 24 and 22%, respectively) followed by OOA-b (13%), BBOA (8%) and N-OA (7%). As expected, OOAs were the most oxygenated factors with organic matter:organic carbon (OM : OC) ratios ranging from 1.9 to 2.2. The diurnal variability of the aerosol chemical composition was greatly affected by the boundary layer meteorology. Specifically, the effect of the nocturnal layer break-up in morning hours was most evident for nitrate and N-OA indicating that these compounds originated mainly from the local sources in the Po Valley. For sulfate and OOA-a the concentration did not change during the break-up suggesting their

  14. Chemical characterization of springtime submicrometer aerosol in Po Valley, Italy

    NASA Astrophysics Data System (ADS)

    Saarikoski, S.; Carbone, S.; Decesari, S.; Giulianelli, L.; Angelini, F.; Teinilä, K.; Canagaratna, M.; Ng, N. L.; Trimborn, A.; Facchini, M. C.; Fuzzi, S.; Hillamo, R.; Worsnop, D.

    2012-03-01

    The chemistry of submicron particles was investigated at San Pietro Capofiume (SPC) measurement station in the Po Valley, Italy, in spring 2008. The measurements were performed by using both off-line and on-line instruments. Organic carbon (OC) and elemental carbon, organic acids and biomass burning tracers were measured off-line by using a 24-h PM1 filter sampling. More detailed particle chemistry was achieved by using an Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and analyzing the data by positive matrix factorization (PMF). Oxalic acid had the highest concentrations of organic acids (campaign-average 97.4 ng m-3) followed by methane sulfonic, formic, malonic, and malic acids. Samples were also analyzed for glyoxylic, succinic, azelaic and maleic acids. In total, the nine acids composed 1.9 and 3.8% of OC and water-soluble OC, respectively (average), in terms of carbon atoms. Levoglucosan concentration varied from 17.7 to 495 ng m-3 with the concentration decreasing in the course of the campaign most likely due to the reduced use of domestic heating with wood. Six factors were found for organic aerosol (OA) at SPC by PMF: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), nitrogen-containing OA (N-OA) and three different oxygenated OAs (OOA-a, OOA-b and OOA-c). Most of the OA mass was composed of OOA-a, HOA and OOA-c (26, 24 and 22%, respectively) followed by OOA-b (13%), BBOA (8%) and N-OA (7%). As expected, OOAs were the most oxygenated factors with organic matter:organic carbon (OM:OC) ratios ranging from 1.9 to 2.2. The diurnal variability of the aerosol chemical composition was greatly affected by the boundary layer meteorology. Specifically, the effect of the nocturnal layer break-up in morning hours was most evident for nitrate and N-OA indicating that these compounds originated mainly from the local sources in the Po Valley. For sulfate and OOA-a the concentration did not change during the break-up suggesting their

  15. Online measurement of biogenic organic acids in the boreal forest using atmospheric pressure chemical ionization mass spectrometry (APCI-MS)

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Brüggemann, M.; ńijälä, M.; Ehn, M.; Junninen, H.; Corrigan, A. L.; Petäjä, T.; Worsnop, D. R.; Russell, L. M.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2012-04-01

    Emission of biogenic volatile organic compounds (BVOCs) by vegetation in the boreal forest and their subsequent atmospheric oxidation leads to the formation of secondary organic aerosol (SOA) which has important impacts on climate and human health. Oxidation of BVOCs produces a variety of mostly unidentified species in oxygenated organic aerosol (OOA). Presently aerosol mass spectrometers (AMS) are able to determine quantitative information about the relative oxygen to carbon content of organic aerosols and thereby reveal the photochemical age and volatility of organic aerosol by distinguishing between low volatile oxygenated organic aerosol (LV-OOA), semivolatile oxygenated organic aerosol (SV-OOA) and hydrocarbon like organic aerosol (HOA)[1]. However, the AMS can usually not be used to measure and quantify single organic compounds such as individual biogenic organic marker compounds. Here we show the results of online measurements of gas and particle phase biogenic acids during HUMPPA-COPEC 2010 at Hyytiälä, Finland. This was achieved by coupling a self built miniature Versatile Aerosol Concentration Enrichment System (mVACES) as described by Geller et al. [2] with an Atmospheric Pressure Chemical Ionization Ion Trap Mass Spectrometer (APCI IT MS; Hoffmann et al., [3]). The benefits of the on-line APCI-MS are soft ionization with little fragmentation compared to AMS, high measurement frequency and less sampling artifacts than in the common procedure of taking filter samples, extraction and detection with LC-MS. Furthermore, the ion trap of the instrument allows MS/MS experiments to be performed by isolation of single m/z ratios of selected molecular species. By subsequent addition of energy, the trapped ions form characteristic fragments which enable structural insight on the molecular level. Comparison of APCI-MS data to AMS data, acquired with a C-ToF-AMS [4], revealed a good correlation coefficient for total organics and sulphate. Furthermore, data show

  16. Microbiology and atmospheric processes: chemical interactions of Primary Biological Aerosols

    NASA Astrophysics Data System (ADS)

    Deguillaume, L.; Leriche, M.; Amato, P.; Ariya, P. A.; Delort, A.-M.; Pöschl, U.; Chaumerliac, N.; Bauer, H.; Flossmann, A. I.; Morris, C. E.

    2008-02-01

    This paper discusses the influence of bioaerosols on atmospheric chemistry and vice versa through microbiological and chemical properties and processes. Several studies have shown that biological matter represents a significant fraction of air particulate matter and hence affects the microstructure and water uptake of aerosol particles. Moreover, airborne micro-organisms can transform chemical constituents of the atmosphere by metabolic activity. Recent studies have emphasized the viability of bacteria and metabolic degradation of organic substances in cloud water. On the other hand, the viability and metabolic activity of airborne micro-organisms depend strongly on physical and chemical atmospheric parameters such as temperature, pressure, radiation, pH value and nutrient concentrations. In spite of recent advances, however, our knowledge of the microbiological and chemical interactions of primary biological particles in the atmosphere is rather limited. Further targeted investigations combining laboratory experiments, field measurements, and modelling studies will be required to characterize the chemical feedbacks, microbiological activities at the air/snow/water interface supplied to the atmosphere.

  17. Differentiation of microorganisms based on pyrolysis-ion trap mass spectrometry using chemical ionization.

    PubMed

    Barshick, S A; Wolf, D A; Vass, A A

    1999-02-01

    The ability to differentiate microorganisms using pyrolysision trap mass spectrometry was demonstrated for five Gram-negative disease-causing organisms: Brucella melitensis, Brucella suis, Vibrio cholera, Yersinia pestis, and Francisella tularensis. Bacterial profiles were generated for gamma-irradiated bacterial samples using pyrolytic methylation and compared for electron ionization and chemical ionization using several liquid reagents with increasing proton affinities. Electron ionization combined with pyrolysis caused extensive fragmentation, resulting in a high abundance of lower mass ions and diminishing the diagnostic value of the technique for compound identification and bacterial profiling. Chemical ionization reduced the amount of fragmentation due to ionization while enhancing the molecular ion region of the fatty acids. As the proton affinity of the reagent increased, the protonated molecular ions of the fatty acids became the predominant ions observed in the mass spectrum. As a result, chemical ionization was shown to be more effective than electron ionization in bacterial profiling. Whereas the bacteria could be distinguished at the Genera level using electron ionization, further differentiation to the subspecies level was possible using chemical ionization. The greatest separation among the five test organisms, in terms of Euclidean distances, was obtained using ethanol as the chemical ionization reagent and using pooled masses representing specific fatty acid biomarkers rather than total ion profiles. PMID:9989380

  18. Simulation of aerosol chemical compositions in the Western Mediterranean Sea

    NASA Astrophysics Data System (ADS)

    Chrit, Mounir; Kata Sartelet, Karine; Sciare, Jean; Marchand, Nicolas; Pey, Jorge; Sellegri, Karine

    2016-04-01

    This work aims at evaluating the chemical transport model (CTM) Polair3d of the air-quality modelling platform Polyphemus during the ChArMex summer campaigns of 2013, using ground-based measurements performed at ERSA (Cape Corsica, France), and at determining the processes controlling organic aerosol concentrations at ERSA. Simulations are compared to measurements for concentrations of both organic and inorganic species, as well as the ratio of biogenic versus anthropogenic particles, and organic aerosol properties (oxidation state). For inorganics, the concentrations of sulphate, sodium, chloride, ammonium and nitrate are compared to measurements. Non-sea-salt sulphate and ammonium concentrations are well reproduced by the model. However, because of the geographic location of the measurement station at Cape Corsica which undergoes strong wind velocities and sea effects, sea-salt sulphate, sodium, chloride and nitrate concentrations are strongly influenced by the parameterizations used for sea-salt emissions. Different parameterizations are compared and a parameterization is chosen after comparison to sodium measurements. For organics, the concentrations are well modelled when compared to experimental values. Anthropogenic particles are influenced by emission of semi-volatile organic compounds (SVOC). Measurements allow us to refine the estimation of those emissions, which are currently missing in emission inventories. Although concentrations of biogenic particles are well simulated, the organic chemical compounds are not enough oxidised in the model. The observed oxidation state of organics shows that the oligomerisation of pinonaldehyde was over-estimated in Polyphemus. To improve the oxidation property of organics, the formation of extremely low volatile organic compounds from autoxidation of monoterpenes is added to Polyphemus, using recently published data from chamber experiments. These chemical compounds are highly oxygenated and are formed rapidly, as first

  19. Chemical, physical, and optical evolution of biomass burning aerosols: a case study

    NASA Astrophysics Data System (ADS)

    Adler, G.; Flores, J. M.; Abo Riziq, A.; Borrmann, S.; Rudich, Y.

    2011-02-01

    In-situ chemical composition measurements of ambient aerosols have been used for characterizing the evolution of submicron aerosols from a large anthropogenic biomass burning (BB) event in Israel. A high resolution Time of Flight Aerosol Mass Spectrometer (HR-RES-TOF-AMS) was used to follow the chemical evolution of BB aerosols during a night-long, extensive nationwide wood burning event and during the following day. While these types of extensive BB events are not common in this region, burning of agricultural waste is a common practice. The aging process of the BB aerosols was followed through their chemical, physical and optical properties. Mass spectrometric analysis of the aerosol organic component showed that aerosol aging is characterized by shifting from less oxidized fresh BB aerosols to more oxidized aerosols. Evidence for aerosol aging during the day following the BB event was indicated by an increase in the organic mass, its oxidation state, the total aerosol concentration, and a shift in the modal particle diameter. The effective broadband refractive index (EBRI) was derived using a white light optical particle counter (WELAS). The average EBRI for a mixed population of aerosols dominated by open fires was m = 1.53(±0.03) + 0.07i(±0.03), during the smoldering phase of the fires we found the EBRI to be m = 1.54(±0.01) + 0.04i(±0.01) compared to m = 1.49(±0.01) + 0.02i(±0.01) of the aged aerosols during the following day. This change indicates a decrease in the overall aerosol absorption and scattering. Elevated levels of particulate Polycyclic Aromatic Hydrocarbons (PAHs) were detected during the entire event, which suggest possible implications for human health during such extensive event.

  20. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: chemical characterization of the products

    NASA Astrophysics Data System (ADS)

    Grgić, Irena; Kitanovski, Zoran; Kroflič, Ana; Čusak, Alen

    2014-05-01

    One of the largest primary sources of organic aerosol in the atmosphere is biomass burning (BB) (Laskin et al. 2009); in Europe its contribution to annual mean of PM10 is between 3 and 14 % (Maenhaut et al. 2012). During the process of wood burning many different products are formed via thermal degradation of wood lignin. Hardwood burning produces mainly syringol (2,6-dimetoxyphenol) derivatives, while softwood burning exclusively guaiacol (2-methoxyphenol) and its derivatives. Taking into account physical properties of methoxyphenols only, their concentrations in atmospheric waters might be underestimated. So, their aqueous phase reactions can be an additional source of SOA, especially in regions under significant influence of wood combustion. An important class of compounds formed during physical and chemical aging of the primary BBA in the atmosphere is nitrocatechols, known as strong absorbers of UV and Vis light (Claeys et al. 2012). Very recently, methyl-nitrocatechols were proposed as suitable markers for highly oxidized secondary BBA (Iinuma et al. 2010, Kitanovski et al. 2012). In the present work, the formation of SOA through aqueous phase photooxidation and nitration of guaiacol was examined. The key objective was to chemically characterize the main low-volatility products and further to check their possible presence in the urban atmospheric aerosols. The aqueous phase reactions were performed in a thermostated reactor under simulated sunlight in the presence of H2O2 and nitrite. Guaiacol reaction products were first concentrated by solid-phase extraction (SPE) and then subjected to semi-preparative liquid chromatography.The main product compounds were fractionated and isolated as pure solids and their structure was further elucidated by using nuclear magnetic resonance spectroscopy (1H, 13C and 2D NMR) and direct infusion negative ion electro-spray ionization tandem mass spectrometry (( )ESI-MS/MS). The main photonitration products of guaiacol (4

  1. Gaseous composition measured by a chemical ionization mass spectrometer in fresh and aged ship plumes

    NASA Astrophysics Data System (ADS)

    Faxon, Cameron; Psichoudaki, Magda; Kuuluvainen, Heino; Hallquist, Åsa; Thomson, Erik; Pettersson, Jan; Hallquist, Mattias

    2015-04-01

    The port of Gothenburg is the largest port of the Nordic countries with numerous ships calling the port daily. The ship exhausts contain numerous pollutants including gases such as SO2 and NOx as well as particulate matter and soot. The exhaust also contains numerous organic compounds, a large fraction of which are unidentified. These organics are oxidized in the atmosphere producing more oxygenated and potentially less volatile compounds that may contribute to the secondary organic aerosol (SOA). This work focuses on the characterization of fresh gaseous species present in the exhaust plumes of the passing ships and also on their photochemical aging. Between 26 September and 12 November 2014 measurements were conducted at a sampling site located on a small peninsula at the entrance of Gothenburg's port. The campaign was divided in two periods. During the first period, the fresh plumes of the passing ships were measured through a main inlet. During the second period, the sample passed through the same inlet and was then introduced into a Potential Aerosol Mass (PAM) reactor. The PAM reactor uses UV lamps and high concentrations of oxidants (OH radicals and O3) to oxidize the organic species present in the plumes. The oxidation that takes place within the reactor can be equivalent to up to one week of atmospheric oxidation. Preliminary tests showed that the oxidation employed in the current camping corresponded to 3.4 days in the atmosphere. A Time-of-Flight Chemical Ionization Mass Spectrometer (ToF-CIMS) was employed to monitor the concentration of different organic species present in the fresh and aged plumes. Water (positive) and iodide (negative) ionization methods were employed were water was primarily used for fresh plumes (large fraction of non-polar compounds) while iodide was used for the aged plumes (primarily oxidised products). The H2O, O3 and SO2 concentrations inside the PAM chamber were monitored, and an organic tracer for OH exposure determination

  2. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    PubMed Central

    Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-01-01

    Abstract Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI‐APi‐TOF (Chemical Ionization‐Atmospheric Pressure interface‐Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI‐APi‐TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4‐H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self‐contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  3. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    PubMed Central

    Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-01-01

    Abstract Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI‐APi‐TOF (Chemical Ionization‐Atmospheric Pressure interface‐Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI‐APi‐TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4‐H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self‐contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit. PMID:27610289

  4. Biokinetics and dosimetry of inhaled Cm aerosols in beagles: effect of aerosol chemical form.

    PubMed

    Guilmette, R A; Kanapilly, G M

    1988-12-01

    This study was designed to provide tissue distribution data of 244Cm that was inhaled by beagle dogs. Two chemical forms that were presumed to bracket the solubility of pure Cm compounds in vivo were used: 244Cm2O3 (oxide) and 244Cm(NO3)3 (nitrate). Adult dogs of both sexes received a single brief pernasal exposure to either a monodisperse aerosol of 244Cm2O3 (1.4 micron activity median aerodynamic diameter, AMAD, and 1.16 geometric standard deviation, sigma g) or a polydisperse aerosol of 244Cm(NO3)3 (1.1 micron AMAD, 1.74 sigma g). The resulting initial pulmonary burdens (IPB) were 1.5 and 1.7 kBq kg-1 body mass for the oxide and nitrate groups, respectively. The tissue distribution data obtained from the dogs that were serially sacrificed from 4 h to 2 y after exposure showed that both chemical forms were very soluble in vivo. For the oxide group, 78% IPB was cleared from the lung with a T 1/2 of 7.6 d, whereas for the nitrate group, 42% IPB cleared with a T 1/2 of 0.6 d. The lung retention for each group was described by three-component exponential functions. Most of the Cm that cleared the lung was redeposited in the liver (37% IPB) and skeleton (27% IPB), with lesser amounts in the muscle, fat and connective tissue (3.5% IPB) and kidney (approximately 2% IPB). The only significant difference noted in the biokinetics of Cm for the two exposure groups was a more rapid translocation of Cm from the lung to liver and bone during the first 10-20 d after exposure to the nitrate compared to the oxide chemical form. Extrapolation of these data to obtain estimates of committed dose equivalents for man indicate substantial agreement with the limits for occupational exposure specified by ICRP 30 (1979). PMID:3198400

  5. Ionization of Samarium by Chemical Releases in the Upper Atmosphere

    NASA Astrophysics Data System (ADS)

    Siefring, C. L.; Bernhardt, P. A.; Holmes, J. M.; Pedersen, T. R.; Caton, R.; Miller, D.; Groves, K. M.

    2014-12-01

    The release of Samarium vapor into the upper atmosphere was studied using during the Air Force Research Laboratory sponsored Metal Oxide Space Cloud (MOSC) rocket launches in May 2009. The Naval Research Laboratory supported these experiments with 3-D photochemical modeling of the artificial plasma cloud including (1) reactions with atomic oxygen, (2) photo excitation, (3) photoionization, (4) dissociative recombination, and (5) ion and neutral diffusion. NRL provided the experimental diagnostic instrument on the rocket which was a dual frequency radio beacon on the rocket to measure changes in total electron content. The AFRL provided ground based diagnostics of incoherent scatter radar and optical spectroscopy and imagery. The NRL Chemical Release Model (CRM) has over 600 excited states of atomic Samarium neutrals, atomic ions, along with Samarium Oxide Ions and electrons. Diffusive transport of neutrals in cylindrical geometry and ions along magnetic field lines is computed along with the reactive flow to predict the concentrations of Sm, Sm-Ion, Sm0, and SmO Ion. Comparison of the CRM with observations demonstrates that Sm release into the upper atmosphere initially produces enhanced electron densities and SmO-Ions. The diatomic ions recombine with electrons to yield neutral Sm and O. Only the photo ionization of Sm yields a stable atomic ion that does not substantially recombine. The MOSC releases in sunlight yielded long duration ion clouds that can be replicated with the CRM. The CRM predicts that Sm releases in darkness would not produce long duration plasma clouds because of the lack of photo excitation and photoionization.

  6. Chemical characterization and physico-chemical properties of aerosols at Villum Research Station, Greenland during spring 2015

    NASA Astrophysics Data System (ADS)

    Glasius, M.; Iversen, L. S.; Svendsen, S. B.; Hansen, A. M. K.; Nielsen, I. E.; Nøjgaard, J. K.; Zhang, H.; Goldstein, A. H.; Skov, H.; Massling, A.; Bilde, M.

    2015-12-01

    The effects of aerosols on the radiation balance and climate are of special concern in Arctic areas, which have experienced warming at twice the rate of the global average. As future scenarios include increased emissions of air pollution, including sulfate aerosols, from ship traffic and oil exploration in the Arctic, there is an urgent need to obtain the fundamental scientific knowledge to accurately assess the consequences of pollutants to environment and climate. In this work, we studied the chemistry of aerosols at the new Villum Research Station (81°36' N, 16°40' W) in north-east Greenland during the "inauguration campaign" in spring 2015. The chemical composition of sub-micrometer Arctic aerosols was investigated using a Soot Particle Time-of-Flight Aerosol Mass Spectrometer (SP-ToF-AMS). Aerosol samples were also collected on filters using both a high-volume sampler and a low-volume sampler equipped with a denuder for organic gases. Chemical analyses of filter samples include determination of inorganic anions and cations using ion-chromatography, and analysis of carboxylic acids and organosulfates of anthropogenic and biogenic origin using ultrahigh-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS). Previous studies found that organosulfates constitute a surprisingly high fraction of organic aerosols during the Arctic Haze period in winter and spring. Investigation of organic molecular tracers provides useful information on aerosol sources and atmospheric processes. The physico-chemical properties of Arctic aerosols are also under investigation. These measurements include particle number size distribution, water activity and surface tension of aerosol samples in order to deduct information on their hygroscopicity and cloud-forming potential. The results of this study are relevant to understanding aerosol sources and processes as well as climate effects in the Arctic, especially during the Arctic haze

  7. Chemical composition of atmospheric aerosols between Moscow and Vladivostok

    NASA Astrophysics Data System (ADS)

    Kuokka, S.; Teinilä, K.; Saarnio, K.; Aurela, M.; Sillanpää, M.; Hillamo, R.; Kerminen, V.-M.; Vartiainen, E.; Kulmala, M.; Skorokhod, A. I.; Elansky, N. F.; Belikov, I. B.

    2007-05-01

    The TROICA-9 expedition (Trans-Siberian Observations Into the Chemistry of the Atmosphere) was carried out at the Trans-Siberian railway between Moscow and Vladivostok in October 2005. Measurements of aerosol physical and chemical properties were made from an observatory carriage connected to a passenger train. Black carbon (BC) concentrations in fine particles (PM2.5, aerodynamic diameter <2.5 μm) were measured with an aethalometer using a five-minute time resolution. Concentrations of inorganic ions and some organic compounds (Cl-, NO3-, SO42-, Na+, NH4+, K+, Ca2+, Mg2+, oxalate and methane sulphonate) were measured continuously by using an on-line system with a 15-min time resolution. In addition, particle volume size distributions were determined for particles in the diameter range 3-850 nm using a 10-min. time resolution. The continuous measurements were completed with 24-h. PM2.5 filter samples which were stored in a refrigerator and later analyzed in chemical laboratory. The analyses included mass concentrations of PM2.5, ions, monosaccharide anhydrides (levoglucosan, galactosan and mannosan) and trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V and Zn). The mass concentrations of PM2.5 varied in the range of 4.3-34.8 μg m-3 with an average of 21.6 μg m-3. Fine particle mass consisted mainly of BC (average 27.6%), SO42- (13.0%), NH4+ (4.1%), and NO3- (1.4%). One of the major constituents was obviously also organic carbon which was not determined. The contribution of BC was high compared with other studies made in Europe and Asia. High concentrations of ions, BC and particle volume were observed between Moscow and roughly 4000 km east of it, as well as close to Vladivostok, primarily due to local anthropogenic sources. In the natural background area between 4000 and 7200 km distance from Moscow, observed concentrations were low, even though there were local particle sources, such as forest fires, that increased occasionally concentrations. The

  8. Validation of the assimilation of satellite-based aerosol measurements into a chemical transport model using aerosol component information

    NASA Astrophysics Data System (ADS)

    Martynenko, Dmytro; Holzer-Popp, Thomas; Schroedter-Homscheidt, Marion

    Aerosol monitoring is of growing interest due to the impact of aerosol particle concentration on human health and the global climate. The key question of this paper is to understand how the assimilation of satellite atmospheric aerosol observations with enhanced observation and background covariance matrices improves the capability of a chemical transport model in reproducing the distribution of tropospheric particles. The task of this study is a validation of assimilation results by using ground-based AERONET measurements for 2006-2008 at stations from Europe and Africa regions. The study is carried out using the Model for Atmospheric Transport and Chemistry (MATCH operated at DLR). As measurement input vector for as-similation satellite data from SCIAMACHY and AATSR instruments onboard ENVISAT was used. Synergetic Aerosol Retrieval (SYNAER) observational and model data have been cou-pled by means of data the two-dimensional variational assimilation. SYNAER measurements are able to distinguish between different aerosol components such as water-soluble, soot, sea salt and long-range transported mineral aerosols. The final analysis is highly dependent on the specification of the error covariance matrices. Since observation and background error covari-ance matrices are not perfectly known, a large potential for improvements of the analyses is offered by methods allowing their constructing and tuning. In this study, a method proposed by Desroziers and Ivanov (2001) is used to tune background and observational error statistics of the 2D-Var assimilation procedure by using information content analysis of the retrieval algorithm.

  9. Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

    USGS Publications Warehouse

    Thurman, E.M.; Ferrer, I.; Barcelo, D.

    2001-01-01

    An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

  10. Effects of aerosol sources and chemical compositions on cloud drop sizes and glaciation temperatures

    NASA Astrophysics Data System (ADS)

    Zipori, Assaf; Rosenfeld, Daniel; Tirosh, Ofir; Teutsch, Nadya; Erel, Yigal

    2015-09-01

    The effect of aerosols on cloud properties, such as its droplet sizes and its glaciation temperatures, depends on their compositions and concentrations. In order to examine these effects, we collected rain samples in northern Israel during five winters (2008-2011 and 2013) and determined their chemical composition, which was later used to identify the aerosols' sources. By combining the chemical data with satellite-retrieved cloud properties, we linked the aerosol types, sources, and concentrations with the cloud glaciation temperatures (Tg). The presence of dust increased Tg from -26°C to -12°C already at relatively low dust concentrations. This result is in agreement with the conventional wisdom that desert dust serves as good ice nuclei (INs). With higher dust concentrations, Tg saturated at -12°C, even though cloud droplet sizes decreased as a result of the cloud condensation nucleating (CCN) activity of the dust. Marine air masses also encouraged freezing, but in this case, freezing was enhanced by the larger cloud droplet sizes in the air masses (caused by low CCN concentrations) and not by IN concentrations or by aerosol type. An increased fraction of anthropogenic aerosols in marine air masses caused a decrease in Tg, indicating that these aerosols served as poor IN. Anthropogenic aerosols reduced cloud droplet sizes, which further decreased Tg. Our results could be useful in climate models for aerosol-cloud interactions, as we investigated the effects of aerosols of different sources on cloud properties. Such parameterization can simplify these models substantially.

  11. Methodology for the passive detection and discrimination of chemical and biological aerosols

    NASA Astrophysics Data System (ADS)

    Marinelli, William J.; Shokhirev, Kirill N.; Konno, Daisei; Rossi, David C.; Richardson, Martin

    2013-05-01

    The standoff detection and discrimination of aerosolized biological and chemical agents has traditionally been addressed through LIDAR approaches, but sensor systems using these methods have yet to be deployed. We discuss the development and testing of an approach to detect these aerosols using the deployed base of passive infrared hyperspectral sensors used for chemical vapor detection. The detection of aerosols requires the inclusion of down welling sky and up welling ground radiation in the description of the radiative transfer process. The wavelength and size dependent ratio of absorption to scattering provides much of the discrimination capability. The approach to the detection of aerosols utilizes much of the same phenomenology employed in vapor detection; however, the sensor system must acquire information on non-line-of-sight sources of radiation contributing to the scattering process. We describe the general methodology developed to detect chemical or biological aerosols, including justifications for the simplifying assumptions that enable the development of a real-time sensor system. Mie scattering calculations, aerosol size distribution dependence, and the angular dependence of the scattering on the aerosol signature will be discussed. This methodology will then be applied to two test cases: the ground level release of a biological aerosol (BG) and a nonbiological confuser (kaolin clay) as well as the debris field resulting from the intercept of a cruise missile carrying a thickened VX warhead. A field measurement, conducted at the Utah Test and Training Range will be used to illustrate the issues associated with the use of the method.

  12. Aerosol matrix-assisted laser desorption ionization. Effects of analyte concentration and matrix-to-analyte ratio

    SciTech Connect

    Beeson, M.D.; Murray, K.K.; Russell, D.H.

    1995-07-01

    We have recently developed an aerosol-liquid introduction interface for matrix-assisted laser desorption ionization (MALDI) mass spectrometry. In this study, we examine the effect of matrix-to-analyte ratio and analyte concentration on analyte ion yield. These studies were performed using bradykinin, gramicidin S, bovine insulin, and myoglobin as analytes and {alpha}-cyano-4-hydroxycinnamic acid and 4-nitroaniline as matrices. The optimum matrix-to-analyte molar ratio for aerosol MALDI was determined to be 10-100:1, which is lower than that typically used for conventional surface MALDI (100-10 000:1). The ion yield was found to be a nonlinear function of analyte concentration. Possible explanations for these observations are discussed. 43 refs., 3 figs., 1 tab.

  13. Direct aerosol chemical composition measurements to evaluate the physicochemical differences between controlled sea spray aerosol generation schemes

    NASA Astrophysics Data System (ADS)

    Collins, D. B.; Zhao, D. F.; Ruppel, M. J.; Laskina, O.; Grandquist, J. R.; Modini, R. L.; Stokes, M. D.; Russell, L. M.; Bertram, T. H.; Grassian, V. H.; Deane, G. B.; Prather, K. A.

    2014-11-01

    Controlled laboratory studies of the physical and chemical properties of sea spray aerosol (SSA) must be under-pinned by a physically and chemically accurate representation of the bubble-mediated production of nascent SSA particles. Bubble bursting is sensitive to the physico-chemical properties of seawater. For a sample of seawater, any important differences in the SSA production mechanism are projected into the composition of the aerosol particles produced. Using direct chemical measurements of SSA at the single-particle level, this study presents an intercomparison of three laboratory-based, bubble-mediated SSA production schemes: gas forced through submerged sintered glass filters ("frits"), a pulsed plunging-waterfall apparatus, and breaking waves in a wave channel filled with natural seawater. The size-resolved chemical composition of SSA particles produced by breaking waves is more similar to particles produced by the plunging waterfall than those produced by sintered glass filters. Aerosol generated by disintegrating foam produced by sintered glass filters contained a larger fraction of organic-enriched particles and a different size-resolved elemental composition, especially in the 0.8-2 μm dry diameter range. Interestingly, chemical differences between the methods only emerged when the particles were chemically analyzed at the single-particle level as a function of size; averaging the elemental composition of all particles across all sizes masked the differences between the SSA samples. When dried, SSA generated by the sintered glass filters had the highest fraction of particles with spherical morphology compared to the more cubic structure expected for pure NaCl particles produced when the particle contains relatively little organic carbon. In addition to an intercomparison of three SSA production methods, the role of the episodic or "pulsed" nature of the waterfall method on SSA composition was under-taken. In organic-enriched seawater, the continuous

  14. Characterization of aromaticity in analogues of titan's atmospheric aerosols with two-step laser desorption ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Mahjoub, Ahmed; Schwell, Martin; Carrasco, Nathalie; Benilan, Yves; Cernogora, Guy; Szopa, Cyril; Gazeau, Marie-Claire

    2016-10-01

    The role of polycyclic aromatic hydrocarbons (PAH) and Nitrogen containing PAH (PANH) as intermediates of aerosol production in the atmosphere of Titan has been a subject of controversy for a long time. An analysis of the atmospheric emission band observed by the Visible and Infrared Mapping Spectrometer (VIMS) at 3.28 μm suggests the presence of neutral polycyclic aromatic species in the upper atmosphere of Titan. These molecules are seen as the counter part of negative and positive aromatics ions suspected by the Plasma Spectrometer onboard the Cassini spacecraft, but the low resolution of the instrument hinders any molecular speciation. In this work we investigate the specific aromatic content of Titan's atmospheric aerosols through laboratory simulations. We report here the selective detection of aromatic compounds in tholins, Titan's aerosol analogs, produced with a capacitively coupled plasma in a N2:CH4 95:5 gas mixture. For this purpose, Two-Step Laser Desorption Ionization Time-of-Flight Mass Spectrometry (L2DI-TOF-MS) technique is used to analyze the so produced analogs. This analytical technique is based on the ionization of molecules by Resonance Enhanced Multi-Photon Ionization (REMPI) using a λ=248 nm wavelength laser which is selective for aromatic species. This allows for the selective identification of compounds having at least one aromatic ring. Our experiments show that tholins contain a trace amount of small PAHs with one to three aromatic rings. Nitrogen containing PAHs (PANHs) are also detected as constituents of tholins. Molecules relevant to astrobiology are detected as is the case of the substituted DNA base adenine.

  15. Chemical and size effects of hygroscopic aerosols on light scattering coefficients

    NASA Astrophysics Data System (ADS)

    Tang, Ignatius N.

    1996-08-01

    The extensive thermodynamic and optical properties recently reported [Tang and Munkelwitz, 1994a] for sulfate and nitrate solution droplets are incorporated into a visibility model for computing light scattering by hygroscopic aerosols. The following aerosol systems are considered: NH4HSO4, (NH4)2SO4, (NH4)3H(SO4), NaHSO4, Na2SO4, NH4NO3, and NaNO3. In addition, H2SO4 and NaCl are included to represent freshly formed sulfate and background sea-salt aerosols, respectively. Scattering coefficients, based on 1 μg dry salt per cubic meter of air, are calculated as a function of relative humidity for aerosols of various chemical compositions and lognormal size distributions. For a given size distribution the light scattered by aerosol particles per unit dry-salt mass concentration is only weakly dependent on chemical constituents of the hygroscopic sulfate and nitrate aerosols. Sulfuric acid and sodium chloride aerosols, however, are exceptions and scatter light more efficiently than all other inorganic salt aerosols considered in this study. Both internal and external mixtures exhibit similar light-scattering properties. Thus for common sulfate and nitrate aerosols, since the chemical effect is outweighed by the size effect, it follows that observed light scattering by the ambient aerosol can be approximated, within practical measurement uncertainties, by assuming the aerosol being an external mixture. This has a definite advantage for either visibility degradation or climatic impact modeling calculations, because relevant data are now available for external mixtures but only very scarce for internal mixtures.

  16. Chemical characterization of organosulfates in secondary organic aerosol derived from the photooxidation of alkanes

    NASA Astrophysics Data System (ADS)

    Riva, Matthieu; Da Silva Barbosa, Thais; Lin, Ying-Hsuan; Stone, Elizabeth A.; Gold, Avram; Surratt, Jason D.

    2016-09-01

    We report the formation of aliphatic organosulfates (OSs) in secondary organic aerosol (SOA) from the photooxidation of C10-C12 alkanes. The results complement those from our laboratories reporting the formation of OSs and sulfonates from gas-phase oxidation of polycyclic aromatic hydrocarbons (PAHs). Both studies strongly support the formation of OSs from the gas-phase oxidation of anthropogenic precursors, as hypothesized on the basis of recent field studies in which aromatic and aliphatic OSs were detected in fine aerosol collected from several major urban locations. In this study, dodecane, cyclodecane and decalin, considered to be important SOA precursors in urban areas, were photochemically oxidized in an outdoor smog chamber in the presence of either non-acidified or acidified ammonium sulfate seed aerosol. Effects of acidity and relative humidity on OS formation were examined. Aerosols collected from all experiments were characterized by ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS). Most of the OSs identified could be explained by formation of gaseous epoxide precursors with subsequent acid-catalyzed reactive uptake onto sulfate aerosol and/or heterogeneous reactions of hydroperoxides. The OSs identified here were also observed and quantified in fine urban aerosol samples collected in Lahore, Pakistan, and Pasadena, CA, USA. Several OSs identified from the photooxidation of decalin and cyclodecane are isobars of known monoterpene organosulfates, and thus care must be taken in the analysis of alkane-derived organosulfates in urban aerosol.

  17. The chemical evolution & physical properties of organic aerosol: A molecular structure based approach

    NASA Astrophysics Data System (ADS)

    Wei, Yiyi; Cao, Tingting; Thompson, Jonathan E.

    2012-12-01

    Global climate, atmospheric chemistry, and air quality are affected by tropospheric particulate matter. Recent measurements suggest organic compounds present in this haze comprise roughly half of total aerosol fine mass concentration globally. Unlike the well-constrained processes which result in formation of nitrate or sulfate aerosol, the oxidation of volatile organics in the atmosphere can lead to thousands of stable compounds in the aerosol phase. Development of a tractable framework to consider the chemical and physical evolution of the organic aerosol is crucial for modeling its effect on global climate. Here we show coupling a 3-dimensional coordinate system defined by the molecular descriptors of molecular weight, heteroatom mass, and double bond equivalents (D.B.E.) with high-resolution molecular mass spectrometry is a powerful approach for describing key properties of the organic aerosol. The scheme is conceptually simple, yet maintains sufficient complexity to be compatible with quantitative structure-property relationships (QSPRs) used to predict chemical and physical properties that govern aerosol behavior. From available data, both ambient organic aerosol and laboratory generated organic aerosol frequently occupy the region characterized by <10 D.B.E. <600 M.W. and <200 heteroatom mass. A QSPR analysis conducted illustrates spatial trends within the 3D space for volatility and Henry's law constants for 31,000 organic compounds considered.

  18. REPRESENTING AEROSOL DYNAMICS AND PROPERTIES IN CHEMICAL TRANSPORT MODELS BY THE METHOD OF MOMENTS.

    SciTech Connect

    SCHWARTZ, S.E.; MCGRAW, R.; BENKOVITZ, C.M.; WRIGHT, D.L.

    2001-04-01

    Atmospheric aerosols, suspensions of solid or liquid particles, are an important multi-phase system. Aerosols scatter and absorb shortwave (solar) radiation, affecting climate (Charlson et al., 1992; Schwartz, 1996) and visibility; nucleate cloud droplet formation, modifying the reflectivity of clouds (Twomey et al., 1984; Schwartz and Slingo, 1996) as well as contributing to composition of cloudwater and to wet deposition (Seinfeld and Pandis, 1998); and affect human health through inhalation (NRC, 1998). Existing and prospective air quality regulations impose standards on concentrations of atmospheric aerosols to protect human health and welfare (EPA, 1998). Chemical transport and transformation models representing the loading and geographical distribution of aerosols and precursor gases are needed to permit development of effective and efficient strategies for meeting air quality standards, and for examining aerosol effects on climate retrospectively and prospectively for different emissions scenarios. Important aerosol properties and processes depend on their size distribution: light scattering, cloud nucleating properties, dry deposition, and penetration into airways of lungs. The evolution of the mass loading itself depends on particle size because of the size dependence of growth and removal processes. For these reasons it is increasingly recognized that chemical transport and transformation models must represent not just the mass loading of atmospheric particulate matter but also the aerosol microphysical properties and the evolution of these properties if aerosols are to be accurately represented in these models. If the size distribution of the aerosol is known, a given property can be evaluated as the integral of the appropriate kernel function over the size distribution. This has motivated the approach of determining aerosol size distribution, and of explicitly representing this distribution and its evolution in chemical transport models.

  19. Physico-chemical properties of aerosols in Sao Paulo, Brazil and mechanisms of secondary organic aerosol formation.

    NASA Astrophysics Data System (ADS)

    Artaxo, Paulo; Ferreira de Brito, Joel; Varanda Rizzo, Luciana; Luiza Godoy, Maria; Godoy, Jose Marcus

    2013-04-01

    Megacities emissions are increasingly becoming a global issue, where emissions from the transportation sector play an increasingly important role. Sao Paulo is a megacity with a population of about 18 million people, 7 million cars and large-scale industrial emissions. As a result of the vehicular and industrial emissions, the air quality in Sao Paulo is bellow WMO standards for aerosol particles and ozone. Many uncertainties are found on gas- and particulate matter vehicular emission factors and their following atmospheric processes, e.g. secondary organic aerosol formation. Due to the uniqueness of the vehicular fuel in Brazil, largely based on ethanol use, such characterization currently holds further uncertainties. To improve the understanding of the role of this unique emission characteristics, we are running a source apportionment study in Sao Paulo focused on the mechanisms of organic aerosol formation. One of the goals of this study is a quantitative aerosol source apportionment focused on vehicular emissions, including ethanol and gasohol (both fuels used by light-duty vehicles). This study comprises four sampling sites with continuous measurements for one year, where trace elements and organic aerosol are being measured for PM2.5 and PM10 along with real-time NOx, O3, PM10 and CO measurements. Aerosol optical properties and size distribution are being measured on a rotation basis between sampling stations. Furthermore, a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) and an Aerosol Chemical Speciation Monitor (ACSM) are used to measure in real time VOCs and aerosol composition, respectively. Trace elements were measured using XRF and OC/EC analysis was determined with a Sunset OC/EC instrument. A TSI Nephelometer with 3 wavelengths measure light scattering and a MAAP measure black carbon. Results show aerosol number concentrations ranging between 10,000 and 35,000 cm-3, mostly concentrated in the nucleation and Aitken modes, with a peak in size at 80

  20. Atmospheric Amines and Ammonia Measured with a Chemical Ionization Mass Spectrometer (CIMS)

    SciTech Connect

    You, Y.; Kanawade, V. P.; de Gouw, J. A.; Guenther, Alex B.; Madronich, Sasha; Sierra-Hernandez, M. R.; Lawler, M.; Smith, James N.; Takahama, S.; Ruggeri, G.; Koss, A.; Olson, K.; Baumann, K.; Weber, R. J.; Nenes, A.; Guo, H.; Edgerton, Eric S.; Porcelli, L.; Brune, W. H.; Goldstein, Allen H.; Lee, S.-H

    2014-11-19

    We report ambient measurements of amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a Southeastern U.S. forest in Alabama and a moderately polluted Midwestern site during the summer. In the Alabama forest, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected on a daily basis. C3-amines and ammonia showed similar diurnal trends and temperature and wind direction dependences, and were not associated with transported CO and SO2 plumes. Consistent with temperature dependences, amine and ammonia in the gas and aerosol phases showed opposite diurnal trends, indicating gas-to-particle partitioning of amines and ammonia. Temperature dependences also imply reversible processes of amines and ammonia evaporation from soil surfaces in daytime and deposition of amines and ammonia to soil surfaces at nighttime. Various amines (C1-C6) at the pptv level were observed in the transported biomass burning plumes, showing that biomass burning can be a substantial source of amines in the Southeast U.S. At the moderately polluted Kent site, higher concentrations of amines (C1-C6, from pptv to tens of pptv) and ammonia (up to 6 ppbv) were detected. Diurnal variations of C1- to C3-amines and ammonia were correlated with the ambient temperature. C4- to C6-amines showed abrupt increases during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Lower amine concentrations at the rural forested site highlight the importance of constraining anthropogenic sources of amines.

  1. Characterization of ice-nucleating bacteria using on-line electron impact ionization aerosol mass spectrometry.

    PubMed

    Wolf, R; Slowik, J G; Schaupp, C; Amato, P; Saathoff, H; Möhler, O; Prévôt, A S H; Baltensperger, U

    2015-04-01

    The mass spectral signatures of airborne bacteria were measured and analyzed in cloud simulation experiments at the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) facility. Suspensions of cultured cells in pure water were sprayed into the aerosol and cloud chambers forming an aerosol which consisted of intact cells, cell fragments and residual particles from the agar medium in which the bacteria were cultured. The aerosol particles were analyzed with a high-resolution time-of-flight aerosol mass spectrometer equipped with a newly developed PM2.5 aerodynamic lens. Positive matrix factorization (PMF) using the multilinear engine (ME-2) source apportionment was applied to deconvolve the bacteria and agar mass spectral signatures. The bacteria mass fraction contributed between 75 and 95% depending on the aerosol generation, with the remaining mass attributed to agar. We present mass spectra of Pseudomonas syringae and Pseudomonas fluorescens bacteria typical for ice-nucleation active bacteria in the atmosphere to facilitate the distinction of airborne bacteria from other constituents in ambient aerosol, e.g. by PMF/ME-2 source apportionment analyses. Nitrogen-containing ions were the most salient feature of the bacteria mass spectra, and a combination of C4 H8 N(+) (m/z 70) and C5 H12 N(+) (m/z 86) may be used as marker ions. PMID:26149110

  2. Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Secondary Organic Aerosols

    SciTech Connect

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

    2012-07-02

    The applicability of high resolution electrospray ionization mass spectrometry (HR ESI-MS) to measurements of the average oxygen to carbon ratio (O/C) in organic aerosols was investigated. Solutions with known average O/C containing up to 10 standard compounds representative of secondary organic aerosol (SOA) were analyzed and corresponding electrospray ionization efficiencies were quantified. The assumption of equal ionization efficiency commonly used in estimating O/C ratios of organic aerosols was found to be reasonably accurate. We found that the accuracy of the measured O/C ratios increases by averaging the values obtained from both (+) and (-) modes. A correlation was found between the ratio of the ionization efficiencies in the positive and negative ESI modes with the octanol-water partition constant, and more importantly, with the compound's O/C. To demonstrate the utility of this correlation for estimating average O/C values of unknown mixtures, we analyzed the ESI (+) and ESI (-) data for SOA produced by oxidation of limonene and isoprene and compared to online O/C measurements using an aerosol mass spectrometer (AMS). This work demonstrates that the accuracy of the HR ESI-MS methods is comparable to that of the AMS, with the added benefit of molecular identification of the aerosol constituents.

  3. Mass spectrometric behavior of anabolic androgenic steroids using gas chromatography coupled to atmospheric pressure chemical ionization source. Part I: ionization.

    PubMed

    Raro, M; Portolés, T; Sancho, J V; Pitarch, E; Hernández, F; Marcos, J; Ventura, R; Gómez, C; Segura, J; Pozo, O J

    2014-06-01

    The detection of anabolic androgenic steroids (AAS) is one of the most important topics in doping control analysis. Gas chromatography coupled to (tandem) mass spectrometry (GC-MS(/MS)) with electron ionization and liquid chromatography coupled to tandem mass spectrometry have been traditionally applied for this purpose. However, both approaches still have important limitations, and, therefore, detection of all AAS is currently afforded by the combination of these strategies. Alternative ionization techniques can minimize these drawbacks and help in the implementation of a single method for the detection of AAS. In the present work, a new atmospheric pressure chemical ionization (APCI) source commercialized for gas chromatography coupled to a quadrupole time-of-flight analyzer has been tested to evaluate the ionization of 60 model AAS. Underivatized and trimethylsylil (TMS)-derivatized compounds have been investigated. The use of GC-APCI-MS allowed for the ionization of all AAS assayed irrespective of their structure. The presence of water in the source as modifier promoted the formation of protonated molecules ([M+H](+)), becoming the base peak of the spectrum for the majority of studied compounds. Under these conditions, [M+H](+), [M+H-H2O](+) and [M+H-2·H2O](+) for underivatized AAS and [M+H](+), [M+H-TMSOH](+) and [M+H-2·TMSOH](+) for TMS-derivatized AAS were observed as main ions in the spectra. The formed ions preserve the intact steroid skeleton, and, therefore, they might be used as specific precursors in MS/MS-based methods. Additionally, a relationship between the relative abundance of these ions and the AAS structure has been established. This relationship might be useful in the structural elucidation of unknown metabolites.

  4. Aerosol Optical Properties Measured Onboard the Ronald H. Brown During ACE Asia as a Function of Aerosol Chemical Composition and Source Region

    NASA Technical Reports Server (NTRS)

    Quinn, P. K.; Coffman, D. J.; Bates, T. S.; Welton, E. J.; Covert, D. S.; Miller, T. L.; Johnson, J. E.; Maria, S.; Russell, L.; Arimoto, R.

    2004-01-01

    During the ACE Asia intensive field campaign conducted in the spring of 2001 aerosol properties were measured onboard the R/V Ronald H. Brown to study the effects of the Asian aerosol on atmospheric chemistry and climate in downwind regions. Aerosol properties measured in the marine boundary layer included chemical composition; number size distribution; and light scattering, hemispheric backscattering, and absorption coefficients. In addition, optical depth and vertical profiles of aerosol 180 deg backscatter were measured. Aerosol within the ACE Asia study region was found to be a complex mixture resulting from marine, pollution, volcanic, and dust sources. Presented here as a function of air mass source region are the mass fractions of the dominant aerosol chemical components, the fraction of the scattering measured at the surface due to each component, mass scattering efficiencies of the individual components, aerosol scattering and absorption coefficients, single scattering albedo, Angstrom exponents, optical depth, and vertical profiles of aerosol extinction. All results except aerosol optical depth and the vertical profiles of aerosol extinction are reported at a relative humidity of 55 +/- 5%. An over-determined data set was collected so that measured and calculated aerosol properties could be compared, internal consistency in the data set could be assessed, and sources of uncertainty could be identified. By taking into account non-sphericity of the dust aerosol, calculated and measured aerosol mass and scattering coefficients agreed within overall experimental uncertainties. Differences between measured and calculated aerosol absorption coefficients were not within reasonable uncertainty limits, however, and may indicate the inability of Mie theory and the assumption of internally mixed homogeneous spheres to predict absorption by the ACE Asia aerosol. Mass scattering efficiencies of non-sea salt sulfate aerosol, sea salt, submicron particulate organic

  5. Quantum Chemical Calculations Resolved Identification of Methylnitrocatechols in Atmospheric Aerosols.

    PubMed

    Frka, Sanja; Šala, Martin; Kroflič, Ana; Huš, Matej; Čusak, Alen; Grgić, Irena

    2016-06-01

    Methylnitrocatechols (MNCs) are secondary organic aerosol (SOA) tracers and major contributors to atmospheric brown carbon; however, their formation and aging processes in atmospheric waters are unknown. To investigate the importance of aqueous-phase electrophilic substitution of 3-methylcatechol with nitronium ion (NO2(+)), we performed quantum calculations of their favorable pathways. The calculations predicted the formation of 3-methyl-5-nitrocatechol (3M5NC), 3-methyl-4-nitrocatechol (3M4NC), and a negligible amount of 3-methyl-6-nitrocatechol (3M6NC). MNCs in atmospheric PM2 samples were further inspected by LC/(-)ESI-MS/MS using commercial as well as de novo synthesized authentic standards. We detected 3M5NC and, for the first time, 3M4NC. In contrast to previous reports, 3M6NC was not observed. Agreement between calculated and observed 3M5NC/3M4NC ratios cannot unambiguously confirm the electrophilic mechanism as the exclusive formation pathway of MNCs in aerosol water. However, the examined nitration by NO2(+) is supported by (1) the absence of 3M6NC in the ambient aerosols analyzed and (2) the constant 3M5NC/3M4NC ratio in field aerosol samples, which indicates their common formation pathway. The magnitude of error one could make by incorrectly identifying 3M4NC as 3M6NC in ambient aerosols was also assessed, suggesting the importance of evaluating the literature regarding MNCs with special care.

  6. Quantum Chemical Calculations Resolved Identification of Methylnitrocatechols in Atmospheric Aerosols.

    PubMed

    Frka, Sanja; Šala, Martin; Kroflič, Ana; Huš, Matej; Čusak, Alen; Grgić, Irena

    2016-06-01

    Methylnitrocatechols (MNCs) are secondary organic aerosol (SOA) tracers and major contributors to atmospheric brown carbon; however, their formation and aging processes in atmospheric waters are unknown. To investigate the importance of aqueous-phase electrophilic substitution of 3-methylcatechol with nitronium ion (NO2(+)), we performed quantum calculations of their favorable pathways. The calculations predicted the formation of 3-methyl-5-nitrocatechol (3M5NC), 3-methyl-4-nitrocatechol (3M4NC), and a negligible amount of 3-methyl-6-nitrocatechol (3M6NC). MNCs in atmospheric PM2 samples were further inspected by LC/(-)ESI-MS/MS using commercial as well as de novo synthesized authentic standards. We detected 3M5NC and, for the first time, 3M4NC. In contrast to previous reports, 3M6NC was not observed. Agreement between calculated and observed 3M5NC/3M4NC ratios cannot unambiguously confirm the electrophilic mechanism as the exclusive formation pathway of MNCs in aerosol water. However, the examined nitration by NO2(+) is supported by (1) the absence of 3M6NC in the ambient aerosols analyzed and (2) the constant 3M5NC/3M4NC ratio in field aerosol samples, which indicates their common formation pathway. The magnitude of error one could make by incorrectly identifying 3M4NC as 3M6NC in ambient aerosols was also assessed, suggesting the importance of evaluating the literature regarding MNCs with special care. PMID:27136117

  7. Chemical ionization of clusters formed from sulfuric acid and dimethylamine or diamines

    NASA Astrophysics Data System (ADS)

    Jen, Coty N.; Zhao, Jun; McMurry, Peter H.; Hanson, David R.

    2016-10-01

    Chemical ionization (CI) mass spectrometers are used to study atmospheric nucleation by detecting clusters produced by reactions of sulfuric acid and various basic gases. These instruments typically use nitrate to deprotonate and thus chemically ionize the clusters. In this study, we compare cluster concentrations measured using either nitrate or acetate. Clusters were formed in a flow reactor from vapors of sulfuric acid and dimethylamine, ethylene diamine, tetramethylethylene diamine, or butanediamine (also known as putrescine). These comparisons show that nitrate is unable to chemically ionize clusters with high base content. In addition, we vary the ion-molecule reaction time to probe ion processes which include proton-transfer, ion-molecule clustering, and decomposition of ions. Ion decomposition upon deprotonation by acetate/nitrate was observed. More studies are needed to quantify to what extent ion decomposition affects observed cluster content and concentrations, especially those chemically ionized with acetate since it deprotonates more types of clusters than nitrate.Model calculations of the neutral and ion cluster formation pathways are also presented to better identify the cluster types that are not efficiently deprotonated by nitrate. Comparison of model and measured clusters indicate that sulfuric acid dimers with two diamines and sulfuric acid trimers with two or more base molecules are not efficiently chemical ionized by nitrate. We conclude that acetate CI provides better information on cluster abundancies and their base content than nitrate CI.

  8. CCN frequency distributions and aerosol chemical composition from long-term observations at European ACTRIS supersites

    NASA Astrophysics Data System (ADS)

    Decesari, Stefano; Rinaldi, Matteo; Schmale, Julia Yvonne; Gysel, Martin; Fröhlich, Roman; Poulain, Laurent; Henning, Silvia; Stratmann, Frank; Facchini, Maria Cristina

    2016-04-01

    Cloud droplet number concentration is regulated by the availability of aerosol acting as cloud condensation nuclei (CCN). Predicting the air concentrations of CCN involves knowledge of all physical and chemical processes that contribute to shape the particle size distribution and determine aerosol hygroscopicity. The relevance of specific atmospheric processes (e.g., nucleation, coagulation, condensation of secondary organic and inorganic aerosol, etc.) is time- and site-dependent, therefore the availability of long-term, time-resolved aerosol observations at locations representative of diverse environments is strategic for the validation of state-of-the-art chemical transport models suited to predict CCN concentrations. We focused on long-term (year-long) datasets of CCN and of aerosol composition data including black carbon, and inorganic as well as organic compounds from the Aerosol Chemical Speciation Monitor (ACSM) at selected ACTRIS supersites (http://www.actris.eu/). We discuss here the joint frequency distribution of CCN levels and of aerosol chemical components concentrations for two stations: an alpine site (Jungfraujoch, CH) and a central European rural site (Melpitz, DE). The CCN frequency distributions at Jungfraujoch are broad and generally correlated with the distributions of the concentrations of aerosol chemical components (e.g., high CCN concentrations are most frequently found for high organic matter or black carbon concentrations, and vice versa), which can be explained as an effect of the strong seasonality in the aerosol characteristics at the mountain site. The CCN frequency distributions in Melpitz show a much weaker overlap with the distributions of BC concentrations or other chemical compounds. However, especially at high CCN concentration levels, a statistical correlation with organic matter (OM) concentration can be observed. For instance, the number of CCN (with particle diameter between 20 and 250 nm) at a supersaturation of 0.7% is

  9. Physico-chemical aspects of sewage ionizing radiation treatment

    NASA Astrophysics Data System (ADS)

    Vysotskaya, N. A.; Shevchuk, L. G.

    The ionizing radiation treatment of sewage and redundant activated sludges at doses ranging from 5 to 10 kGy was shown to decrease the specific resistance to filtration, the ɣ-potential of colloidal particles, the bound water content of sewage sludge and to increase the amount of highly molecular substances of filtrate. The dependence of viscosity on concentration and temperature obtained in the radiolysis of gelatin solutions acting as model system allow us to suggest that the straightening out of the dissolved protein molecules and their flocculating properties may be one of the reasons of the improved filtrability of irradiated sludges.

  10. Aerosol Chemical and Physical Characterization in Central Amazonia during the 2013 Dry Season

    NASA Astrophysics Data System (ADS)

    Artaxo, P.; Stern, R.; Brito, J.; Carbone, S.

    2015-12-01

    During the dry season, the central Amazon forest is highly influenced by forest fires transported through large distances, changing drastically the atmospheric composition even in remote places. This work focuses on a physical-chemical characterization of the aerosol population over a pristine site in Central Amazonia during the dry season. The submicrometer organic aerosols were measured with the Aerodyne ACSM (Aerosol Chemical Speciation Monitor, Aerodyne Inc). Optical properties, size distribution and other micro-physical characteristics were also analyzed. Other instruments were simultaneously used. The measurements were taken during the dry season of 2013 in the Cuieiras ecological reserve (ZF2), northwest of Manaus. The statistical analysis of the data was done with the PMF (Positive Matrix Factorization) technique, in which the organic aerosol was separated into different factors, and then its sources and forming processes were attributed. Results show that the mean aerosol loading was 5,91 μg m-3, from which 78% are of organic composition, 8.5% are sulfate, 6.5% are equivalent black carbon, 4% are ammonium and 3% are nitrate. The mass spectra variability can be explained by 3 factors only, determined with the PMF technique. They were identified as BBOA (Biomass Burning Organic Aerosol), representing 12% of the total organic mass, OOA (Oxygenated Organic Aerosol), representing 66% of the total organic mass and IEPOX-SOA (Isoprene derived Epoxydiol-Secondary Organic Aerosol), representing 21% of the total organic mass. Even in remote and pristine regions, Central Amazonia is highly impacted by biomass burning. Biogenic secondary organic aerosols are also present during the dry season, and the suppression of its wet deposition processes increases their concentration. The oxidation level and other physical-chemical characteristics indicate that the long range transport is responsible for the regional range of this impact.

  11. The chemical composition of organic nitrogen in marine rainwater and aerosols

    NASA Astrophysics Data System (ADS)

    Altieri, K. E.; Hastings, M. G.; Peters, A.; Sigman, D. M.

    2010-12-01

    The current state of knowledge on organic nitrogen in the atmosphere is very limited. Atmospheric water soluble organic nitrogen (WSON) is a subset of the complex water soluble organic matter measured in atmospheric aerosols and rainwater; as such, it impacts cloud condensation processes and aerosol chemical and optical properties. In marine and continental atmospheric deposition, the organic N fraction can be 20-80% of total N potentially influencing receiving ecosystems. Therefore, atmospheric WSON plays an important role in both atmospheric chemistry and the global biogeochemical N cycle. However, the sources (i.e., anthropogenic vs. terrestrial vs. marine), composition (e.g., reduced or oxidized N), potential connections to inorganic N (NO3- and NH4+), and spatio-temporal variability of atmospheric WSON are largely unknown. Samples were collected on or near the island of Bermuda (32.27°N, 64.87°W), which is located in the western North Atlantic and experiences seasonal changes in transport that allow for study of both anthropogenically and primarily marine influenced air masses. Rainwater samples (n=7) and aqueous extracted aerosol samples (n=4) were analyzed by positive ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to characterize the chemical composition of the water soluble organic N on a per compound level. We found ~ 800 N containing compounds in 8 compound classes. The CHON+ compound class contained the largest number of N compounds (~ 460). Compared to continental rainwater [Altieri et al., ES&T, 2009], the CHON+ compounds in the marine samples are as dominant in number, yet have less regular patterns and lower O:C ratios for comparable N:C ratios. In fact, average O:C ratios of all N containing compound classes were lower in the marine samples than in continental rainwater samples. No organosulfates or nitrooxy-organosulfates were detected in the marine samples, both of

  12. Exploring Atmospheric Aqueous Chemistry (and Secondary Organic Aerosol Formation) through OH Radical Oxidation Experiments, Droplet Evaporation and Chemical Modeling

    NASA Astrophysics Data System (ADS)

    Turpin, B. J.; Kirkland, J. R.; Lim, Y. B.; Ortiz-Montalvo, D. L.; Sullivan, A.; Häkkinen, S.; Schwier, A. N.; Tan, Y.; McNeill, V. F.; Collett, J. L.; Skog, K.; Keutsch, F. N.; Sareen, N.; Carlton, A. G.; Decesari, S.; Facchini, C.

    2013-12-01

    Gas phase photochemistry fragments and oxidizes organic emissions, making water-soluble organics ubiquitous in the atmosphere. My group and others have found that several water-soluble compounds react further in the aqueous phase forming low volatility products under atmospherically-relevant conditions (i.e., in clouds, fogs and wet aerosols). Thus, secondary organic aerosol can form as a result of gas followed by aqueous chemistry (aqSOA). We have used aqueous OH radical oxidation experiments coupled with product analysis and chemical modeling to validate and refine the aqueous chemistry of glyoxal, methylglyoxal, glycolaldehyde, and acetic acid. The resulting chemical model has provided insights into the differences between oxidation chemistry in clouds and in wet aerosols. Further, we conducted droplet evaporation experiments to characterize the volatility of the products. Most recently, we have conducted aqueous OH radical oxidation experiments with ambient mixtures of water-soluble gases to identify additional atmospherically-important precursors and products. Specifically, we scrubbed water-soluble gases from the ambient air in the Po Valley, Italy using four mist chambers in parallel, operating at 25-30 L min-1. Aqueous OH radical oxidation experiments and control experiments were conducted with these mixtures (total organic carbon ≈ 100 μM-C). OH radicals (3.5E-2 μM [OH] s-1) were generated by photolyzing H2O2. Precursors and products were characterized using electrospray ionization mass spectrometry (ESI-MS), ion chromatography (IC), IC-ESI-MS, and ultra high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chemical modeling suggests that organic acids (e.g., oxalate, pyruvate, glycolate) are major products of OH radical oxidation at cloud-relevant concentrations, whereas organic radical - radical reactions result in the formation of oligomers in wet aerosols. Products of cloud chemistry and droplet evaporation have

  13. Modelling of primary aerosols in the chemical transport model MOCAGE: development and evaluation of aerosol physical parameterizations

    NASA Astrophysics Data System (ADS)

    Sič, B.; El Amraoui, L.; Marécal, V.; Josse, B.; Arteta, J.; Guth, J.; Joly, M.; Hamer, P.

    2014-04-01

    This paper deals with recent improvements to the chemical transport model of Météo-France MOCAGE that consists of updates to different aerosol parameterizations. MOCAGE only contains primary aerosol species. We introduced important changes to the aerosol parameterization concerning emissions, wet deposition and sedimentation. For the emissions, size distribution and wind calculations are modified for desert dust aerosols, and a surface sea temperature dependant source function is introduced for sea salt aerosols. Wet deposition is modified toward a more physically realistic representation by introducing re-evaporation of falling rain and snowfall scavenging, and by changing in-cloud scavenging scheme along with calculations of precipitation cloud cover and rain properties. The sedimentation scheme update includes changes regarding the stability and viscosity calculations. Independent data from satellites (MODIS, SEVIRI), the ground (AERONET), and a model inter-comparison project (AeroCom) is compared with MOCAGE simulations and showed that the introduced changes brought a significant improvement on aerosol representation, properties and global distribution. Emitted quantities of desert dust and sea salt, as well their lifetimes, moved closer towards values of AeroCom estimates and the multi-model average. When comparing the model simulations with MODIS aerosol optical depth (AOD) observations over the oceans, the updated model configuration shows a decrease in the bias (from 0.032 to 0.002) and a better correlation (from 0.062 to 0.322) in terms of the geographical distribution and the temporal variability. The updates corrected a strong positive bias in the sea salt representation at high latitudes (from 0.153 to 0.026), and a negative bias in the desert dust representation in the African dust outflow region (from -0.179 to -0.051). The updates in sedimentation produced a modest difference; the bias with MODIS data from 0.002 in the updated configuration went to

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

    SciTech Connect

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

    2010-10-01

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

  15. CHEMICAL PROCESSES IN PROTOPLANETARY DISKS. II. ON THE IMPORTANCE OF PHOTOCHEMISTRY AND X-RAY IONIZATION

    SciTech Connect

    Walsh, Catherine; Millar, T. J.; Nomura, Hideko; Aikawa, Yuri

    2012-03-10

    We investigate the impact of photochemistry and X-ray ionization on the molecular composition of, and ionization fraction in, a protoplanetary disk surrounding a typical T Tauri star. We use a sophisticated physical model, which includes a robust treatment of the radiative transfer of UV and X-ray radiation, and calculate the time-dependent chemical structure using a comprehensive chemical network. In previous work, we approximated the photochemistry and X-ray ionization; here, we recalculate the photoreaction rates using the explicit UV wavelength spectrum and wavelength-dependent reaction cross sections. We recalculate the X-ray ionization rate using our explicit elemental composition and X-ray energy spectrum. We find that photochemistry has a larger influence on the molecular composition than X-ray ionization. Observable molecules sensitive to the photorates include OH, HCO{sup +}, N{sub 2}H{sup +}, H{sub 2}O, CO{sub 2}, and CH{sub 3}OH. The only molecule significantly affected by the X-ray ionization is N{sub 2}H{sup +}, indicating that it is safe to adopt existing approximations of the X-ray ionization rate in typical T Tauri star-disk systems. The recalculation of the photorates increases the abundances of neutral molecules in the outer disk, highlighting the importance of taking into account the shape of the UV spectrum in protoplanetary disks. A recalculation of the photoreaction rates also affects the gas-phase chemistry due to the adjustment of the H/H{sub 2} and C{sup +}/C ratios. The disk ionization fraction is not significantly affected by the methods adopted to calculate the photochemistry and X-ray ionization. We determine that there is a probable 'dead zone' where accretion is suppressed, present in a layer, Z/R {approx}< 0.1-0.2, in the disk midplane, within R Almost-Equal-To 200 AU.

  16. Aerosols and clouds in chemical transport models and climate models.

    SciTech Connect

    Lohmann,U.; Schwartz, S. E.

    2008-03-02

    Clouds exert major influences on both shortwave and longwave radiation as well as on the hydrological cycle. Accurate representation of clouds in climate models is a major unsolved problem because of high sensitivity of radiation and hydrology to cloud properties and processes, incomplete understanding of these processes, and the wide range of length scales over which these processes occur. Small changes in the amount, altitude, physical thickness, and/or microphysical properties of clouds due to human influences can exert changes in Earth's radiation budget that are comparable to the radiative forcing by anthropogenic greenhouse gases, thus either partly offsetting or enhancing the warming due to these gases. Because clouds form on aerosol particles, changes in the amount and/or composition of aerosols affect clouds in a variety of ways. The forcing of the radiation balance due to aerosol-cloud interactions (indirect aerosol effect) has large uncertainties because a variety of important processes are not well understood precluding their accurate representation in models.

  17. Aerosol Size and Chemical Composition in the Canadian High Arctic

    NASA Astrophysics Data System (ADS)

    Chang, R. Y. W.; Hayes, P. L.; Leaitch, W. R.; Croft, B.; O'Neill, N. T.; Fogal, P.; Drummond, J. R.; Sloan, J. J.

    2015-12-01

    Arctic aerosol have a strong annual cycle, with winter months dominated by long range transport from lower latitudes resulting in high mass loadings. Conversely, local emissions are more prominent in the summer months because of the decreased influence of transported aerosol, allowing us to regularly observe both transported and local aerosol. This study will present observations of aerosol chemical composition and particle number size distribution collected at the Polar Environment Artic Research Laboratory and the Alert Global Atmospheric Watch Observatory at Eureka (80N, 86W) and Alert (82N, 62W), Nunavut, respectively. Summer time observations of the number size distribution reveal a persistent mode of particles centered between 30-50 nm, with occasional bursts of smaller particles. The non-refractory aerosol chemical composition, measured by the Canadian Network for the Detection of Atmospheric Change quadrupole aerosol mass spectrometer, is primarily organic, with contributions from both aged and fresher organic aerosol. Factor analysis will be conducted to better understand these sources. The site at Eureka is more susceptible to long range transport since it is at the top of a mountain ridge (610 m above sea level) and will be compared to the site at Alert on an elevated plain (200 m above sea level). This will allow us to determine the relative contributions from processes and sources at the sites at different elevations. Comparisons with aerosol optical depth and GEOS-Chem model output will also be presented to put these surface measurements into context with the overlying and regional atmosphere. Results from this study contribute to our knowledge of aerosol in the high Arctic.

  18. Aerosol chemical characterization and role of carbonaceous aerosol on radiative effect over Varanasi in central Indo-Gangetic Plain

    NASA Astrophysics Data System (ADS)

    Tiwari, S.; Dumka, U. C.; Kaskaoutis, D. G.; Ram, Kirpa; Panicker, A. S.; Srivastava, M. K.; Tiwari, Shani; Attri, S. D.; Soni, V. K.; Pandey, A. K.

    2016-01-01

    This study investigates the chemical composition of PM10 aerosols at Varanasi, in the central Indo-Gangetic Plain (IGP) during April to July 2011, with emphasis on examining the contribution of elemental carbon (EC) to the estimates of direct aerosol radiative effect (DARE). PM10 samples are analysed for carbonaceous aerosols (Organic Carbon, OC and EC) and water-soluble ionic species (WSIS: Cl-, SO42-, NO3-, PO42- NH4+, Na+, K+, Mg2+ and Ca2+) and several diagnostic ratios (OC/EC, K+/EC, etc) have been also used for studying the aerosol sources at Varanasi. PM10 mass concentration varies between 53 and 310 μg m-3 (mean of 168 ± 73 μg m-3), which is much higher than the National and International air quality standards. The OC mass concentration varies from 6 μg m-3 to 24 μg m-3 (mean of 12 ± 5 μg m-3; 7% of PM10 mass), whereas EC ranges between 1.0 and 14.3 μg m-3 (4.4 ± 3.9 μg m-3; ˜3% of PM10 mass). The relative low OC/EC of 3.9 ± 2.0 and strong correlation (R2 = 0.82) between them suggest the dominance of primary carbonaceous aerosols. The contribution of WSIS to PM10 is found to be ˜12%, out of which ˜57% and 43% are anions and cations, respectively. The composite DARE estimates via SBDART model reveal significant radiative effect and atmospheric heating rates (0.9-2.3 K day-1). Although the EC contributes only ˜3% to the PM10 mass, its contribution to the surface and atmospheric forcing is significantly high (37-63% and 54-77%, respectively), thus playing a major role in climate implications over Varanasi.

  19. Chemical Aging and Cloud Condensation Nuclei Activity of Biomass Burning Aerosol Proxies in the Presence of OH Radicals

    NASA Astrophysics Data System (ADS)

    Slade, Jonathan H., Jr.

    Biomass burning aerosol (BBA) can adversely impact regional and global air quality and represents a significant source of organic aerosol (OA) to the atmosphere that can affect climate. Aerosol particles can alter the transfer of radiation in earth's atmosphere directly by scattering and absorbing radiation or indirectly via cloud formation. Gas-to-particle, also termed heterogeneous, oxidation reactions can significantly alter the particle's physical and chemical properties. In turn, this can lead to the degradation of biomolecular markers for air quality-related aerosol source apportionment studies, the particles' lifetime, and modify the particles' abilities to serve as cloud condensation nuclei (CCN). However, the rates, mechanisms, and conditions by which these multiphase oxidation reactions occur and influence the CCN activity of OA is not well understood. The work presented here aims to determine the reactivity and products from the interaction of BBA surrogate-particles and trace gas-phase oxidants and to link the effects of OA chemical aging on the particles' ability to nucleate clouds. The reactive uptake of OH by BBA surrogate-substrates and particles, including levoglucosan, nitroguaiacol, abietic acid, and methyl-nitrocatechol, was determined as a function of both OH concentration and relative humidity (RH) using chemical ionization mass spectrometry coupled to various flow reactors. OH reactive uptake decreased with increasing OH concentration, indicative of OH adsorption followed by reaction. OH oxidation led to significant volatilization, i.e. mass loss of the organic material, as determined by application of high resolution proton transfer reaction time-of-flight mass spectrometry. Volatilized reaction products were identified, providing mechanistic insight of the chemical pathways in the heterogeneous OH oxidation of BBA. The reactive uptake of OH by levoglucosan particles increased with RH due to enhanced OH and organic bulk diffusivity. In

  20. Measured and modelled cloud condensation nuclei (CCN) concentration in São Paulo, Brazil: the importance of aerosol size-resolved chemical composition on CCNhack concentration prediction

    NASA Astrophysics Data System (ADS)

    Almeida, G. P.; Brito, J.; Morales, C. A.; Andrade, M. F.; Artaxo, P.

    2014-07-01

    Measurements of cloud condensation nuclei (CCN), aerosol size distribution and non-refractory chemical composition were performed from 16 to 31 October 2012 in the São Paulo Metropolitan Area (SPMA), Brazil. CCN measurements were performed at 0.23, 0.45, 0.68, 0.90 and 1.13% water supersaturation and were subsequently compared with the Köhler theory, considering the chemical composition. Real-time chemical composition has been obtained by deploying, for the first time in the SPMA, an aerosol chemical ionization monitor (ACSM). CCN closure analyses were performed considering internal mixtures. Average aerosol composition during the studied period yielded (arithmetic mean~± standard deviation) 4.81 ± 3.05, 3.26 ± 2.10, 0.30 ± 0.27, 0.52 ± 0.32, 0.37 ± 0.21 and 0.04 ± 0.04 μg m-3 for organics, BC, NH4, SO4, NO3 and Cl, respectively. Particle number concentration was 12 813 ± 5350 cm-3, with a dominant nucleation mode. CCN concentrations were on average 1090 ± 328 and 3570 ± 1695 cm-3 at SS = 0.23% and SS = 1.13%, respectively. Results show an increase in aerosol hygroscopicity in the afternoon as a result of aerosol photochemical processing, leading to an enhancement of both organic and inorganic secondary aerosols in the atmosphere, as well as an increase in aerosol average diameter. Considering the bulk composition alone, observed CCN concentrations were substantially overpredicted when compared with the Köhler theory (44.1 ± 47.9% at 0.23% supersaturation and 91.4 ± 40.3% at 1.13% supersaturation). Overall, the impact of composition on the calculated CCN concentration (NCCN) decreases with decreasing supersaturation, partially because using bulk composition introduces less bias for large diameters and lower critical supersaturations, defined as the supersaturation at which the cloud droplet activation will take place. Results suggest that the consideration of only inorganic fraction improves the calculated NCCN. Introducing a size-dependent chemical

  1. A Comparison of Aerosol Optical, Microphysical, and Chemical Measurements between LAX and Long Beach Harbor

    NASA Astrophysics Data System (ADS)

    Thornhill, K. L.; Anderson, B. E.; Chen, G.; Winstead, E.; Ziemba, L. D.; Beyersdorf, A. J.; Diskin, G. S.; Nenes, A.; Lathem, T. L.; Arctas Science Team

    2010-12-01

    In the summer of 2008, measurements of aerosols were made on-board the NASA DC-8 over the state of California, as part of the second phase of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) on behalf of the California Air resources Board (CARB). The DC-8 made four flights, between 18 June and 26 June, totaling 33 hours, to examine California’s atmosphere to better understand the chemical dynamics of smog and greenhouse gases over the state. The NASA DC-8 had a suite of aerosol instruments, capable of measuring the number concentrations, optical properties, and size distributions of aerosols between 0.003 and 1500 um. In this presentation, we will compare aerosol observations made at two areas within the Los Angeles Basin, Los Angeles International airport (LAX) and Long Beach Harbor. LAX is in the middle of the second most populated metropolitan area in the United States and is the fifth busiest airport in the world, while Long Beach Harbor (20 miles south of LAX) is the world’s 2nd busiest container port. Initial results suggest a greater aerosol loading and additional presence of ultrafine aerosols during the week due to vehicular emissions. We will also present analysis of aerosol observations as a function of time of day from the four missed approaches at LAX and four over flights of Long Beach Harbor.

  2. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt-1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion-molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.

  3. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kim, M. J.; Zoerb, M. C.; Campbell, N. R.; Zimmermann, K. J.; Blomquist, B. W.; Huebert, B. J.; Bertram, T. H.

    2015-10-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e. DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt-1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a weaker electric field, demonstrated that ion-molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer. Measurements from the two instruments were highly correlated (R2=0.80) over a wide range of sampling conditions.

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

    SciTech Connect

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

    2009-09-09

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

  5. Direct aerosol chemical composition measurements to evaluate the physicochemical differences between controlled sea spray aerosol generation schemes

    NASA Astrophysics Data System (ADS)

    Collins, D. B.; Zhao, D. F.; Ruppel, M. J.; Laskina, O.; Grandquist, J. R.; Modini, R. L.; Stokes, M. D.; Russell, L. M.; Bertram, T. H.; Grassian, V. H.; Deane, G. B.; Prather, K. A.

    2014-07-01

    Controlled laboratory studies of the physical and chemical properties of sea spray aerosol (SSA) must be underpinned by a physically and chemically accurate representation of the bubble mediated production of nascent SSA particles. Since bubble bursting is sensitive to the physicochemical properties of seawater, any important differences in the SSA production mechanism are projected into SSA composition. Using direct chemical measurements of SSA at the single-particle level, this study presents an inter-comparison of three laboratory-based, bubble-mediated SSA production schemes: gas forced through submerged sintered glass filters ("frits"), a pulsed plunging waterfall apparatus, and breaking waves in a wave channel filled with natural seawater. The size-resolved chemical composition of SSA particles produced by breaking waves is more similar to particles produced by the plunging waterfall than sintered glass filters. Aerosol generated by disintegrating foam produced by sintered glass filters contained a larger fraction of organic enriched particles and a different size-resolved elemental composition, especially in the 0.8-2 μm size range. These particles, when dried, had more spherical morphologies compared to the more cubic structure expected for pure NaCl particles, which can be attributed to the presence of additional organic carbon. In addition to an inter-comparison of three SSA production methods, the role of the episodic or "pulsed" nature of the waterfall method utilized in this study on SSA composition was undertaken. In organic-enriched seawater, the continuous operation of the plunging waterfall mechanism resulted in the accumulation of surface foam and an over-expression of organic matter in SSA particles compared to pulsed plunging waterfall. Throughout this set of experiments, comparative differences in the SSA number size distribution were coincident with differences in aerosol composition, indicating that the production mechanism of SSA exerts

  6. Influence of aqueous chemistry on the chemical composition of fog water and interstitial aerosol in Fresno

    NASA Astrophysics Data System (ADS)

    Kim, Hwajin; Ge, Xinlei; Collier, Sonya; Xu, Jianzhong; Sun, Yele; Wang, Youliang; Herckes, Pierre; Zhang, Qi

    2015-04-01

    A measurement study was conducted in the Central Valley (Fresno) of California in January 2010, during which radiation fog events were frequently observed. Fog plays important roles in atmospheric chemistry by scavenging aerosol particles and trace gases and serving as a medium for various aqueous-phase reactions. Understanding the effects of fog on the microphysical and chemical processing of aerosol particles requires detailed information on their chemical composition. In this study, we characterized the chemical composition of fog water and interstitial aerosol particles to study the effects of fog processing on aerosol properties. Fog water samples were collected during the 2010 Fresno campaigns with a Caltech Active Strand Cloud water Collector (CASCC) while interstitial submicron aerosols were characterized in real time with an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a scanning Mobility Particle Sizer (SMPS). The fog water samples were later analyzed using the HR-ToF-AMS, ion chromatography, and a total carbon analyzer. The chemical composition and characteristics of interstitial particles during the fog events were compared to those of dissolved inorganic and organic matter in fog waters. Compared to interstitial aerosols, fog water is composed of a higher fraction of ammonium nitrate and oxygenated organics, due to aqueous formation of secondary aerosol species as well as enhanced gas-to-particle partitioning of water soluble species under water rich conditions. Sulfate is formed most efficiently in fog water although its contribution to total dissolved mass is relatively low. The HR-ToF-AMS mass spectra of organic matter in fog water (FOM) are very similar to that of oxygenated organic aerosols (OOA) derived from positive matrix factorization (PMF) of the HR-ToF-AMS spectra of ambient aerosol (r2 = 0.96), but FOM appears to contain a large fraction of acidic functional groups than OOA. FOM is also enriched of

  7. Fundamentals of ambient metastable-induced chemical ionization mass spectrometry and atmospheric pressure ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Harris, Glenn A.

    Molecular ionization is owed much of its development from the early implementation of electron ionization (EI). Although dramatically increasing the library of compounds discovered, an inherent problem with EI was the low abundance of molecular ions detected due to high fragmentation leading to the difficult task of the correct chemical identification after mass spectrometry (MS). These problems stimulated the research into new ionization methods which sought to "soften" the ionization process. In the late 1980s the advancements of ionization techniques was thought to have reached its pinnacle with both electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). Both ionization techniques allowed for "soft" ionization of large molecular weight and/or labile compounds for intact characterization by MS. Albeit pervasive, neither ESI nor MALDI can be viewed as "magic bullet" ionization techniques. Both techniques require sample preparation which often included native sample destruction, and operation of these techniques took place in sealed enclosures and often, reduced pressure conditions. New open-air ionization techniques termed "ambient MS" enable direct analysis of samples of various physical states, sizes and shapes. One particular technique named Direct Analysis In Real Time (DART) has been steadily growing as one of the ambient tools of choice to ionize small molecular weight (< 1000 Da) molecules with a wide range of polarities. Although there is a large list of reported applications using DART as an ionization source, there have not been many studies investigating the fundamental properties of DART desorption and ionization mechanisms. The work presented in this thesis is aimed to provide in depth findings on the physicochemical phenomena during open-air DART desorption and ionization MS and current application developments. A review of recent ambient plasma-based desorption/ionization techniques for analytical MS is presented in

  8. Activation of "synthetic ambient" aerosols - Relation to chemical composition of particles <100 nm

    NASA Astrophysics Data System (ADS)

    Burkart, J.; Hitzenberger, R.; Reischl, G.; Bauer, H.; Leder, K.; Puxbaum, H.

    2012-07-01

    Cloud condensation nuclei (CCN) are an important fraction of atmospheric aerosols because of their role in cloud formation. Experimental studies focus either on direct field measurements of complex ambient aerosols or laboratory investigations on well defined aerosols produced from single substances or substance mixtures. In this study, we focussed on the ultrafine aerosol because in terms of number concentration, the majority of the CCN are expected to have sizes in this range. A field study was performed from July 2007 to October 2008 to investigate the activation behaviour of the atmospheric aerosol in Vienna (Burkart et al., 2011). Filter samples of the aerosol <0.1 μm aerodynamic equivalent diameter were collected, elutriated and used to generate "synthetic ambient" aerosol in a nebulizer. Chemical analyses of the ultrafine water soluble material were also performed. The CCN properties of the "synthetic ambient" aerosol were obtained using the University of Vienna CCN counter (Giebl et al., 2002; Dusek et al., 2006b) at a nominal supersaturation (SS) of 0.5%. Activation diameters dact ranged from 54.5 nm to 66 nm, were larger than dact of typical single inorganic salts and showed no seasonal pattern in contrast to the fraction of water soluble organic carbon (WSOC), which ranged from 44% in spring to 15% in winter. The average hygroscopicity parameter κ (Petters and Kreidenweis, 2007) obtained from the activation curves ranged from 0.20 to 0.30 (average 0.24), which was significantly lower than κchem calculated from the chemical composition (0.43 ± 0.07).

  9. ELECTRON AFFINITIES OF POLYNUCLEAR AROMATIC HYDROCARBONS AND NEGATIVE ION CHEMICAL IONIZATION SENSITIVITIES

    EPA Science Inventory

    Negative-ion chemical-ionization mass spectrometry (NICI MS) has the potential to be a very useful technique in identifying various polycyclic aromatic hydrocarbons (PAHs) in soil and sediment samples. Some PAHs give much stronger signals under NICI MS conditions than others. On ...

  10. Effects of Chemical Aging on the Heterogeneous Freezing of Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Collier, K.; Brooks, S. D.

    2014-12-01

    Organic aerosols are emitted into the atmosphere from a variety of sources and display a wide range of effectiveness in promoting the nucleation of ice in clouds. Soot and polycyclic aromatic hydrocarbons (PAHS) arise from incomplete combustion and other pollutant sources. Hydrocarbon compounds in diesel motor oil and other fuel blends include compounds such as octacosane (a straight saturated alkane), squalane (a branched saturated alkane) and squalene (an unsaturated branched alkene). At temperatures above -36°C, the formation of ice crystals in the atmosphere is facilitated by heterogeneous freezing processes in which atmospheric aerosols act as ice nuclei (IN). The variability in ability of organic particles to facilitate heterogeneous ice nucleation causes major uncertainties in predictions of aerosol effects on climate. Further, atmospheric aerosol composition and ice nucleation ability can be altered via chemical aging and reactions with atmospheric oxidants such as ozone. In this study, we take a closer look at the role of chemical oxidation on the efficiency of specific IN during contact freezing laboratory experiments. The freezing temperatures of droplets in contact with representative organic aerosols are determined through the use of an optical microscope apparatus equipped with a cooling stage and a digital camera. Chemical changes at the surface of aerosols due to ozone exposure are characterized using Raman Microspectroscopy and Fourier Transform Infrared Spectroscopy with Horizontal Attenuated Total Reflectance. Our results indicate that oxidation of certain atmospheric organics (soot and PAHS) enhances their ice nucleation ability. In this presentation, results of heterogeneous nucleation on various types of organic aerosols will be presented, and the role of structure in promoting freezing will be discussed.

  11. Tying Biological Activity to Changes in Sea Spray Aerosol Chemical Composition via Single Particle Analyses

    NASA Astrophysics Data System (ADS)

    Sultana, C. M.; Lee, C.; Collins, D. B.; Axson, J. L.; Laskina, O.; Grandquist, J. R.; Grassian, V. H.; Prather, K. A.

    2014-12-01

    In remote marine environments, sea spray aerosols (SSA) often represent the greatest aerosol burden, thus having significant impacts on direct radiative interactions and cloud processes. Previous studies have shown that SSA is a complex mixture of inorganic salts and an array of dissolved and particulate organic components. Enrichment of SSA organic content is often correlated to seawater chlorophyll concentrations, a measure of oceanic biological activity. As the physical and chemical properties of aerosols control their radiative effects, recent studies conducted by the Center for Aerosol Impacts on Climate and the Environment have endeavored to further elucidate the ties between marine biological activity and primary SSA chemical composition using highly time resolved single particle analyses. A series of experiments performed in the recently developed Marine Aerosol Reference Tank evaluated the effect of changing marine microbial populations on SSA chemical composition, which was monitored via an aerosol time-of-flight mass spectrometer and a variety of offline spectroscopic and microscopic techniques. Each experiment was initiated using unfiltered and untreated seawater, thus maintaining a high level of biogeochemical complexity. This study is the first of its kind to capture daily changes in the primary SSA mixing state over the growth and death of a natural phytoplankton bloom. Increases in organic aerosol types (0.4-3 μm), internally and externally mixed with sea salt, could not be correlated to chlorophyll concentrations. Maximum production of these populations occurred two to four days after the in vivo chlorophyll fluorescence peaked in intensity. This work is in contrast to the current paradigm of correlating SSA organic content to seawater chlorophyll concentration.

  12. Assessment of microphysical and chemical factors of aerosols over seas of the Russian Artic Eastern Section

    NASA Astrophysics Data System (ADS)

    Golobokova, Liudmila; Polkin, Victor

    2014-05-01

    The newly observed kickoff of the Northern Route development drew serious attention to state of the Arctic Resource environment. Occurring climatic and environmental changes are more sensitively seen in polar areas in particular. Air environment control allows for making prognostic assessments which are required for planning hazardous environmental impacts preventive actions. In August - September 2013, RV «Professor Khlustin» Northern Sea Route expeditionary voyage took place. En-route aerosol sampling was done over the surface of the Beringov, Chukotka and Eastern-Siberia seas (till the town of Pevek). The purpose of sampling was to assess spatio-temporal variability of optic, microphysical and chemical characteristics of aerosol particles of the surface layer within different areas adjacent to the Northern Sea Route. Aerosol test made use of automated mobile unit consisting of photoelectric particles counter AZ-10, aetalometr MDA-02, aspirator on NBM-1.2 pump chassis, and the impactor. This set of equipment allows for doing measurements of number concentration, dispersed composition of aerosols within sizes d=0.3-10 mkm, mass concentration of submicron sized aerosol, and filter-conveyed aerosols sampling. Filter-conveyed aerosols sampling was done using method accepted by EMEP and EANET monitoring networks. The impactor channel was upgraded to separate particles bigger than 1 mkm in size, and the fine grain fraction settled down on it. Reverse 5-day and 10-day trajectories of air mass transfer executed at heights of 10, 1500 and 3500 m were analyzed. The heights were selected by considerations that 3000 m is the height which characterizes air mass trend in the lower troposphere. 1500 m is the upper border of the atmospheric boundary layer, and the sampling was done in the Earth's surface layer at less than 10 m. Minimum values of the bespoken microphysical characteristics are better characteristic of higher latitudes where there are no man induced sources of

  13. Systematic Relationships among Background SE U.S. Aerosol Optical, Micro-physical, and Chemical Properties-Development of an Optically-based Aerosol Characterization

    NASA Astrophysics Data System (ADS)

    Sherman, J. P.; Link, M. F.; Zhou, Y.

    2014-12-01

    Remote sensing-based retrievals of aerosol composition require known or assumed relationships between aerosol optical properties and types. Most optically-based aerosol classification schemes apply some combination of the spectral dependence of aerosol light scattering and absorption-using the absorption and either scattering or extinction Angstrom exponents (AAE, SAE and EAE), along with single-scattering albedo (SSA). These schemes can differentiate between such aerosol types as dust, biomass burning, and urban/industrial but no such studies have been conducted in the SE U.S., where a large fraction of the background aerosol is a variable mixture of biogenic SOA, sulfates, and black carbon. In addition, AERONET retrievals of SSA are often highly uncertain due to low AOD in the region during most months. The high-elevation, semi-rural AppalAIR facility at Appalachian State University in Boone, NC (1090m ASL, 36.210N, 81.690W) is home to the only co-located NOAA-ESRL and AERONET monitoring sites in the eastern U.S. Aerosol chemistry measured at AppalAIR is representative of the background SE U.S (Link et al. 2014) Dried aerosol light absorption and dried and humidified aerosol light scattering and hemispheric backscattering at 3 visible wavelengths and 2 particle size cuts (sub-1μm and sub-10μm) are measured continuously. Measurements of size-resolved, non-refractory sub-1μm aerosol composition were made by a co-located AMS during the 2012-2013 summers and 2013 winter. Systematic relationships among aerosol optical, microphysical, and chemical properties were developed to better understand aerosol sources and processes and for use in higher-dimension aerosol classification schemes. The hygroscopic dependence of visible light scattering is sensitive to the ratio of sulfate to organic aerosol(OA), as are SSA and AAE. SAE is a less sensitive indicator of fine-mode aerosol size than hemispheric backscatter fraction (b) and is more sensitive to fine-mode aerosol

  14. Modelling the optical properties of aerosols in a chemical transport model

    NASA Astrophysics Data System (ADS)

    Andersson, E.; Kahnert, M.

    2015-12-01

    According to the IPCC fifth assessment report (2013), clouds and aerosols still contribute to the largest uncertainty when estimating and interpreting changes to the Earth's energy budget. Therefore, understanding the interaction between radiation and aerosols is both crucial for remote sensing observations and modelling the climate forcing arising from aerosols. Carbon particles are the largest contributor to the aerosol absorption of solar radiation, thereby enhancing the warming of the planet. Modelling the radiative properties of carbon particles is a hard task and involves many uncertainties arising from the difficulties of accounting for the morphologies and heterogeneous chemical composition of the particles. This study aims to compare two ways of modelling the optical properties of aerosols simulated by a chemical transport model. The first method models particle optical properties as homogeneous spheres and are externally mixed. This is a simple model that is particularly easy to use in data assimilation methods, since the optics model is linear. The second method involves a core-shell internal mixture of soot, where sulphate, nitrate, ammonia, organic carbon, sea salt, and water are contained in the shell. However, by contrast to previously used core-shell models, only part of the carbon is concentrated in the core, while the remaining part is homogeneously mixed with the shell. The chemical transport model (CTM) simulations are done regionally over Europe with the Multiple-scale Atmospheric Transport and CHemistry (MATCH) model, developed by the Swedish Meteorological and Hydrological Institute (SMHI). The MATCH model was run with both an aerosol dynamics module, called SALSA, and with a regular "bulk" approach, i.e., a mass transport model without aerosol dynamics. Two events from 2007 are used in the analysis, one with high (22/12-2007) and one with low (22/6-2007) levels of elemental carbon (EC) over Europe. The results of the study help to assess the

  15. Aerosolization, Chemical Characterization, Hygroscopicity and Ice Formation of Marine Biogenic Particles

    NASA Astrophysics Data System (ADS)

    Alpert, P. A.; Radway, J.; Kilthau, W.; Bothe, D.; Knopf, D. A.; Aller, J. Y.

    2013-12-01

    The oceans cover the majority of the earth's surface, host nearly half the total global primary productivity and are a major source of atmospheric aerosol particles. However, effects of biological activity on sea spray generation and composition, and subsequent cloud formation are not well understood. Our goal is to elucidate these effects which will be particularly important over nutrient rich seas, where microorganisms can reach concentrations of 10^9 per mL and along with transparent exopolymer particles (TEP) can become aerosolized. Here we report the results of mesocosm experiments in which bubbles were generated by two methods, either recirculating impinging water jets or glass frits, in natural or artificial seawater containing bacteria and unialgal cultures of three representative phytoplankton species, Thalassiosira pseudonana, Emiliania huxleyi, and Nannochloris atomus. Over time we followed the size distribution of aerosolized particles as well as their hygroscopicity, heterogeneous ice nucleation potential, and individual physical-chemical characteristics. Numbers of cells and the mass of dissolved and particulate organic carbon (DOC, POC), TEP (which includes polysaccharide-containing microgels and nanogels >0.4 μm in diameter) were determined in the bulk water, the surface microlayer, and aerosolized material. Aerosolized particles were also impacted onto substrates for ice nucleation and water uptake experiments, elemental analysis using computer controlled scanning electron microscopy and energy dispersive analysis of X-rays (CCSEM/EDX), and determination of carbon bonding with scanning transmission X-ray microscopy and near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Regardless of bubble generation method, the overall concentration of aerosol particles, TEP, POC and DOC increased as concentrations of bacterial and phytoplankton cells increased, stabilized, and subsequently declined. Particles <100 nm generated by means of jets

  16. Seasonal variations in the physico-chemical characteristics of aerosols in North Taiwan

    NASA Astrophysics Data System (ADS)

    Chou, Charles

    2014-05-01

    From 2007 to 2012, this study investigated the mass concentration and chemical composition of ambient aerosols (i.e. PM10, PM2.5, and PMc = PM10-PM2.5) at Cape Fuguei, Yangminshan, and NTU (National Taiwan University) stations in northern Taiwan. It was found that the concentration and composition of aerosols exhibited significant seasonal variations but without an inter-annual trend during the study period. Moderate correlations (R2 = 0.4-0.6) were observed among the aerosol concentrations at the respective stations, indicating that the aerosol concentrations were dominated by factors on regional scales. During the seasons of northeasterly winter monsoons, long range transport of dust and particulate air pollutants from the Asia Continent had negatively impacted the atmospheric environment in this area. On the other hand, as a highly developed urban area, Taipei has substantial local emissions of air pollutants that should have transported to the surrounding areas of Taipei basin and caused deterioration of air quality and visibility in Cape Fuguei and Yangminshan. The results indicated that the major components of aerosols in Taipei include sulfate, sea salts, dust, and organic matters. In addition, contributions from nitrate, ammonium, and elemental carbon were also significant. In terms of mass concentration, most of the sea salts and dust particles existed in the coarse mode of aerosols, whereas sulfate and EC were confined within PM2.5. This suggests that the dust and sea salts particles were externally mixed with EC and sulfate in the aerosols over Taipei area. Further, it was found that nitrate were closely associated with sea salts in aerosols, suggesting the reaction between nitric acid and sea salt particles. Different seasonality was observed for sea salt and dust: sea salts peaked in fall and dust reached the maximal level in springtime, implying their sources were regulated by independent seasonal factors. Particulate pollutants (i.e. sulfate, nitrate

  17. [Development of a membrane inlet-single photon ionization/chemical ionization-mass spectrometer for online analysis of VOCs in water].

    PubMed

    Hua, Lei; Wu, Qing-Hao; Hou, Ke-Yong; Cui, Hua-Peng; Chen, Ping; Zhao, Wu-Duo; Xie, Yuan-Yuan; Li, Hai-Yang

    2011-12-01

    A home-made membrane inlet- single photon ionization/chemical ionization- time-of-flight mass spectrometer has been described. A vacuum ultraviolet (VUV) lamp with photon energy of 10.6 eV was used as the light source for single photon ionization (SPI). Chemical ionization (CI) was achieved through ion-molecule reactions with O2- reactant ions generated by photoelectron ionization. The two ionization modes could be rapidly switched by adjusting electric field in the ionization region within 2 s. Membrane inlet system used for rapid enrichment of volatile organic compounds (VOCs) in water was constructed by using a polydimethylsiloxane (PDMS) membrane with a thickness of 50 microm. A purge gas was added to accelerate desorption of analytes from the membrane surface. The purge gas could also help to prevent the pump oil back-streaming into the ionization region from the analyzer chamber and improve the signal to noise ratio (S/N). Achieved detection limits were 2 microg x L(-1) for methyl tert-butyl ether (MTBE) in SPI mode and 1 microg x L(-1) for chloroform in SPI-CI mode within 10 s analysis time, respectively. The instrument has been successfully applied to the rapid analysis of MTBE in simulated underground water nearby petrol station and VOCs in disinfected drinking water. The results indicate that the instrument has a great application prospect for online analysis of VOCs in water.

  18. Production Mechanism, Number Concentration, Size Distribution, Chemical Composition, and Optical Properties of Sea Spray Aerosols Workshop, Summer 2012

    SciTech Connect

    Meskhidze, Nicholas

    2013-10-21

    The objective of this workshop was to address the most urgent open science questions for improved quantification of sea spray aerosol-radiation-climate interactions. Sea spray emission and its influence on global climate remains one of the most uncertain components of the aerosol-radiation-climate problem, but has received less attention than other aerosol processes (e.g. production of terrestrial secondary organic aerosols). Thus, the special emphasis was placed on the production flux of sea spray aerosol particles, their number concentration and chemical composition and properties.

  19. Chemical characterization of the main secondary organic aerosol (SOA) products formed through aqueous-phase photonitration of guaiacol

    NASA Astrophysics Data System (ADS)

    Kitanovski, Z.; Čusak, A.; Grgić, I.; Claeys, M.

    2014-04-01

    Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e. burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed in the atmospheric gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the low-volatility SOA products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of H2O2 and nitrite. The formed guaiacol reaction products were concentrated by using solid-phase extraction (SPE) and then purified by means of semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state 1H, 13C and 2D nuclear magnetic resonance (NMR) spectroscopy and direct infusion negative ion electrospray ionization tandem mass spectrometry ((-)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(-)ESI-MS/MS. Owing to the strong absorption of UV and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

  20. Chemical composition of Eastern Black Sea aerosol--preliminary results.

    PubMed

    Balcılar, Ilker; Zararsız, Abdullah; Kalaycı, Yakup; Doğan, Güray; Tuncel, Gürdal

    2014-08-01

    Trace element composition of atmospheric particles collected at a high altitude site on the Eastern Black Sea coast of Turkey was investigated to understand atmospheric transport of pollutants to this semi-closed basin. Aerosol samples were collected at a timber-storage area, which is operated by the General Directorate of Forestry. The site is situated at a rural area and is approximately 50 km to the Black Sea coast and 200 km to the Georgia border of Turkey. Coarse (PM2.5-10) and fine (PM2.5) aerosol samples were collected between 2011 and 2013 using a "stacked filter unit". Collected samples were shipped to the Middle East Technical University in Ankara, where Na, Mg, Al, Si, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Ba, Pb were measured by Energy dispersive x-ray fluorescence technique (EDXRF). Comparison of measured concentrations of elements with corresponding data generated at other parts of Turkey demonstrated that concentrations of pollution derived elements are higher at Eastern Black Sea than their corresponding concentrations measured at other parts of Turkey, which is attributed to frequent transport of pollutants from north wind sector. Positive matric factorization revealed four factors including three anthropogenic and a crustal factor. Southeastern parts of Turkey, Georgia and Black Sea coast of Ukraine were identified as source regions affecting composition of particles at our site, using trajectory statistics, namely "potential source contribution function" (PSCF). PMID:24373640

  1. Aerosol chemical vapor deposition of metal oxide films

    DOEpatents

    Ott, K.C.; Kodas, T.T.

    1994-01-11

    A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said substrate.

  2. Application of Aerosol Assimilation System of MODIS Radiances to Regional Chemical Transport Model

    NASA Astrophysics Data System (ADS)

    D'Allura, A.; Charmichael, G. R.; Tang, Y.; Chai, T.; Chung, C. E.; Anderson, T. L.

    2006-12-01

    We present results from an assimilation system of radiances from the MODIS channels that sense atmospheric aerosols over land and ocean on the chemical transport model STEM. A test case is designed to simulate transport of aerosols tracers over the area of interest which includes India, east and south Asia at 50km horizontal resolution. A detailed treatment of the source, transport and deposition of the aerosol species are included. The model simulates five aerosol components: sulfate, organic carbon, black carbon, dust and sea salt. Total AODs at 550nm wavelength over land and ocean and fine mode AODs at 550nm wavelength over ocean are the level 2 aerosol products from Terra MODIS channel four used in this application. The intent of the study is to verify the improvement in the model performances while the initial conditions are corrected using an Optimum Interpolation technique to assimilate the MODIS data. The model results are compared with ground-based measurements of aerosol optical depth (AOD) from the AERONET network. Sensitivity analyses are provided in order to describe the effect of changing in assimilation technique's free parameters. The method is designed to optimize the use of the information provided by fine mode AODs, which are available over ocean, coupled with the total AODs available also over land. Improvements on the model results using this approach are highlighted during specific event where the model has experienced low agreement with observed data. Results are also compared to other assimilations methods.

  3. Chemical Characterization of Secondary Organic Aerosol from Oxidation of Isoprene Hydroxyhydroperoxides.

    PubMed

    Riva, Matthieu; Budisulistiorini, Sri H; Chen, Yuzhi; Zhang, Zhenfa; D'Ambro, Emma L; Zhang, Xuan; Gold, Avram; Turpin, Barbara J; Thornton, Joel A; Canagaratna, Manjula R; Surratt, Jason D

    2016-09-20

    Atmospheric oxidation of isoprene under low-NOx conditions leads to the formation of isoprene hydroxyhydroperoxides (ISOPOOH). Subsequent oxidation of ISOPOOH largely produces isoprene epoxydiols (IEPOX), which are known secondary organic aerosol (SOA) precursors. Although SOA from IEPOX has been previously examined, systematic studies of SOA characterization through a non-IEPOX route from 1,2-ISOPOOH oxidation are lacking. In the present work, SOA formation from the oxidation of authentic 1,2-ISOPOOH under low-NOx conditions was systematically examined with varying aerosol compositions and relative humidity. High yields of highly oxidized compounds, including multifunctional organosulfates (OSs) and hydroperoxides, were chemically characterized in both laboratory-generated SOA and fine aerosol samples collected from the southeastern U.S. IEPOX-derived SOA constituents were observed in all experiments, but their concentrations were only enhanced in the presence of acidified sulfate aerosol, consistent with prior work. High-resolution aerosol mass spectrometry (HR-AMS) reveals that 1,2-ISOPOOH-derived SOA formed through non-IEPOX routes exhibits a notable mass spectrum with a characteristic fragment ion at m/z 91. This laboratory-generated mass spectrum is strongly correlated with a factor recently resolved by positive matrix factorization (PMF) of aerosol mass spectrometer data collected in areas dominated by isoprene emissions, suggesting that the non-IEPOX pathway could contribute to ambient SOA measured in the Southeastern United States. PMID:27466979

  4. A model for studying the composition and chemical effects of stratospheric aerosols

    NASA Technical Reports Server (NTRS)

    Tabazadeh, Azadeh; Turco, Richard P.; Jacobson, Mark Z.

    1994-01-01

    We developed polynomial expressions for the temperature dependence of the mean binary and water activity coefficients for H2SO4 and HNO3 solutions. These activities were used in an equilibrium model to predict the composition of stratospheric aerosols under a wide range of environmental conditions. For typical concentrations of H2O, H2SO4, HNO3, HCl, HBr, HF, and HOCl in the lower stratosphere, the aerosol composition is estimated as a function of the local temperature and the ambient relative humidity. For temperatures below 200 K, our results indicate that (1) HNO3 contributes a significant mass fraction to stratospheric aerosols, and (2) HCl solubility is considerably affected by HNO3 dissolution into sulfate aerosols. We also show that, in volcanically disturbed periods, changes in stratospheric aerosol composition can significantly alter the microphysics that leads to the formation of polar stratospheric clouds. The effects caused by HNO3 dissolution on the physical and chemical properties of stratospheric aerosols are discussed.

  5. Physical and Chemical Properties of Aerosols at the Tropical Coastal Site, Trivandrum

    NASA Astrophysics Data System (ADS)

    George, Susan K.; Nair, Prabha R.; Parameswaran, Krishnaswamy; Jacob, Salu; Abraham, Annamma; Abhilash, K. S.

    The influence of tropospheric aerosols on the regional climate is fairly well accepted though there exists large uncertainties in assessing its exact magnitude. This is mainly due to the fact that the aerosol properties are highly variable at short spatial and temporal extents and the information available is rather limited. To overcome these deficiency it is highly essential to gather and analyse long term data covering different seasons over varying climatic regimes. Trivandrum (8.55o N, 77o E), a tropical coastal site situated near the southern tip of Indian Peninsula, is a location where systematic monitoring of different aerosol parameters are being carried out since last two decades. With progressing time new techniques and instruments are also being incorporated. This paper presents the results from the observations on aerosols carried out during the period 2003 to 2005 at this location. Different aerosol properties such as total mass concentration, number density, size distribution, optical depth, chemical composition, etc. are studied systematically during this period. A High Volume Sampler (for measuring total mass loading), Aerosol Spectrometer (for measuring size segregated number density from which size distribution can be derived), and Microtops Sunphotometer (which measures optical depth at 1020 nm) are used to study the physical/optical properties of aerosols. The chemical composition of atmospheric aerosols is examined employing Ion Chromatography, Atomic Absorption Spectroscopy and Inductively Couple Plasma - Atomic Emission Spectroscopy. The mean mass concentration of aerosols observed at this site is 54 µg m-3 , which varies by ±19 µg m-3 depending on season and prevailing meteorology. The aerosol number density is 108 particles/m3 . The mass loading at this location is significantly low compared to the northern parts of India as well as the national ambient air quality standards indicating that the environment is relatively less polluted as

  6. Characterization of Nitrogen-Containing Species in Coal and Petroleum-Derived Products by Ammonia Chemical Ionization-High Resolution Mass Spectrometry

    SciTech Connect

    Veloski, Garret A.; Lynn, Ronald J.; Sprecher, Richard F.

    1997-01-01

    A coal-derived light distillate and a petroleum-derived residuum have been studied by high resolution mass spectrometry using both low-pressure ammonia chemical ionization and low-voltage electron impact ionization. A mass calibration mixture for use with ammonia chemical ionization has been developed. Selective ionization of the basic nitrogen-containing compounds by ammonia chemical ionization and compound type characterization of the resulting quasi-molecular species has been demonstrated. Several homologous series of nitrogen-containing compounds were identified in a basic extract by electron impact ionization and compared with quasimolecular analogs identified by ammonia chemical ionization.

  7. Atmospheric aerosols: A literature summary of their physical characteristics and chemical composition

    NASA Technical Reports Server (NTRS)

    Harris, F. S., Jr.

    1976-01-01

    This report contains a summary of 199 recent references on the characterization of atmospheric aerosols with respect to their composition, sources, size distribution, and time changes, and with particular reference to the chemical elements measured by modern techniques, especially activation analysis.

  8. Winter time chemical characteristics of aerosols over the Bay of Bengal: continental influence.

    PubMed

    Aryasree, S; Nair, Prabha R; Girach, I A; Jacob, Salu

    2015-10-01

    As part of the Integrated Campaign for Aerosols, gases and Radiation Budget (ICARB) conducted under the Geosphere Biosphere Programme of Indian Space Research Organisation, ship-based aerosol sampling was carried out over the marine environment of Bay of Bengal (BoB) during the northern winter months of December 2008 to January 2009. About 101 aerosol samples were collected, covering the region from 3.4° to 21° N latitude and 76° to 98° E longitude-the largest area covered-including the south east (SE) BoB for the first time. These samples were subjected to gravimetric and chemical analysis and the total aerosol loading as well the mass concentration of the ionic species namely F(-), Cl(-), Br(-), NO2 (-), NO3 (-), PO4 (2-), SO4 (2-), NH4 (+), etc. and the metallic species, Na, Mg, Ca, K, Al, Fe, Mn, Zn, and Pb were estimated for each sample. Based on the spatial distribution of individual chemical species, the air flow pattern, and airmass back trajectory analysis, the source characteristics of aerosols for different regions of BoB were identified. Significant level of continental pollution was noticed over BoB during winter. While transport of pollution from Indo-Gangetic Plain (IGP) contributed to aerosols over north BoB, those over SE BoB were influenced by SE Asia. A quantitative study on the wind-induced production of sea salt aerosols and a case study on the species dependent effect of rainfall are also presented in this paper. PMID:25994269

  9. Modelling of primary aerosols in the chemical transport model MOCAGE: development and evaluation of aerosol physical parameterizations

    NASA Astrophysics Data System (ADS)

    Sič, B.; El Amraoui, L.; Marécal, V.; Josse, B.; Arteta, J.; Guth, J.; Joly, M.; Hamer, P. D.

    2015-02-01

    This paper deals with recent improvements to the global chemical transport model of Météo-France MOCAGE (Modèle de Chimie Atmosphérique à Grande Echelle) that consists of updates to different aerosol parameterizations. MOCAGE only contains primary aerosol species: desert dust, sea salt, black carbon, organic carbon, and also volcanic ash in the case of large volcanic eruptions. We introduced important changes to the aerosol parameterization concerning emissions, wet deposition and sedimentation. For the emissions, size distribution and wind calculations are modified for desert dust aerosols, and a surface sea temperature dependant source function is introduced for sea salt aerosols. Wet deposition is modified toward a more physically realistic representation by introducing re-evaporation of falling rain and snowfall scavenging and by changing the in-cloud scavenging scheme along with calculations of precipitation cloud cover and rain properties. The sedimentation scheme update includes changes regarding the stability and viscosity calculations. Independent data from satellites (MODIS, SEVIRI), the ground (AERONET, EMEP), and a model inter-comparison project (AeroCom) are compared with MOCAGE simulations and show that the introduced changes brought a significant improvement on aerosol representation, properties and global distribution. Emitted quantities of desert dust and sea salt, as well their lifetimes, moved closer towards values of AeroCom estimates and the multi-model average. When comparing the model simulations with MODIS aerosol optical depth (AOD) observations over the oceans, the updated model configuration shows a decrease in the modified normalized mean bias (MNMB; from 0.42 to 0.10) and a better correlation (from 0.06 to 0.32) in terms of the geographical distribution and the temporal variability. The updates corrected a strong positive MNMB in the sea salt representation at high latitudes (from 0.65 to 0.16), and a negative MNMB in the desert

  10. Fragmentation of Allylmethylsulfide by Chemical Ionization: Dependence on Humidity and Inhibiting Role of Water

    PubMed Central

    2013-01-01

    We report on a previously unknown reaction mechanism involving water in the fragmentation reaction following chemical ionization. This result stems from a study presented here on the humidity-dependent and energy-dependent endoergic fragmentation of allyl methyl sulfide (AMS) upon protonation in a proton transfer reaction-mass spectrometer (PTR-MS). The fragmentation pathways were studied with experimental (PTR-MS) and quantum chemical methods (polarizable continuum model (PCM), microhydration, studied at the MP2/6-311+G(3df,2p)//MP2/6-31G(d,p) level of theory). We report in detail on the energy profiles, reaction mechanisms, and proton affinities (G4MP2 calculations). In the discovered reaction mechanism, water reduces the fragmentation of protonated species in chemical ionization. It does so by direct interaction with the protonated species via covalent binding (C3H5+) or via association (AMS·H+). This stabilizes intermediate complexes and thus overall increases the activation energy for fragmentation. Water thereby acts as a reusable inhibitor (anticatalyst) in chemical ionization. Moreover, according to the quantum chemical (QC) results, when water is present in abundance it has the opposite effect and enhances fragmentation. The underlying reason is a concentration-dependent change in the reaction principle from active inhibition of fragmentation to solvation, which then enhances fragmentation. This amphoteric behavior of water is found for the fragmentation of C3H5+ to C3H3+, and similarly for the fragmentation of AMS·H+ to C3H5+. The results support humidity-dependent quantification efforts for PTR-MS and chemical ionization mass spectrometry (CIMS). Moreover, the results should allow for a better understanding of ion-chemistry in the presence of water. PMID:23682687

  11. Chemical Composition and Size Distributions of Coastal Aerosols Observed on the U.S. East Coast

    NASA Astrophysics Data System (ADS)

    Xia, L.; Song, F.; Jusino-Atresino, R.; Thuman, C.; Gao, Y.

    2008-12-01

    Aerosol input is an important source of certain limiting nutrients, such as iron, for phytoplankton growth in several large oceanic regions. As the efficiency of biological uptake of nutrients may depend on the aerosol properties, a better knowledge of aerosol properties is critically important. Characterizing aerosols over the coastal ocean needs special attention, because the properties of aerosols could be altered by many anthropogenic processes in this land-ocean transition zone before they are transported over the remote ocean. The goal of this experiment was to examine aerosol properties, in particular chemical composition, particle-size distributions and iron solubility, over the US Eastern Seaboard, an important boundary for the transport of continental substances from North America to the North Atlantic Ocean. Our field sampling site was located at Tuckerton (39°N, 74°W) on the southern New Jersey coast. Fourteen sets of High-Volume aerosol samples and three sets of size segregated aerosol samples by a 10-stage MOUDI impactor were collected during 2007 and 2008. The ICP-MS methodology was used to analyze aerosol samples for the concentrations of thirteen trace elements: Al, Fe, Mn, Sc, Cd, Pb, Sb, Ni, Co, Cr, Cu, Zn and V. The IC procedures were applied to determine five cations (sodium, ammonium, potassium, magnesium and calcium) and eleven anions (fluoride, acetate, propionate, formate, MSA, chloride, nitrate, succinate, malonate, sulfate and oxalate). The UV spectrometry was employed for the determination of iron solubility. Preliminary results suggest three major sources of aerosols: anthropogenic, crustal and marine. At this location, the concentrations of iron (II) ranged from 2.8 to 29ng m-3, accounting for ~20% of the total iron. The iron concentrations at this coastal site were substantially lower than those observed in Newark, an urban site in northern NJ. High concentrations of iron (II) were associated with both fine and coarse aerosol

  12. Atmospheric Pressure Chemical Ionization Sources Used in The Detection of Explosives by Ion Mobility Spectrometry

    SciTech Connect

    Waltman, Melanie J.

    2010-05-01

    Explosives detection is a necessary and wide spread field of research. From large shipping containers to airline luggage, numerous items are tested for explosives every day. In the area of trace explosives detection, ion mobility spectrometry (IMS) is the technique employed most often because it is a quick, simple, and accurate way to test many items in a short amount of time. Detection by IMS is based on the difference in drift times of product ions through the drift region of an IMS instrument. The product ions are created when the explosive compounds, introduced to the instrument, are chemically ionized through interactions with the reactant ions. The identity of the reactant ions determines the outcomes of the ionization process. This research investigated the reactant ions created by various ionization sources and looked into ways to manipulate the chemistry occurring in the sources.

  13. Medium Vacuum Electron Emitter as Soft Atmospheric Pressure Chemical Ionization Source for Organic Molecules.

    PubMed

    Liedtke, Sascha; Ahlmann, Norman; Marggraf, Ulrich; Schütz, Alexander; Vautz, Wolfgang; Franzke, Joachim

    2016-05-01

    An electron emitter as a soft atmospheric pressure chemical ionization source is presented, which operates at inner pressures of the device in the medium vacuum range (>10(-3) hPa). Conventional nonradioactive electron emitters require high vacuum (<10(-6) hPa) to prevent electrical sparkovers. The emitter presented here contains structural modifications of an existing setup, which inhibits electrical breakdowns up to 10(-2) hPa at 8 kV acceleration voltage. The increased inner pressure reduces the ionization efficiency until 10(-3) hPa-achievable without a turbomolecular pump-by 2% compared to high-vacuum conditions. This can be compensated with an increase of the electron source output. The functionality of this ion source is demonstrated with mass spectrometric and ion mobility measurements of acetone, eucalyptol, and diisopropyl methanephosphonate. Additional mass spectrometric measurements of 20 different organic compounds demonstrate the soft characteristics of this ionization source. PMID:27046293

  14. All year round chemical composition of aerosol reaching the inner Antarctic Plateau (Dome C - East Antarctica)

    NASA Astrophysics Data System (ADS)

    Udisti, R.; Becagli, S.; Castellano, E.; Cerri, O.; Marino, F.; Morganti, A.; Nava, S.; Rugi, F.; Severi, M.; Traversi, R.

    2009-04-01

    Since 2005, continuous, all-year-round aerosol sampling was carried out at Dome C (Central East Antarctica, 3233 m a.s.l., about 1100 km far from the coast-line), in the framework of Station Concordia project. Size-segregated aerosol samples were collected in summer and winter period by using different low- and medium-volume systems, including pre-selected cut-off samplers (with PM10, PM2.5 and PM1 heads) and multi-stage (Andersen 8-stage and Dekati 4-stage) impactors. Sampling resolution and volume range from 1 day to 1 month and from 2.3 to 12 m3/h respectively. Aerosol study at Dome C aims to improve our knowledge on present day source intensity, transport efficiency and pathways (including stratosphere-to-troposphere interchanges) of particles reaching internal sites of Antarctica and to understand size- and chemical-fractionation effects occurring during the transport (by comparison with coastal aerosol composition). Besides, more information on atmosphere-snow interaction, including depositional and post depositional processes, as well as the effect of sublimation/condensation processes on snow surface, improves the reconstruction of past atmosphere composition from EPICA-DC deep ice core, drilled in the same site. Here we report some results of the chemical composition of the Antarctic background aerosol reaching Dome C, pointing out the seasonal pattern and the temporal trend of some ionic components used as tracers of sea spray, marine biogenic and crustal emissions. The atmospheric load in the summer is more than one order of magnitude lower than that measured in coastal sites and chemical composition is dominated by secondary aerosol, mainly originated by biological marine activity (S-cycle), and distributed in the finest aerosol fractions. H2SO4 from oxidation of biogenic DMS is the main component, while the contribution of HNO3 to the ionic budget is difficult to evaluate because of the re-emission into the atmosphere from the filter surface (acidic

  15. Physical and chemical characterization of marine atmospheric aerosols over the North and South Pacific Oceans using single particle mass spectrometry

    NASA Astrophysics Data System (ADS)

    Furutani, H.; Jung, J.; Miura, K.; Uematsu, M.

    2010-12-01

    Physical and chemical properties of marine atmospheric aerosols were characterized and compared over the North and South Pacific Ocean during two trans-Pacific cruises (from Japan to Chile and Australia to Japan) during the period of January-June 2009, which cover broad region of Pacific Ocean from 40°N to 55°S and 140°E to 70°W. The measured parameters of aerosol properties were single particle size-resolved chemical composition (D = 100 ~ 1500 nm), cloud condensation nuclei (CCN) and condensation nuclei (CN) concentrations, size distribution from 10 nm to 5 μm, total aerosol nitrate and sulfate concentrations, and filter-based chemical composition. Trace gas concentrations of O3 and CO were also measured to aid air parcel categorization during the cruises. Reflecting larger anthropogenic emission in the Northern Hemisphere, pronounced concentration gradient between the North and South Pacific Ocean was observed for aerosol nitrate, CO, and O3. Aerosol sulfate also showed a similar concentration drop in the equatorial region, relatively higher sulfate concentration was observed in 30°S-40°S and 55°S regions, which was associated with increased aerosol methanesulfonic acid (MSA) concentration but little increase in local marine chlorophyll concentration, suggesting contribution of long-range transported marine biogenic sulfur from the high primary production area over the South Pacific high latitude region. Aerosol chemical classification by single particle chemical analysis revealed that certain aerosol types, such as biomass burning, elemental carbon, and elemental/organic carbon mixed type, were mainly observed in the North Pacific region, while several specific organic aerosol types with abundant aged organic and disulfur composition were identified in the South Pacific region. Further comparison of aerosol properties, aerosol sources, and atmospheric aerosol processing in the North and South Pacific Oceans will be discussed.

  16. a Study on the Physical and Chemical Properties of Stratospheric Aerosols.

    NASA Astrophysics Data System (ADS)

    Tabazadeh, Azadeh

    The physical and chemical properties of stratospheric aerosols under background and perturbed conditions are discussed. First, a multi-component aerosol physical chemistry model was developed to study the composition and reactivity of stratospheric aerosols. The compositions are predicted from an equilibrium assumption between the condensed-and gas-phases, and they are calculated as a function of ambient temperature, relative humidity, and the total mass of nitric acid and sulfuric acid present per unit volume of air. The water and solute activity parameters in the aerosol model are derived from various laboratory sources, and the set of equilibrium equations are solved using a unique numerical scheme. The aerosol model is applied to study the formation of nitric acid-containing aerosols in the stratosphere. Also, the equilibrium compositions are used to estimate the extent of aqueous phase processing of chlorine species in the aerosol solutions. This processing can contribute to the depletion of the stratospheric ozone layer, especially after major volcanic eruptions where sulfate aerosols are more abundant. Second, a surface chemistry model was constructed that includes Langmuir trace-gas adsorption and desorption, Brunauer, Emmett and Teller adsorption of water vapor, surface poisoning, solvation and diffusion of molecules on the surface, chemical activation and reaction of adsorbates, and product desorption or reaction. This model is used to study the effects of relative humidity and other physical parameters on the efficiency of heterogeneous chemical processes which occur on the surfaces of solid polar stratospheric clouds. These heterogeneous chemical processes are responsible for the formation of the "ozone hole", can contribute to global ozone depletion, and may have tropospheric significance. Finally, a fluid dynamics and thermodynamics model of volcanic eruption columns was used to develop a scheme for predicting the extent of HCl removal from volcanic

  17. Secondary ionization of chemical warfare agent simulants: atmospheric pressure ion mobility time-of-flight mass spectrometry.

    PubMed

    Steiner, Wes E; Clowers, Brian H; Haigh, Paul E; Hill, Herbert H

    2003-11-15

    For the first time, the use of a traditional ionization source for ion mobility spectrometry (radioactive nickel ((63)Ni) beta emission ionization) and three alternative ionization sources (electrospray ionization (ESI), secondary electrospray ionization (SESI), and electrical discharge (corona) ionization (CI)) were employed with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer (IM(tof)MS) to detect chemical warfare agent (CWA) simulants from both aqueous- and gas-phase samples. For liquid-phase samples, ESI was used as the sample introduction and ionization method. For the secondary ionization (SESI, CI, and traditional (63)Ni ionization) of vapor-phase samples, two modes of sample volatilization (heated capillary and thermal desorption chamber) were investigated. Simulant reference materials, which closely mimic the characteristic chemical structures of CWA as defined and described by Schedule 1, 2, or 3 of the Chemical Warfare Convention treaty verification, were used in this study. A mixture of four G/V-type nerve simulants (dimethyl methylphosphonate, pinacolyl methylphosphonate, diethyl phosphoramidate, and 2-(butylamino)ethanethiol) and one S-type vesicant simulant (2-chloroethyl ethyl sulfide) were found in each case (sample ionization and introduction methods) to be clearly resolved using the IM(tof)MS method. In many cases, reduced mobility constants (K(o)) were determined for the first time. Ion mobility drift times, flight times, relative signal intensities, and fragmentation product signatures for each of the CWA simulants are reported for each of the methods investigated. PMID:14615983

  18. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ.

  19. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ. PMID:27098411

  20. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As+) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH+) of DA, DC, DPAH, and BDPAO could produce Ph2As+ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As+ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH+ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As+.

  1. Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

    NASA Technical Reports Server (NTRS)

    Borsdorf, H.; Nazarov, E. G.; Eiceman, G. A.

    2002-01-01

    The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. c. 2002 American Society for Mass Spectrometry.

  2. Characterization of triacetone triperoxide by ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical ionization

    SciTech Connect

    Ewing, Robert G.; Waltman, Melanie J.; Atkinson, David A.

    2011-04-28

    The atmospheric pressure chemical ionization of triacetone triperoxide (TATP) with subsequent separation and detection by ion mobility spectrometry has been studied. Positive ionization with hydronium reactant ions produced only fragments of the TATP molecule, with m/z 91 ion being the most predominant species. Ionization with ammonium reactant ions produced a molecular adduct at m/z 240. The reduced mobility value of this ion was constant at 1.36 cm{sup 2}V{sup -1}s{sup -1} across the temperature range from 60 to 140 C. The stability of this ion was temperature dependent and did not exist at temperatures above 140 C, where only fragment ions were observed. The introduction of ammonia vapors with TATP resulted in the formation of m/z 58 ion. As the concentration of ammonia increased, this smaller ion appeared to dominate the spectra and the TATP-ammonium adduct decreased in intensity. The ion at m/z 58 has been noted by several research groups upon using ammonia reagents in chemical ionization, but the identity was unknown. Evidence presented here supports the formation of protonated 2-propanimine. A proposed mechanism involves the addition of ammonia to the TATP-ammonium adduct followed by an elimination reaction. A similar mechanism involving the chemical ionization of acetone with excess ammonia also showed the formation of m/z 58 ion. TATP vapors from a solid sample were detected with a hand-held ion mobility spectrometer operated at room temperature. The TATP-ammonium molecular adduct was observed in the presence of ammonia and TATP vapors with this spectrometer.

  3. Characterization of triacetone triperoxide by ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical ionization.

    PubMed

    Ewing, Robert G; Waltman, Melanie J; Atkinson, David A

    2011-06-15

    The atmospheric pressure chemical ionization of triacetone triperoxide (TATP) with subsequent separation and detection by ion mobility spectrometry has been studied. Positive ionization with hydronium reactant ions produced only fragments of the TATP molecule, with m/z 91 ion being the most predominant species. Ionization with ammonium reactant ions produced a molecular adduct at m/z 240. The reduced mobility value of this ion was constant at 1.36 cm(2)V(-1)s(-1) across the temperature range from 60 to 140 °C. The stability of this ion was temperature dependent and did not exist at temperatures above 140 °C, where only fragment ions were observed. The introduction of ammonia vapors with TATP resulted in the formation of m/z 58 ion. As the concentration of ammonia increased, this smaller ion appeared to dominate the spectra and the TATP-ammonium adduct decreased in intensity. The ion at m/z 58 has been noted by several research groups upon using ammonia reagents in chemical ionization, but the identity was unknown. Evidence presented here supports the formation of protonated 2-propanimine. A proposed mechanism involves the addition of ammonia to the TATP-ammonium adduct followed by an elimination reaction. A similar mechanism involving the chemical ionization of acetone with excess ammonia also showed the formation of m/z 58 ion. TATP vapors from a solid sample were detected with a hand-held ion mobility spectrometer operated at room temperature. The TATP-ammonium molecular adduct was observed in the presence of ammonia and TATP vapors with this spectrometer. PMID:21524145

  4. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    DOE PAGES

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-01-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combination of ligand-switching and directmore » charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  5. Coupling aerosol optics to the MATCH (v5.5.0) chemical transport model and the SALSA (v1) aerosol microphysics module

    NASA Astrophysics Data System (ADS)

    Andersson, Emma; Kahnert, Michael

    2016-05-01

    A new aerosol-optics model is implemented in which realistic morphologies and mixing states are assumed, especially for black carbon particles. The model includes both external and internal mixing of all chemical species, it treats externally mixed black carbon as fractal aggregates, and it accounts for inhomogeneous internal mixing of black carbon by use of a novel "core-grey-shell" model. Simulated results of aerosol optical properties, such as aerosol optical depth, backscattering coefficients and the Ångström exponent, as well as radiative fluxes are computed with the new optics model and compared with results from an older optics-model version that treats all particles as externally mixed homogeneous spheres. The results show that using a more detailed description of particle morphology and mixing state impacts the aerosol optical properties to a degree of the same order of magnitude as the effects of aerosol-microphysical processes. For instance, the aerosol optical depth computed for two cases in 2007 shows a relative difference between the two optics models that varies over the European region between -28 and 18 %, while the differences caused by the inclusion or omission of the aerosol-microphysical processes range from -50 to 37 %. This is an important finding, suggesting that a simple optics model coupled to a chemical transport model can introduce considerable errors affecting radiative fluxes in chemistry-climate models, compromising comparisons of model results with remote sensing observations of aerosols, and impeding the assimilation of satellite products for aerosols into chemical-transport models.

  6. Chemical and Aerosol Signatures of Biomass Burning via Long Range Transport observed at Storm Peak Laboratory

    NASA Astrophysics Data System (ADS)

    Hallar, A. G.; Obrist, D.; McCubbin, I. B.; Fain, X.; Rahn, T.

    2008-12-01

    The Desert Research Institute operates a high elevation facility, Storm Peak Laboratory (SPL), located on the Steamboat Springs Ski Resort in Colorado at an elevation 3.2 km. During the spring of 2008, two field projects were conducted at SPL; Storm Peak Cloud and Aerosol Characterization (SPACC) and a State of Colorado Mercury Monitoring project. Measurements of gaseous elemental mercury (GEM), along with CO, ozone and aerosol concentrations and aerosol size distributions will be presented from April 28 to July 1st 2008. This work focuses on specific case studies pertaining to long range transport events. Specifically, high levels of GEM and CO will be presented from May 15, 2008. This data will be coupled with HYSPLIT backtrajectories, chemical modeling via MOZART, and satellite imagery (MODIS) to present evidence that Siberian wildfires impacted the air quality at Storm Peak Laboratory.

  7. Bringing the ocean into the laboratory to probe the chemical complexity of sea spray aerosol

    PubMed Central

    Prather, Kimberly A.; Bertram, Timothy H.; Grassian, Vicki H.; Deane, Grant B.; Stokes, M. Dale; DeMott, Paul J.; Aluwihare, Lihini I.; Palenik, Brian P.; Azam, Farooq; Seinfeld, John H.; Moffet, Ryan C.; Molina, Mario J.; Cappa, Christopher D.; Geiger, Franz M.; Roberts, Gregory C.; Russell, Lynn M.; Ault, Andrew P.; Baltrusaitis, Jonas; Collins, Douglas B.; Corrigan, Craig E.; Cuadra-Rodriguez, Luis A.; Ebben, Carlena J.; Forestieri, Sara D.; Guasco, Timothy L.; Hersey, Scott P.; Kim, Michelle J.; Lambert, William F.; Modini, Robin L.; Mui, Wilton; Pedler, Byron E.; Ruppel, Matthew J.; Ryder, Olivia S.; Schoepp, Nathan G.; Sullivan, Ryan C.; Zhao, Defeng

    2013-01-01

    The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll-a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60–180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climate-relevant properties. PMID:23620519

  8. Bringing the ocean into the laboratory to probe the chemical complexity of sea spray aerosol.

    PubMed

    Prather, Kimberly A; Bertram, Timothy H; Grassian, Vicki H; Deane, Grant B; Stokes, M Dale; Demott, Paul J; Aluwihare, Lihini I; Palenik, Brian P; Azam, Farooq; Seinfeld, John H; Moffet, Ryan C; Molina, Mario J; Cappa, Christopher D; Geiger, Franz M; Roberts, Gregory C; Russell, Lynn M; Ault, Andrew P; Baltrusaitis, Jonas; Collins, Douglas B; Corrigan, Craig E; Cuadra-Rodriguez, Luis A; Ebben, Carlena J; Forestieri, Sara D; Guasco, Timothy L; Hersey, Scott P; Kim, Michelle J; Lambert, William F; Modini, Robin L; Mui, Wilton; Pedler, Byron E; Ruppel, Matthew J; Ryder, Olivia S; Schoepp, Nathan G; Sullivan, Ryan C; Zhao, Defeng

    2013-05-01

    The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll-a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60-180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climate-relevant properties.

  9. Bringing the ocean into the laboratory to probe the chemical complexity of sea spray aerosol.

    PubMed

    Prather, Kimberly A; Bertram, Timothy H; Grassian, Vicki H; Deane, Grant B; Stokes, M Dale; Demott, Paul J; Aluwihare, Lihini I; Palenik, Brian P; Azam, Farooq; Seinfeld, John H; Moffet, Ryan C; Molina, Mario J; Cappa, Christopher D; Geiger, Franz M; Roberts, Gregory C; Russell, Lynn M; Ault, Andrew P; Baltrusaitis, Jonas; Collins, Douglas B; Corrigan, Craig E; Cuadra-Rodriguez, Luis A; Ebben, Carlena J; Forestieri, Sara D; Guasco, Timothy L; Hersey, Scott P; Kim, Michelle J; Lambert, William F; Modini, Robin L; Mui, Wilton; Pedler, Byron E; Ruppel, Matthew J; Ryder, Olivia S; Schoepp, Nathan G; Sullivan, Ryan C; Zhao, Defeng

    2013-05-01

    The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll-a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60-180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climate-relevant properties. PMID:23620519

  10. A new method for assessing the aerosol to rain chemical composition relationships

    NASA Astrophysics Data System (ADS)

    Bourcier, L.; Masson, O.; Laj, P.; Chausse, P.; Pichon, J. M.; Paulat, P.; Bertrand, G.; Sellegri, K.

    2012-11-01

    Measurements were conducted at three sampling sites located at different altitudes in the centre of France during two years, both in the rain and aerosol phases. The rain was sampled at a boundary layer site while the aerosol particles were collected at two different altitudes, which allow a better characterization of the vertical atmospheric column being washed out. Various chemical analyses were performed to characterize reactive (NO3-, SO42-, NH4+ and K+) and inert (7Be, 210Pb and 137Cs) species transfer from the aerosol to the rain phase. This set-up was ideal to calculate the washout ratio (WR) using different concentrations of the aerosol phase. Using the classical WR calculated with the aerosol concentration sampled at the same altitude than the rain collectors, we observed a seasonality of WR, with higher value in winter and lower value in summer for radionuclides. At the higher altitude site, local contaminations do not influence the aerosol concentration, which then should be representative of the whole atmospheric column. The annual variability is high at this site maybe because aerosol concentrations can be less concentrated than the whole atmospheric column when this later one is not well mixed. In order to increase the reliability of the WR, we propose a new method for calculating washout ratio from measurements at the rain collector level. This new calculation takes into account the height of the boundary layer, we observed that it decreased the variability of the washout ratio (for 7Be, 210Pb and NO3-), with less dependence to the season.

  11. High resolution simulations of aerosol microphysics in a global and regionally nested chemical transport model

    NASA Astrophysics Data System (ADS)

    Adams, P. J.; Marks, M.

    2015-12-01

    The aerosol indirect effect is the largest source of forcing uncertainty in current climate models. This effect arises from the influence of aerosols on the reflective properties and lifetimes of clouds, and its magnitude depends on how many particles can serve as cloud droplet formation sites. Assessing levels of this subset of particles (cloud condensation nuclei, or CCN) requires knowledge of aerosol levels and their global distribution, size distributions, and composition. A key tool necessary to advance our understanding of CCN is the use of global aerosol microphysical models, which simulate the processes that control aerosol size distributions: nucleation, condensation/evaporation, and coagulation. Previous studies have found important differences in CO (Chen, D. et al., 2009) and ozone (Jang, J., 1995) modeled at different spatial resolutions, and it is reasonable to believe that short-lived, spatially-variable aerosol species will be similarly - or more - susceptible to model resolution effects. The goal of this study is to determine how CCN levels and spatial distributions change as simulations are run at higher spatial resolution - specifically, to evaluate how sensitive the model is to grid size, and how this affects comparisons against observations. Higher resolution simulations are necessary supports for model/measurement synergy. Simulations were performed using the global chemical transport model GEOS-Chem (v9-02). The years 2008 and 2009 were simulated at 4ox5o and 2ox2.5o globally and at 0.5ox0.667o over Europe and North America. Results were evaluated against surface-based particle size distribution measurements from the European Supersites for Atmospheric Aerosol Research project. The fine-resolution model simulates more spatial and temporal variability in ultrafine levels, and better resolves topography. Results suggest that the coarse model predicts systematically lower ultrafine levels than does the fine-resolution model. Significant

  12. Predicting the Mineral and Chemical Composition of Dust Aerosols: Evaluation and Implications

    NASA Astrophysics Data System (ADS)

    Perlwitz, J. P.; Pérez García-Pando, C.; Miller, R. L.

    2014-12-01

    Soil dust aerosols in Earth system models are typically assumed to have globally uniform properties. However, important climate processes related to dust depend on the aerosol mineral and chemical composition, which varies regionally. Such processes include aerosol radiative forcing, transport of bioavailable iron that catalyzes marine photosynthesis, heterogeneous chemistry, ice nucleation, and cloud condensation.We have implemented a new version of the soil dust aerosol scheme in the NASA GISS Earth System ModelE that takes into account the mineral composition of the dust particles. Dust aerosols are represented as an external mixture of minerals such as illite, kaolinite, smectite, carbonates, quartz, feldspar and gypsum, as well as iron oxides and accretions of iron oxides with each of the these minerals.We present a new publically available compilation of measurements of mineral fractions derived from ca. 50 references from the literature. This compilation is used to evaluate our new model of mineral and elemental composition within ModelE. We discuss the challenges of comparing simulated mineral fractions to measurements, which often come from field campaigns and ship cruises of limited duration. Despite uncertainties of the measurements, we show the importance of estimating the undisturbed size distribution of the parent soil prior to wet sieving, along with the modification of this size distribution during emission. In particular, our new model reproduces measurements showing greater amount of aerosols at silt sizes (whose diameters exceed 2 μm) including significant amounts of clay mineral aerosols (like illite) at silt sizes. Our model also reduces the systematic overestimation of quartz, while allowing iron to be transported farther from its source as impurities than in its pure, crystalline form.

  13. Experimental Determination of Chemical Diffusion within Secondary Organic Aerosol Particles

    SciTech Connect

    Abramson, Evan H.; Imre, D.; Beranek, Josef; Wilson, Jacqueline; Zelenyuk, Alla

    2013-02-28

    Formation, properties, transformations, and temporal evolution of secondary organic aerosols (SOA) particles strongly depend on particle phase. Recent experimental evidence from a number of groups indicates that SOA is in a semi-solid phase, the viscosity of which remained unknown. We find that when SOA is made in the presence of vapors of volatile hydrophobic molecules the SOA particles absorb and trap them. Here, we illustrate that it is possible to measure the evaporation rate of these molecules that is determined by their diffusion in SOA, which is then used to calculate a reasonably accurate value for the SOA viscosity. We use pyrene as a tracer molecule and a-pinene SOA as an illustrative case. It takes ~24 hours for half the pyrene to evaporate to yield a viscosity of 10^8 Pa s for a-pinene. This viscosity is consistent with measurements of particle bounce and evaporation rates. We show that viscosity of 10^8 Pa s implies coalescence times of minutes, consistent with the findings that SOA particles are spherical. Similar measurements on aged SOA particles doped with pyrene yield a viscosity of 10^9 Pa s, indicating that hardening occurs with time, which is consistent with observed decrease in water uptake and evaporation rate with aging.

  14. Self-consistent solution of cosmological radiation-hydrodynamics and chemical ionization

    SciTech Connect

    Reynolds, Daniel R. Hayes, John C. Paschos, Pascal Norman, Michael L.

    2009-10-01

    We consider a PDE system comprising compressible hydrodynamics, flux-limited diffusion radiation transport and chemical ionization kinetics in a cosmologically-expanding universe. Under an operator-split framework, the cosmological hydrodynamics equations are solved through the piecewise parabolic method, as implemented in the Enzo community hydrodynamics code. The remainder of the model, including radiation transport, chemical ionization kinetics, and gas energy feedback, form a stiff coupled PDE system, which we solve using a fully-implicit inexact Newton approach, and which forms the crux of this paper. The inner linear Newton systems are solved using a Schur complement formulation, and employ a multigrid-preconditioned conjugate gradient solver for the inner Schur systems. We describe this approach and provide results on a suite of test problems, demonstrating its accuracy, robustness, and scalability to very large problems.

  15. Electron impact and chemical ionization mass spectral analysis of a volatile uranyl derivative

    SciTech Connect

    Reutter, D.J.; Hardy, D.R.

    1981-01-01

    Quadrupole mass spectral analysis of the volatile uranium ligand complex bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) dioxouranium-di-n-butyl sulfoxide is described utilizing electron impact (EI) and methane chemical ionization (CI) ion sources. All major ions are tentatively identified and the potential usefulness of this complex for determining uranium isotope /sup 235/U//sup 238/U abundance is demonstrated.

  16. Real-time monitoring of volatile organic compounds using chemical ionization mass spectrometry

    DOEpatents

    Mowry, Curtis Dale; Thornberg, Steven Michael

    1999-01-01

    A system for on-line quantitative monitoring of volatile organic compounds (VOCs) includes pressure reduction means for carrying a gaseous sample from a first location to a measuring input location maintained at a low pressure, the system utilizing active feedback to keep both the vapor flow and pressure to a chemical ionization mode mass spectrometer constant. A multiple input manifold for VOC and gas distribution permits a combination of calibration gases or samples to be applied to the spectrometer.

  17. Dependences of Ratio of the Luminosity to Ionization on Velocity and Chemical Composition of Meteors

    NASA Technical Reports Server (NTRS)

    Narziev, M.

    2011-01-01

    On the bases of results simultaneous photographic and radio echo observations, the results complex radar and television observations of meteors and also results of laboratory modeling of processes of a luminescence and ionization, correlation between of luminous intensity Ip to linear electronic density q from of velocities and chemical structure are investigated. It is received that by increasing value of velocities of meteors and decrease of nuclear weight of substance of particles, lg Ip/q decreased more than one order.

  18. Measurements of the aerosol chemical composition and mixing state in the Po Valley using multiple spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Decesari, S.; Allan, J.; Plass-Duelmer, C.; Williams, B. J.; Paglione, M.; Facchini, M. C.; O'Dowd, C.; Harrison, R. M.; Gietl, J. K.; Coe, H.; Giulianelli, L.; Gobbi, G. P.; Lanconelli, C.; Carbone, C.; Worsnop, D.; Lambe, A. T.; Ahern, A. T.; Moretti, F.; Tagliavini, E.; Elste, T.; Gilge, S.; Zhang, Y.; Dall'Osto, M.

    2014-11-01

    The use of co-located multiple spectroscopic techniques can provide detailed information on the atmospheric processes regulating aerosol chemical composition and mixing state. So far, field campaigns heavily equipped with aerosol mass spectrometers have been carried out mainly in large conurbations and in areas directly affected by their outflow, whereas lesser efforts have been dedicated to continental areas characterised by a less dense urbanisation. We present here the results obtained at a background site in the Po Valley, Italy, in summer 2009. For the first time in Europe, six state-of-the-art spectrometric techniques were used in parallel: aerosol time-of-flight mass spectrometer (ATOFMS), two aerosol mass spectrometers (high-resolution time-of-flight aerosol mass spectrometer - HR-ToF-AMS and soot particle aerosol mass spectrometer - SP-AMS), thermal desorption aerosol gas chromatography (TAG), chemical ionisation mass spectrometry (CIMS) and (offline) proton nuclear magnetic resonance (1H-NMR) spectroscopy. The results indicate that, under high-pressure conditions, atmospheric stratification at night and early morning hours led to the accumulation of aerosols produced by anthropogenic sources distributed over the Po Valley plain. Such aerosols include primary components such as black carbon (BC), secondary semivolatile compounds such as ammonium nitrate and amines and a class of monocarboxylic acids which correspond to the AMS cooking organic aerosol (COA) already identified in urban areas. In daytime, the entrainment of aged air masses in the mixing layer is responsible for the accumulation of low-volatility oxygenated organic aerosol (LV-OOA) and also for the recycling of non-volatile primary species such as black carbon. According to organic aerosol source apportionment, anthropogenic aerosols accumulating in the lower layers overnight accounted for 38% of organic aerosol mass on average, another 21% was accounted for by aerosols recirculated in

  19. Chemical ionization mass spectrometric measurements of SO2 emissions from jet engines in flight and test chamber operations

    NASA Astrophysics Data System (ADS)

    Hunton, D. E.; Ballenthin, J. O.; Borghetti, J. F.; Federico, G. S.; Miller, T. M.; Thorn, W. F.; Viggiano, A. A.; Anderson, B. E.; Cofer, W. R.; McDougal, D. S.; Wey, C. C.

    2000-11-01

    We report the results of two measurements of the concentrations and emission indices of gas-phase sulfur dioxide (EI(SO2)) in the exhaust of an F100-200E turbofan engine. The broad goals of both experiments were to obtain exhaust sulfur speciation and aerosol properties as a function of fuel sulfur content. In the first campaign, an instrumented NASA T-39 Sabreliner aircraft flew in close formation behind several F-16 fighter aircraft to obtain near-field plume composition and aerosol properties. In the second, an F-100 engine of the same type was installed in an altitude test chamber at NASA Glenn Research Center where gas composition and nonvolatile aerosol concentrations and size distributions were obtained at the exit plane of the engine. In both experiments, SO2 concentrations were measured with the Air Force Research Laboratory chemical ionization mass spectrometer as a function of altitude, engine power, and fuel sulfur content. A significant aspect of the program was the use of the same fuels, the same engine type, and many of the same diagnostics in both campaigns. Several different fuels were purchased specifically for these experiments, including high-sulfur Jet A (˜1150 ppmm S), low-sulfur Jet A (˜10 ppmm S), medium-sulfur mixtures of these two fuels, and military JP-8+100 (˜170 and ˜300 ppmm S). The agreement between the flight and test cell measurements of SO2 concentrations was excellent, showing an overall precision of better than ±10% and an estimated absolute accuracy of ±20%. The EI(SO2) varied from 2.49 g SO2/kg fuel for the high-sulfur fuel in the test chamber to less than 0.01 g/kg for the lowest-sulfur fuel. No dependence of emission index on engine power, altitude or simulated altitude, separation distance or plume age, or the presence of contrails was observed. In all experiments the measured EI(SO2) was consistent with essentially all of the fuel sulfur appearing as gas-phase SO2 in the exhaust. However, accurate determination of S

  20. Eddy covariance measurements with high-resolution time-of-flight aerosol mass spectrometry: a new approach to chemically-resolved aerosol fluxes

    NASA Astrophysics Data System (ADS)

    Farmer, D. K.; Kimmel, J. R.; Phillips, G.; Docherty, K. S.; Worsnop, D. R.; Sueper, D.; Nemitz, E.; Jimenez, J. L.

    2010-12-01

    Although laboratory studies show that biogenic volatile organic compounds (VOCs) yield substantial secondary organic aerosol (SOA), production of biogenic SOA as indicated by upward fluxes has not been conclusively observed over forests. Further, while aerosols are known to deposit to surfaces, few techniques exist to provide chemically-resolved particle deposition fluxes. To better constrain aerosol sources and sinks, we have developed a new technique to directly measure fluxes of chemically-resolved submicron aerosols using the high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) in a new, fast eddy covariance mode. This approach takes advantage of the instrument's ability to quantitatively identify both organic and inorganic components, including ammonium, sulphate and nitrate, at a temporal resolution of several Hz. The new approach has been successfully deployed over a temperate ponderosa pine plantation in California during the BEARPEX-2007 campaign, providing both total and chemically resolved non-refractory (NR) PM1 fluxes. Average deposition velocity for total NR-PM1 aerosol at noon was 2.05 ± 0.04 mm/s. Using a high resolution measurement of the NH2+ and NH3+ fragments, we demonstrate the first eddy covariance flux measurements of particulate ammonium, which show a noon-time deposition velocity of 1.9 ± 0.7 mm/s and are dominated by deposition of ammonium sulphate.

  1. Eddy covariance measurements with high-resolution time-of-flight aerosol mass spectrometry: a new approach to chemically resolved aerosol fluxes

    NASA Astrophysics Data System (ADS)

    Farmer, D. K.; Kimmel, J. R.; Phillips, G.; Docherty, K. S.; Worsnop, D. R.; Sueper, D.; Nemitz, E.; Jimenez, J. L.

    2011-06-01

    Although laboratory studies show that biogenic volatile organic compounds (VOCs) yield substantial secondary organic aerosol (SOA), production of biogenic SOA as indicated by upward fluxes has not been conclusively observed over forests. Further, while aerosols are known to deposit to surfaces, few techniques exist to provide chemically-resolved particle deposition fluxes. To better constrain aerosol sources and sinks, we have developed a new technique to directly measure fluxes of chemically-resolved submicron aerosols using the high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) in a new, fast eddy covariance mode. This approach takes advantage of the instrument's ability to quantitatively identify both organic and inorganic components, including ammonium, sulphate and nitrate, at a temporal resolution of several Hz. The new approach has been successfully deployed over a temperate ponderosa pine plantation in California during the BEARPEX-2007 campaign, providing both total and chemically resolved non-refractory (NR) PM1 fluxes. Average deposition velocities for total NR-PM1 aerosol at noon were 2.05 ± 0.04 mm s-1. Using a high resolution measurement of the NH2+ and NH3+ fragments, we demonstrate the first eddy covariance flux measurements of particulate ammonium, which show a noon-time deposition velocity of 1.9 ± 0.7 mm s-1 and are dominated by deposition of ammonium sulphate.

  2. Chemical characterization of synthetic cannabinoids by electrospray ionization FT-ICR mass spectrometry.

    PubMed

    Kill, Jade B; Oliveira, Izabela F; Tose, Lilian V; Costa, Helber B; Kuster, Ricardo M; Machado, Leandro F; Correia, Radigya M; Rodrigues, Rayza R T; Vasconcellos, Géssica A; Vaz, Boniek G; Romão, Wanderson

    2016-09-01

    The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the Δ(9)-THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT-ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(-). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE-double bond equivalent) and exact mass (<1ppm) of a total of 55 chemical species without the prior separation step. PMID:27471991

  3. Chemical characterization of synthetic cannabinoids by electrospray ionization FT-ICR mass spectrometry.

    PubMed

    Kill, Jade B; Oliveira, Izabela F; Tose, Lilian V; Costa, Helber B; Kuster, Ricardo M; Machado, Leandro F; Correia, Radigya M; Rodrigues, Rayza R T; Vasconcellos, Géssica A; Vaz, Boniek G; Romão, Wanderson

    2016-09-01

    The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the Δ(9)-THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT-ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(-). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE-double bond equivalent) and exact mass (<1ppm) of a total of 55 chemical species without the prior separation step.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  5. Organic aerosol characterization by complementary measurements of chemical bonds and molecular fragments

    NASA Astrophysics Data System (ADS)

    Russell, Lynn M.; Bahadur, Ranjit; Hawkins, Lelia N.; Allan, James; Baumgardner, Darrel; Quinn, Patricia K.; Bates, Timothy S.

    2009-12-01

    Organic aerosol chemical markers from normalized concentrations of independent measurements of mass fragments (using Aerosol Mass Spectrometry, AMS) are compared to bond-based functional groups (from Fourier Transform Infrared spectroscopy, FTIR) during eight field projects in the western hemisphere. Several field projects show weak correlations between alcohol group fractions and m/ z 60 fractions, consistent with the organic hydroxyl groups and the fragmentation of saccharides, but the weakness of the correlations indicate chemical differences among the relationships for ambient aerosols in different regions. Carboxylic acid group fractions and m/ z 44 fractions are correlated weakly for three projects, with correlations expected for aerosols dominated by di-acid compounds since their fragmentation is typically dominated by m/ z 44. Despite differences for three projects with ratios of m/ z 44 to m/ z 57 fragments less than 10, five projects showed a linear trend between the project-average m/ z 44 to m/ z 57 ratio and the ratio of acid and alkane functional groups. While this correlation explains only a fraction of the fragment and bond variability measured, the consistency of this relationship at multiple sites indicates a general agreement with the interpretation of the relative amount of m/ z 44 as a carboxylic acid group marker and m/ z 57 as an alkane group marker.

  6. Hygroscopic properties of the Paris urban aerosol in relation to its chemical composition

    NASA Astrophysics Data System (ADS)

    Kamilli, K. A.; Poulain, L.; Held, A.; Nowak, A.; Birmili, W.; Wiedensohler, A.

    2014-01-01

    Aerosol hygroscopic growth factors and chemical properties were measured as part of the MEGAPOLI "Megacities Plume Case Study" at the urban site Laboratoire d'Hygiène de la Ville de Paris (LHVP) in the city center of Paris from June to August 2009, and from January to February 2010. Descriptive hygroscopic growth factors (DGF) were derived in the diameter range from 25 to 350 nm at relative humidities of 30, 55, 75, and 90% by applying the summation method on humidified and dry aerosol size distributions measured simultaneously with a humidified differential mobility particle sizer (HDMPS) and a twin differential mobility particle sizer (TDMPS). For 90% relative humidity, the DGF varied from 1.06 to 1.46 in summer, and from 1.06 to 1.66 in winter. Temporal variations in the observed mean DGF could be well explained with a simple growth model based on the aerosol chemical composition measured by aerosol mass spectrometry (AMS) and black carbon photometry (MAAP). In particular, good agreement was observed when sulfate was the predominant inorganic factor. A clear overestimation of the predicted growth factor was found when the nitrate mass concentration exceeded values of 10 μg m-3, e.g., during winter.

  7. Hygroscopic properties of the Paris urban aerosol in relation to its chemical composition

    NASA Astrophysics Data System (ADS)

    Kamilli, K. A.; Poulain, L.; Held, A.; Nowak, A.; Birmili, W.; Wiedensohler, A.

    2013-05-01

    Aerosol hygroscopic growth factors and chemical properties were measured as part of the MEGAPOLI "Megacities Plume Case Study" at the urban site LHVP in the city center of Paris from June to August 2009, and from January to February 2010. Descriptive hygroscopic growth factors (DGF) were derived in the diameter range from 25 to 350 nm at relative humidities of 30, 55, 75, and 90% by applying the summation method on humidified and dry aerosol size distributions measured simultaneously with a humidified differential mobility particle sizer (HDMPS) and a twin differential mobility particle sizer (TDMPS). For 90% relative humidity, the DGF varied from 1.06 to 1.46 in summer, and from 1.06 to 1.66 in winter. Temporal variations in the observed mean DGF could be well explained with a simple growth model based on the aerosol chemical composition measured by aerosol mass spectrometry (AMS) and black carbon photometry (MAAP). In particular, good agreement was observed when sulfate was the predominant inorganic factor. A clear overestimation of the predicted growth factor was found when the nitrate mass concentration exceeded values of 10 μg m3, e.g. during winter.

  8. Chemical Composition of Atmospheric Aerosols Above a Pristine South East Asian Rainforest

    NASA Astrophysics Data System (ADS)

    Robinson, N. H.; Allan, J. D.; Williams, P. I.; Coe, H.; Hamilton, J.; Chen, Q.; Martin, S.; Trembath, J.

    2009-04-01

    conjunction with a constant pressure inlet. The aerosols' chemical origins have been further investigated by comparing these spectra to chamber experiments, mass spectral libraries and data from comparable experiments in other locations. These data are also being analysed in conjunction with offline techniques applied to samples collected using filters and a Particle-Into-Liquid Sampler (PILS). Methods used include liquid chromatography and comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry. These techniques provide a more detailed chemical characterisation of the SOA and water soluble organic carbon, allowing direct links back to gas phase precursors. In conjunction with the field measurements, a programme of chamber experiments is being carried out at Manchester as part of the ACES project. This will generate comparable SOA under controlled conditions and subjecting them to similar analysis.

  9. Characterization of the physical, chemical, and optical properties of atmospheric aerosol particles in New Hampshire

    NASA Astrophysics Data System (ADS)

    Slater, John Frederick

    Tropospheric aerosol particles directly affect the radiative budget of the Earth, and degrade visibility, by scattering and absorbing short-wavelength solar radiation. However, the radiative effect of aerosols is highly uncertain due to the non-uniform spatial distribution of the particles over Earth, their heterogeneous chemical composition, and their variable size. This dissertation quantifies some of the physical, chemical, and optical (radiative) properties of aerosols at different locations within New Hampshire (NH) from spring 2000 to fall 2001. During spring 2000, a 1-month study conducted at a mountaintop location adjacent to the White Mountain National Forest in northern NH showed that synoptic-scale air mass transport heavily influenced aerosol properties, and hence regional visibility. During W/SW flow, aerosol parameters and haziness were generally twice as high as times of N/NE flow. Similar transport dependent results were observed in October 2000 during a regional pollution event. Pollutants built-up in concentration during 22--28 October, culminated on 28 October, and then dropped 10-fold to background levels within a 6-hour period. Synoptic weather conditions during the transition from high to low pollutant levels indicated that an intense frontal boundary traversed the region, serving as a divide between a warm, humid, and polluted air mass from the W/SW, and a cold, dry, and clean air mass advancing out of Canada. Further work connecting air mass transport and aerosol variability in southern NH revealed that maximum aerosol optical depth (AOD) occurred in summer and was primarily associated with W/SW flow. Minimum AOD occurred in winter and was generally associated with N/NE flow. Mass scattering and absorption efficiencies of PM2.5 did not vary significantly between times of transport from different source regions and were very close to theoretical values. Maximum positive values of aerosol direct radiative forcing occurred in winter and maximum

  10. Aerosol Optical Properties and Chemical Composition Measured on the Ronald H. Brown During ACE-Asia

    NASA Astrophysics Data System (ADS)

    Quinn, P. K.; Bates, T. S.; Miller, T. L.; Coffman, D.

    2001-12-01

    Measurements of aerosol chemical, physical, and optical properties were made onboard the NOAA R/V Ronald H. Brown during the ACE-Asia Intensive Field Program to characterize Asian aerosol as it was transported across the Pacific Ocean. The ship traveled across the Pacific from Hawaii to Japan and into the East China Sea and the Sea of Japan. Trajectories indicate that remote marine air masses were sampled on the transit to Japan. In the ACE-Asia study region air masses from Japan, China, Mongolia, and the Korea Peninsula were sampled. A variety of aerosol types were encountered including those of marine, volcanic, crustal, and industrial origin. Presented here, for the different air masses encountered, are aerosol optical properties (scattering and absorption coefficients, single scattering albedo, Angstrom Exponent, and aerosol optical depth) and chemical composition (major ions, total organic and black carbon, and trace elements). Scattering by submicron aerosol (55 % RH and 550 nm) was less than 20 1/Mm during the transit from Hawaii to Japan. In continental air masses, values ranged from 60 to 320 1/Mm with the highest submicron scattering coefficients occurring during prefrontal conditions with a low marine boundary layer height and trajectories from Japan. For the continental air masses, the ratio of scattering by submicron to sub-10 micron aerosol during polluted conditions averaged 0.8 and during a dust event 0.41. Aerosol optical depth (500 nm) ranged from 0.08 during the Pacific transit to 1.3 in the prefrontal conditions described above. Optical depths during dust events ranged from 0.2 to 0.6. Submicron non-sea salt (nss) sulfate concentrations ranged from 0.5 ug/m-3 during the Pacific transit to near 30 ug/m-3 during the prefrontal conditions described above. Black carbon to total carbon mass ratios in air masses from Asia averaged 0.18 with highest values (0.32) corresponding to trajectories crossing the Yangtze River valley.

  11. Seasonal contrast in aerosol abundance over northern south Asia using a chemical transport model

    NASA Astrophysics Data System (ADS)

    Venkataraman, C.; Sadavarte, P.; Madhavan, B. L.; Kulkarni, S.; Carmichael, G. R.; Adhikary, B.; D'Allura, A.; Cherian, R.; Das, S.; Gupta, T.; Streets, D. G.; Wei, C.; Zhang, Q.

    2012-12-01

    Northern South-Asia, home to about half a billion people, experiences large aerosol abundances almost all year around. There are gaps in our understanding of seasonal variations in regional aerosol emissions, abundance and radiative effects. The present study uses chemical transport model simulations (at ~ 60km resolution), with regionally estimated emissions, to investigate the contrast in aerosol surface and columnar abundance during pre-monsoon transition, monsoon and inter-monsoon transition periods over than Gangetic plain (GP) and Tibetan plateau. The interplay between aerosol emissions and atmospheric transport is examined to explain the variability. Model predictions were evaluated with available in-situ measurements and AOD from AERONET and MODIS level-2 retrievals (at 10 km resolution) processed with quality weighting to the model resolution. During April, AOD was dominated by dust at most sites across the GP and Tibet. However, AOD from organic carbon (emitted from agricultural residue burning) is also significant at several sites (Pantnagar, Godavari, Kolkata, Dhaka, and at high altitude Pyramid and Lhasa sites), consistent with recently reported MISR climatology in this region. In contrast, during July and September, AOD was dominated by sulfate at all sites. In April, aerosols over the GP could be attributed to emissions from large industrial sources (thermal power plant, cement industries, iron & steel and other industries) and agricultural residue burning transported from the northwest, along with forest burning emissions transported from the east. Large fluxes of open burning emissions in the east GP, along with prevailing easterly wind flow into the GP led to an east-west gradient in anthropogenic aerosols. During July, there was little open burning, so aerosol concentrations were largely from industrial emissions transported out through the north. In the Tibet region, dust was predominant during both April and July. During September

  12. Chemical Analysis of Fractionated Halogens in Atmospheric Aerosols Collected in Okinawa, Japan

    NASA Astrophysics Data System (ADS)

    Tsuhako, A.; Miyagi, Y.; Somada, Y.; Azechi, S.; Handa, D.; Oshiro, Y.; Murayama, H.; Arakaki, T.

    2013-12-01

    Halogens (Cl, Br and I) play important roles in the atmosphere, e.g. ozone depletion by Br during spring in Polar Regions. Sources of halogens in atmospheric aerosols are mainly from ocean. But, for example, when we analyzed Br- with ion chromatography, its concentrations were almost always below the detection limit, which is also much lower than the estimated concentrations from sodium ion concentrations. We hypothesized that portions of halogens are escaped to the atmosphere, similar to chlorine loss, changed their chemical forms to such as BrO3- and IO3-, and/or even formed precipitates. There was few reported data so far about fractionated halogen concentrations in atmospheric aerosols. Thus, purpose of this study was to determine halogen concentrations in different fractions; free ion, water-soluble chemically transformed ions and precipitates using the authentic aerosols. Moreover, we analyzed seasonal variation for each fraction. Atmospheric aerosol samples were collected at Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS) of Okinawa, Japan during January 2010 and August 2013. A high volume air sampler was used for collecting total particulate matters on quartz filters on a weekly basis. Ultrapure water was used to extract water-soluble factions of halogens. The extracted solutions were filtered with the membrane filter and used for chemical analysis with ion chromatography and ICP-MS. Moreover, the total halogens in aerosols were obtained after digesting aerosols with tetramethylammonium hydroxide (TMAH) using the microwave and analysis with ICP-MS. For Cl, water-soluble Cl- accounted for about 70% of the estimates with Na content. No other forms of water-soluble Cl were found. About 30% of Cl was assumed volatilized to the gas-phase. For Br, water-soluble Br accounted for about 43% of the estimates with Na content, and within the 43%, about 10% of Br was not in the form of Br-. About 46% of Br was assumed volatilized to the gas-phase. For I

  13. Rotation planar chromatography coupled on-line with atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Van Berkel, Gary J; Llave, Jonathan J; De Apadoca, Marilyn F; Ford, Michael J

    2004-01-15

    The coupling of a rotation planar preparative thin-layer chromatography system on-line with mass spectrometry is demonstrated using a simple plumbing scheme and a self-aspirating heated nebulizer probe of a corona discharge atmospheric pressure chemical ionization source. The self-aspiration of the heated nebulizer delivers approximately 20 microL/min of the 3.0 mL/min eluate stream to the mass spectrometer, eliminating the need for an external pump in the system. The viability of the coupling is demonstrated with a three-dye mixture composed of fat red 7B, solvent green 3, and solvent blue 35 separated and eluted from a silica gel-coated rotor using toluene. The real-time characterization of the dyes eluting from the rotor is illustrated in positive ion full-scan mode. Other self-aspirating ion source systems including atmospheric pressure photoionization, electrospray ionization, and inductively coupled plasma ionization, for example, might be configured and used in a similar manner coupled to the chromatograph to expand the types of analytes that could be ionized, detected, and characterized effectively. PMID:14719901

  14. Laser-Induced Acoustic Desorption/Atmospheric Pressure Chemical Ionization Mass Spectrometry

    PubMed Central

    Gao, Jinshan; Borton, David J.; Owen, Benjamin C.; Jin, Zhicheng; Hurt, Matt; Amundson, Lucas M.; Madden, Jeremy T.; Qian, Kuangnan; Kenttämaa, Hilkka I.

    2010-01-01

    Laser-induced acoustic desorption (LIAD) was successfully coupled to a conventional atmospheric pressure chemical ionization (APCI) source in a linear quadrupole ion trap mass spectrometer (LQIT). Model compounds representing a wide variety of different types, including basic nitrogen and oxygen compounds, aromatic and aliphatic compounds, as well as unsaturated and saturated hydrocarbons, were tested separately and as a mixture. These model compounds were successfully evaporated into the gas phase by using LIAD and then ionized by using APCI with different reagents. Four APCI reagent systems were tested: the traditionally used mixture of methanol and water, neat benzene, neat carbon disulfide, and nitrogen gas (no liquid reagent). The mixture of methanol and water produced primarily protonated molecules, as expected. However, only the most basic compounds yielded ions under these conditions. In sharp contrast, using APCI with either neat benzene or neat carbon disulfide as the reagent resulted in the ionization of all the analytes studied to predominantly yield stable molecular ions. Benzene yielded a larger fraction of protonated molecules than carbon disulfide, which is a disadvantage. A similar amount of fragmentation was observed for these reagents. When the experiment was performed without a liquid reagent(nitrogen gas was the reagent), more fragmentation was observed. Analysis of a known mixture as well as a petroleum cut was also carried out. In summary, the new experiment presented here allows the evaporation of thermally labile compounds, both polar and nonpolar, without dissociation or aggregation, and their ionization to form stable molecular ions. PMID:21472571

  15. Rotation planar chromatography coupled on-line with atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Van Berkel, Gary J; Llave, Jonathan J; De Apadoca, Marilyn F; Ford, Michael J

    2004-01-15

    The coupling of a rotation planar preparative thin-layer chromatography system on-line with mass spectrometry is demonstrated using a simple plumbing scheme and a self-aspirating heated nebulizer probe of a corona discharge atmospheric pressure chemical ionization source. The self-aspiration of the heated nebulizer delivers approximately 20 microL/min of the 3.0 mL/min eluate stream to the mass spectrometer, eliminating the need for an external pump in the system. The viability of the coupling is demonstrated with a three-dye mixture composed of fat red 7B, solvent green 3, and solvent blue 35 separated and eluted from a silica gel-coated rotor using toluene. The real-time characterization of the dyes eluting from the rotor is illustrated in positive ion full-scan mode. Other self-aspirating ion source systems including atmospheric pressure photoionization, electrospray ionization, and inductively coupled plasma ionization, for example, might be configured and used in a similar manner coupled to the chromatograph to expand the types of analytes that could be ionized, detected, and characterized effectively.

  16. Biomass burning aerosol over the Amazon during SAMBBA: impact of chemical composition on radiative properties

    NASA Astrophysics Data System (ADS)

    Morgan, William; Allan, James; Flynn, Michael; Darbyshire, Eoghan; Hodgson, Amy; Liu, Dantong; O'shea, Sebastian; Bauguitte, Stephane; Szpek, Kate; Langridge, Justin; Johnson, Ben; Haywood, Jim; Longo, Karla; Artaxo, Paulo; Coe, Hugh

    2014-05-01

    Biomass burning represents one of the largest sources of particulate matter to the atmosphere, resulting in a significant perturbation to the Earth's radiative balance coupled with serious impacts on public health. Globally, biomass burning aerosols are thought to exert a small warming effect but with the uncertainty being 4 times greater than the central estimate. On regional scales, the impact is substantially greater, particularly in areas such as the Amazon Basin where large, intense and frequent burning occurs on an annual basis for several months. Absorption by atmospheric aerosols is underestimated by models over South America, which points to significant uncertainties relating to Black Carbon (BC) aerosol properties. Initial results from the South American Biomass Burning Analysis (SAMBBA) field experiment, which took place during September and October 2012 over Brazil on-board the UK Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft, are presented here. Aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and a DMT Single Particle Soot Photometer (SP2). The physical, chemical and optical properties of the aerosols across the region will be characterized in order to establish the impact of biomass burning on regional air quality, weather and climate. The aircraft sampled a range of conditions including sampling of pristine Rainforest, fresh biomass burning plumes, regional haze and elevated biomass burning layers within the free troposphere. The aircraft sampled biomass burning aerosol across the southern Amazon in the states of Rondonia and Mato Grosso, as well as in a Cerrado (Savannah-like) region in Tocantins state. This presented a range of fire conditions, both in terms of their number, intensity, vegetation-type and their combustion efficiencies. Near-source sampling of fires in Rainforest environments suggested that smouldering combustion dominated, while flaming combustion dominated

  17. Daily and hourly chemical impact of springtime transboundary aerosols on Japanese air quality

    NASA Astrophysics Data System (ADS)

    Moreno, T.; Kojima, T.; Amato, F.; Lucarelli, F.; de la Rosa, J.; Calzolai, G.; Nava, S.; Chiari, M.; Alastuey, A.; Querol, X.; Gibbons, W.

    2013-02-01

    The regular eastward drift of transboundary aerosol intrusions from the Asian mainland into the NW Pacific region has a pervasive impact on air quality in Japan, especially during springtime. Analysis of 24-h filter samples with Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Mass Spectrometry (ICP-MS), and hourly Streaker with Particle Induced X-ray Emission (PIXE) samples collected continuously for six weeks reveal the chemistry of successive waves of natural mineral desert dust ("Kosa") and metalliferous sulphatic pollutants arriving in western Japan during spring 2011. The main aerosol sources recognised by Positive Matrix Factorization (PMF) analysis of Streaker data are mineral dust and fresh sea salt (both mostly in the coarser fraction PM2.5-10), As-bearing sulphatic aerosol (PM0.1-2.5), metalliferous sodic particulate matter (PM) interpreted as aged, industrially contaminated marine aerosol, and ZnCu-bearing aerosols. Whereas mineral dust arrivals are typically highly transient, peaking over a few hours, sulphatic intrusions build up and decline more slowly, and are accompanied by notable rises in ambient concentrations of metallic trace elements such as Pb, As, Zn, Sn and Cd. The magnitude of the loss in regional air quality due to the spread and persistence of pollution from mainland Asia is especially clear when cleansing oceanic air advects westward across Japan, removing the continental influence and reducing concentrations of the undesirable metalliferous pollutants by over 90%. Our new chemical database, especially the Streaker data, demonstrates the rapidly changing complexity of ambient air inhaled during these transboundary events, and implicates Chinese coal combustion as the main source of the anthropogenic aerosol component.

  18. Optical, physical, and chemical properties of springtime aerosol over Barrow Alaska in 2008

    SciTech Connect

    Shantz, Nicole C.; Gultepe, Ismail; Andrews, Elisabeth; Earle, Michael; MacDonald, A. M.; Liu, Peter S.K.; Leaitch, W. R.

    2014-03-06

    Airborne observations from four flights during the 2008 Indirect and Semi-Direct Aerosol Campaign (ISDAC) are used to examine some cloud-free optical, physical, and chemical properties of aerosol particles in the springtime Arctic troposphere. The number concentrations of particles larger than 0.12 μm (Na>120), important for light extinction and cloud droplet formation, ranged from 15 to 2260 cm-3, with the higher Na>120 cases dominated by measurements from two flights of long-range transported biomass burning (BB) aerosols. The two other flights examined here document a relatively clean aerosol and an Arctic Haze aerosol impacted by larger particles largely composed of dust. For observations from the cleaner case and the BB cases, the particle light scattering coefficients at low relative humidity (RH<20%) increased nonlinearly with increasing Na>120, driven mostly by an increase in mean sizes of particles with increasing Na>120 (BB cases). For those three cases, particle light absorption coefficients also increased nonlinearly with increasing Na>120 and linearly with increasing submicron particle volume concentration. In addition to black carbon, brown carbon was estimated to have increased light absorption coefficients by 27% (450 nm wavelength) and 14% (550 nm) in the BB cases. For the case with strong dust influence, the absorption relative to submicron particle volume was small compared with the other cases. There was a slight gradient of Passive Cavity Aerosol Spectrometer Probe (PCASP) mean volume diameter (MVD) towards smaller sizes with increasing height, which suggests more scavenging of the more elevated particles, consistent with a typically longer lifetime of particles higher in the atmosphere. However, in approximately 10% of the cases, the MVD increased (>0.4 μm) with increasing altitude, suggesting transport of larger fine particle mass (possibly coarse particle mass) at high levels over the Arctic. This may be because of transport of

  19. Daily and hourly chemical impact of springtime transboundary aerosols on Japanese air quality

    NASA Astrophysics Data System (ADS)

    Moreno, T.; Kojima, T.; Amato, F.; Lucarelli, F.; Nava, S.; de la Rosa, J.; Calzolai, G.; Chiari, M.; Alastuey, A.; Querol, X.; Gibbons, W.

    2012-09-01

    The regular eastward drift of transboundary aerosol intrusions from the Asian mainland into the NW Pacific region has a~pervasive impact on air quality in Japan, especially during springtime. Analysis of 24-h filter samples (ICP-AES and ICP-MS) and hourly Streaker (PIXE) samples of particulate matter collected continuously for six weeks reveal the chemistry of successive waves of natural mineral desert dust ("Kosa") and metalliferous sulphatic pollutants arriving in Western Japan during spring 2011. The main aerosol sources recognised by PMF analysis of Streaker data are mineral dust and fresh sea salt (both mostly in the coarser fraction PM2.5-10), As-bearing sulphatic aerosol (PM0.1-2.5), metalliferous sodic PM interpreted as aged, industrially contaminated marine aerosol, and ZnCu-bearing aerosols. Whereas mineral dust arrivals are typically highly transient, peaking over a few hours, sulphatic intrusions build up and decline more slowly, and are accompanied by notable rises in ambient concentrations of metallic trace elements such as Pb, As, Zn, Sn and Cd. The magnitude of the loss in regional air quality due to the spread and persistence of pollution from mainland Asia is especially clear when cleansing oceanic air advects westward across Japan, removing the continental influence and reducing concentrations of the more undesirable metalliferous pollutants by over 90%. Our new chemical database, especially the Streaker data, demonstrates the rapidly changing complexity of ambient air inhaled during these transboundary events, and implicates Chinese coal combustion as the main source of the anthropogenic aerosol component.

  20. Formic and Acetic Acid Observations over Colorado by Chemical Ionization Mass Spectrometry and Organic Acids' Role in Air Quality

    NASA Astrophysics Data System (ADS)

    Treadaway, V.; O'Sullivan, D. W.; Heikes, B.; Silwal, I.; McNeill, A.

    2015-12-01

    Formic acid (HFo) and acetic acid (HAc) have both natural and anthropogenic sources and a role in the atmospheric processing of carbon. These organic acids also have an increasing importance in setting the acidity of rain and snow as precipitation nitrate and sulfate concentrations have decreased. Primary emissions for both organic acids include biomass burning, agriculture, and motor vehicle emissions. Secondary production is also a substantial source for both acids especially from biogenic precursors, secondary organic aerosols (SOAs), and photochemical production from volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs). Chemical transport models underestimate organic acid concentrations and recent research has sought to develop additional production mechanisms. Here we report HFo and HAc measurements during two campaigns over Colorado using the peroxide chemical ionization mass spectrometer (PCIMS). Iodide clusters of both HFo and HAc were recorded at mass-to-charge ratios of 173 and 187, respectively. The PCIMS was flown aboard the NCAR Gulfstream-V platform during the Deep Convective Clouds and Chemistry Experiment (DC3) and aboard the NCAR C-130 during the Front Range Air Pollution and Photochemistry Experiment (FRAPPE). The DC3 observations were made in May and June 2012 extending from the surface to 13 km over the central and eastern United States. FRAPPE observations were made in July and August 2014 from the surface to 7 km over Colorado. DC3 measurements reported here are focused over the Colorado Front Range and complement the FRAPPE observations. DC3 HFo altitude profiles are characterized by a decrease up to 6 km followed by an increase either back to boundary layer mixing ratio values or higher (a "C" shape). Organic acid measurements from both campaigns are interpreted with an emphasis on emission sources (both natural and anthropogenic) over Colorado and in situ photochemical production especially ozone precursors.

  1. Development of aerosol assisted chemical vapor deposition for thin film fabrication

    NASA Astrophysics Data System (ADS)

    Maulana, Dwindra Wilham; Marthatika, Dian; Panatarani, Camellia; Mindara, Jajat Yuda; Joni, I. Made

    2016-02-01

    Chemical vapor deposition (CVD) is widely used to grow a thin film applied in many industrial applications. This paper report the development of an aerosol assisted chemical vapor deposition (AACVD) which is one of the CVD methods. Newly developed AACVD system consists of a chamber of pyrex glass, two wire-heating elements placed to cover pyrex glass, a substrate holder, and an aerosol generator using an air brush sprayer. The temperature control system was developed to prevent condensation on the chamber walls. The control performances such as the overshoot and settling time were obtained from of the developed temperature controller. Wire-heating elements were controlled at certain setting value to heat the injected aerosol to form a thin film in the substrate. The performance of as-developed AACVD system tested to form a thin film where aerosol was sprayed into the chamber with a flow rate of 7 liters/minutes, and vary in temperatures and concentrations of precursor. The temperature control system have an overshoot around 25 °C from the desired set point temperature, very small temperature ripple 2 °C and a settling time of 20 minutes. As-developed AACVD successfully fabricated a ZnO thin film with thickness of below 1 µm. The performances of system on formation of thin films influenced by the generally controlled process such as values of setting temperature and concentration where the aerosol flow rate was fixed. Higher temperature was applied, the more uniform ZnO thin films were produced. In addition, temperature of the substrate also affected on surface roughness of the obtained films, while concentration of ZnO precursor determined the thickness of produce films. It is concluded that newly simple AACVD can be applied to produce a thin film.

  2. Online hygroscopicity and chemical measurement of urban aerosol in Shanghai, China

    NASA Astrophysics Data System (ADS)

    Wang, Xinning; Ye, Xingnan; Chen, Hong; Chen, Jianmin; Yang, Xin; Gross, Deborah S.

    2014-10-01

    Submicron aerosol hygroscopicity and composition were simultaneously measured with a Hygroscopicity-Tandem Differential Mobility Analyzer (HTDMA) in-line with an Aerosol Time-of-Flight mass spectrometer (ATOFMS) in wintertime of 2009 in Shanghai. 250 nm dry diameter aerosol particles were humidified (85% RH) and selected based on their hygroscopicity. Two Growth Factor (GF) modes were observed persistently: a weak nearly-hydrophobic (NH) mode with GF at around 1.05 and a strong hydrophilic mode with GF around 1.46. Aerosol particles at different GFs were chemically analyzed by ATOFMS to link the aerosol hygroscopicity and chemistry. Particles were grouped into five major classes: inorganic dust/ash, biomass burning particles (BB), elemental carbon and organic carbon mixed particles (ECOC), Amine rich organic carbon particles (OC-Amine), and high mass organic carbon particles (HMOC). Different particle types were found enriched in the two GF modes. ECOC and OC-Amine particles internally mixed with secondary inorganic species were found mostly in the hydrophilic mode. Pure EC particles and a small group of clay particles among the dust/ash type with strong signals of aluminum and silicon oxides appeared in the NH mode. HMOC particles were exclusively found in the NH mode. Chemical signature intensities were analyzed to examine the particle mixing states and their impact on the diversity of hygroscopicity for each particle type. BB particles in the NH mode had stronger organic carbon signals, while those in hydrophilic mode had stronger potassium salt signals. In general, an elevated OC mass fraction increased particle's hydrophobicity. Amine and secondary inorganic species such as nitrate strongly increased particle's hygroscopicity.

  3. Effects of Chemical Aging on Global Secondary Organic Aerosol using the Volatility Basis Set Approach

    NASA Astrophysics Data System (ADS)

    Park, R.; Jo, D.; Kim, M.; Spracklen, D. V.; Hodzic, A.

    2014-12-01

    Organic aerosol (OA) constitutes significant mass fractions (20-90%) of total dry fine aerosols in the atmosphere. However, global models of OA have shown large discrepancies when compared to the observations because of the limited capability to simulate secondary OA (SOA). For reducing the discrepancies between observations and models, recent studies have shown that chemical aging reactions in the atmosphere are important because they can lead to decreases in organic volatility, resulting in increase of SOA mass yields. To efficiently simulate chemical aging of SOA in the atmosphere, we implemented the volatility basis set approach in a global 3-D chemical transport model (GEOS-Chem). We present full-year simulations and their comparisons with multiple observations - global aerosol mass spectrometer dataset, the Interagency Monitoring of Protected Visual Environments from the United States, the European Monitoring and Evaluation Programme dataset and water-soluble organic carbon observation data collected over East Asia. Using different input parameters in the model, we also explore the uncertainty of the SOA simulation for which we use an observational constraint to find the optimized values with which the model reduces the discrepancy from the observations. Finally, we estimate the effect of OA on climate using our best simulation results.

  4. Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Krüger, H.; Platt, U.; Schmitt-Kopplin, P.; Zetzsch, C.

    2011-12-01

    Reactive halogen species are released by various sources like photo-activated sea-salt aerosol or salt pans and salt lakes. These heterogeneous release mechanisms have been overlooked so far, although their potential of interaction with organic aerosols like Secondary Organic Aerosol (SOA), Biomass Burning Organic Aerosol (BBOA) or Atmospheric Humic LIke Substances (HULIS) is completely unknown. Such reactions can constitute sources of gaseous organo-halogen compounds or halogenated organic particles in the atmospheric boundary layer. To study the interaction of organic aerosols with reactive halogen species (RHS), SOA was produced from α-pinene, catechol and guaiacol using an aerosol smog-chamber. The model SOAs were characterized in detail using a variety of physico-chemical methods (Ofner et al., 2011). Those aerosols were exposed to molecular halogens in the presence of UV/VIS irradiation and to halogens, released from simulated natural halogen sources like salt pans, in order to study the complex aerosol-halogen interaction. The heterogeneous reaction of RHS with those model aerosols leads to different gaseous species like CO2, CO and small reactive/toxic molecules like phosgene (COCl2). Hydrogen containing groups on the aerosol particles are destroyed to form HCl or HBr, and a significant formation of C-Br bonds could be verified in the particle phase. Carbonyl containing functional groups of the aerosol are strongly affected by the halogenation process. While changes of functional groups and gaseous species were visible using FTIR spectroscopy, optical properties were studied using Diffuse Reflectance UV/VIS spectroscopy. Overall, the optical properties of the processed organic aerosols are significantly changed. While chlorine causes a "bleaching" of the aerosol particles, bromine shifts the maximum of UV/VIS absorption to the red end of the UV/VIS spectrum. Further physico-chemical changes were recognized according to the aerosol size-distributions or the

  5. Chemical Abundances and Properties of the Ionized Gas in NGC 1705

    NASA Astrophysics Data System (ADS)

    Annibali, F.; Tosi, M.; Pasquali, A.; Aloisi, A.; Mignoli, M.; Romano, D.

    2015-11-01

    We obtained [O iii] narrow-band imaging and multi-slit MXU spectroscopy of the blue compact dwarf (BCD) galaxy NGC 1705 with FORS2@VLT to derive chemical abundances of planetary nebulae and H ii regions and, more in general, to characterize the properties of the ionized gas. The auroral [O iii]λ 4363 line was detected in all but 1 of the 11 analyzed regions, allowing for a direct estimate of their electron temperature. The only object for which the [O iii]λ 4363 line was not detected is a possible low-ionization PN, the only one detected in our data. For all the other regions, we derived the abundances of nitrogen, oxygen, neon, sulfur, and argon out to ˜1 kpc from the galaxy center. We detect for the first time in NGC 1705 a negative radial gradient in the oxygen metallicity of -0.24+/- 0.08 dex kpc-1. The element abundances are all consistent with values reported in the literature for other samples of dwarf irregular and BCD galaxies. However, the average (central) oxygen abundance, 12+{log}({{O}}/{{H}})=7.96+/- 0.04, is ˜0.26 dex lower than previous literature estimates for NGC 1705 based on the [O iii]λ 4363 line. From classical emission line diagnostic diagrams, we exclude a major contribution from shock excitation. On the other hand, the radial behavior of the emission line ratios is consistent with the progressive dilution of radiation with increasing distance from the center of NGC 1705. This suggests that the strongest starburst located within the central ˜150 pc is responsible for the ionization of the gas out to at least ˜1 kpc. The gradual dilution of the radiation with increasing distance from the center reflects the gradual and continuous transition from the highly ionized H ii regions in the proximity of the major starburst into the diffuse ionized gas.

  6. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

    PubMed

    Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ.

  7. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

    PubMed

    Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ. PMID:27126470

  8. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

    NASA Astrophysics Data System (ADS)

    Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

  9. Gas Chromatography/Atmospheric Pressure Chemical Ionization Tandem Mass Spectrometry for Fingerprinting the Macondo Oil Spill.

    PubMed

    Lobodin, Vladislav V; Maksimova, Ekaterina V; Rodgers, Ryan P

    2016-07-01

    We report the first application of a new mass spectrometry technique (gas chromatography combined to atmospheric pressure chemical ionization tandem mass spectrometry, GC/APCI-MS/MS) for fingerprinting a crude oil and environmental samples from the largest accidental marine oil spill in history (the Macondo oil spill, the Gulf of Mexico, 2010). The fingerprinting of the oil spill is based on a trace analysis of petroleum biomarkers (steranes, diasteranes, and pentacyclic triterpanes) naturally occurring in crude oil. GC/APCI enables soft ionization of petroleum compounds that form abundant molecular ions without (or little) fragmentation. The ability to operate the instrument simultaneously in several tandem mass spectrometry (MS/MS) modes (e.g., full scan, product ion scan, reaction monitoring) significantly improves structural information content and sensitivity of analysis. For fingerprinting the oil spill, we constructed diagrams and conducted correlation studies that measure the similarity between environmental samples and enable us to differentiate the Macondo oil spill from other sources.

  10. Interpreting C-13 NMR spectra of technical lignins based on ionization chemical shifts

    SciTech Connect

    Akim, L.G.; Fedulina, T.G.; Shevchenko, S.M.

    1996-10-01

    Newly developed technique of C-13 NMR spectroscopy of ionized lignins in aqueous alkali has been applied to analysis of the chemical structure of technical lignins. Ionization of phenolic and carboxylic hydroxyl groups has a strong effect on the electronic structure of lignin and leads to significant changes in C-13 NMR spectra of the polymer. Comparative analysis of the spectra of organosolv and alkali lignins in neutral organic and aqueous alkaline media based on the data obtained for lignin model compounds demonstrated the usefulness and scope of applicability of the method. This method was especially useful when applied to a highly degraded alkaline lignin, enhancing our ability to analyze the poorly resolved spectrum. A technique is developed that permits the user to analyze a lignin spectrum in an aqueous alkaline solution without the accompanying spectrum in an organic solution. The research described was made possible by Grant No. NWFOOO from the International Science Foundation.

  11. Chemical Characterization of the Aerosol During the CLAMS Experiment Using Aircraft and Ground Stations

    NASA Astrophysics Data System (ADS)

    Castanho, A. D.; Martins, J.; Artaxo, P.; Hobbs, P. V.; Remer, L.; Yamasoe, M.; Fattori, A.

    2002-05-01

    During the Chesapeake Lighthouse and Aircraft Measurements for Satellites (CLAMS) Experiment Nuclepore filters were collected in two ground stations and aboard the University of Wasghington's Convair 580 Reserarch Aircraft. The two ground stations were chosen in strategic positions to characterize the chemical composition, the mass concentration, black carbon (BC) content, and the absorption properties of the aerosol particles at the surface level. One of the stations was located at the Cheasapeake lighthouse (25 km from the coast) and the other one was located at the Wallops Island. Aerosol particles where collected in two stages, fine (d<2.5um) and coarse mode (2.5aerosol in the atmospheric column in the CLAMS Experiment area. Some of the filters were also submitted to Scanning Electron Microscopy analysis. The particulate matter mass for all the samples were obtained gravimetrically. The concentration of black carbon in the fine filters was optically determined by a broadband reflectance technique. The spectral (from UV to near IR) reflectance in the fine and coarse mode filter were also obtained with a FieldSpec ASD spectrometer. Aerosol elemental characterization (Na through Pb) was obtained by the PIXE (Particle induced X ray emission) analyses of the nuclepore filters. The sources of the aerosol measured at the ground stations were estimated by principal component analyses mainly in the Wallops Island, where a longer time series was collected. One of the main urban components identified in the aerosol during the experiment was sulfate. Black carbon

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

    NASA Astrophysics Data System (ADS)

    Brophy, Patrick; Farmer, Delphine K.

    2016-08-01

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

  13. Improving aerosol interaction with clouds and precipitation in a regional chemical weather modeling system

    NASA Astrophysics Data System (ADS)

    Zhou, C.; Zhang, X.; Gong, S.

    2015-12-01

    A comprehensive aerosol-cloud-precipitation interaction (ACI) scheme has been developed under CMA chemical weather modeling system GRAPES/CUACE. Calculated by a sectional aerosol activation scheme based on the information of size and mass from CUACE and the thermal-dynamic and humid states from the weather model GRAPES at each time step, the cloud condensation nuclei (CCN) is fed online interactively into a two-moment cloud scheme (WDM6) and a convective parameterization to drive the cloud physics and precipitation formation processes. The modeling system has been applied to study the ACI for January 2013 when several persistent haze-fog events and eight precipitation events occurred. The results show that interactive aerosols with the WDM6 in GRAPES/CUACE obviously increase the total cloud water, liquid water content and cloud droplet number concentrations while decrease the mean diameter of cloud droplets with varying magnitudes of the changes in each case and region. These interactive micro-physical properties of clouds improve the calculation of their collection growth rates in some regions and hence the precipitation rate and distributions in the model, showing 24% to 48% enhancements of TS scoring for 6-h precipitation in almost all regions. The interactive aerosols with the WDM6 also reduce the regional mean bias of temperature by 3 °C during certain precipitation events, but the monthly means bias is only reduced by about 0.3°C.

  14. Growth of ultra long multiwall carbon nanotube arrays by aerosol-assisted chemical vapor deposition.

    PubMed

    Byeon, Heejun; Kim, Sang Yong; Koh, Ken Ha; Lee, Soonil

    2010-09-01

    Using a home-made aerosol nebulizer, we developed a new aerosol-assisted chemical vapor deposition (AACVD) process that made it possible to synthesize vertically-aligned carbon nanotube (VACNT) arrays with heights over a few millimeters routinely. An essential part of this technique was in-situ formation of metal catalyst nanoparticles via pyrolysis of ferrocene-ethanol aerosol right before CNT synthesis. Through the optimization of aerosol supply and CVD process parameters, we were able to synthesize clean VACNT arrays as long as 4.38 mm with very low metal contents in 20 min. Furthermore, it is worthy noting that such an outstanding height is achieved very quickly without supporting materials and water-assistance. By taking advantage of almost complete inhibition of CNT growth on low melting-temperature metals, we were able to fabricate patterned VACNT arrays by combining AACVD process with a conventional photolithograpic patterning of gold lines. Characterizations of as-grown nanotubes such as morphology, purity, and metal contents are presented. PMID:21133158

  15. Investigating the Chemical Pathways to PAH- and PANH-Based Aerosols in Titan's Atmospheric chemistry

    NASA Technical Reports Server (NTRS)

    Sciamma-O'Brien, Ella Marion; Contreras, Cesar; Ricketts, Claire Louise; Salama, Farid

    2011-01-01

    A complex organic chemistry between Titan's two main constituents, N2 and CH4, leads to the production of more complex molecules and subsequently to solid organic aerosols. These aerosols are at the origin of the haze layers giving Titan its characteristic orange color. In situ measurements by the Ion Neutral Mass Spectrometer (INMS) and Cassini Plasma Spectrometer (CAPS) instruments onboard Cassini have revealed the presence of large amounts of neutral, positively and negatively charged heavy molecules in the ionosphere of Titan. In particular, benzene (C6H6) and toluene (C6H5CH3), which are critical precursors of polycyclic aromatic hydrocarbon (PAH) compounds, have been detected, suggesting that PAHs might play a role in the production of Titan s aerosols. Moreover, results from numerical models as well as laboratory simulations of Titan s atmospheric chemistry are also suggesting chemical pathways that link the simple precursor molecules resulting from the first steps of the N2-CH4 chemistry (C2H2, C2H4, HCN ...) to benzene, and to PAHs and nitrogen-containing PAHs (or PANHs) as precursors to the production of solid aerosols.

  16. Technical note: Detection of dimethylamine in the low pptv range using nitrate Chemical Ionization-Atmospheric Pressure interface-Time Of Flight (CI-APi-TOF) mass spectrometry

    NASA Astrophysics Data System (ADS)

    Simon, M.; Heinritzi, M.; Herzog, S.; Leiminger, M.; Bianchi, F.; Praplan, A.; Dommen, J.; Curtius, J.; Kürten, A.

    2015-12-01

    Amines are potentially important for atmospheric new particle formation and therefore the demand for highly sensitive gas phase amine measurements has emerged in the last several years. Nitrate Chemical Ionization Mass Spectrometry (CIMS) is routinely used for the measurement of gas phase-sulfuric acid in the sub-pptv range. Furthermore, Extremely Low Volatile Organic Compounds (ELVOCs) can be detected with a nitrate CIMS. In this study we demonstrate that a nitrate CIMS can also be used for the sensitive measurement of dimethylamine ((CH3)2NH, DMA) using the NO3-(HNO3)1-2(DMA) cluster ion signals. This observation was made at the CLOUD aerosol chamber, which was also used for calibration measurements. Good linearity between 0 and ~120 pptv of DMA as well as a sub-pptv detection limit of 0.7 pptv for a 10 min integration time are demonstrated at 278 K and 38 % RH.

  17. Long-term Chemical Characterization of Submicron Aerosol Particles in the Amazon Forest - ATTO Station

    NASA Astrophysics Data System (ADS)

    Carbone, S.; Brito, J.; Rizzo, L. V.; Holanda, B. A.; Cirino, G. G.; Saturno, J.; Krüger, M. L.; Pöhlker, C.; Ng, N. L.; Xu, L.; Andreae, M. O.; Artaxo, P.

    2015-12-01

    The study of the chemical composition of aerosol particles in the Amazon forest represents a step forward to understand the strong coupling between the atmosphere and the forest. For this reason submicron aerosol particles were investigated in the Amazon forest, where biogenic and anthropogenic aerosol particles coexist at the different seasons (wet/dry). The measurements were performed at the ATTO station, which is located about 150 km northeast of Manaus. At ATTO station the Aerosol chemical speciation monitor (ACSM, Aerodyne) and the Multiangle absorption photometer (MAAP, Thermo 5012) have been operated continuously from March 2014 to July 2015. In this study, long-term measurements (near-real-time, ~30 minutes) of PM1 chemical composition were investigated for the first time in this environment.The wet season presented lower concentrations than the dry season (~5 times). In terms of chemical composition, both seasons were dominated by organics (75 and 63%) followed by sulfate (11 and 13%). Nitrate presented different ratio values between the mass-to-charges 30 to 46 (main nitrate fragments) suggesting the presence of nitrate as inorganic and organic nitrate during both seasons. The results indicated that about 75% of the nitrate signal was from organic nitrate during the dry season. In addition, several episodes with elevated amount of chloride, likely in the form of sea-salt from the Atlantic Ocean, were observed during the wet season. During those episodes, chloride comprised up to 7% of the PM1. During the dry season, chloride was also observed; however, with different volatility, which suggested that Chloride was present in different form and source. Moreover, the constant presence of sulfate and BC during the wet season might be related to biomass burning emissions from Africa. BC concentration was 2.5 times higher during the dry season. Further characterization of the organic fraction was accomplished with the positive matrix factorization (PMF), which

  18. Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Eiceman, G. A.; Bergloff, J. F.; Rodriguez, J. E.; Munro, W.; Karpas, Z.

    1999-01-01

    Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

  19. LC-MS analysis of estradiol in human serum and endometrial tissue: Comparison of electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization.

    PubMed

    Keski-Rahkonen, Pekka; Huhtinen, Kaisa; Desai, Reena; Harwood, D Tim; Handelsman, David J; Poutanen, Matti; Auriola, Seppo

    2013-09-01

    Accurate measurement of estradiol (E2) is important in clinical diagnostics and research. High sensitivity methods are critical for specimens with E2 concentrations at low picomolar levels, such as serum of men, postmenopausal women and children. Achieving the required assay performance with LC-MS is challenging due to the non-polar structure and low proton affinity of E2. Previous studies suggest that ionization has a major role for the performance of E2 measurement, but comparisons of different ionization techniques for the analysis of clinical samples are not available. In this study, female serum and endometrium tissue samples were used to compare electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) in both polarities. APPI was found to have the most potential for E2 analysis, with a quantification limit of 1 fmol on-column. APCI and ESI could be employed in negative polarity, although being slightly less sensitive than APPI. In the presence of biological background, ESI was found to be highly susceptible to ion suppression, while APCI and APPI were largely unaffected by the sample matrix. Irrespective of the ionization technique, background interferences were observed when using the multiple reaction monitoring transitions commonly employed for E2 (m/z 271 > 159; m/z 255 > 145). These unidentified interferences were most severe in serum samples, varied in intensity between ionization techniques and required efficient chromatographic separation in order to achieve specificity for E2.

  20. Long-term measurement of aerosol chemical composition in Athens, Greece.

    NASA Astrophysics Data System (ADS)

    Paraskevopoulou, Despina; Liakakou, Eleni; Theodosi, Christina; Gerasopoulos, Evangelos; Mihalopoulos, Nikolaos

    2014-05-01

    The collection of our samples was conducted for a period of five years (2008 - 2013) in Athens, Greece. The site is situated at the premises of the National Observatory of Athens on Penteli Hill, northeast Athens suburbs, and is considered an urban background station. The aim of our study was a first long-term estimation of the chemical mass closure of aerosol. For the purposes of the study, we applied three filter samplers during the sampling period: two Partisol FRM Model 2000 air samplers (one of them collecting PM10 and the other PM2.5 fractions of aerosol) and one Dichotomous Partisol auto-sampler (with PM2.5 and PM2.5-10 inlet). Aerosols were collected on Whatman QM-A quartz fiber filters and the mass of the collected samples was estimated by weighing the pre-combusted filters before and after sampling, under controlled conditions, using a microbalance. All quartz filters were analysed for organic (OC) and elemental carbon (EC) by a thermal - optical transmission technique. The concentration of water soluble organic carbon (WSOC) was defined for each filter using a total organic carbon analyzer, while the content in main water soluble ions (Cl-, Br-, NO-3, SO4-2, PO4-3, C2O4-2, NH4+, K+, Na+, Mg+2, Ca+2) was determined by ion chromatography. Additionally the filters were analyzed for trace metals by inductively coupled plasma optical emission spectrometry (ICP-OES). Aerosol chemical mass closure calculations were conducted for the PM2.5 fraction. The area of Athens is characterized by aged aerosol that can originate from the marine boundary layer, the European mainland and occasionally from North African desert areas. The contribution of dust and particulate organic matter on PM levels was estimated taking into consideration the location of the sampling site, while identification and evaluation of sources was performed. Additionally, non-sea salt concentrations of the main ions were estimated to complete the chemical closure in the extended area. According to

  1. Direct Measurement of Atmospheric Ammonia from an Airborne Miniature Chemical Ionization Mass Spectrometer (miniCIMS)

    NASA Astrophysics Data System (ADS)

    Casados, K.; Schill, S.; Freeman, S.; Zoerb, M.; Bertram, T. H.; Lefer, B. L.

    2015-12-01

    Ammonia is emitted into the atmosphere from a variety of sources such as trees, ocean, diary fields, biomass burning, and fuel emissions. Previous studies have investigated the environmental impacts of atmospheric ammonia which can include chemical reactivity, nucleation of fine particulate matter 2.5 (PM 2.5 ), and implications for human health, but its chemical nature and relatively short lifetime make direct measurement of atmospheric ammonia difficult. During the 2015 NASA Student Airborne Research Program (SARP) an airborne miniature Chemical Ionization Mass Spectrometer (miniCIMS) was deployed on the NASA DC-8 flying laboratory in the Southern California region. The spatial and temporal variability of measured atmospheric ammonia concentrations will be discussed.

  2. Triacylglycerol analysis of potential margarine base stocks by high-performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry and flame ionization detection.

    PubMed

    Byrdwell, W C; Neff, W E; List, G R

    2001-01-01

    Several margarine base stock candidates have previously been prepared for the purpose of finding better, more oxidatively stable food components: high-saturate vegetable oils, randomized vegetable oils, vegetable oil-hard stock blends, and interesterified vegetable oil-hard stock blends. Here are reported the triacylglycerol compositions of these products, determined using reverse-phase high-performance liquid chromatography (HPLC) coupled with a flame ionization detector or a quadrupole mass spectrometer with an atmospheric pressure chemical ionization source. Triacylglycerol percent composition results for samples of known composition (randomized and interesterified samples) exhibited less average error by HPLC coupled with a quadrupole mass spectrometer with an atmospheric pressure chemical ionization source, after application of response factors, than the results by HPLC coupled with a flame ionization detector. The fatty acid compositions calculated from the mass spectrometric data exhibited less average error than the fatty acid compositions resulting from the flame ionization detector data. The average error of the fatty acid compositions by the mass spectrometer was lowest for interesterified blend samples, next lowest for randomized samples, then followed by high-saturated fatty acid oils, normal oils, and blends. Analysis of the vegetable oil-hard stock blends by mass spectrometer required special treatment for calculation of response factors.

  3. Multisensor analyzer detector (MSAD) for low cost chemical and aerosol detection and pattern fusion

    NASA Astrophysics Data System (ADS)

    Swanson, David C.; Merdes, Daniel W.; Lysak, Daniel B., Jr.; Curtis, Richard C.; Lang, Derek C.; Mazzara, Andrew F.; Nicholas, Nicholas C.

    2002-08-01

    MSAD is being developed as a low-cost point detection chemical and biological sensor system designed around an information fusion inference engine that also allows additional sensors to be included in the detection process. The MSAD concept is based on probable cause detection of hazardous chemical vapors and aerosols of either chemical or biological composition using a small portable unit containing an embedded computer system and several integrated sensors with complementary capabilities. The configuration currently envisioned includes a Surface-Enhanced Raman Spectroscopy (SERS) sensor of chemical vapors and a detector of respirable aerosols based on Fraunhofer diffraction. Additional sensors employing Ion Mobility Spectrometry (IMS), Surface Acoustic Wave (SAW) detection, Flame Photometric Detection (FPD), and other principles are candidates for integration into the device; also, available commercial detectors implementing IMS, SAW, and FPD will be made accessible to the unit through RS232 ports. Both feature and decision level information fusion is supported using a Continuous Inference Network (CINET) of fuzzy logic. Each class of agents has a unique CINET with information inputs from a number of available sensors. Missing or low confidence sensor information is gracefully blended out of the output confidence for the particular agent. This approach constitutes a plug and play arrangement between the sensors and the information pattern recognition algorithms. We are currently doing simulant testing and developing out CINETs for actual agent testing at Edgewood Chemical and Biological Center (ECBC) later this year.

  4. Application of high-resolution time-of-flight chemical ionization mass spectrometry measurements to estimate volatility distributions of α-pinene and naphthalene oxidation products

    DOE PAGES

    Chhabra, P. S.; Lambe, A. T.; Canagaratna, M. R.; Stark, H.; Jayne, J. T.; Onasch, T. B.; Davidovits, P.; Kimmel, J. R.; Worsnop, D. R.

    2015-01-05

    Recent developments in high-resolution time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made it possible to directly detect atmospheric organic compounds in real time with high sensitivity and with little or no fragmentation, including low-volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, using ions identified by high-resolution spectra from an HR-ToF-CIMS with acetate reagent ion chemistry, we develop an algorithm to estimate the vapor pressures of measured organic acids. The algorithm uses identified ion formulas and calculated double bond equivalencies, information unavailable in quadrupole CIMS technology, as constraints for the number of possible oxygen-containing functionalmore » groups. The algorithm is tested with acetate chemical ionization mass spectrometry (acetate-CIMS) spectra of O3 and OH oxidation products of α-pinene and naphthalene formed in a flow reactor with integrated OH exposures ranged from 1.2 × 1011 to 9.7 × 1011 molec s cm−3, corresponding to approximately 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. The predicted condensed-phase secondary organic aerosol (SOA) average acid yields and O/C and H/C ratios agree within uncertainties with previous chamber and flow reactor measurements and ambient CIMS results. While acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.« less

  5. Laboratory and Ambient Measurements of Oxidized Organic Compounds in the Gas Phase Using Nitrate Ion Chemical Ionization Coupled with High Resolution Time-of-Flight Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Massoli, P.; Stark, H.; Canagaratna, M. R.; Krechmer, J.; Lambe, A. T.; Isaacman-VanWertz, G. A.; Nowak, J. B.; Kimmel, J.; Kroll, J. H.; Jayne, J. T.; Worsnop, D. R.

    2015-12-01

    Chemical Ionization Mass Spectrometry (CIMS) is a widely used technique for molecular level characterization of inorganic and organic gas phase species. Here we present laboratory and ambient measurements of gaseous organic compounds by means of a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometry (HR-ToF-CIMS) using nitrate ion (NO3-) chemistry, which recently has proven capable of selectively detecting oxidized organic molecules in the gas-phase via clustering with NO3- and its high order clusters. Such low and extremely low volatility organic compounds (LVOC, ELVOC) have an important role in particulate phase chemistry and formation of secondary organic aerosol (SOA). The HR-ToF-CIMS was deployed during the Southern Oxidant and Aerosol Study (SOAS) at the forest site in Centreville, AL (June 1 - July 15, 2013), where emissions were dominated by biogenic volatile organic compounds (BVOC), occasionally mixing with anthropogenic emissions. During SOAS, the HR-ToF-CIMS detected oxidation products of both isoprene (typically C5 LVOC) and terpenes (typically C10 ELVOC). The isoprene-related LVOC showed a diurnal cycle with a day time peak, while two groups of terpene ELVOC were identified, one peaking at night and one peaking during the day. Positive Matrix Factorization (PMF) analyses are applied to the dataset to further interpret these observations. The effect of anthropogenic pollution on the biogenic-dominated environment was also investigated during periods of elevated nitrous and sulfur dioxide levels. To further aid in interpretation of the SOAS dataset, oxidized organic molecules were produced via OH and O3 initiated oxidation of biogenic gas-phase precursors in targeted laboratory studies and detected using the HR-ToF-CIMS. Spectra were obtained in these studies over a range of simulated atmospheric conditions.

  6. Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts

    DOE PAGES

    Lopez-Hilfiker, Felipe D.; Iyer, Siddarth; Mohr, Claudia; Lee, Ben H.; D'Ambro, Emma L.; Kurtén, Theo; Thornton, Joel A.

    2016-04-06

    The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion–molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N2O5, known to react with iodide at the collision limit, to constrain the combined effects of ion–molecule reaction time, which is strongly influenced by mixing and ion losses in the ion–molecule reaction drift tube. A mass spectrometric voltage scanning procedure elucidatesmore » the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. We describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.« less

  7. Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts

    NASA Astrophysics Data System (ADS)

    Lopez-Hilfiker, Felipe D.; Iyer, Siddarth; Mohr, Claudia; Lee, Ben H.; D'Ambro, Emma L.; Kurtén, Theo; Thornton, Joel A.

    2016-04-01

    The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion-molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N2O5, known to react with iodide at the collision limit, to constrain the combined effects of ion-molecule reaction time, which is strongly influenced by mixing and ion losses in the ion-molecule reaction drift tube. A mass spectrometric voltage scanning procedure elucidates the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. We describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.

  8. Real-time monitoring of volatile organic compounds using chemical ionization mass spectroscopy: Final report

    SciTech Connect

    Thornberg, S.M.; Mowry, C.D.; Keenan, M.R.; Bender, S.F.A.; Owen, T.

    1997-04-01

    Volatile organic compound (VOC) emission to the atmosphere is of great concern to semiconductor manufacturing industries, research laboratories, the public, and regulatory agencies. Some industries are seeking ways to reduce emissions by reducing VOCs at the point of use (or generation). This paper discusses the requirements, design, calibration, and use of a sampling inlet/quadrupole mass spectrometer system for monitoring VOCs in a semiconductor manufacturing production line. The system uses chemical ionization to monitor compounds typically found in the lithography processes used to manufacture semiconductor devices (e.g., acetone, photoresist). The system was designed to be transportable from tool to tool in the production line and to give the operator real-time feedback so the process(es) can be adjusted to minimize VOC emissions. Detection limits ranging from the high ppb range for acetone to the low ppm range fore other lithography chemicals were achieved using chemical ionization mass spectroscopy at a data acquisition rate of approximately 1 mass spectral scan (30 to 200 daltons) per second. A demonstration of exhaust VOC monitoring was performed at a working semiconductor fabrication facility during actual wafer processing.

  9. Portable Aerosol Contaminant Extractor

    DOEpatents

    Carlson, Duane C.; DeGange, John J.; Cable-Dunlap, Paula

    2005-11-15

    A compact, portable, aerosol contaminant extractor having ionization and collection sections through which ambient air may be drawn at a nominal rate so that aerosol particles ionized in the ionization section may be collected on charged plate in the collection section, the charged plate being readily removed for analyses of the particles collected thereon.

  10. Chemical insights, explicit chemistry and yields of secondary organic aerosol from methylglyoxal and glyoxal

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Tan, Y.; Turpin, B. J.

    2013-02-01

    Atmospherically abundant, volatile water soluble organic compounds formed through gas phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3) and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud relevant concentrations (∼ 10-6-∼ 10-3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ∼ 120% for glyoxal and ∼ 80% for methylglyoxal. Oligomerization of unreacted aldehydes during droplet evaporation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (∼ 10 M), the major products are oligomers formed via organic radical-radical reactions, and simulated SOA yields (by mass) are ∼ 90% for both glyoxal and methylglyoxal.

  11. Chemical and physical properties of bulk aerosols within four sectors observed during TRACE-P

    NASA Astrophysics Data System (ADS)

    Jordan, C. E.; Anderson, B. E.; Talbot, R. W.; Dibb, J. E.; Fuelberg, H. E.; Hudgins, C. H.; Kiley, C. M.; Russo, R.; Scheuer, E.; Seid, G.; Thornhill, K. L.; Winstead, E.

    2003-11-01

    Chemical and physical aerosol data collected on the DC-8 during TRACE-P were grouped into four sectors based on back trajectories. The four sectors represent long-range transport from the west (WSW), regional circulation over the western Pacific and Southeast Asia (SE Asia), polluted transport from northern Asia with substantial sea salt at low altitudes (NNW) and a substantial amount of dust (Channel). WSW has generally low mixing ratios at both middle and high altitudes, with the bulk of the aerosol mass due to non-sea-salt water-soluble inorganic species. Low altitude SE Asia also has low mean mixing ratios in general, with the majority of the aerosol mass comprised of non-sea-salts, however, soot is also relatively important in this region. NNW had the highest mean sea salt mixing ratios, with the aerosol mass at low altitudes (<2 km) evenly divided between sea salts, non-sea-salts, and dust. The highest mean mixing ratios of water-soluble ions and soot were observed at the lowest altitudes (<2 km) in the Channel sector. The bulk of the aerosol mass exported from Asia emanates from Channel at both low and midaltitudes, due to the prevalence of dust compared to other sectors. Number densities show enhanced fine particles for Channel and NNW, while their volume distributions are enhanced due to sea salt and dust. Low-altitude Channel exhibits the highest condensation nuclei (CN) number densities along with enhanced scattering coefficients, compared to the other sectors. At midaltitudes (2-7 km), low mean CN number densities coupled with a high proportion of nonvolatile particles (≥65%) observed in polluted sectors (Channel and NNW) are attributed to wet scavenging which removes hygroscopic CN particles. Low single scatter albedo in SE Asia reflects enhanced soot.

  12. Investigation of the detailed chemical composition of organic aerosol in a South East Asian Rainforest

    NASA Astrophysics Data System (ADS)

    Hamilton, Jacqueline; Ward, Martyn; Rami Alfarra, M.; Lewis, Alastair; McFiggans, Gordon; Robinson, Niall

    2010-05-01

    The formation of secondary organic aerosol (SOA) in tropical regions is a key uncertainty in quantifying the effect of man made emissions on the climate. Large quantities of volatile organic compounds are emitted from natural biogenic sources in the tropics, including isoprene, monoterpenes and sequiterpenes. There are very few studies of the detailed chemical composition of organic aerosols in tropical rainforest regions, but these would provide information on the importance of primary versus secondary organic aerosols, the key VOC precursors, oxidation state and volatility. Particle samples were collected in a tropical rainforest at Danum Valley in Borneo as part of the OP3 field campaign in 2008. Twenty four hour filter samples were collected at the Global Atmospheric Watch station at a height of around 10 m and shipped back to the laboratory (below -4 °C) for offline analysis. The OA composition was studied using multiple high resolution chromatographic techniques including comprehensive two dimensional gas chromatography coupled to time of flight mass spectrometry (GCXGC-TOFMS) and liquid chromatography coupled to ion trap mass spectrometry (LC-MSn). The composition was directly compared to chamber generated SOA (as part of the Aerosol Coupling in the Earths System , ACES, experiment) to determine SOA tracers. A biogenic SOA tracer MS fragmentation library was constructed and a number of SOA components from limonene, linalool and -pinene were identified in the rainforest OA. Very high resolution mass spectrometry (Fourier Transform Ion Cyclotron Resonance FTICR-MS) allowed the O:C and H:C ratios to be determined and these will be compared to those obtained by aerosol mass spectrometry (AMS). In addition, the OA composition from the rainforest will be compared to other locations.

  13. Chemical characteristics of ambient aerosols contributed by cooking process at Noorpur village near New Delhi

    NASA Astrophysics Data System (ADS)

    Singh, Sudha

    Generally, industrial and transport sectors are considered as major contributors of air pollution but recently, biomass burning is also reported as a major source of atmospheric aerosols (1, 2) especially in the developing world where solid fuels such as dung cake, wood and crop residues are used in traditional cooking which are responsible for poor air quality, respiratory problems and radiative forcing etc .In India, most of the research has been focused on emission estimates from biomass burning and cooking. No effort has been made to understand the chemistry and sources of fine aerosols in rural areas during cooking hours. This study fills this knowledge gap and strengthens our understanding about abundance of various chemical constituents of atmospheric aerosols emitted during cooking hours.Aerosol samples were collected from village called Noorpur (28.470 N, 77.030 E) which lies near Delhi city. Sampling was carried out during August 2011-May 2012 by using handy sampler (Envirotech model APM 821) installed at the terrace of a building (~6m). The aerosol samples were collected on 8 hourly basis at a flow rate of 1 LPM. Water extracts of these filters were analyzed for major anions (F-, Cl-, NO3-, SO42-) and major cations (Na+, NH4+, K+, Ca2+ Mg2+) by ion chromatography (Metrohm 883 Basic IC Plus). During cooking period, the concentration of the major ions followed the order of Ca2+> SO42-> NO3-> Cl-> K+> NH4+> Mg2+> Na2+> F-. Among anion SO42 (5 µg/m3) showed highest value and in case of cations Ca2+ (7.32µg/m3) has highest value.

  14. Relating aerosol absorption due to soot, organic carbon, and dust to emission sources determined from in-situ chemical measurements

    NASA Astrophysics Data System (ADS)

    Cazorla, A.; Bahadur, R.; Suski, K. J.; Cahill, J. F.; Chand, D.; Schmid, B.; Ramanathan, V.; Prather, K. A.

    2013-09-01

    Estimating the aerosol contribution to the global or regional radiative forcing can take advantage of the relationship between the spectral aerosol optical properties and the size and chemical composition of aerosol. Long term global optical measurements from observational networks or satellites can be used in such studies. Using in-situ chemical mixing state measurements can help us to constrain the limitations of such estimates. In this study, the Absorption Ångström Exponent (AAE) and the Scattering Ångström Exponent (SAE) derived from 10 operational AERONET sites in California are combined for deducing chemical speciation based on wavelength dependence of the optical properties. In addition, in-situ optical properties and single particle chemical composition measured during three aircraft field campaigns in California between 2010 and 2011 are combined in order to validate the methodology used for the estimates of aerosol chemistry using spectral optical properties. Results from this study indicate a dominance of mixed types in the classification leading to an underestimation of the primary sources, however secondary sources are better classified. The distinction between carbonaceous aerosols from fossil fuel and biomass burning origins is not clear, since their optical properties are similar. On the other hand, knowledge of the aerosol sources in California from chemical studies help to identify other misclassification such as the dust contribution.

  15. Differential analysis of camphor wood products by desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zhu, Liang; Yan, Jianping; Zhu, Zhiqiang; Ouyang, Yongzhong; Zhang, Xinglei; Zhang, Wenjun; Dai, Ximo; Luo, Liping; Chen, Huanwen

    2013-01-23

    In the course of this study, desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS) was applied to readily acquire the mass spectral fingerprints of camphor wood and other wood samples under ambient conditions. Characteristic natural analytes, such as camphor and geraniol, were successfully detected in their protonated form and then identified by tandem mass spectrometry (MS(n)). Further principal component analysis (PCA) and cluster analysis (CA) of the mass spectrometric results allow a confident discrimination of camphor wood products from inferior/fake ones. These experimental findings demonstrate that DAPCI-MS is a valuable tool for differential analysis of untreated camphor wood products with sufficient sensitivity and high throughput.

  16. Chemical Analysis of Complex Organic Mixtures Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Laskin, Julia; Eckert, Peter A.; Roach, Patrick J.; Heath, Brandi S.; Nizkorodov, Sergey A.; Laskin, Alexander

    2012-08-21

    Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies showed that LSOA constituents are multifunctional compounds containing aldehyde and ketone groups. In this study, we used the selectivity of the Girard T (GT) reagent towards carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures. In these experiments, 1-100 {micro}M GT solution was used as a working solvent for reactive nano-DESI analysis. Abundant products of a single addition of GT to LSOA constituents were observed at GT concentrations in excess of 10 {micro}M. We found that LSOA compounds with 18-20 carbon atoms (dimers) and 27-30 carbon atoms (trimers) react with GT through a simple addition reaction resulting in formation of the carbinolamine derivative. In contrast, reactions of GT with monomeric species result in formation of both the carbinolamine and the hydrazone derivatives. In addition, several monomers did not react with GT on the timescale of our experiment. These molecules were characterized by relatively high values of the double bond equivalent (DBE) and low oxygen content. Furthermore, because addition of a charged GT tag to a neutral molecule eliminates the discrimination against the low proton affinity compounds in the ionization process, reactive nano-DESI analysis enables quantification of individual compounds in the complex mixture. For example, we were able to estimate for the first time the amounts of dimers and trimers in the LSOA mixture. Specifically, we found that the most abundant LSOA dimer was detected at ca. 0.5 pg level and the total amount of dimers and trimers in the analyzed sample was just around 11 pg. Our results indicate that reactive nano-DESI is a valuable approach for examining the presence of specific functional groups and

  17. Chemical analysis of complex organic mixtures using reactive nanospray desorption electrospray ionization mass spectrometry.

    PubMed

    Laskin, Julia; Eckert, Peter A; Roach, Patrick J; Heath, Brandi S; Nizkorodov, Sergey A; Laskin, Alexander

    2012-08-21

    Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies have shown that LSOA constituents are multifunctional compounds containing at least one aldehyde or ketone groups. In this study, we used the selectivity of the Girard's reagent T (GT) toward carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures. In these experiments, 1-100 μM GT solutions were used as the working solvents for reactive nano-DESI analysis. Abundant products from the single addition of GT to LSOA constituents were observed at GT concentrations in excess of 10 μM. We found that LSOA dimeric and trimeric compounds react with GT through a simple addition reaction resulting in formation of the carbinolamine derivative. In contrast, reactions of GT with monomeric species result in the formation of both the carbinolamine and the hydrazone derivatives. In addition, several monomers did not react with GT on the time scale of our experiment. These molecules were characterized by relatively high values of the double bond equivalent and low oxygen content. Furthermore, because addition of a charged GT tag to a neutral molecule eliminates the discrimination against the low proton affinity compounds in the ionization process, reactive nano-DESI analysis enables quantification of individual compounds in the complex mixture. For example, we were able to estimate for the first time the amounts of dimers and trimers in the LSOA mixture. Specifically, we found that the most abundant LSOA dimer was detected at the ~0.5 pg level and the total amount of dimers and trimers in the analyzed sample was ~11 pg. Our results indicate that reactive nano-DESI is a valuable approach for examining the presence of specific functional groups and for the quantification of compounds possessing

  18. Halogen-induced organic aerosol (XOA): a study on ultra-fine particle formation and time-resolved chemical characterization.

    PubMed

    Ofner, Johannes; Kamilli, Katharina A; Held, Andreas; Lendl, Bernhard; Zetzsch, Cornelius

    2013-01-01

    The concurrent presence of high values of organic SOA precursors and reactive halogen species (RHS) at very low ozone concentrations allows the formation of halogen-induced organic aerosol, so-called XOA, in maritime areas where high concentrations of RHS are present, especially at sunrise. The present study combines aerosol smog-chamber and aerosol flow-reactor experiments for the characterization of XOA. XOA formation yields from alpha-pinene at low and high concentrations of chlorine as reactive halogen species (RHS) were determined using a 700 L aerosol smog-chamber with a solar simulator. The chemical transformation of the organic precursor during the aerosol formation process and chemical aging was studied using an aerosol flow-reactor coupled to an FTIR spectrometer. The FTIR dataset was analysed using 2D correlation spectroscopy. Chlorine induced homogeneous XOA formation takes place at even 2.5 ppb of molecular chlorine, which was photolysed by the solar simulator. The chemical pathway of XOA formation is characterized by the addition of chlorine and abstraction of hydrogen atoms, causing simultaneous carbon-chlorine bond formation. During further steps of the formation process, carboxylic acids are formed, which cause a SOA-like appearance of XOA. During the ozone-free formation of secondary organic aerosol with RHS a special kind of particulate matter (XOA) is formed, which is afterwards transformed to SOA by atmospheric aging or degradation pathways.

  19. Gaseous and particulate composition of fresh and aged emissions of diesel, RME and CNG buses using Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Psichoudaki, Magda; Le Breton, Michael; Hallquist, Mattias; Watne, Ågot; Hallquist, Asa

    2016-04-01

    Urban air pollution is becoming a significant global problem, especially for large cities around the world. Traffic emissions contribute significantly to both elevated particle concentrations and to gaseous pollutants in cities. The latter also have the potential of forming more particulate mass via their photochemical oxidation in the atmosphere. The International Agency for Research on Cancer and the US EPA have characterised diesel exhausts as a likely human carcinogen that can also contribute to other health problems. In order to meet the challenges with increased transportation and enhanced greenhouse gas emissions, the European Union have decided on a 10% substitution of traditional fuels in the road transport sector by alternative fuels (e.g. biodiesel, CNG) before the year 2020. However, it is also important to study the influence of fuel switches on other primary pollutants as well as the potential to form secondary aerosol mass. This work focuses on the characterisation of the chemical composition of the gas and the condensed phase of fresh bus emissions during acceleration, in order to mimic the exhaust plume that humans would inhale under realistic conditions. In addition, photochemical aging of the exhaust emissions was achieved by employing a Potential Aerosol Mass (PAM) flow reactor, allowing the characterization of the composition of the corresponding aged emissions. The PAM reactor uses UV lamps and high concentrations of oxidants (OH radicals and O3) to oxidize the organic species present in the chamber. The oxidation that takes place within the reactor can be equivalent to up to one week of atmospheric oxidation. Preliminary tests showed that the oxidation employed in these measurements corresponded to a range from 4 to 8 days in the atmosphere. During June and July 2015, a total of 29 buses, 5 diesel, 13 CNG and 11 RME (rapeseed methyl ester), were tested in two different locations with limited influence from other types of emissions and traffic

  20. Aerosol Physical and Chemical Properties Before and After the Manaus Plume in the GoAmazon2014 Experiment

    NASA Astrophysics Data System (ADS)

    Artaxo, P.; Barbosa, H. M.; Ferreira De Brito, J.; Wurm, F.; Holanda, B. A.; Carbone, S.; Arana, A.; Cirino, G. G.; Souza, R. A. F. D.; Rizzo, L. V.; Martin, S. T.; Andreae, M. O.; Holben, B. N.; Schafer, J.

    2014-12-01

    As part of the GoAmazon2014 experiment, several aerosol and trace gas monitoring stations are being operated for at least one year before and after the Manaus plume. Three sites are being operated in pristine conditions, with atmospheric properties under natural biogenic conditions. These three sites called T0 are: ATTO (Amazon Tall Tower Observatory), ZF2 ecological research site and a third site called EMBRAPA. After the air masses are exposed to the Manaus plume, one site (called T2) is being operated right on the opposite side of the Negro River under the direct influence of the Manaus plume at 5 Km downwind of Manaus. Finally, at about 150 Km downwind of Manaus is the T3 Manacapuru site. Aerosol chemical composition is being analyzed using filters for fine (PM2.5) and coarse mode aerosol as well as three Aerodyne ACSM (Aerosol Chemical Speciation Monitors) instruments. Aerosol absorption is being studied with several aethalometers and MAAP (Multi Angle Absorption Photometers). Aerosol light scattering are being measured at several wavelengths using nephelometers. Aerosol size distribution is determined using scanning mobility particle sizers. The aerosol column is measures using AERONET sunphotometers before and after the Manaus plume, as well as several Lidar systems. The three sites before the Manaus plume show remarkable similar variability in aerosol concentrations and optical properties. This pattern is very different at the T2 site, with large aerosol concentrations enhancing aerosol absorption and scattering significantly. The aerosol is very oxidized before being exposed to the Manaus plume, and this pattern changes significantly for T2 and T3 sites, with a much higher presence of less oxidized aerosol. Typical ozone concentrations at mid-day before Manaus plume is a low 10-12 ppb, value that changes to 50-70 ppb for air masses suffering the influence of Manaus plume. A detailed comparison of aerosol characteristics and composition for the several

  1. Providing Size-Resolved Mixing State Inputs to Improve Aerosol Optics Models: Comparison of ACE-Asia Aerosol Chemical Measurements for Different Source Regions With Simultaneous Optical Measurements

    NASA Astrophysics Data System (ADS)

    Sullivan, R. C.; Poon, G.; Guazzotti, S.; Sodeman, D.; Holecek, J.; Spencer, M.; Prather, K.

    2005-12-01

    Measurements made of the aerodynamic size and chemical composition of single aerosol particles on board the R/V Ronald H. Brown sailing between Hawaii and the Sea of Japan during ACE-Asia in 2001 revealed a complex mixture of mineral dust, organic carbon, elemental carbon, sulfates, nitrates, chloride, ammonium, and sea salt. The air mass source regions included influences from the Pacific Ocean, Miyakejima volcano, Gobi and Taklimakan Deserts, Shanghai, Japan, and Korea. The particle composition sampled from each of these regions showed unique changes in the aerosol's mixing state. This complexity presents major challenges in accurately modeling the optical properties of the Asian aerosol. The degree of closure between the measured chemical and optical properties of this aerosol and those predicted by models has been presented by Quinn et al. [JGR, 109, D19S01, doi: 10.1029/2003JD004010, 2004]. Differences between measured and calculated aerosol absorption coefficients were partly attributed to the assumption of internally mixed homogeneous spheres for the aerosol population. Good correlations between measured and calculated aerosol mass and light scattering were found but relied on particle shapes not confirmed by measurements. To better our understanding of the relationship between aerosol chemistry and optical measurements, and provide more detailed inputs to improve the predictions of optical models, we present size-resolved single-particle mixing state results obtained by an ATOFMS for the seven air mass source regions described by Quinn et al. (2004). Our results do not support the assumption of a homogeneous internally mixed aerosol population for many of the source regions. Particular focus is given to the mixing state and chemical associations of sulfate, nitrate, chloride, ammonium, OC, EC, dust, and sea salt. We demonstrate the segregation of ammonium, sulfate, and nitrate within individual particles throughout the study and discuss the different

  2. Chemical, Physical and Optical Properties of Saharan Dust Aerosols at a Marine Site in Puerto Rico

    NASA Astrophysics Data System (ADS)

    Ortiz Montalvo, D. L.; Mayol Bracero, O. L.; Morales, F.; Sheridan, P.; Ogren, J. A.

    2005-12-01

    Atmospheric dust particles blown from the Sahara across the Atlantic into the Caribbean have an impact on its climate and public health. These particles may play a significant role in radiative forcing, affecting the extinction of solar radiation and thus having an influence on climate. About half of the dust that travels from Africa contains particles that are small enough to inhale. Human breathe them into the respiratory system and they settle in the lungs causing respiratory problems. To have a better understanding of these effects, information is needed on the properties of these aerosols. As part of this study, chemical, physical and optical characterization is being performed on aerosol samples collected at a marine site on the northeastern tip of Puerto Rico (Cabezas de San Juan, Fajardo), during periods with and without Saharan incursions. Stacked-filter units (SFU) are used to collect particles with diameters smaller than 1.7 μm, using Nuclepore, quartz and Teflon filters. These filter samples are analyzed to obtain the chemical composition of the particles. Initially we are focusing on the carbonaceous fraction (elemental and organic carbon, EC, and OC) of the aerosol using thermal/optical analysis. Online measurements of total particle number concentrations and aerosol light scattering coefficients are performed using a condensation particle counter and an integrating nephelometer, respectively. In addition, a sunphotometer, part of AERONET (http://aeronet.gsfc.nasa.gov/), is used to obtain the aerosol optical thickness (AOT). Preliminary results include only samples collected from air masses under the influence of Saharan dust, as signified by AOT satellite images from MODIS and the results from the air masses backward trajectories calculated with the NOAA HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) model. In terms of the chemical composition, EC concentrations were at low-to-undetectable levels, indicating that OC concentrations

  3. All-year-round aerosol chemical composition at Dome C, Antarctica

    NASA Astrophysics Data System (ADS)

    Udisti, Roberto; Becagli, Silvia; Frosini, Daniele; Galli, Gaia; Ghedini, Costanza; Rugi, Francesco; Severi, Mirko; Traversi, Rita

    2010-05-01

    Since 2005, continuous, all-year-round aerosol sampling was carried out at Dome C (Central East Antarctica, 3233 m a.s.l., about 1100 km far from the coastline), in the framework of "Station Concordia" project, an Italian PNRA - French IPEV joint program. Size-segregated aerosol samples were collected in summer and winter periods by using different low- and medium-volume systems, including pre-selected cut-off samplers (with PM10, PM2.5 and PM1 cut-off heads) and multi-stage (Andersen 8-stage and Dekati 4-stage) impactors. Sampling resolution and volumes ranged from 1 day to 1 month and from 2.3 to 12 m3/h, respectively. Aerosol study at Dome C is expected improving our knowledge on present-day source intensity, transport efficiency and pathways (including stratosphere-troposphere interchanges) of particles reaching internal sites of Antarctica. Besides, more detailed information on atmosphere-snow interactions, including depositional and post-depositional processes, as well as the effect of sublimation/condensation processes on snow surface, will be used for improving the reconstruction of past atmosphere composition from ice core chemical stratigraphies (EPICA Dome C ice core). Here we report major results from the chemical composition of the Antarctic background aerosol reaching Dome C, pointing out the seasonal pattern and the temporal trend of some ionic components used as tracers of sea spray, marine biogenic and crustal emissions. Oxidised sulfur compounds are assumed to affect the climate system by influencing the Earth's radiative budget, both directly (solar light scattering) and indirectly (acting as cloud condensation nuclei). Among these compounds, methanesulphonic acid (MSA) and H2SO4 (arising from the atmospheric oxidation of phytoplanktonic dimethylsulphide - DMS), are considered the best tracers of marine productivity. Their use as reliable markers of oceanic biogenic emissions is hindered by poorly known mechanisms (temperature and photochemistry

  4. Isobutane Made Practical as a Reagent Gas for Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Newsome, G. Asher; Steinkamp, F. Lucus; Giordano, Braden C.

    2016-11-01

    As a reagent gas for positive- and negative-mode chemical ionization mass spectrometry (CI-MS), isobutane ( i-C4H10) produces superior analyte signal abundance to methane. Isobutane has never been widely adopted for CI-MS because it fouls the ion source more rapidly and produces positive CI spectra that are more strongly dependent on reagent gas pressure compared with methane. Isobutane was diluted to various concentrations in argon for use as a reagent gas with an unmodified commercial gas chromatograph-mass spectrometer. Analyte spectra were directly compared using methane, isobutane, and isobutane/argon mixtures. A mixture of 10% i-C4H10 in argon produced twice the positive-mode analyte signal of methane, equal to pure isobutane, and reduced spectral dependence on reagent gas pressure. Electron capture negative chemical ionization using 1% i-C4H10 in argon tripled analyte signal compared with methane and was reproducible, unlike pure isobutane. The operative lifetime of the ion source using isobutane/argon mixtures was extended exponentially compared with pure isobutane, producing stable and reproducible CI signal throughout. By diluting the reagent gas in an inert buffer gas, isobutane CI-MS experiments were made as practical to use as methane CI-MS experiments but with superior analytical performance.

  5. Laser Microdissection and Atmospheric Pressure Chemical Ionization Mass Spectrometry Coupled for Multimodal Imaging

    SciTech Connect

    Lorenz, Matthias; Ovchinnikova, Olga S; Kertesz, Vilmos; Van Berkel, Gary J

    2013-01-01

    This paper describes the coupling of ambient laser ablation surface sampling, accomplished using a laser capture microdissection system, with atmospheric pressure chemical ionization mass spectrometry for high spatial resolution multimodal imaging. A commercial laser capture microdissection system was placed in close proximity to a modified ion source of a mass spectrometer designed to allow for sampling of laser ablated material via a transfer tube directly into the ionization region. Rhodamine 6G dye of red sharpie ink in a laser etched pattern as well as cholesterol and phosphatidylcholine in a cerebellum mouse brain thin tissue section were identified and imaged from full scan mass spectra. A minimal spot diameter of 8 m was achieved using the 10X microscope cutting objective with a lateral oversampling pixel resolution of about 3.7 m. Distinguishing between features approximately 13 m apart in a cerebellum mouse brain thin tissue section was demonstrated in a multimodal fashion including co-registered optical and mass spectral chemical images.

  6. Isobutane Made Practical as a Reagent Gas for Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Newsome, G. Asher; Steinkamp, F. Lucus; Giordano, Braden C.

    2016-08-01

    As a reagent gas for positive- and negative-mode chemical ionization mass spectrometry (CI-MS), isobutane (i-C4H10) produces superior analyte signal abundance to methane. Isobutane has never been widely adopted for CI-MS because it fouls the ion source more rapidly and produces positive CI spectra that are more strongly dependent on reagent gas pressure compared with methane. Isobutane was diluted to various concentrations in argon for use as a reagent gas with an unmodified commercial gas chromatograph-mass spectrometer. Analyte spectra were directly compared using methane, isobutane, and isobutane/argon mixtures. A mixture of 10% i-C4H10 in argon produced twice the positive-mode analyte signal of methane, equal to pure isobutane, and reduced spectral dependence on reagent gas pressure. Electron capture negative chemical ionization using 1% i-C4H10 in argon tripled analyte signal compared with methane and was reproducible, unlike pure isobutane. The operative lifetime of the ion source using isobutane/argon mixtures was extended exponentially compared with pure isobutane, producing stable and reproducible CI signal throughout. By diluting the reagent gas in an inert buffer gas, isobutane CI-MS experiments were made as practical to use as methane CI-MS experiments but with superior analytical performance.

  7. Cooperative biological effects between ionizing radiation and other physical and chemical agents.

    PubMed

    Manti, Lorenzo; D'Arco, Annalisa

    2010-01-01

    Exposure to ionizing radiation (IR), at environmentally and therapeutically relevant doses or as a result of diagnostics or accidents, causes cyto- and genotoxic damage. However, exposure to IR alone is a rare event as it occurs in spatial and temporal combination with several physico-chemical agents. Some of these are of known noxiousness, as is the case with chemical compounds at high dose, hence additive/synergistic effects can be expected or have been demonstrated. Conversely, the cellular toxicity of other agents, such as non-ionizing electromagnetic fields (EMFs), is only presumed and their short- and long-term cooperation on IR-induced damage remains undetermined. In this review, we shall examine evidence in support of the interplay between spatially and/or temporally related environmentally relevant stressors. In vitro or animal-based studies as well as epidemiological surveys have generally examined the combined action of no more than a couple of known or potentially DNA-damaging agents. Moreover, most existing research mainly focused on short-term effects of combined exposures. Hence, it is important that quantitative research addresses the issue of the possible cooperation between chronic exposure to environmental trace contaminants and exposure to EMFs, examining not only the modulation of damage acutely induced by IR but also long-term genome stability.

  8. Real time monitoring of accelerated chemical reactions by ultrasonication-assisted spray ionization mass spectrometry.

    PubMed

    Lin, Shu-Hsuan; Lo, Ta-Ju; Kuo, Fang-Yin; Chen, Yu-Chie

    2014-01-01

    Ultrasonication has been used to accelerate chemical reactions. It would be ideal if ultrasonication-assisted chemical reactions could be monitored by suitable detection tools such as mass spectrometry in real time. It would be helpful to clarify reaction intermediates/products and to have a better understanding of reaction mechanism. In this work, we developed a system for ultrasonication-assisted spray ionization mass spectrometry (UASI-MS) with an ~1.7 MHz ultrasonic transducer to monitor chemical reactions in real time. We demonstrated that simply depositing a sample solution on the MHz-based ultrasonic transducer, which was placed in front of the orifice of a mass spectrometer, the analyte signals can be readily detected by the mass spectrometer. Singly and multiply charged ions from small and large molecules, respectively, can be observed in the UASI mass spectra. Furthermore, the ultrasonic transducer used in the UASI setup accelerates the chemical reactions while being monitored via UASI-MS. The feasibility of using this approach for real-time acceleration/monitoring of chemical reactions was demonstrated. The reactions of Girard T reagent and hydroxylamine with steroids were used as the model reactions. Upon the deposition of reactant solutions on the ultrasonic transducer, the intermediate/product ions are readily generated and instantaneously monitored using MS within 1 s. Additionally, we also showed the possibility of using this reactive UASI-MS approach to assist the confirmation of trace steroids from complex urine samples by monitoring the generation of the product ions.

  9. Evaluation of the performance of four chemical transport models in predicting the aerosol chemical composition in Europe in 2005

    NASA Astrophysics Data System (ADS)

    Prank, Marje; Sofiev, Mikhail; Tsyro, Svetlana; Hendriks, Carlijn; Semeena, Valiyaveetil; Vazhappilly Francis, Xavier; Butler, Tim; Denier van der Gon, Hugo; Friedrich, Rainer; Hendricks, Johannes; Kong, Xin; Lawrence, Mark; Righi, Mattia; Samaras, Zissis; Sausen, Robert; Kukkonen, Jaakko; Sokhi, Ranjeet

    2016-05-01

    Four regional chemistry transport models were applied to simulate the concentration and composition of particulate matter (PM) in Europe for 2005 with horizontal resolution ~ 20 km. The modelled concentrations were compared with the measurements of PM chemical composition by the European Monitoring and Evaluation Programme (EMEP) monitoring network. All models systematically underestimated PM10 and PM2.5 by 10-60 %, depending on the model and the season of the year, when the calculated dry PM mass was compared with the measurements. The average water content at laboratory conditions was estimated between 5 and 20 % for PM2.5 and between 10 and 25 % for PM10. For majority of the PM chemical components, the relative underestimation was smaller than it was for total PM, exceptions being the carbonaceous particles and mineral dust. Some species, such as sea salt and NO3-, were overpredicted by the models. There were notable differences between the models' predictions of the seasonal variations of PM, mainly attributable to different treatments or omission of some source categories and aerosol processes. Benzo(a)pyrene concentrations were overestimated by all the models over the whole year. The study stresses the importance of improving the models' skill in simulating mineral dust and carbonaceous compounds, necessity for high-quality emissions from wildland fires, as well as the need for an explicit consideration of aerosol water content in model-measurement comparison.

  10. The real part of the refractive indices and effective densities for chemically segregated ambient aerosols in Guangzhou by a single particle aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Zhang, G.; Bi, X.; Qiu, N.; Han, B.; Lin, Q.; Peng, L.; Chen, D.; Wang, X.; Peng, P.; Sheng, G.; Zhou, Z.

    2015-12-01

    Microphysical properties of atmospheric aerosols are essential to better evaluate their radiative forcing. This paper first presents an estimate of the real part of the refractive indices (n) and effective densities (ρeff) of chemically segregated atmospheric aerosols in China. Vacuum aerodynamic diameter, chemical compositions, and light scattering intensities of individual particles were simultaneously measured by a single particle aerosol mass spectrometer (SPAMS) during fall of 2012 in Guangzhou. On the basis of Mie theory, n and ρeff were estimated for 17 particle types in four categories: organics (OC), elemental carbon (EC), internally mixed EC and OC (ECOC), and metal rich, respectively. Results indicate the presence of spherical or nearly spherical shape for majority of particle types, whose partial scattering cross section vs. sizes were well fitted to Mie theoretical modeling results. While sharing n in a narrow range (1.47-1.53), majority of particle types exhibited a wide range of ρeff (0.87-1.51 g cm-3). OC group is associated with the lowest ρeff (0.87-1.07 g cm-3), while metal rich group with the highest ones (1.29-1.51 g cm-3). It is noteworthy that a specific EC type exhibits a complex scattering curve vs. size due to the presence of both compact and irregularly shape particles. Overall, the results on detailed relationship between physical and chemical properties benefits future researches on the impact of aerosols on visibility and climate.

  11. Integrating biomass, sulphate and sea-salt aerosol responses into a microphysical chemical parcel model: implications for climate studies.

    PubMed

    Ghosh, S; Smith, M H; Rap, A

    2007-11-15

    Aerosols are known to influence significantly the radiative budget of the Earth. Although the direct effect (whereby aerosols scatter and absorb solar and thermal infrared radiation) has a large perturbing influence on the radiation budget, the indirect effect (whereby aerosols modify the microphysical and hence the radiative properties and amounts of clouds) poses a greater challenge to climate modellers. This is because aerosols undergo chemical and physical changes while in the atmosphere, notably within clouds, and are removed largely by precipitation. The way in which aerosols are processed by clouds depends on the type, abundance and the mixing state of the aerosols concerned. A parametrization with sulphate and sea-salt aerosol has been successfully integrated within the Hadley Centre general circulation model (GCM). The results of this combined parametrization indicate a significantly reduced role, compared with previous estimates, for sulphate aerosol in cloud droplet nucleation and, consequently, in indirect radiative forcing. However, in this bicomponent system, the cloud droplet number concentration, N(d) (a crucial parameter that is used in GCMs for radiative transfer calculations), is a smoothly varying function of the sulphate aerosol loading. Apart from sea-salt and sulphate aerosol particles, biomass aerosol particles are also present widely in the troposphere. We find that biomass smoke can significantly perturb the activation and growth of both sulphate and sea-salt particles. For a fixed salt loading, N(d) increases linearly with modest increases in sulphate and smoke masses, but significant nonlinearities are observed at higher non-sea-salt mass loadings. This non-intuitive N(d) variation poses a fresh challenge to climate modellers.

  12. Influences of relative humidity and particle chemical composition on aerosol scattering properties during the 2006 PRD campaign

    NASA Astrophysics Data System (ADS)

    Liu, Xingang; Cheng, Yafang; Zhang, Yuanhang; Jung, Jinsang; Sugimoto, Nobuo; Chang, Shih-Yu; Kim, Young J.; Fan, Shaojia; Zeng, Limin

    In situ measurements of the physical, chemical, and optical properties of aerosols were carried out in Guangzhou city, China, from 1 to 31 July 2006 during the Pearl River Delta (PRD) Campaign. The light extinction coefficient of the ambient atmosphere, the aerosol scattering coefficient under dry conditions, the aerosol absorption coefficient under ambient conditions, NO 2 concentration, and relative humidity (RH) were measured by transmissionmeter, an integrating nephelometer, a multi-angle absorption photometer (MAAP), a NO X analyzer, and an automatic meteorological station, respectively. Meanwhile, the molecular scattering coefficient was calculated by the Rayleigh scattering function using the US Standard Atmosphere. A method to calculate the aerosol hygroscopic growth factor f(RH), defined as the ratio of the aerosol scattering coefficient under a wet condition to that under a dry condition (40% RH), is proposed based on these optical parameters. The mean and standard deviation aerosol hygroscopic growth factors at 80% RH ( f(RH)=80%) in Ganzhou were 2.04±0.28, 2.29±0.28, and 2.68±0.59 for urban aerosols, mixed aerosols, and marine aerosols, respectively, with the air mass classification being based on the air mass source region. The relationship between f(RH) and RH is fitted by empirical equations and the fitting parameters are calculated. The relationships between f(RH)=80% and total carbon mass fraction (TCF) in PM 2.5, the water-soluble mass fraction (WSF) in PM 10, and the sea-salt aerosol mass fraction (SSF) in PM 10 reveal that the hygroscopic properties of the observed aerosol have a good positive correlation with the WSF and SSF, but have a negative correlation with the TCF.

  13. Molecular corridors and kinetic regimes in the multiphase chemical evolution of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Berkemeier, T.; Schilling-Fahnestock, K. A.; Seinfeld, J. H.; Pöschl, U.

    2014-08-01

    The dominant component of atmospheric, organic aerosol is that derived from the oxidation of volatile organic compounds (VOCs), so-called secondary organic aerosol (SOA). SOA consists of a multitude of organic compounds, only a small fraction of which has historically been identified. Formation and evolution of SOA is a complex process involving coupled chemical reaction and mass transport in the gas and particle phases. Current SOA models do not embody the full spectrum of reaction and transport processes, nor do they identify the dominant rate-limiting steps in SOA formation. Based on molecular identification of SOA oxidation products, we show here that the chemical evolution of SOA from a variety of VOC precursors adheres to characteristic "molecular corridors" with a tight inverse correlation between volatility and molar mass. The slope of these corridors corresponds to the increase in molar mass required to decrease volatility by one order of magnitude (-dM / dlogC0). It varies in the range of 10-30 g mol-1, depending on the molecular size of the SOA precursor and the O : C ratio of the reaction products. Sequential and parallel reaction pathways of oxidation and dimerization or oligomerization progressing along these corridors pass through characteristic regimes of reaction-, diffusion-, or accommodation-limited multiphase chemical kinetics that can be classified according to reaction location, degree of saturation, and extent of heterogeneity of gas and particle phases. The molecular corridors and kinetic regimes help to constrain and describe the properties of the products, pathways, and rates of SOA evolution, thereby facilitating the further development of aerosol models for air quality and climate.

  14. Molecular corridors and kinetic regimes in the multiphase chemical evolution of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Berkemeier, T.; Schilling-Fahnestock, K.; Seinfeld, J.; Poeschl, U.

    2014-12-01

    The dominant component of atmospheric organic aerosol is that derived from the oxidation of volatile organic compounds (VOCs), so-called secondary organic aerosol (SOA). SOA consists of a multitude of organic compounds, only a small fraction of which has historically been identified. Formation and evolution of SOA is a complex process involving coupled chemical reaction and mass transport in the gas and particle phases. Current SOA models do not embody the full spectrum of reaction and transport processes nor do they identify the dominant rate-limiting steps in SOA formation. Based on molecular identification of SOA oxidation products, we show here that the chemical evolution of SOA from a variety of VOC precursors adheres to characteristic "molecular corridors" with a tight inverse correlation between volatility and molar mass. The slope of these corridors corresponds to the increase in molar mass required to decrease volatility by one order of magnitude (-dM/dlogC0). It varies in the range of 10-30 g mol-1 depending on the molecular size of the SOA precursor and the O:C ratio of the reaction products. Sequential and parallel reaction pathways of oxidation and dimerization or oligomerization progressing along these corridors pass through characteristic regimes of reaction-, diffusion-, or accommodation-limited multiphase chemical kinetics that can be classified according to reaction location, degree of saturation, and extent of heterogeneity of gas and particle phases. The molecular corridors and kinetic regimes help to constrain and described the properties of the products, pathways and rates of SOA evolution, thereby facilitating the further development of aerosol models for air quality and climate.

  15. Formation and chemical aging of secondary organic aerosol during the β-caryophyllene oxidation

    NASA Astrophysics Data System (ADS)

    Tasoglou, A.; Pandis, S. N.

    2015-06-01

    The secondary organic aerosol (SOA) production during the oxidation of β-caryophyllene by ozone (O3) and hydroxyl radicals (OH) and the subsequent chemical aging of the products during reactions with OH were investigated. Experiments were conducted with ozone and with hydroxyl radicals at low NOx (zero added NOx) and at high NOx (hundreds of parts per billion). The SOA mass yield at 10 μg m-3 of organic aerosol was 27% for the ozonolysis, 20% for the reaction with OH at low NOx, and 38% at high NOx under dry conditions, 20 °C, and ozone excess. Parameterizations of the fresh SOA yields have been developed. The average fresh SOA atomic O : C ratio varied from 0.24 to 0.34 depending on the oxidant and the NOx level, while the H : C ratio was close to 1.5 for all systems examined. An average density of 1.06 ± 0.1 μg m-3 of the β-caryophyllene SOA was estimated. The exposure to UV light had no effect on the β-caryophyllene SOA concentration and aerosol mass spectrometer (AMS) measurements. The chemical aging of the β-caryophyllene SOA produced was studied by exposing the fresh SOA to high concentrations (107 molecules cm-3) of OH for several hours. These additional reactions increased the SOA concentration by 15-40% and O : C by approximately 25%. A limited number of experiments suggested that there was a significant impact of the relative humidity on the chemical aging of the SOA. The evaporation rates of β-caryophyllene SOA were quantified by using a thermodenuder allowing us to estimate the corresponding volatility distributions and effective vaporization enthalpies.

  16. Formation and aging of secondary organic aerosol from toluene: changes in chemical composition, volatility, and hygroscopicity

    DOE PAGES

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; Nenes, A.; Donahue, N. M.; Pandis, S. N.

    2015-07-24

    Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OSc), and mass yield. The OA oxidation state generally increased duringmore » photo-oxidation, and the final OA OSc ranged from -0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

  17. Formation and aging of secondary organic aerosol from toluene: changes in chemical composition, volatility, and hygroscopicity

    NASA Astrophysics Data System (ADS)

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; Nenes, A.; Donahue, N. M.; Pandis, S. N.

    2015-07-01

    Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OSc), and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OSc ranged from -0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.

  18. Aerosol assisted chemical vapor deposition of superconducting YBa 2Cu 3O 7-χ

    NASA Astrophysics Data System (ADS)

    Salazar, K. V.; Ott, K. C.; Dye, R. C.; Hubbard, K. M.; Peterson, E. J.; Coulter, J. Y.; Kodas, T. T.

    1992-08-01

    A hybrid process, aerosol-assisted chemical vapor deposotion (AACVD), is described for reproducible preparation of superconducting thin films of YBa 2Cu 3O 7-χ. The process consists of atomizing a toluene solution of the Y, Ba, and Cu tetramethylheptanedionato complexes using an aerosol generator. The aerosol is transported into a CVD reactor where solvent and precursor evaporation and deposition occur at atmospheric pressure on heated substrates. The process provides stable evaporation rates for all three precursors, yielding constant film stoichiometry throughout the deposition period and from film to film. Superconducting films may be deposited in-situ at substrate heater temperatures above 825°C, or may be formed at lower temperatures by deposition followed by post-deposition annealing at higher temperatures. The microstructure and quality of films are highly dependent on the conditions employed in deposition and in the case of films deposited below 825°C, the post-deposition annealing conditions. Superconducting films prepared by the AACVD/post-annealing process have a metallic normal state resistivity signature with a zero resistance temperature typically above 88K, and are highly c-axis oriented. Transport critical current densities measured at 75 K on polycrystalline films prepared by the AACVD process are 220 000 A/cm 2 and 84 000 A/cm 2 at self-field and 0.1 T, respectively.

  19. Effect of phytoplankton biomass in seawater on chemical properties of sea spray aerosols.

    PubMed

    Park, Jiyeon; Kim, Dohyung; Lee, Kwangyul; Han, Seunghee; Kim, Hyunji; Williams, Leah R; Joo, Hung Soo; Park, Kihong

    2016-09-15

    This study is to investigate the effect of biological seawater properties on sea spray aerosols (SSA). Concentrations of chlorophyll-a and bacteria were measured at coastal site in Korea in fall and summer seasons. Also, aerosol mass spectrometer (AMS) was used to determine chemical constituents (organics, sulfate, nitrate, ammonium, and chloride) of non-refractory submicrometer aerosols sprayed from seawaters using a bubble bursting system. The average concentration of chlorophyll-a in seawater in fall was 1.75±0.78μg/l, whereas it significantly increased to 5.11±2.16μg/l in summer. It was found that the fraction of organics in the submicrometer SSA was higher in summer (68%) than fall (49%), and that the organic fraction in the SSA increased as the concentration of chlorophyll-a increased in seawater, suggesting that the high phytoplankton biomass in seawater could lead to the enhancement of organic species in the SSA.

  20. Application of Ni-63 photo and corona discharge ionization for the analysis of chemical warfare agents and toxic wastes

    NASA Technical Reports Server (NTRS)

    Stach, J.; Adler, J.; Brodacki, M.; Doring, H.-R.

    1995-01-01

    Over the past decade, advances in instrumental design and refinements in the understanding of ion molecule reactions at atmospheric pressure enabled the application of Ion Mobility Spectrometry (IMS) as a simple inexpensive and sensitive analytical method for the detection of organic trace compounds. Positive and negative gas-phase ions for ion mobility spectrometry have been produced by a variety of methods, including photo-ionization, laser multi photon ionization, surface ionization, corona discharge ionization. The most common ion source used in ion mobility spectrometry is a radioactive Ni-63 foil which is favored due to simplicity, stability, convenience, and high selectivity. If reactant ions like (H2O(n)H)(+) or (H2O(n)O2)(-) dominate in the reaction region, nearly all kinds of compounds with a given proton or electron affinity; are ionized. However, the radioactivity of the Ni-63 foil is one disadvantage of this ion source that stimulates the development and application of other ionization techniques. In this paper, we report analyses of old chemical warfare agents and toxic wastes using Bruker RAID ion mobility spectrometers. Due to the modular construction of the measuring cell, the spectrometers can be equipped with different ion sources. The combined use of Ni-63, photo- and corona discharge ionization allows the identification of different classes of chemical compounds and yields in most cases comparable results.

  1. Aerosol assisted chemical vapour deposition control parameters for selective deposition of tungsten oxide nanostructures.

    PubMed

    Vallejos, S; Umek, P; Blackman, C

    2011-09-01

    Tungsten oxide films were deposited via Aerosol Assisted Chemical Vapour Deposition (AACVD) from the single-source precursor W(OPh)6. Film morphology and optimum deposition temperatures for formation of quasi-one-dimensional structures is influenced by the solvent 'carrier' used for deposition of the films with bulk porous films and nanostructured needles, hollow tubes and fibres obtained dependent on the solvent used and the deposition temperature. This influence of solvent could be exploited for the synthesis of other nanomaterials, and so provide a new and versatile route to develop and integrate nanostructured materials for device applications. PMID:22097557

  2. Chemical composition and sources of coastal marine aerosol particles during the 2008 VOCALS-REx campaign

    SciTech Connect

    Lee, Y. -N.; Springston, S.; Jayne, J.; Wang, J.; Hubbe, J.; Senum, G.; Kleinman, L.; Daum, P. H.

    2014-01-01

    The chemical composition of aerosol particles (Dp ≤ 1.5 μm) was measured over the southeast Pacific Ocean during the VAMOS (Variability of the American Monsoon Systems) Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-Rex) between 16 October and 15 November 2008 using the US Department of Energy (DOE) G-1 aircraft. The objective of these flights was to gain an understanding of the sources and evolution of these aerosols, and of how they interact with the marine stratus cloud layer that prevails in this region of the globe. Our measurements showed that the marine boundary layer (MBL) aerosol mass was dominated by non-sea-salt SO42−, followed by Na+, Cl, Org (total organics), NH4+, and NO3, in decreasing order of importance; CH3SO3 (MSA), Ca2+, and K+ rarely exceeded their limits of detection. Aerosols were strongly acidic with a NH4+ to SO42− equivalents ratio typically < 0.3. Sea-salt aerosol (SSA) particles, represented by NaCl, exhibited Cl deficits caused by both HNO3 and H2SO4, but for the most part were externally mixed with particles, mainly SO42−. SSA contributed only a small fraction of the total accumulation mode particle number concentration. It was inferred that all aerosol species (except SSA) were of predominantly continental origin because of their strong land-to-sea concentration gradient. Comparison of relative changes in median values suggests that (1) an oceanic source of NH3 is present between 72° W and 76° W, (2) additional organic aerosols from biomass burns or biogenic precursors were emitted from coastal regions south of 31° S, with possible cloud processing, and (3) free tropospheric (FT) contributions to MBL gas and aerosol

  3. Improving aerosol interaction with clouds and precipitation in a regional chemical weather modeling system

    NASA Astrophysics Data System (ADS)

    Zhou, C.; Zhang, X.; Gong, S.; Wang, Y.; Xue, M.

    2016-01-01

    A comprehensive aerosol-cloud-precipitation interaction (ACI) scheme has been developed under a China Meteorological Administration (CMA) chemical weather modeling system, GRAPES/CUACE (Global/Regional Assimilation and PrEdiction System, CMA Unified Atmospheric Chemistry Environment). Calculated by a sectional aerosol activation scheme based on the information of size and mass from CUACE and the thermal-dynamic and humid states from the weather model GRAPES at each time step, the cloud condensation nuclei (CCN) are interactively fed online into a two-moment cloud scheme (WRF Double-Moment 6-class scheme - WDM6) and a convective parameterization to drive cloud physics and precipitation formation processes. The modeling system has been applied to study the ACI for January 2013 when several persistent haze-fog events and eight precipitation events occurred.

    The results show that aerosols that interact with the WDM6 in GRAPES/CUACE obviously increase the total cloud water, liquid water content, and cloud droplet number concentrations, while decreasing the mean diameters of cloud droplets with varying magnitudes of the changes in each case and region. These interactive microphysical properties of clouds improve the calculation of their collection growth rates in some regions and hence the precipitation rate and distributions in the model, showing 24 to 48 % enhancements of threat score for 6 h precipitation in almost all regions. The aerosols that interact with the WDM6 also reduce the regional mean bias of temperature by 3 °C during certain precipitation events, but the monthly means bias is only reduced by about 0.3 °C.

  4. Chemical Nature Of Titan’s Organic Aerosols Constrained from Spectroscopic and Mass Spectrometric Observations

    NASA Astrophysics Data System (ADS)

    Imanaka, Hiroshi; Cruikshank, D. P.

    2012-10-01

    The Cassini-Huygens observations greately extend our knowledge about Titan’s organic aerosols. The Cassini INMS and CAPS observations clearly demonstrate the formation of large organic molecules in the ionosphere [1, 2]. The VIMS and CIRS instruments have revealed spectral features of the haze covering the mid-IR and far-IR wavelengths [3, 4, 5, 6]. This study attempts to speculate the possible chemical nature of Titan’s aerosols by comparing the currently available observations with our laboratory study. We have conducted a series of cold plasma experiment to investigate the mass spectrometric and spectroscopic properties of laboratory aerosol analogs [7, 8]. Titan tholins and C2H2 plasma polymer are generated with cold plasma irradiations of N2/CH4 and C2H2, respectively. Laser desorption mass spectrum of the C2H2 plasma polymer shows a reasonable match with the CAPS positive ion mass spectrum. Furthermore, spectroscopic features of the the C2H2 plasma polymer in mid-IR and far-IR wavelegths qualitatively show reasonable match with the VIMS and CIRS observations. These results support that the C2H2 plasma polymer is a good candidate material for Titan’s aerosol particles at the altitudes sampled by the observations. We acknowledge funding supports from the NASA Cassini Data Analysis Program, NNX10AF08G, and from the NASA Exobiology Program, NNX09AM95G, and the Cassini Project. [1] Waite et al. (2007) Science 316, 870-875. [2] Crary et al. (2009) Planet. Space Sci. 57, 1847-1856. [3] Bellucci et al. (2009) Icarus 201, 198-216. [4] Anderson and Samuelson (2011) Icarus 212, 762-778. [5] Vinatier et al. (2010) Icarus 210, 852-866. [6] Vinatier et al. (2012) Icarus 219, 5-12. [7] Imanaka et al. (2004) Icarus 168, 344-366. [8] Imanaka et al. (2012) Icarus 218, 247-261.

  5. Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

    NASA Technical Reports Server (NTRS)

    Elshorbany, Y. F.; Crutzen, P. J.; Steil, B.; Pozzer, A.; Tost, H.; Lelieveld, J.

    2014-01-01

    Recently, realistic simulation of nitrous acid (HONO) based on the HONO / NOx ratio of 0.02 was found to have a significant impact on the global budgets of HOx (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation

  6. Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

    NASA Technical Reports Server (NTRS)

    Elshorbany, Y. F.; Crutzen, P. J.; Steil, B.; Pozzer, A.; Tost, H.; Lelieveld, J.

    2014-01-01

    Recently, realistic simulation of nitrous acid (HONO) based on the HONO/NO(sub x) ratio of 0.02 was found to have a significant impact on the global budgets of HO(sub x) (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation.

  7. Influence of Aerosol Chemical Composition on Heterogeneous Ice Formation under Mid-Upper Troposphere Conditions

    NASA Astrophysics Data System (ADS)

    Kanji, Z. A.; Niemand, M.; Saathoff, H.; Möhler, O.; Chou, C.; Abbatt, J.; Stetzer, O.

    2011-12-01

    Aerosols are involved in cooling/warming the atmosphere directly via interaction with incoming solar radiation (aerosol direct effect), or via their ability to act as cloud condensation or ice nuclei (IN) and thus play a role in cloud formation (indirect effect). In particular, the physical properties of aerosols such as size and solubility and chemical composition can influence their behavior and fate in the atmosphere. Ice nucleation taking place via IN is termed as heterogeneous ice nucleation and can take place with via deposition (ice forming on IN directly from the vapor phase), condensation/immersion (freezing via formation of the liquid phase on IN) or condensation (IN colliding with supercooled liquid drops). This presentation shows how the chemical composition and surface area of various tropospherically relevant aerosols influence conditions of temperature (T) and relative humidity (RH) required for heterogeneous ice formation conditions in the mid-upper troposphere regime (253 - 220K)? Motivation for this comes first from, the importance of being able to predict ice formation accurately so as to understand the hydrological cycle since the ice is the primary initiator of precipitation forming clouds. Second, the tropospheric budget of water vapour, an especially active greenhouse gas is strongly influenced by ice nucleation and growth. Third, ice surfaces in the atmosphere act as heterogeneous surfaces for chemical reactions of trace gases (e.g., SO2, O3, NOx and therefore being able to accurately estimate ice formation rates and quantify ice surface concentrations will allow a more accurate calculation of trace gas budgets in the troposphere. Ice nucleation measurements were conducted using a self-developed continuous flow diffusion chamber and static chamber. A number of tropospherically relevant particulates with naturally-varying and laboratory-modified surface chemistry/structure were investigated for their ice formation efficiency based on highest

  8. Chemical speciation of chlorine in atmospheric aerosol samples by high-resolution proton induced X-ray emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Kertész, Zsófia; Furu, Enikő; Kavčič, Matjaž

    2013-01-01

    Chlorine is a main elemental component of atmospheric particulate matter (APM). The knowledge of the chemical form of chlorine is of primary importance for source apportionment and for estimation of health effects of APM. In this work the applicability of high-resolution wavelength dispersive proton induced X-ray emission (PIXE) spectroscopy for chemical speciation of chlorine in fine fraction atmospheric aerosols is studied. A Johansson-type crystal spectrometer with energy resolution below the natural linewidth of Cl K lines was used to record the high-resolution Kα and Kβ proton induced spectra of several reference Cl compounds and two atmospheric aerosol samples, which were collected for conventional PIXE analysis. The Kα spectra which refers to the oxidation state, showed very minor differences due to the high electronegativity of Cl. However, the Kβ spectra exhibited pronounced chemical effects which were significant enough to perform chemical speciation. The major chlorine component in two fine fraction aerosol samples collected during a 2010 winter campaign in Budapest was clearly identified as NaCl by comparing the high-resolution Cl Kβ spectra from the aerosol samples with the corresponding reference spectra. This work demonstrates the feasibility of high-resolution PIXE method for chemical speciation of Cl in aerosols.

  9. Measurements of Oxidized Organic Compounds during SOAS 2013 using nitrate ion chemical ionization coupled with High Resolution Time-of-Flight Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Massoli, P.; Stark, H.; Cnagaratna, M.; Junninen, H.; Hakala, J. P.; Mauldin, R.; Ehn, M.; Sipila, M.; Krechmer, J.; Kimmel, J.; Jimenez, J. L.; Jayne, J. T.; Worsnop, D. R.

    2013-12-01

    We present ambient measurements of gaseous organic compounds by means of a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometry (HR-ToF-CIMS) using nitrate ion (NO3-) chemistry. This technique allows to selectively detect oxidized gas-phase species, e.g., oxidized organic molecules and sulfuric acid via clustering with NO3- and its high order clusters. The capability of making such measurements is important because both sulfuric acid and organic gas molecules have a recognized key role in new particle formation (NPF) processes and likely have an important role in particulate phase chemistry and formation of secondary organic aerosols (SOA). The HR-ToF-CIMS was deployed during the Southern Oxidant and Aerosol Study (SOAS) at the forest supersite in Centreville, AL, from June 1 to July 15, 2013. The main goal of the SOAS campaign was to investigate the composition and sources of SOA in the Southeast US, where emissions are mainly represented by biogenic volatile organic compounds (BVOC) emissions and in less extent by anthropogenic emissions (AVOC). During SOAS, the HR-ToF-CIMS detected a range of organic ions that based on previous literature could be identified as oxidation products of both isoprene and terpenes. The isoprene products were 5 to 10 times more abundant than the terpene products. The isoprene-related molecules showed a diurnal cycle with a day time peak, typically after 1500 local time, while the terpene products were higher at night (between 2000 and 0600 local time). These results are consistent with the diurnal trends of primary BVOC emissions from other co-located instruments. The ambient data are also compared to laboratory measurements where oxidized organic vapors are produced using a Potential Aerosol Mass (PAM) flow reactor by the OH oxidation of biogenic gas-phase precursors (isoprene, a-pinene) over multiple days of equivalent atmospheric exposure.

  10. Optical, physical and chemical properties of transported African mineral dust aerosols in the Mediterranean region

    NASA Astrophysics Data System (ADS)

    Denjean, Cyrielle; Di Biagio, Claudia; Chevaillier, Servanne; Gaimoz, Cécile; Grand, Noel; Loisil, Rodrigue; Triquet, Sylvain; Zapf, Pascal; Roberts, Greg; Bourrianne, Thierry; Torres, Benjamin; Blarel, Luc; Sellegri, Karine; Freney, Evelyn; Schwarzenbock, Alfons; Ravetta, François; Laurent, Benoit; Mallet, Marc; Formenti, Paola

    2014-05-01

    The transport of mineral dust aerosols is a global phenomenon with strong climate implications. Depending on the travel distance over source regions, the atmospheric conditions and the residence time in the atmosphere, various transformation processes (size-selective sedimentation, mixing, condensation of gaseous species, and weathering) can modify the physical and chemical properties of mineral dust, which, in turn, can change the dust's optical properties. The model predictions of the radiative effect by mineral dust still suffer of the lack of certainty of these properties, and their temporal evolution with transport time. Within the frame of the ChArMex project (Chemistry-Aerosol Mediterranean experiment, http://charmex.lsce.ipsl.fr/), two intensive airborne campaigns (TRAQA, TRansport and Air QuAlity, 18 June - 11 July 2012, and ADRIMED, Aerosol Direct Radiative Impact in the regional climate in the MEDiterranean region, 06 June - 08 July 2013) have been performed over the Central and Western Mediterranean, one of the two major transport pathways of African mineral dust. In this study we have set up a systematic strategy to determine the optical, physical and optical properties of mineral dust to be compared to an equivalent dataset for dust close to source regions in Africa. This study is based on airborne observations onboard the SAFIRE ATR-42 aircraft, equipped with state of the art in situ instrumentation to measure the particle scattering and backscattering coefficients (nephelometer at 450, 550, and 700 nm), the absorption coefficient (PSAP at 467, 530, and 660 nm), the extinction coefficient (CAPS at 530 nm), the aerosol optical depth (PLASMA at 340 to 1640 nm), the size distribution in the extended range 40 nm - 30 µm by the combination of different particle counters (SMPS, USHAS, FSSP, GRIMM) and the chemical composition obtained by filter sampling. The chemistry and transport model CHIMERE-Dust have been used to classify the air masses according to

  11. Measurements of the chemical, physical, and optical properties of single aerosol particles

    NASA Astrophysics Data System (ADS)

    Moffet, Ryan Christopher

    Knowledge of aerosol physical, chemical, optical properties is essential for judging the effect that particulates have on human health, climate and visibility. The aerosol time-of-flight mass spectrometer (ATOFMS) is capable of measuring, in real-time, the size and chemical composition of atmospheric aerosols. This was exemplified by the recent deployments of the ATOFMS to Mexico City and Riverside. The ATOFMS provided rapid information about the major particle types present in the atmosphere. Industrial sources of particles, such as fine mode particles containing lead, zinc and chloride were detected in Mexico City. The rapid time response of the ATOFMS was also exploited to characterize a coarse particle concentrator used in human health effects studies. The ATOFMS showed the ability to detect changes in particle composition with a time resolution of 15 min during short 2 hour human exposure studies. As a major component of this work, an optical measurement has been added to the ATOFMS. The scattered light intensity was acquired for each sized and chemically analyzed particle. This scattering information together with the particle aerodynamic diameter, enabled the refractive index and density of the aerosol to be retrieved. This method was validated in the laboratory using different test particles such as oils, aqueous salt solutions and black carbon particles. It was found that the nozzle-type inlet does not evaporate aqueous salt particles as has been observed for aerodynamic lens inlets. These new optical and microphysical measurements were integrated into the ATOFMS for field deployment in Riverside and Mexico City. For both cities, the different mixing states were found to have unique refractive indexes and densities. A fraction of the strongly absorbing elemental carbon particles were observed to have a spherical morphology due to heavy mixing with secondary species. In addition to the quantitative refractive index and effective density measurements

  12. Chemical properties and morphology of Marine Aerosol in the Mediterranean atmosphere: a mesocosm study

    NASA Astrophysics Data System (ADS)

    D'Anna, Barbara; Sellegri, Karine; Charrière, Bruno; Sempéré, Richard; Mas, Sébastien; Marchand, Nicolas; George, Christian; Même, Aurèlie; R'mili, Badr; Delmont, Anne; Schwier, Allison; Rose, Clémence; Colomb, Aurèlie; Pey, Jorge; Langley Dewitt, Helen

    2014-05-01

    The Mediterranean Sea is a special marine environment characterized by low biological activity and high anthropogenic pressure. It is often difficult to discriminate the contribution of Primary Sea Salt Aerosol formed at the sea surface from background level of the aerosol. An alternative tool to study the sea-air exchanges in a controlled environment is provided by the mesocosms, which represent an important link between field studies and laboratory experiments. The sea-air transfer of particles and gases was investigated in relation to water chemical composition and biological activity during a mesocosm experiment within the SAM project (Sources of marine Aerosol in the Mediterranean) at the Oceanographic and Marine Station STARESO in Western Corsica (May 2013). Three 2 m mesocosms were filled with screened (<1000 µm) 2260 L of subsurface (1 m) seawater and covered with a transparent Teflon film dome to minimize atmospheric contamination. The mesocosms were equipped with a pack of optical and physicochemical sensors and received different treatments: one was left unchanged as control and two were enriched by addition of nitrates and phosphates respecting Redfield ratio (N:P = 16). The evolution of the three systems was followed for 20 days. The set of sensors in each mesocosm was allowed to monitor, at high frequency (every 10 min), the water temperature, conductivity, pH, incident light, fluorescence of chlorophyll a and dissolved oxygen concentration. The mesocosm seawaters were daily sampled for chemical (colored dissolved organic matter, particulate matter and related polar compounds, transparent polysaccharides and nutrients concentration) and biological (chlorophyll a, virus, phytoplankton and zooplankton) analyses. Both dissolved and gaseous VOCs were also analyzed. In addition, few liters of seawater from each mesocosm were daily and immediately collected and transferred to a bubble-bursting apparatus to simulate nascent sea spray aerosol. On

  13. Modal structure of chemical mass size distribution in the high Arctic aerosol

    NASA Astrophysics Data System (ADS)

    Hillamo, Risto; Kerminen, Veli-Matti; Aurela, Minna; MäKelä, Timo; Maenhaut, Willy; Leek, Caroline

    2001-11-01

    Chemical mass size distributions of aerosol particles were measured in the remote marine boundary layer over the central Arctic Ocean as part of the Atmospheric Research Program on the Arctic Ocean Expedition 1996 (AOE-96). An inertial impaction method was used to classify aerosol particles into different size classes for subsequent chemical analysis. The particle chemical composition was determined by ion chromatography and by the particle-induced X-ray emission technique. Continuous particle size spectra were extracted from the raw data using a data inversion method. Clear and varying modal structures for aerosols consisting of primary sea-salt particles or of secondary particles related to dimethyl sulfide emissions were found. Concentration levels of all modes decreased rapidly when the distance from open sea increased. In the submicrometer size range the major ions found by ion chromatography were sulfate, methane sulfonate, and ammonium. They had most of the time a clear Aitken mode and one or two accumulation modes, with aerodynamic mass median diameters around 0.1 μm, 0.3 μm, and between 0.5-1.0 μm, respectively. The overall submicron size distributions of these three ions were quite similar, suggesting that they were internally mixed over most of this size range. The corresponding modal structure was consistent with the mass size distributions derived from the particle number size distributions measured with a differential mobility particle sizer. The Aitken to accumulation mode mass ratio for nss-sulfate and MSA was substantially higher during clear skies than during cloudy periods. Primary sea-salt particles formed a mode with an aerodynamic mass median diameter around 2 μm. In general, the resulting continuous mass size distributions displayed a clear modal structure consistent with our understanding of the two known major source mechanisms. One is the sea-salt aerosol emerging from seawater by bubble bursting. The other is related to

  14. Water-Soluble Organic Species in Biomass Burning Aerosols in Southern Africa: Their Chemical Identification and Spatial Distribution

    NASA Astrophysics Data System (ADS)

    Gao, S.; Hegg, D. A.; Hobbs, P. V.; Kirchstetter, T. W.; Magi, B.

    2001-12-01

    During the SAFARI-2000 field campaign, 14 aerosol samples were collected from an aircraft in plumes from biomass fires (under both flaming and smoldering conditions), at various distances from the fire source. Also collected were 36 aerosol samples in haze layers ranging from the surface to 16,000 feet, some of which could be associated with specific fires. The samples were collected on teflon membrane filters (lower size limit of about 30nm in diameter) which were analyzed for total aerosol mass loading and chemical composition using several analytical techniques. Particular effort was made to speciate the water-soluble portion of the aerosol organics. Seven organic acids and seven carbohydrate species (and their possible stereoisomers) were identified and quantified, along with three inorganic anions and five inorganic cations. The identified organic species accounted for up to 32% of the total aerosol mass; compared with concurrent total carbon and organic carbon measurements, the identified organics constituted at least 5% to 30% of the mass of the total aerosol organics. A number of conspicuous spatial distribution patterns were observed for these species. For instance, using K+ to correct for dilution, it was found that gluconate, oxalate, succinate, and glutarate, along with sulfate and nitrate, all increased significantly in mass concentration from the fire source going downwind. This suggests secondary formation of these species during aerosol aging. On the other hand, formate and acetate showed decreasing trends downwind, probably due to the loss of these volatile species to the gas phase. Another striking pattern is that anhydrosugars (e.g. levoglucosan) had the highest aerosol mass fraction near smoldering fires but a very low fraction in the haze layers, whereas, dicarboxylic acids showed an almost opposite trend. This implies possible chemical reaction processes converting intermediate organic products, such as levoglucosan, to smaller products like

  15. Aerosol Observability and Predictability: From Research to Operations for Chemical Weather Forecasting. Lagrangian Displacement Ensembles for Aerosol Data Assimilation

    NASA Technical Reports Server (NTRS)

    da Silva, Arlindo

    2010-01-01

    A challenge common to many constituent data assimilation applications is the fact that one observes a much smaller fraction of the phase space that one wishes to estimate. For example, remotely sensed estimates of the column average concentrations are available, while one is faced with the problem of estimating 3D concentrations for initializing a prognostic model. This problem is exacerbated in the case of aerosols because the observable Aerosol Optical Depth (AOD) is not only a column integrated quantity, but it also sums over a large number of species (dust, sea-salt, carbonaceous and sulfate aerosols. An aerosol transport model when driven by high-resolution, state-of-the-art analysis of meteorological fields and realistic emissions can produce skillful forecasts even when no aerosol data is assimilated. The main task of aerosol data assimilation is to address the bias arising from inaccurate emissions, and Lagrangian misplacement of plumes induced by errors in the driving meteorological fields. As long as one decouples the meteorological and aerosol assimilation as we do here, the classic baroclinic growth of error is no longer the main order of business. We will describe an aerosol data assimilation scheme in which the analysis update step is conducted in observation space, using an adaptive maximum-likelihood scheme for estimating background errors in AOD space. This scheme includes e explicit sequential bias estimation as in Dee and da Silva. Unlikely existing aerosol data assimilation schemes we do not obtain analysis increments of the 3D concentrations by scaling the background profiles. Instead we explore the Lagrangian characteristics of the problem for generating local displacement ensembles. These high-resolution state-dependent ensembles are then used to parameterize the background errors and generate 3D aerosol increments. The algorithm has computational complexity running at a resolution of 1/4 degree, globally. We will present the result of

  16. Chemical Characterization of Submicron Aerosol Particles in São Paulo, Brazil

    NASA Astrophysics Data System (ADS)

    Ferreira De Brito, J.; Rizzo, L. V.; Godoy, J.; Godoy, M. L.; de Assunção, J. V.; Alves, N. D.; Artaxo, P.

    2013-12-01

    Megacities, large urban conglomerates with a population of 10 million or more inhabitants, are increasingly receiving attention as strong pollution hotspots with significant global impact. The emissions from such large centers in both the developed and developing parts of the world are strongly impacted by the transportation sector. The São Paulo Metropolitan Area (SPMA), located in the Southeast of Brazil, is a megacity with a population of 18 million people and 7 million vehicles, many of which fuelled by a considerably amount of anhydrous ethanol. Such fleet is considered a unique case of large scale biofuel usage worldwide. Despite the large impact on human health and atmospheric chemistry/dynamics, many uncertainties are found in terms of gas and particulate matter emissions from vehicles and their atmospheric reactivity, e.g. secondary organic aerosol formation. In order to better understand aerosol life cycle on such environment, a suite of instruments for gas and particulate matter characterization has been deployed in two sampling sites within the SPMA, including an Aerosol Chemical Speciation Monitor (ACSM). The instrumentation was deployed at the rooftop of a 45m high building in the University of São Paulo during winter/spring 2012. The site is located roughly 6km downwind of the city center with little influence from local sources. The second site is located in a downtown area, sampling at the top floor of the Public Health Faculty, approximately 10m above ground. The instrumentation was deployed at the Downtown site during summer/fall 2013. The average non-refractory submicron aerosol concentration at the University site was 6.7 μg m-3, being organics the most abundant specie (70%), followed by NO3 (12%), NH4 (8%), SO4 (8%) and Chl (2%). At the Downtown site, average aerosol concentration was 15.1 μg m-3, with Organics composing 65% of the mass, followed by NH4 (12%), NO3 (11%), SO4 (11%) and Chl (1%). The analysis of specific fragmentation

  17. Chemical composition and characteristics of ambient aerosols and rainwater residues during Indian summer monsoon: Insight from aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chakraborty, Abhishek; Gupta, Tarun; Tripathi, Sachchida N.

    2016-07-01

    Real time composition of non-refractory submicron aerosol (NR-PM1) is measured via Aerosol mass spectrometer (AMS) for the first time during Indian summer monsoon at Kanpur, a polluted urban location located at the heart of Indo Gangetic Plain (IGP). Submicron aerosols are found to be dominated by organics followed by nitrate. Source apportionment of organic aerosols (OA) via positive matrix factorization (PMF) revealed several types of secondary/oxidized and primary organic aerosols. On average, OA are completely dominated by oxidized OA with a very little contribution from biomass burning OA. During rain events, PM1 concentration is decreased almost by 60%, but its composition remains nearly the same. Oxidized OA showed slightly more decrease than primary OAs, probably due to their higher hygroscopicity. The presence of organo nitrates (ON) is also detected in ambient aerosols. Apart from real-time sampling, collected fog and rainwater samples were also analyzed via AMS in offline mode and in the ICP-OES (Inductively coupled plasma - Optical emission spectrometry) for elements. The presence of sea salt, organo nitrates and sulfates has been observed. Rainwater residues are also dominated by organics but their O/C ratios are 15-20% lower than the observed values for ambient OA. Alkali metals such as Ca, Na, K are found to be most abundant in the rainwater followed by Zn. Rainwater residues are also found to be much less oxidized than the aerosols present inside the fog water, indicating presence of less oxidized organics. These findings indicate that rain can act as an effective scavenger of different types of pollutants even for submicron particle range. Rainwater residues also contain organo sulfates which indicate that some portion of the dissolved aerosols has undergone aqueous processing, possibly inside the cloud. Highly oxidized and possibly hygroscopic OA during monsoon period compared to other seasons (winter, post monsoon), indicates that they can act

  18. Analysis of isomeric polycyclic aromatic hydrocarbons by charge-exchange chemical ionization mass spectrometry

    SciTech Connect

    Simonsick, W.J. Jr.; Hites, R.A.

    1984-12-01

    Charge-exchange chemical ionization mass spectrometry (using a 15% mixture of methane in argon) yields abundant M/sup +/, M + H/sup +/, M + C/sub 2/H/sub 5//sup +/ ions of polycyclic aromatic hydrocarbons (PAH). On the basis of the relative intensities of the M + H/sup +/ ion to the M/sup +/ ion, this technique can differentiate, in a predictable manner, isomeric structures of PAH. The operating conditions were evaluated and optimized; the most significant contributions to the variations in the (M + H)/sup +//M/sup +/ ratios are the temperature, pressure, and condition of the ion source. The optimum ion source temperature (250/sup 0/C) and pressure (0.8 torr) are easily controlled and regulated. The variable contamination of the ion source is compensated by an internal standard 1,2,3,5-tetrafluorobenzene. The analyses of Standard Reference Materials 1648 and 1649 (air particulate samples) and a carbon black extract are reported. Triphenylene and chrysene, although not chromatographically resolved, can be quantitated by using this technique. The identification of acephenanthrylene based on the measurement of ratios and calculated ionization potentials is also presented.

  19. Rapid detection of drugs in biofluids using atmospheric pressure chemi/chemical ionization mass spectrometry.

    PubMed

    Chen, Lee Chuin; Hashimoto, Yutaka; Furuya, Hiroko; Takekawa, Kenichi; Kubota, Takeo; Hiraoka, Kenzo

    2009-02-01

    We have demonstrated that, with simple pH adjustment, volatile drugs such as methamphetamine, amphetamine, 3,4-methylenedioxymethamphetamine (MDMA), ketamine, and valproic acid could be analyzed rapidly from raw biofluid samples (e.g. urine and serum) without dilution, or extraction, using atmospheric pressure ionization. The ion source was a variant type of atmospheric pressure chemical ionization (APCI) that used a dielectric barrier discharge (DBD) to generate the metastable helium gas and reagent ions. The sample solution was loaded in a disposable glass pipette, and the volatile compounds were purged by nitrogen gas to be reacted with the metastable helium gas. The electrodes of the DBD were arranged in such a way that the generated glow discharge was confined within the discharge tube and was not exposed to the analytes. A needle held at 100-500 V was placed between the ion-sampling orifice and the discharge tube to guide the analyte ions into the mass spectrometer. After pH adjustment of the biofluid sample, the amphiphilic drugs were in the form of a water-insoluble oil, which could be concentrated on the liquid surface. By gentle heating of the sample to increase the evaporation rate, rapid and sensitive detection of these drugs in raw urine and serum samples could be achieved in less than 2 min for each sample. PMID:19125420

  20. Picoelectrospray Ionization Mass Spectrometry Using Narrow-bore Chemically Etched Emitters

    SciTech Connect

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

    2014-01-01

    Electrospray ionization mass spectrometry (ESI-MS) at flow rates below ~10 nL/min has been only sporadically explored due to difficulty in reproducibly fabricating emitters that can operate at lower flow rates. Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min. Depending on the analyte concentration, we observe two types of MS signal response as a function of flow rate. At low concentrations, an optimum flow rate is observed slightly above 1 nL/min, while the signal decreases monotonically with decreasing flow rates at higher concentrations. In spite of lower MS signal, the ion utilization efficiency increases exponentially with decreasing flow rate in all cases. No unimolecular response was observed within this flow rate range during the analysis of an equimolar mixture of peptides, indicating that ionization efficiency is an analyte-dependent characteristic in given experimental conditions. While little to no gain in signal-to-noise was achieved at ultralow flow rates for concentration-limited analyses, experiments consuming the same amount of analyte suggest that mass-limited analyses will benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution. By operating under optimal conditions, consumption of just 500 zmol of sample yielded signal-to-noise ratios ~10 for some peptides. These findings have important implications for the analysis of trace biological samples.

  1. Gas Chromatography/Atmospheric Pressure Chemical Ionization Tandem Mass Spectrometry for Fingerprinting the Macondo Oil Spill.

    PubMed

    Lobodin, Vladislav V; Maksimova, Ekaterina V; Rodgers, Ryan P

    2016-07-01

    We report the first application of a new mass spectrometry technique (gas chromatography combined to atmospheric pressure chemical ionization tandem mass spectrometry, GC/APCI-MS/MS) for fingerprinting a crude oil and environmental samples from the largest accidental marine oil spill in history (the Macondo oil spill, the Gulf of Mexico, 2010). The fingerprinting of the oil spill is based on a trace analysis of petroleum biomarkers (steranes, diasteranes, and pentacyclic triterpanes) naturally occurring in crude oil. GC/APCI enables soft ionization of petroleum compounds that form abundant molecular ions without (or little) fragmentation. The ability to operate the instrument simultaneously in several tandem mass spectrometry (MS/MS) modes (e.g., full scan, product ion scan, reaction monitoring) significantly improves structural information content and sensitivity of analysis. For fingerprinting the oil spill, we constructed diagrams and conducted correlation studies that measure the similarity between environmental samples and enable us to differentiate the Macondo oil spill from other sources. PMID:27281271

  2. Chemical sinks of organic aerosol: kinetics and products of the heterogeneous oxidation of erythritol and levoglucosan.

    PubMed

    Kessler, Sean H; Smith, Jared D; Che, Dung L; Worsnop, Douglas R; Wilson, Kevin R; Kroll, Jesse H

    2010-09-15

    The heterogeneous oxidation of pure erythritol (C(4)H(10)O(4)) and levoglucosan (C(6)H(10)O(5)) particles was studied in order to evaluate the effects of atmospheric aging on the mass and chemical composition of atmospheric organic aerosol. In contrast to what is generally observed for the heterogeneous oxidation of reduced organics, substantial volatilization is observed in both systems. However, the ratio of the decrease in particle mass to the decrease in the concentration of the parent species is about three times higher for erythritol than for levoglucosan, indicating that details of chemical structure (such as carbon number, cyclic moieties, and oxygen-containing functional groups) play a governing role in the importance of volatilization reactions. The kinetics of the reaction indicate that while both compounds react at approximately the same rate, reactions of their oxidation products appear to be slowed substantially. Estimates of volatilities of organic species based on elemental composition measurements suggest that the heterogeneous oxidation of oxygenated organics may be an important loss mechanism of organic aerosol.

  3. Aerosol-Assisted Chemical Vapor Deposited Thin Films for Space Photovoltaics

    NASA Technical Reports Server (NTRS)

    Hepp, Aloysius F.; McNatt, Jeremiah; Dickman, John E.; Jin, Michael H.-C.; Banger, Kulbinder K.; Kelly, Christopher V.; AquinoGonzalez, Angel R.; Rockett, Angus A.

    2006-01-01

    Copper indium disulfide thin films were deposited via aerosol-assisted chemical vapor deposition using single source precursors. Processing and post-processing parameters were varied in order to modify morphology, stoichiometry, crystallography, electrical properties, and optical properties in order to optimize device-quality material. Growth at atmospheric pressure in a horizontal hot-wall reactor at 395 C yielded best device films. Placing the susceptor closer to the evaporation zone and flowing a more precursor-rich carrier gas through the reactor yielded shinier, smoother, denser-looking films. Growth of (112)-oriented films yielded more Cu-rich films with fewer secondary phases than growth of (204)/(220)-oriented films. Post-deposition sulfur-vapor annealing enhanced stoichiometry and crystallinity of the films. Photoluminescence studies revealed four major emission bands (1.45, 1.43, 1.37, and 1.32 eV) and a broad band associated with deep defects. The highest device efficiency for an aerosol-assisted chemical vapor deposited cell was 1.03 percent.

  4. Aerosols near by a coal fired thermal power plant: chemical composition and toxic evaluation.

    PubMed

    Jayasekher, T

    2009-06-01

    Industrial processes discharge fine particulates containing organic as well as inorganic compounds into the atmosphere which are known to induce damage to cell and DNA, both in vitro and in vivo. Source and area specific studies with respect to the chemical composition, size and shape of the particles, and toxicity evaluations are very much limited. This study aims to investigate the trace elements associated with the aerosol particles distributed near to a coal burning thermal power plant and to evaluate their toxicity through Comet assay. PM(10) (particles determined by mass passing an inlet with a 50% cut-off efficiency having a 10-microm aerodynamic diameter) samples were collected using respirable dust samplers. Twelve elements (Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Se, Hg, and As) were analyzed using ICP-AES. Comet assay was done with the extracts of aerosols in phosphate buffered saline (PBS). Results show that Fe and Zn were found to be the predominant elements along with traces of other analyzed elements. Spherical shaped ultrafine particles of <1 microm aerodynamic diameter were detected through scanning electron microscope. PM(10) particles near to the coal burning power plant produced comets indicating their potential to induce DNA damage. DNA damage property is found to be depending upon the chemical characteristics of the components associated with the particles besides the physical properties such as size and shape.

  5. From consumption to harvest: Environmental fate prediction of excreted ionizable trace organic chemicals.

    PubMed

    Polesel, Fabio; Plósz, Benedek Gy; Trapp, Stefan

    2015-11-01

    Excreted trace organic chemicals, e.g., pharmaceuticals and biocides, typically undergo incomplete elimination in municipal wastewater treatment plants (WWTPs) and are released to surface water via treated effluents and to agricultural soils through sludge amendment and/or irrigation with freshwater or reclaimed wastewater. Recent research has shown the tendency for these substances to accumulate in food crops. In this study, we developed and applied a simulation tool to predict the fate of three ionizable trace chemicals (triclosan-TCS, furosemide-FUR, ciprofloxacin-CIP) from human consumption/excretion up to the accumulation in soil and plant, following field amendment with sewage sludge or irrigation with river water (assuming dilution of WWTP effluent). The simulation tool combines the SimpleTreat model modified for fate prediction of ionizable chemicals in a generic WWTP and a recently developed dynamic soil-plant uptake model. The simulation tool was tested using country-specific (e.g., consumption/emission rates, precipitation and temperature) input data. A Monte Carlo-based approach was adopted to account for the uncertainty associated to physico-chemical and biokinetic model parameters. Results obtained in this study suggest significant accumulation of TCS and CIP in sewage sludge (1.4-2.8 mg kgDW(-1)) as compared to FUR (0.02-0.11 mg kgDW(-1)). For the latter substance, more than half of the influent load (60.1%-72.5%) was estimated to be discharged via WWTP effluent. Specific emission rates (g ha(-1) a(-1)) of FUR to soil via either sludge application or irrigation were up to 300 times lower than for TCS and CIP. Nevertheless, high translocation potential to wheat was predicted for FUR, reaching concentrations up to 4.3 μg kgDW(-1) in grain. Irrigation was found to enhance the relative translocation of FUR to plant (45.3%-48.9% of emission to soil), as compared to sludge application (21.9%-27.6%). A comparison with peer-reviewed literature showed

  6. Morphological and chemical changes of aerosolized E. coli treated with a dielectric barrier discharge.

    PubMed

    Romero-Mangado, Jaione; Nordlund, Dennis; Soberon, Felipe; Deane, Graham; Maughan, Kevin; Sainio, Sami; Singh, Gurusharan; Daniels, Stephen; Saunders, Ian T; Loftus, David; Meyyappan, M; Koehne, Jessica; Gandhiraman, Ram P

    2016-06-01

    This study presents the morphological and chemical modification of the cell structure of aerosolized Escherichia coli treated with a dielectric barrier discharge (DBD). Exposure to DBD results in severe oxidation of the bacteria, leading to the formation of hydroxyl groups and carbonyl groups and a significant reduction in amine functionalities and phosphate groups. Near edge x-ray absorption fine structure (NEXAFS) measurements confirm the presence of additional oxide bonds upon DBD treatment, suggesting oxidation of the outer layer of the cell wall. Electron microscopy images show that the bacteria undergo physical distortion to varying degrees, resulting in deformation of the bacterial structure. The electromagnetic field around the DBD coil causes severe damage to the cell structure, possibly resulting in leakage of vital cellular materials. The oxidation and chemical modification of the bacterial components are evident from the Fourier transform infrared spectroscopy and NEXAFS results. The bacterial reculture experiments confirm inactivation of airborne E. coli upon treating with DBD. PMID:26872580

  7. Comparison of atmospheric pressure chemical ionization, electrospray ionization, and atmospheric pressure photoionization for the determination of cyclosporin A in rat plasma.

    PubMed

    Wang, Ganfeng; Hsieh, Yunsheng; Korfmacher, Walter A

    2005-01-15

    Atmospheric pressure chemical ionization was compared with electrospray ionization and atmospheric pressure photoionization (APPI) as an interface of high-performance liquid chromatography (HPLC)-tandem mass spectrometry (MS/MS) for the determination of cyclosporin A (CsA) in biological fluids in support of in vivo pharmacodynamic studies. These ion sources were investigated in terms of their suitability and sensitivity for the detection of CsA. The effects of the eluent flow rate and composition as well as the nebulizer temperatures on the photoionization efficiency of CsA in the positive ion mode under normal-phase HPLC conditions were explored. The ionization mechanism in the APPI environment with and without the use of the dopant was studied using two test compounds and a few solvent systems employed for normal-phase chromatography. The test compounds were observed to be ionized mainly by proton transfer with the self-protonated solvent molecules produced through photon irradiation. Furthermore, ion suppression due to sample matrix interference in the normal-phase HPLC-APPI-MS/MS system was monitored by the postcolumn infusion technique. The applicability of these proposed HPLC-API-MS/MS approaches for the determination of CsA at low nanogram per milliliter levels in rat plasma was examined. These proposed methods were then compared with respect to specificity, linearity, detection limit, and accuracy.

  8. Fast Differential Analysis of Propolis Using Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry

    PubMed Central

    Huang, Xue-yong; Guo, Xia-li; Luo, Huo-lin; Fang, Xiao-wei; Zhu, Teng-gao; Zhang, Xing-lei; Chen, Huan-wen; Luo, Li-ping

    2015-01-01

    Mass spectral fingerprints of 24 raw propolis samples, including 23 from China and one from the United States, were directly obtained using surface desorption atmospheric pressure chemical ionization mass spectrometry (SDAPCI-MS) without sample pretreatment. Under the optimized experimental conditions, the most abundant signals were detected in the mass ranges of 70 to 500 m/z and 200 to 350 m/z, respectively. Principal component analyses (PCA) for the two mass ranges showed similarities in that the colors had a significant correlation with the first two PCs; in contrast there was no correlation with the climatic zones from which the samples originated. Analytes such as chrysin, pinocembrin, and quercetin were detected and identified using multiple stage mass spectrometry within 3 min. Therefore, SDAPCI-MS can be used for rapid and reliable high-throughput analysis of propolis. PMID:26339245

  9. Demonstration of real-time monitoring of a photolithographic exposure process using chemical ionization mass spectrometry

    SciTech Connect

    Mowry, C.D.

    1998-02-01

    Silicon wafers are coated with photoresist and exposed to ultraviolet (UV) light in a laboratory to simulate typical conditions expected in an actual semiconductor manufacturing process tool. Air is drawn through the exposure chamber and analyzed using chemical ionization mass spectrometry (CI/MS). Species that evaporate or outgas from the wafer are thus detected. The purpose of such analyses is to determine the potential of CI/MS as a real-time process monitoring tool. Results demonstrate that CI/MS can remotely detect the products evolved before, during, and after wafer UV exposure; and that the quantity and type of products vary with the photoresist coated on the wafer. Such monitoring could provide semiconductor manufacturers benefits in quality control and process analysis. Tool and photoresist manufacturers could also realize benefits from this measurement technique with respect to new tool, method, or photoresist development. The benefits realized can lead to improved device yields and reduced product and development costs.

  10. Determination of dexamethasone in urine by gas chromatography with negative chemical ionization mass spectrometry.

    PubMed

    Huetos Hidalgo, Olga; Jiménez López, Manuel; Ajenjo Carazo, Elisa; San Andrés Larrea, Manuel; Reuvers, Thea B A

    2003-05-01

    Dexamethasone, as some other synthetic corticosteroids, is licensed for therapy in veterinary practice, but its misuse as a growth promotor, often in combination with beta-agonists, is forbidden. In this report an analytical method is described for the detection and confirmation of very low concentrations of dexamethasone in urine. The influence of enzymatic hydrolysis time of samples with glucuronidase was studied. The proposed method consisted of the enzymatic hydrolysis of urine samples, which were then extracted and concentrated using solid-phase cartridges with mixed reversed-phase materials (OASIS). No further clean-up step was found to be necessary. Eluates were derivatized following a previously described method [Analyst 119 (1994) 2557]. Detection, identification and quantification of residues of this compound was carried out by gas chromatography with mass spectrometry in the negative chemical ionization mode. The proposed procedure permits the determination of dexamethasone in urine at levels as low as 0.2 ng ml(-1)

  11. Water chemical ionization mass spectrometry of aldehydes, ketones esters, and carboxylic acids

    SciTech Connect

    Hawthorne, S.B.; Miller, D.J.

    1986-11-01

    Chemical ionization mass spectrometry (CI) of aliphatic and aromatic carbonyl compounds using water as the reagent gas provides intense pseudomolecular ions and class-specific fragmentation patterns that can be used to identify aliphatic aldehydes, ketones, carboxylic acids, and esters. The length of ester acyl and alkyl groups can easily be determined on the basis of loss of alcohols from the protonated parent. Water CI provides for an approximately 200:1 selectivity of carbonyl species over alkanes. No reagent ions are detected above 55 amu, allowing species as small as acetone, propanal, acetic acid, and methyl formate to be identified. When deuterate water was used as the reagent, only the carboxylic acids and ..beta..-diketones showed significant H/D exchange. The use of water CI to identify carbonyl compounds in a wastewater from the supercritical water extraction of lignite coal, in lemon oil, and in whiskey volatiles is discussed.

  12. Tracing origins of complex pharmaceutical preparations using surface desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zhang, Xinglei; Jia, Bin; Huang, Keke; Hu, Bin; Chen, Rong; Chen, Huanwen

    2010-10-01

    A novel strategy to trace the origins of commercial pharmaceutical products has been developed based on the direct chemical profiling of the pharmaceutical products by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS). Besides the unambiguous identification of active drug components, various compounds present in the matrixes are simultaneously detected without sample pretreatment, providing valuable information for drug quality control and origin differentiation. Four sources of commercial amoxicillin products made by different manufacturers have been successfully differentiated. This strategy has been extended to secerning six sources of Liuwei Dihuang Teapills, which are herbal medicine preparations with extremely complex matrixes. The photolysis status of chemical drug products and the inferior natural herd medicine products prepared with different processes (e.g., extra heating) were also screened using the method reported here. The limit of detection achieved in the MS/MS experiments was estimated to be 1 ng/g for amoxicillin inside the capsule product. Our experimental data demonstrate that DAPCI-MS is a useful tool for rapid pharmaceutical analysis, showing promising perspectives for tracking the entire pharmaceutical supply chain to prevent counterfeit intrusions.

  13. Differentiation of (Mixed) Halogenated Dibenzo-p-Dioxins by Negative Ion Atmospheric Pressure Chemical Ionization.

    PubMed

    Fernando, Sujan; Green, M Kirk; Organtini, Kari; Dorman, Frank; Jones, Rhys; Reiner, Eric J; Jobst, Karl J

    2016-05-17

    Brominated and mixed halogenated dibenzo-p-dioxins (PBDDs and PXDDs) may well be as toxic as 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2378-TCDD), a compound reputed as one of the most toxic chemicals known to exist. However, studies on the occurrence of PXDDs have been hampered by a lack of authentic standards as well as separation techniques capable of resolving the enormous number of potential isomers. Electron ionization (EI) mass spectrometry based methods are of limited value due to the lack of isomer specific fragmentation. Negative ion atmospheric pressure chemical ionization (APCI(-)) of 2378-TCDD was described in this journal over 30 years ago. Under these conditions, the reaction between O2(-•) and 2378-TCDD results in structure diagnostic cleavages of the C-O bonds, which can distinguish TCDD isomers on the basis of Cl distribution between the two aromatic rings. In the present study, the analogous ether cleavages of PBDDs and PXDDs were studied using a gas chromatograph-quadrupole time-of-flight (GC-QTOF) mass spectrometer coupled using APCI. The results indicate comparable detection limits for the radical cations [M(•+)] and negative pseudomolecular ions [M-Cl+O](-): approximately 5 fg and 10 fg, respectively, for 2378-TCDD and 5-10 fg and 10-30 fg, respectively, for the 2,3,7,8-substituted PXDDs. Detection limits obtained by monitoring the ether cleavage products were somewhat higher (between 100 and 600 fg) but still acceptable for trace analysis of PXDDs. Such reactions may resolve coeluting isomers, which is crucial for the identification of PXDDs. The technique is demonstrated by differentiating PXDD isomer classes in a sample obtained from a major industrial fire that would not be feasible using EI or positive ion APCI(+). PMID:27074061

  14. Evolution of biomass burning aerosol over the Amazon: airborne measurements of aerosol chemical composition, microphysical properties, mixing state and optical properties during SAMBBA

    NASA Astrophysics Data System (ADS)

    Morgan, W.; Allan, J. D.; Flynn, M.; Darbyshire, E.; Hodgson, A.; Liu, D.; O'Shea, S.; Bauguitte, S.; Szpek, K.; Johnson, B.; Haywood, J.; Longo, K.; Artaxo, P.; Coe, H.

    2013-12-01

    Biomass burning represents one of the largest sources of particulate matter to the atmosphere, resulting in a significant perturbation to the Earth's radiative balance coupled with serious impacts on public health. On regional scales, the impacts are substantial, particularly in areas such as the Amazon Basin where large, intense and frequent burning occurs on an annual basis for several months. Absorption by atmospheric aerosols is underestimated by models over South America, which points to significant uncertainties relating to Black Carbon (BC) aerosol properties. Initial results from the South American Biomass Burning Analysis (SAMBBA) field experiment, which took place during September and October 2012 over Brazil on-board the UK Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft, are presented here. Aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and a DMT Single Particle Soot Photometer (SP2). The physical, chemical and optical properties of the aerosols across the region will be characterized in order to establish the impact of biomass burning on regional air quality, weather and climate. The aircraft sampled a range of conditions including sampling of pristine Rainforest, fresh biomass burning plumes, regional haze and elevated biomass burning layers within the free troposphere. The aircraft sampled biomass burning aerosol across the southern Amazon in the states of Rondonia and Mato Grosso, as well as in a Cerrado (Savannah-like) region in Tocantins state. This presented a range of fire conditions, in terms of their number, intensity, vegetation-type and their combustion efficiencies. Near-source sampling of fires in Rainforest environments suggested that smouldering combustion dominated, while flaming combustion dominated in the Cerrado. This led to significant differences in aerosol chemical composition, particularly in terms of the BC content, with BC being enhanced in the Cerrado

  15. [Chemical Composition of the Single Particle Aerosol in Winter in Nanning Using SPAMS].

    PubMed

    Liu, Hui-lin; Song, Hong-jun; Chen, Zhi-ming; Huang, Jiong-li; Yang, Jun-chao; Mao, Jing-ying; Li, Hong; Liang, Gui-yun; Mo, Zhao-yu

    2016-02-15

    Single Particle Aerosol Mass Spectrometry (SPAMS) was performed to characterize the PM2.5 in Nanning from 15 to 24 February 2015. The correlation (R2) between the PM2.5 number concentration and the mass concentration of PM2.5 obtained using SPAMS was 0.76. The particle number concentration could reflect the atmospheric pollution situation to some degree. The Art-2a classification method was used to classify the chemical composition of PM2.5. The results showed that the principal chemical constituents were elemental carbon, organic elements carbon hybrid particles, organic carbon, rich potassium particles, mineral substance, rich sodium particles, second inorganic particles, levoglucosan and other heavy metals. Among them, the composition of elemental carbon was the highest, followed by organic carbon and rich potassium particles. The particle size of 80% of PM2.5 was mainly concentrated in the range of 0.2 microm to 1.0 microm with a peak value occurring at 0. 62 microm. The particle size distribution characteristics of different chemical components were similar. The number concentration of the chemical components in PM2.5 had the same variation tread with the mass concentration of PM2.5 over time. To a certain extent, the change in chemical composition could reflect the instantaneous pollution source.

  16. [Chemical Composition of the Single Particle Aerosol in Winter in Nanning Using SPAMS].

    PubMed

    Liu, Hui-lin; Song, Hong-jun; Chen, Zhi-ming; Huang, Jiong-li; Yang, Jun-chao; Mao, Jing-ying; Li, Hong; Liang, Gui-yun; Mo, Zhao-yu

    2016-02-15

    Single Particle Aerosol Mass Spectrometry (SPAMS) was performed to characterize the PM2.5 in Nanning from 15 to 24 February 2015. The correlation (R2) between the PM2.5 number concentration and the mass concentration of PM2.5 obtained using SPAMS was 0.76. The particle number concentration could reflect the atmospheric pollution situation to some degree. The Art-2a classification method was used to classify the chemical composition of PM2.5. The results showed that the principal chemical constituents were elemental carbon, organic elements carbon hybrid particles, organic carbon, rich potassium particles, mineral substance, rich sodium particles, second inorganic particles, levoglucosan and other heavy metals. Among them, the composition of elemental carbon was the highest, followed by organic carbon and rich potassium particles. The particle size of 80% of PM2.5 was mainly concentrated in the range of 0.2 microm to 1.0 microm with a peak value occurring at 0. 62 microm. The particle size distribution characteristics of different chemical components were similar. The number concentration of the chemical components in PM2.5 had the same variation tread with the mass concentration of PM2.5 over time. To a certain extent, the change in chemical composition could reflect the instantaneous pollution source. PMID:27363128

  17. Characterizing the Asian Tropopause Aerosol Layer (ATAL) Using Satellite Observations, Balloon Measurements and a Chemical Transport Model

    NASA Technical Reports Server (NTRS)

    Fairlie, T. D.; Vernier, J.-P.; Liu, H.; Deshler, T.; Natarajan, M.; Bedka, K.; Wegner, T.; Baker, N.; Gadhavi, H.; Ratnam, M. V.; Jayaraman, A.; Pandit, A.; Raj, A.; Kumar, H.; Kumar, S.; Singh, A.; Stenchikov, G.; Wienhold, F.; Bian, J.

    2016-01-01

    Satellite observations and numerical modeling studies have demonstrated that the Asian Summer Monsoon (ASM) provide a conduit for gas-phase pollutants in south Asia to reach the lower stratosphere. Now, observations from the CALIPSO satellite have revealed the Asian Tropopause Aerosol Layer (ATAL), a summertime accumulation of aerosols in the upper troposphere and lower stratosphere (UTLS), associated with the ASM anticyclone. The ATAL has potential implications for regional cloud properties, climate, and chemical processes in the UTLS. Here, we show in situ measurements from balloon-borne instruments, aircraft, and satellite observations, together with trajectory and chemical transport model (CTM) simulations to explore the origin, composition, physical, and optical properties of aerosols in the ATAL. In particular, we show balloon-data from our BATAL-2015 field campaign to India and Saudi Arabia in summer 2015, which includes in situ backscatter measurements from COBALD instruments, and the first observations of size and volatility of aerosols in the ATAL layer using optical particle counters (OPCs). Back trajectory calculations initialized from CALIPSO observations point to deep convection over North India as a principal source of ATAL aerosols. Available aircraft observations suggest significant sulfur and carbonaceous components to the ATAL, which is supported by simulations using the GEOS-Chem CTM. Source elimination studies conducted with the GEOS-Chem indicate that ATAL aerosols originate primary from south Asian sources, in contrast with some earlier studies.

  18. Semi-Continuous Measurements of Aerosol Chemical Composition During the Summer 2002 Yosemite National Park Special Study

    SciTech Connect

    Collette, J; Lee, T; Heath, J; Carrico, C; Herckes, P; Engling, G; McMeeking, G; Kreidenweis, S; Day, D; Malm, W; Cahill, T

    2003-02-16

    Semi-continuous measurements of fine particle composition were made over a period of several weeks in summer 2002 in Yosemite National Park, California. These included measurement of aerosol ionic composition (by PILS- Particle-Into-Liquid System) and aerosol carbon (by dual wavelength aethalometer and an R&P particulate carbon monitor). The data reveal that aerosol composition at the site is highly :variable in time, with a strong diurnal cycle. Interestingly, however, different diurnal cycles were sometimes observed for different chemical constituents of the particles. Organic carbon was observed to dominate fine particle mass, with some periods apparently associated with influx of smoke from wildfires in the western U.S. Measurements of fine particle carbon isotopes revealed the fraction of carbon from biogenic sources to range from approximately 73 to 95%. The ionic fraction of the aerosol was usually dominated by ammoniated sulfate. During most periods, PM{sub 2.5} nitrate was found primarily in sea salt particles from which chloride had been displaced. Strong variations in the extent of ammonia neutralization of sulfate were also observed. The ability to observe rapid changes in aerosol composition using these semi-continuous aerosol composition measurements is helpful for understanding the dynamic chemical composition of fine particles responsible for regional haze.

  19. The optical, physical and chemical properties of the products of glyoxal uptake on ammonium sulfate seed aerosols

    NASA Astrophysics Data System (ADS)

    Trainic, M.; Riziq, A. A.; Lavi, A.; Flores, J. M.; Rudich, Y.

    2011-07-01

    The heterogeneous reaction between gas phase glyoxal and ammonium sulfate (AS) aerosols, a proxy for inorganic atmospheric aerosol, was studied in terms of the dependence of the optical, physical and chemical properties of the product aerosols on initial particle size and ambient RH. The reactions were studied under different relative humidity (RH) conditions, varying from dry conditions (~20 % RH) and up to 90 % RH, covering conditions prevalent in many atmospheric environments. At λ = 355 nm, the reacted aerosols demonstrate a substantial growth in optical extinction cross section, as well as in mobility diameter under a broad range of RH values (35-90 %). The ratio of the product aerosol to seed aerosol geometric cross section reached up to ~3.5, and the optical extinction cross-section up to ~250. The reactions show a trend of increasing physical and optical growth with decreasing seed aerosol size, from 100nm to 300 nm, as well as with decreasing RH values from 90 % to ~40 %. Optically inactive aerosols, at the limit of the Mie range (100 nm diameter) become optically active as they grow due to the reaction. AMS analyses of the reaction of 300 nm AS at RH values of 50 %, 75 % and 90 % show that the main products of the reaction are glyoxal oligomers, formed by acetal formation in the presence of AS. In addition, imidazole formation, which is a minor channel, is observed for all reactions, yielding a product which absorbs at λ = 290 nm, with possible implications on the radiative properties of the product aerosols. The ratio of absorbing substances (C-N compounds, including imidazoles) increases with increasing RH value. A core/shell model used for the investigation of the optical properties of the reaction products of AS 300nm with gas phase glyoxal, shows that the refractive index (RI) of the reaction products are in the range between 1.57-1.71 for the real part and between 0-0.02 for the imaginary part of the RI at 355 nm. The observed increase in the

  20. Importance of Physico-Chemical Properties of Aerosols in the Formation of Arctic Ice Clouds

    NASA Astrophysics Data System (ADS)

    Keita, S. A.; Girard, E.

    2014-12-01

    Ice clouds play an important role in the Arctic weather and climate system but interactions between aerosols, clouds and radiation are poorly understood. Consequently, it is essential to fully understand their properties and especially their formation process. Extensive measurements from ground-based sites and satellite remote sensing reveal the existence of two Types of Ice Clouds (TICs) in the Arctic during the polar night and early spring. TIC-1 are composed by non-precipitating very small (radar-unseen) ice crystals whereas TIC-2 are detected by both sensors and are characterized by a low concentration of large precipitating ice crystals. It is hypothesized that TIC-2 formation is linked to the acidification of aerosols, which inhibit the ice nucleating properties of ice nuclei (IN). As a result, the IN concentration is reduced in these regions, resulting to a smaller concentration of larger ice crystals. Over the past 10 years, several parameterizations of homogeneous and heterogeneous ice nucleation have been developed to reflect the various physical and chemical properties of aerosols. These parameterizations are derived from laboratory studies on aerosols of different chemical compositions. The parameterizations are also developed according to two main approaches: stochastic (that nucleation is a probabilistic process, which is time dependent) and singular (that nucleation occurs at fixed conditions of temperature and humidity and time-independent). This research aims to better understand the formation process of TICs using a newly-developed ice nucleation parameterizations. For this purpose, we implement some parameterizations (2 approaches) into the Limited Area version of the Global Multiscale Environmental Model (GEM-LAM) and use them to simulate ice clouds observed during the Indirect and Semi-Direct Arctic Cloud (ISDAC) in Alaska. We use both approaches but special attention is focused on the new parameterizations of the singular approach. Simulation

  1. Chemical characterization of atmospheric aerosol in urban areas with different anthropic impact.

    NASA Astrophysics Data System (ADS)

    Fattori, I.; Bellandi, S.; Innocenti, M.; Largiuni, O.; Lucarelli, F.; Mannini, A.; Udisti, R.

    2003-04-01

    direction and intensity and rainfall frequency on ionic load and chemical composition of the aerosol was evaluated. Trends in seasonal and annual variability for some aerosol source markers were evaluated. Preliminary measurements on size and morphology of the particulate matter collected on coarse and fine filters by surface spectroscopy techniques (SEM and Atomic Force Microscopy) revealed a scarce efficiency of the dimensional selection on the coarse filter, where also several particles with size lower than nominal filter porosity were deposited. Due to the higher mass contribution of coarse particles, however, the chemical composition of this fraction does not seem to be significantly affected.

  2. Chemical compositions of past soluble aerosols reconstructed from NEEM (Greenland) and Dome C (Antarctica) ice cores

    NASA Astrophysics Data System (ADS)

    Oyabu, Ikumi; Iizuka, Yoshinori; Fukui, Manabu; Fischer, Hubertus; Schüpbach, Simon; Gfeller, Gideon; Mulvaney, Robert; Hansson, Margareta

    2015-04-01

    Polar ice core preserve past atmospheric aerosols, which is a useful proxy for understanding the interaction between climate changes and atmospheric aerosols. One useful technique for reconstructing past soluble aerosols from ice core is the determination of dissolved ion species. However, since salts and acids melt into ions, chemical compositions of soluble aerosols in the ice cores have not been cleared. To clarify the temporal variations in the chemical compositions of past soluble aerosols, this study investigated chemical compositions of soluble particles preserved in the NEEM (Greenland) and Dome C (Antarctica) ice cores using new method 'ice-sublimation method'. The ice-sublimation method can extract soluble salts particles as a solid state without melting. The ice core samples are selected from the sections from the last termination (the Last Glacial Maximum (LGM) to Holocene) of Dome C (inland Antarctica) and NEEM ice cores. Using ice-sublimation method, soluble salts particles were extracted. Chemical components of extracted particles were analysed by scanning electron microscope and energy dispersive spectroscopy, and micro-Raman spectroscopy. The major components of soluble salts particles in the Dome C ice core are CaSO4, Na2SO4 and NaCl. The CaSO4 and NaCl fractions were high in the first half of the last termination, whereas the Na2SO4 fraction is high in the latter half of the last termination. The major components of soluble salts particles in the NEEM ice core are CaCO3, CaSO4, NaCl and Na2SO4. The fractions of CaCO3, CaSO4 and NaCl were high in LGM, whereas those of NaCl and Na2SO4 were high in Holocene. The changes in the salts compositions in Dome C ice core are mainly controlled by concentration of terrestrial material (Ca2+). In the first half of the last termination, most of the terrestrial material (CaCO3) reacted with H2SO4 but some of sea-salt (NaCl) was not reacted with H2SO4 due to high Ca2+ concentration. As a result, the CaSO4 and Na

  3. [Development of a chemical ionization time-of-flight mass spectrometer for continuous measurements of atmospheric hydroxyl radical].

    PubMed

    Dou, Jian; Hua, Lei; Hou, Ke-Yong; Jiang, Lei; Xie, Yuan-Yuan; Zhao, Wu-Duo; Chen, Ping; Wang, Wei-Guo; Di, Tian; Li, Hai-Yang

    2014-05-01

    A home-made chemical ionization time-of-flight mass spectrometer (TOFMS) has been developed for continuous measurements of atmospheric hydroxyl radical. Based on the atmospheric pressure chemical ionization technique, an ionization source with orthogonal dual tube structure was adopted in the instrument, which minimized the interference between the reagent gas ionization and the titration reaction. A 63Ni radioactive source was fixed inside one of the orthogonal tubes to generate reactant ion of NO(-)(3) from HNO3 vapor. Hydroxyl radical was first titrated by excess SO2 to form equivalent concentrations of H2SO4 in the other orthogonal tube, and then reacted with NO(-)(3) ions in the chemical ionization chamber, leading to HSO(-)(4) formation. The concentration of atmospheric hydroxyl radical can be directly calculated by measuring the intensities of the HSOj product ions and the NO(-)(3) reactant ions. The analytical capability of the instrument was demonstrated by measuring hydroxyl radical in laboratory air, and the concentration of the hydroxyl radical in the investigated air was calculated to be 1.6 x 106 molecules*cm ', based on 5 seconds integration. The results have shown that the instrument is competent for in situ continuous measurements of atmospheric trace radical.

  4. Ship diesel emission aerosols: A comprehensive study on the chemical composition, the physical properties and the molecular biological and toxicological effects on human lung cells of aerosols from a ship diesel engine operated with heavy or light diesel fuel oil

    NASA Astrophysics Data System (ADS)

    Zimmermann, R.; Buters, J.; Öder, S.; Dietmar, G.; Kanashova, T.; Paur, H.; Dilger, M.; Mülhopt, S.; Harndorf, H.; Stengel, B.; Rabe, R.; Hirvonen, M.; Jokiniemi, J.; Hiller, K.; Sapcariu, S.; Berube, K.; Sippula, O.; Streibel, T.; Karg, E.; Schnelle-Kreis, J.; Lintelmann, J.; Sklorz, M.; Arteaga Salas, M.; Orasche, J.; Müller, L.; Reda, A.; Passig, J.; Radischat, C.; Gröger, T.; Weiss, C.

    2013-12-01

    The Virtual Helmholtz Institute-HICE (www.hice-vi.eu) addresses chemical & physical properties, transformation processes and health effects of anthropogenic combustion emissions. This is performed by thorough comprehensive chemical and physical characterization of combustion aerosols (including application of advantageous on-line methods) and studying of biological effects on human lung cell-cultures. A new ALI air-liquid-interface (ALI) exposition system and a mobile S2-biological laboratory were developed for the HICE-measurements. Human alveolar basal epithelial cells (A549 etc.) are ALI-exposed to fresh, diluted (1:40-1:100) combustion aerosols and subsequently were toxicologically and molecular-biologically characterized (e.g. proteomics). By using stable isotope labeling technologies (13C-Glucose/metabolomics; 2H-Lysine/SILAC-proteomics), high sensitivity and accuracy for detection of molecular-biological effects is achievable even at sub-toxic effect dose levels. Aerosols from wood combustion and ship diesel engine (heavy/light fuel oil) have been investigated. The effect of wood combustion and ship diesel PM e.g. on the protein expression of ALI-exposed A549 cells was compared. Filtered aerosol is used as gas-reference for the isotope labeling based method (SILAC). Therefore the effects of wood combustion- and shipping diesel-PM can be directly compared. Ship diesel aerosol causes a broader distribution in the observed fold changes (log2), i.e. more proteins are significantly up-/down-regulated in case of shipping diesel PM-exposure. This corresponds to a stronger biological reaction if compared to wood combustion-PM exposure. The chemical analysis results on wood combustion- and ship diesel-PM depict more polycyclic aromatic hydrocarbons (PAH)/oxidized-PAH but less of some transition metals (V, Fe) in the wood combustion case. Interestingly, alkylated PAH are considerably more abundant in shipping PM, suggesting that PAH/Oxy-PAH may be less relevant for

  5. Wintertime aerosol chemical composition, volatility, and spatial variability in the greater London area

    NASA Astrophysics Data System (ADS)

    Xu, L.; Ng, N. L.; Williams, L. R.; Young, D. E.; Allan, J. D.; Coe, H.; Massoli, P.; Fortner, E.; Chhabra, P. S.; Herndon, S. C.; Brooks, B.; Jayne, J. T.; Worsnop, D. R.; Aiken, A. C.; Liu, S.; Gorkowski, K.; Dubey, M. K.; Fleming, Z.; Visser, S.; Prevot, A. S.

    2015-12-01

    In this study, we investigate the spatial distribution of PM1 in the greater London area during the Clean Air for London (ClearfLo) project in winter 2012 by applying two High-Resolution Time-of-Flight Aerosol Mass Spectrometers (HR-ToF-AMS) at a rural site (Detling, Kent) and an urban site (North Kensington, London). While the concentration of organic aerosol (OA) is comparable between the rural and urban sites, the OA sources are distinctly different. Due to elevated domestic heating in the urban area, the concentration of solid fuel OA at the urban site is about twice as high as at the rural site. In contrast, the OOA concentration at the rural site is almost twice that of the urban site. This is likely caused by a steep concentration gradient of OOA when air masses are advected from polluted mainland Europe. Taking advantage of low biogenic emissions in winter, the sources of OOA, which are highly uncertain, are investigated. Combing Positive Matrix Factorization (PMF) analysis and radiocarbon analysis, the majority of OOA is estimated to arise from aged biomass burning. We deploy a suite of instruments to investigate the organic volatility at the rural Detling site. After heating at 250°C in a thermal-denuder (TD), the mass fraction remaining of organics is 16%, which indicates the presence of non-volatile organics. By comparing the OA associated with refractory black carbon (measured by a soot-particle aerosol mass spectrometer) and total OA (measured by a HR-ToF-AMS), we proposed that the non-volatile organics have similar sources or have undergone similar chemical processing as refractory black carbon in the atmosphere. Finally, we will discuss the relationship between the volatility and the degree of oxidation of organics.

  6. Cloud Formation Potential of Biomass Burning Aerosol Surrogate-Particles Chemically Aged by OH

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Thalman, R. M.; Wang, J.; Li, Z. Q.; Knopf, D. A.

    2014-12-01

    Heterogeneous or multiphase reactions between trace gases such as OH and atmospheric aerosol can influence physicochemical properties of the particles including composition, morphology and lifetime. In this work, the cloud condensation nuclei (CCN) activity of laboratory-generated biomass burning aerosol (BBA) exposed to OH radicals is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type and OH exposure ([OH]×time) using a CCN counter coupled to a custom-built aerosol flow reactor (AFR). The composition of particles collected by a micro-orifice uniform deposit impactor (MOUDI) first subjected to different OH exposures is analyzed by Raman and scanning transmission X-ray microscopy coupled with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative compounds found in BBA that have different hygroscopicity, chemical functionalities, and reactivity with OH radicals. BBA surrogate-particles are generated following atomization of aqueous solutions with mass ratios LEV:MNC:KS of 1:0:0, 0:1:0, 0:0:1, 1:1:0, 0:1:1, 1:0:1, 1:1:1, and 1:0.03:0.3. OH radicals are generated in the AFR following photolysis of O3 in the presence of H2O using a variable intensity ultra-violet (UV) lamp, which allows equivalent atmospheric OH exposures from days to weeks. In addition, we investigate how κ changes i) in response to varying [O3] with and without OH, and ii) at a fixed OH exposure while varying RH. The impact of OH exposure on the CCN activity of BBA will be presented and its atmospheric implications will be discussed.

  7. Atmospheric pressure flow reactor / aerosol mass spectrometer studies of tropospheric aerosol nucleat and growth kinetics. Final report, June, 2001

    SciTech Connect

    Worsnop, Douglas R.

    2001-06-01

    The objective of this program was to determine the mechanisms and rates of growth and transformation and growth processes that control secondary aerosol particles in both the clear and polluted troposphere. The experimental plan coupled an aerosol mass spectrometer (AMS) with a chemical ionization mass spectrometer to provide simultaneous measurement of condensed and particle phases. The first task investigated the kinetics of tropospheric particle growth and transformation by measuring vapor accretion to particles (uptake coefficients, including mass accommodation coefficients and heterogeneous reaction rate coefficients). Other work initiated investigation of aerosol nucleation processes by monitoring the appearance of submicron particles with the AMS as a function of precursor gas concentrations. Three projects were investigated during the program: (1) Ozonolysis of oleic acid aerosols as model of chemical reactivity of secondary organic aerosol; (2) Activation of soot particles by measurement deliquescence in the presence of sulfuric acid and water vapor; (3) Controlled nucleation and growth of sulfuric acid aerosols.

  8. Technical Note: Evaluation of the WRF-Chem "Aerosol Chemical to Aerosol Optical Properties" Module using data from the MILAGRO campaign

    SciTech Connect

    Barnard, James C.; Fast, Jerome D.; Paredes-Miranda, Guadalupe L.; Arnott, W. P.; Laskin, Alexander

    2010-08-09

    A comparison between observed aerosol optical properties from the MILAGRO field campaign, which took place in the Mexico City Metropolitan Area (MCMA) during March 2006, and values simulated by the Weather Research and Forecasting model (WRF-Chem) model, reveals large differences. To help identify the source of the discrepancies, data from the MILAGRO campaign are used to evaluate the "aerosol chemical to aerosol optical properties" module implemented in the full chemistry version of the WRF-Chem model. The evaluation uses measurements of aerosol size distributions and chemical properties obtained at the MILAGRO T1 site. These observations are fed to the module, which makes predictions of various aerosol optical properties, including the scattering coefficient, Bscat; the absorption coefficient, Babs; and the single-scattering albedo, v0; all as a function of time. This simulation is compared with independent measurements obtained from a photoacoustic spectrometer (PAS) at a wavelength of 870 nm. Because of line losses and other factors, only "fine mode" aerosols with aerodynamic diameters less than 2.5 mm are considered here. Over a 10-day period, the simulations of hour-by-hour variations of Bscat are not satisfactory, but simulations of Babs and v0 are considerably better. When averaged over the 10-day period, the computed and observed optical properties agree within the uncertainty limits of the measurements and simulations. Specifically, the observed and calculated values are, respectively: (1) Bscat, 34.1 ± 5.1 Mm-1 versus 30.4 ± 4.3 Mm-1; (2) Babs, 9.7 ± 1.0 Mm-1 versus 11.7 ± 1.5 Mm-1; and (3) v0, 0.78 ± 0.04 and 0.74 ± 0.03. The discrepancies in values of v0 simulated by the full WRF-Chem model thus cannot be attributed to the "aerosol chemistry to optics" module. The discrepancy is more likely due, in part, to poor characterization of emissions near the T1 site, particularly black carbon emissions.

  9. Seasonal Differences in Aerosol Chemical Properties at a Site Along the Eastern Seaboard: Observations from the Two-Column Aerosol Project (TCAP)

    NASA Astrophysics Data System (ADS)

    Berg, L. K.; Fast, J. D.; Comstock, J. M.; Chand, D.; Hubbe, J. M.; Jefferson, A.; Kassianov, E.; Mei, F.; Sedlacek, A. J., III; Schmid, B.; Shilling, J.; Springston, S. R.; Tomlinson, J. M.; Watson, T. B.; Wilson, J. M.; Zelenyuk, A.

    2015-12-01

    There have been relatively few studies that have quantified the seasonal variability of aerosol chemical and optical properties, as well as cloud-aerosol interactions, over a large portion of the atmospheric column. The Two Column Aerosol Project (TCAP), a U.S. Department of Energy (DOE) supported study, was designed to address this shortcoming with a combination of both ground-based and airborne measurements. The TCAP measurement strategy focused on the aerosol and cloud properties in two columns, one over Cape Cod, Massachusetts and one several hundred kilometers to the east. TCAP included the year-long deployment of the DOE Atmospheric Measurement Program (ARM) Mobile Facility and two individual month-long deployments of the ARM Aerial Facility, in July 2012 and in February 2013. Our work highlights a number of important differences between the summer and winter study periods, including differences in atmospheric flow patterns, the mass loading and chemical composition of the aerosol. The median mass loading of organic aerosol measured at the surface was much larger during July (2.3 μg m-3) than February (0.88 μg m-3). These differences are likely the result of the small amount of biogenic emissions during the winter as well as the reduction in the amount of sunlight available for photochemistry. The amount of sulfate loading was approximately a factor of two larger during February, with a median value of 0.66 μg m-3 compared to only 0.30 μg m-3 measured during July. The median mass loading of nitrate and ammonium did not vary with season, but these two components make up a much larger fraction of the total aerosol mass loading in the winter. Interestingly, the difference in median refractory black carbon (rBC) measured at the surface did not change much between winter and summer (63 ng m-3 during February compared to 70 ng m-3 in July), but the 75th percentile of rBC mass loading is much larger, 127 ng m-3, during July compared to only 95 ng m-3 during

  10. Laboratory analogues simulating Titan's atmospheric aerosols: Compared chemical compositions of grains and thin films

    NASA Astrophysics Data System (ADS)

    Carrasco, Nathalie; Jomard, François; Vigneron, Jackie; Etcheberry, Arnaud; Cernogora, Guy

    2016-09-01

    Two sorts of solid organic samples can be produced in laboratory experiments simulating Titan's atmospheric reactivity: grains in the volume and thin films on the reactor walls. We expect that grains are more representative of Titan's atmospheric aerosols, but films are used to provide optical indices for radiative models of Titan's atmosphere. The aim of the present study is to address if these two sorts of analogues are chemically equivalent or not, when produced in the same N2-CH4 plasma discharge. The chemical compositions of both these materials are measured by using elemental analysis, XPS analysis and Secondary Ion Mass Spectrometry. The main parameter probed is the CH4/N2 ratio to explore various possible chemical regimes. We find that films are homogeneous but significantly less rich in nitrogen and hydrogen than grains produced in the same experimental conditions. This surprising difference in their chemical compositions could be explained by the efficient etching occurring on the films, which stay in the discharge during the whole plasma duration, whereas the grains are ejected after a few minutes. The higher nitrogen content in the grains possibly involves a higher optical absorption than the one measured on the films, with a possible impact on Titan's radiative models.

  11. Desorption electrospray ionization mass spectrometry reveals surface-mediated antifungal chemical defense of a tropical seaweed

    PubMed Central

    Lane, Amy L.; Nyadong, Leonard; Galhena, Asiri S.; Shearer, Tonya L.; Stout, E. Paige; Parry, R. Mitchell; Kwasnik, Mark; Wang, May D.; Hay, Mark E.; Fernandez, Facundo M.; Kubanek, Julia

    2009-01-01

    Organism surfaces represent signaling sites for attraction of allies and defense against enemies. However, our understanding of these signals has been impeded by methodological limitations that have precluded direct fine-scale evaluation of compounds on native surfaces. Here, we asked whether natural products from the red macroalga Callophycus serratus act in surface-mediated defense against pathogenic microbes. Bromophycolides and callophycoic acids from algal extracts inhibited growth of Lindra thalassiae, a marine fungal pathogen, and represent the largest group of algal antifungal chemical defenses reported to date. Desorption electrospray ionization mass spectrometry (DESI-MS) imaging revealed that surface-associated bromophycolides were found exclusively in association with distinct surface patches at concentrations sufficient for fungal inhibition; DESI-MS also indicated the presence of bromophycolides within internal algal tissue. This is among the first examples of natural product imaging on biological surfaces, suggesting the importance of secondary metabolites in localized ecological interactions, and illustrating the potential of DESI-MS in understanding chemically-mediated biological processes. PMID:19366672

  12. In situ measurements of atmospheric nitrous acid by chemical ionization mass spectrometry using chloride ion transfer reactions.

    PubMed

    Hirokawa, Jun; Kato, Takehiro; Mafuné, Fumitaka

    2009-10-15

    Recently, chemical ionization mass spectrometry (CIMS) has been widely applied to the in situ measurements of atmospheric trace species. In this article, we propose a new chemical ionization scheme using a chloride ion transfer reaction from SO(2)Cl(-) as the reagent ion and discuss the applicability of this technique to the detection of nitrous acid (HONO) in the atmosphere. From laboratory investigations, the detection sensitivity was found to depend on the flow rate of SO(2) introduced into the ion source region and the pressure inside the chemical ionization region, which suggests that the chemical ionization reaction is reversible. The detection sensitivity was well described in terms of the forward and backward rates. The present limit of detection is estimated to be 60 parts per trillion by volume (pptv) for an integration time of 1 min. Improvement of the CIMS instrument would enable the measurements of the daytime level of HONO, which might be less than 50 pptv. In addition, the possibility of the interference is discussed from thermodynamic considerations based on ab initio calculations, and the effects of the sampling artifacts are experimentally quantified.

  13. UPTAKE AND ELIMINATION OF IONIZABLE ORGANIC CHEMICALS AT FISH GILLS: PART I. MODEL FORMULATION, PARAMETERIZATION, AND BEHAVIOR

    EPA Science Inventory

    Effects of pH and alkalinity on uptake and elimination of ionizable organic chemicals at the gills of large rainbow trout were studied. Increased pH reduced uptake rates of weakly-acidic chlorinated phenols and increased that of weakly-basic 3,4-dichlorobenzylamine, indicating gr...

  14. Determination of BROMATE AT PARTS-PER-TRILLION LEVELS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY WITH NEGATIVE CHEMICAL IONIZATION

    EPA Science Inventory

    The ozonation of bromide-containing source waters produces bromate as a class 2B carcinogenic disinfection by-product. The present work describes the determination of bromate by gas chromatography-negative chemical ionization mass spectrometry (GC-NCIMS) following a bromate react...

  15. In situ measurements of atmospheric nitrous acid by chemical ionization mass spectrometry using chloride ion transfer reactions.

    PubMed

    Hirokawa, Jun; Kato, Takehiro; Mafuné, Fumitaka

    2009-10-15

    Recently, chemical ionization mass spectrometry (CIMS) has been widely applied to the in situ measurements of atmospheric trace species. In this article, we propose a new chemical ionization scheme using a chloride ion transfer reaction from SO(2)Cl(-) as the reagent ion and discuss the applicability of this technique to the detection of nitrous acid (HONO) in the atmosphere. From laboratory investigations, the detection sensitivity was found to depend on the flow rate of SO(2) introduced into the ion source region and the pressure inside the chemical ionization region, which suggests that the chemical ionization reaction is reversible. The detection sensitivity was well described in terms of the forward and backward rates. The present limit of detection is estimated to be 60 parts per trillion by volume (pptv) for an integration time of 1 min. Improvement of the CIMS instrument would enable the measurements of the daytime level of HONO, which might be less than 50 pptv. In addition, the possibility of the interference is discussed from thermodynamic considerations based on ab initio calculations, and the effects of the sampling artifacts are experimentally quantified. PMID:19746928

  16. Chemical characterisation of semi-volatile and aerosol compounds from the photooxidation of toluene and NOx

    NASA Astrophysics Data System (ADS)

    White, Stephen J.; Jamie, Ian M.; Angove, Dennys E.

    2014-02-01

    The chemical composition of a gas phase and secondary organic aerosol (SOA) mixture from toluene photooxidation in NOx was determined. Aerosol from toluene photooxidation was generated in a smog chamber and was collected onto glass fibre filters along with those gas phase compounds which adhered to the filter. The filter bound organic material was extracted, derivatised with O-2,3,4,5,6-pentafluorobenzyl hydroxylamine (PFBHA) and N,O-bistrimethylsilyl-trifluoroacetamide (BSTFA), then analysed using gas chromatography-mass spectrometry (GC-MS). Compound identification was aided by the use of isotopically-labelled toluene. The effect of humidity on product formation was investigated by raising water vapour concentration in one experiment. Sixty compounds were identified, of which twenty had not been identified from toluene photooxidation previously. Small carboxylic acids and dicarbonyls provided the highest proportion of identifiable compounds by relative response. The use of water to extract the filter samples resulted in much higher relative responses for oxocarboxylic acids, such as glyoxylic acid and pyruvic acid, than has been observed in previous studies. The formation of levulinic acid was determined to be due to the reaction of water with aromatic photooxidation products in the gas phase or particle phase of the chamber experiment. Nuclear magnetic resonance (NMR) was used to determine the functional groups of water-extracted organic material, which indicated that the water-soluble components were comprised of compounds which contain similar functional groups, primarily alcohols and carboxylic acids.

  17. Amorphous Carbon Deposited by a Novel Aerosol-Assisted Chemical Vapor Deposition for Photovoltaic Solar Cells

    NASA Astrophysics Data System (ADS)

    Ahmad, Nurfadzilah; Kamaruzzaman, Dayana; Rusop, Mohamad

    2012-06-01

    Amorphous carbon (a-C) solar cells were successfully prepared using a novel and self-designed aerosol-assisted chemical vapor deposition (AACVD) method using camphor oil as a precursor. The fabricated solar cell with the configuration of Au/p-C/n-Si/Au achieved an efficiency of 0.008% with a fill factor of 0.15 for the device deposited at 0.5 h. The current-voltage (I-V) graph emphasized on the linear graph (ohmic) for the a-C thin films, whereas for the p-n device structure, a rectifying curve was obtained. The rectifying curves signify the heterojunction between the p-type a-C film and the n-Si substrate and designate the generation of electron-hole pair of the samples under illumination. Photoresponse characteristics of the deposited a-C was highlighted when being illuminated (AM 1.5 illumination: 100 mW/cm2, 25 °C). Transmittance spectrum exhibit a large transmittance value (>85%) and absorption coefficient value of 103-104 cm-1 at the visible range of 390 to 790 nm. The atomization of a liquid precursor solution into fine sub-micrometre-sized aerosol droplets in AACVD induced the smooth surface of a-C films. To the best of our knowledge, fabrication of a-C solar cell using this AACVD method has not yet been reported.

  18. Chemical characterization of aerosols in the equatorial atmosphere over the Indian Ocean

    NASA Astrophysics Data System (ADS)

    Balasubramanian, Rajasekhar; Karthikeyan, Sathrugnan; Potter, John; Wurl, Oliver; Durville, Caroline

    2013-10-01

    The region of the Indian Ocean and adjacent countries has received increased attention in recent years in the context of particulate air pollution. Aerosol samples were collected over the equatorial Indian Ocean during a one-year-long sailing cruise that covered the northeast and southwest monsoons, and an inter-monsoon period. The concentrations of airborne particulate matter (PM), selected metals and water-soluble ions were measured. In general, the PM concentrations were influenced by the proximity of sampling locations to land and air mass origins. The enrichment of metals in PM relative to those in the crustal material was very high (up to 40,000). The metal concentrations were significantly higher in PM samples which were influenced by volcanic emissions from the land masses of Indonesia. Volcanic plumes were traced using backward air mass trajectory and chemical tracers, and identified as a major particulate pollution source to the otherwise pristine air of the southern hemisphere of the Indian Ocean. NO3-, NH4+ and SO42- were low in aerosols collected over the open ocean, but a linear relationship between NH4+ and SO42- indicates their importance in the formation of cloud condensation nuclei.

  19. Chemical, aerosol and optical measurements in the plumes of three midwestern coal-fired power plants

    NASA Astrophysics Data System (ADS)

    Richards, L. W.; Anderson, J. A.; Blumenthal, D. L.; Mcdonald, J. A.; Macias, E. S.; Hering, S. V.; Wilson, W. E.

    Airborne measurements were made in and near the plumes of the following mid western coal-fired power plants in 1981: Kincaid in central Illinois in February, La Cygne near Kansas City in March and Labadie near St. Louis in August and September. One objective of these measurements was to obtain data (reported elsewhere) to be used for the evaluation of plume visibility models. The results of the chemical and aerosol measurements are reported here. Good agreement was obtained from different measurement methods for SO 2 and sulfate, but not for two different nitrate measurement methods. No more than a few per cent of the NO x emitted by these plants was NO 2, and NO 2 formation in the plumes could be accounted for by the ozone loss at the observed distances (up to 100 km in winter and 40 km in summer). Sulfate formation rates were in agreement with prior data, and there was no evidence of increased sulfate formation rates in a scrubbed plume (La Cygne). Both aerosol size distributions and sulfur particle size distributions were measured and showed reasonable agreement. The amount of light scattering by particles in the plume was quite variable, in pan because of variations in their mean particle size. The summer measurements were conducted during a rainy and hazy period when the Labadie plume typically could be seen from the ground only within a few km of the source. During this time, the visual impact of the plume was minimal.

  20. Chemically-Resolved Volatility Measurements of Organic Aerosol from Different Sources

    NASA Astrophysics Data System (ADS)

    Huffman, J. A.; Docherty, K. S.; Mohr, C.; Ulbrich, I. M.; Ziemann, P. J.; Onasch, T. B.; Jimenez, J. L.

    2009-04-01

    A newly modified fast temperature-stepping thermodenuder (TD) was coupled to a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) for rapid quantification of chemically-resolved volatility of organic aerosols (OA) emitted from individual sources. The TD-AMS system was used to characterize primary OA (POA) from biomass burning, trash burning surrogates (paper and plastic), and meat cooking as well as chamber-generated secondary OA (SOA) from a-pinene and gasoline vapor. Almost all atmospheric models represent POA as non-volatile, with no allowance for evaporation upon heating or dilution, or condensation upon cooling. Our results indicate that all OAs observed show semi-volatile behavior and that most POAs are at least as volatile as SOA measured in urban environments. Biomass-burning OA (BBOA) exhibited a wide range of volatilities, but more often showed volatility similar to urban OA. Paper-burning resembles BBOA because of its high volatility and intermediate atomic oxygen-to-carbon (O/C) ratio, while meat-cooking OAs (MCOA) have consistently lower volatility than ambient OA. Chamber-generated SOA was significantly more volatile than urban SOA, challenging extrapolation of traditional laboratory volatility measurements to the atmosphere. Most OAs sampled show increasing O/C ratio and decreasing H/C (hydrogen-to-carbon) ratio with temperature, further indicating that more oxygenated OA components are less volatile.

  1. The real part of the refractive indices and effective densities for chemically segregated ambient aerosols in Guangzhou measured by a single-particle aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Zhang, Guohua; Bi, Xinhui; Qiu, Ning; Han, Bingxue; Lin, Qinhao; Peng, Long; Chen, Duohong; Wang, Xinming; Peng, Ping'an; Sheng, Guoying; Zhou, Zhen

    2016-03-01

    Knowledge on the microphysical properties of atmospheric aerosols is essential to better evaluate their radiative forcing. This paper presents an estimate of the real part of the refractive indices (n) and effective densities (ρeff) of chemically segregated atmospheric aerosols in Guangzhou, China. Vacuum aerodynamic diameter, chemical compositions, and light-scattering intensities of individual particles were simultaneously measured by a single-particle aerosol mass spectrometer (SPAMS) during the fall of 2012. On the basis of Mie theory, n at a wavelength of 532 nm and ρeff were estimated for 17 particle types in four categories: organics (OC), elemental carbon (EC), internally mixed EC and OC (ECOC), and Metal-rich. The results indicate the presence of spherical or nearly spherical shapes for the majority of particle types, whose partial scattering cross-section versus sizes were well fitted to Mie theoretical modeling results. While sharing n in a narrow range (1.47-1.53), majority of particle types exhibited a wide range of ρeff (0.87-1.51 g cm-3). The OC group is associated with the lowest ρeff (0.87-1.07 g cm-3), and the Metal-rich group with the highest ones (1.29-1.51 g cm-3). It is noteworthy that a specific EC type exhibits a complex scattering curve versus size due to the presence of both compact and irregularly shaped particles. Overall, the results on the detailed relationship between physical and chemical properties benefits future research on the impact of aerosols on visibility and climate.

  2. Chemical apportionment of aerosol optical properties during the Asia-Pacific Economic Cooperation summit in Beijing, China

    NASA Astrophysics Data System (ADS)

    Han, Tingting; Xu, Weiqi; Chen, Chen; Liu, Xingang; Wang, Qingqing; Li, Jie; Zhao, Xiujuan; Du, Wei; Wang, Zifa; Sun, Yele

    2015-12-01

    We have investigated the chemical and optical properties of aerosol particles during the 2014 Asia-Pacific Economic Cooperation (APEC) summit in Beijing, China, using the highly time-resolved measurements by a high-resolution aerosol mass spectrometer and a cavity attenuated phase shift extinction monitor. The average (±σ) extinction coefficient (bext) and absorption coefficient (bap) were 186.5 (±184.5) M m-1 and 23.3 (±21.9) M m-1 during APEC, which were decreased by 63% and 56%, respectively, compared to those before APEC primarily due to strict emission controls. The aerosol composition and size distributions showed substantial changes during APEC; as a response, the mass scattering efficiency (MSE) of PM1 was decreased from 4.7 m2 g-1 to 3.5 m2 g-1. Comparatively, the average single-scattering albedo (SSA) remained relatively unchanged, illustrating the synchronous reductions of bext and bap during APEC. MSE and SSA were found to increase as function of the oxidation degree of organic aerosol (OA), indicating a change of aerosol optical properties during the aging processes. The empirical relationships between chemical composition and particle extinction were established using a multiple linear regression model. Our results showed the largest contribution of ammonium nitrate to particle extinction, accounting for 35.1% and 29.3% before and during APEC, respectively. This result highlights the important role of ammonium nitrate in the formation of severe haze pollution during this study period. We also observed very different optical properties of primary and secondary aerosol. Owing to emission controls in Beijing and surrounding regions and also partly the influences of meteorological changes, the average bext of secondary aerosol during APEC was decreased by 71% from 372.3 M m-1 to 108.5 M m-1, whereas that of primary aerosol mainly from cooking, traffic, and biomass burning emissions showed a smaller reduction from 136.7 M m-1 to 71.3 M m-1. As a result

  3. Molecular characterization of S- and N-containing organic constituents in ambient aerosols by negative ion mode high-resolution Nanospray Desorption Electrospray Ionization Mass Spectrometry: CalNex 2010 field study

    NASA Astrophysics Data System (ADS)

    O'Brien, Rachel E.; Laskin, Alexander; Laskin, Julia; Rubitschun, Caitlin L.; Surratt, Jason D.; Goldstein, Allen H.

    2014-11-01

    Samples of ambient aerosols from the 2010 California Research at the Nexus of Air Quality and Climate Change (CalNex) field study were analyzed using negative ion mode Nanospray Desorption Electrospray Ionization High-Resolution Mass Spectrometry (nano-DESI/MS). Four samples per day (6 h each) were collected in Bakersfield, CA on 20-24 June. Four characteristic groups were identified: molecules composed of carbon, hydrogen, and oxygen only (CHO), sulfur- (CHOS), nitrogen- (CHON), and both nitrogen- and sulfur-containing organics (CHONS). The chemical formula and elemental ratios were consistent with the presence of organonitrates, organosulfate, and nitroxy organosulfates in the negative ion mode mass spectra. The number of observed CHO compounds increased in the afternoon samples, suggesting photochemical processing as a source. The average number of CHOS compounds had the smallest changes during the day, consistent with a more broadly distributed source. Both of the nitrogen-containing groups (CHONS and CHON) had greater numbers of compounds in the early morning (midnight to 6 A.M.) and night (6 P.M. to midnight) samples, respectively, consistent with nitrate radical chemistry as a likely source for those compounds. Most of the compounds were found in submicron particles. The size distribution of the number of CHON compounds was bimodal, potentially indicating two types of sources. We conclude that the majority of the compounds observed were secondary in nature with both biogenic and anthropogenic sources. These data are complementary to previous results from positive ion mode nano-DESI/MS analysis of a subset of the same samples providing a more complete view of aerosol chemical composition at Bakersfield.

  4. Universal imaging: Dissociative ionization of polyatomic molecules, chemical dynamics beamline 9.0.2

    SciTech Connect

    Ahmed, M.; Chen, D.; Suits, A.G.

    1997-04-01

    A third endstation was recently added to the Chemical Dynamics beamline, designed to exploit the high flux broadband undulator light for a range of studies of reactive scattering, photochemistry and photoionization processes using time-of-flight mass spectroscopy coupled with position-sensitive detection. Two molecular beam sources are fixed at right angles, with the undulator light, or laser beams, intersecting the molecular beams at 45{degrees}. To date, beamline experiments have included a study of dissociative photoionization of a variety of molecules including N{sub 2}O and SF{sub 6}. In this mode, a single molecular beam source is used, with the tunable undulator light inducing, in SF{sub 6} for example, the process SF{sub 6} {r_arrow} SF{sub 6}{sup +} + e{sup {minus}} {r_arrow} SF{sub 5}{sup +} + F + e{sup {minus}}. The SF{sub 5}{sup +} ions are accelerated up the flight tube, mass selected and detected as a function of position on a phosphor screen viewed by a CCD camera. The position directly reveals the recoil speed (or translational energy release) and angular distribution for the dissociative ionization process. Furthermore, this measurement is obtained for all recoil speeds and angles simultaneously. Such detailed angular information has not previously been obtained for dissociative ionization processes; typically ion time-of-flight profiles are deconvoluted to yield rough insight into the angular distributions. The recorded image is actually a 2-dimensional projection of the nascent 3-dimensional velocity distribution, but established tomographic techniques enable the authors to reconstruct the 3-D distribution.

  5. Chemical rescue, multiple ionizable groups, and general acid-base catalysis in the HDV genomic ribozyme.

    PubMed

    Perrotta, Anne T; Wadkins, Timothy S; Been, Michael D

    2006-07-01

    In the ribozyme from the hepatitis delta virus (HDV) genomic strand RNA, a cytosine side chain is proposed to facilitate proton transfer in the transition state of the reaction and, thus, act as a general acid-base catalyst. Mutation of this active-site cytosine (C75) reduced RNA cleavage rates by as much as one million-fold, but addition of exogenous cytosine and certain nucleobase or imidazole analogs can partially rescue activity in these mutants. However, pH-rate profiles for the rescued reactions were bell shaped, and only one leg of the pH-rate curve could be attributed to ionization of the exogenous nucleobase or buffer. When a second potential ionizable nucleobase (C41) was removed, one leg of the bell-shaped curve was eliminated in the chemical-rescue reaction. With this construct, the apparent pK(a) determined from the pH-rate profile correlated with the solution pK(a) of the buffer, and the contribution of the buffer to the rate enhancement could be directly evaluated in a free-energy or Brønsted plot. The free-energy relationship between the acid dissociation constant of the buffer and the rate constant for cleavage (Brønsted value, beta, = approximately 0.5) was consistent with a mechanism in which the buffer acted as a general acid-base catalyst. These data support the hypothesis that cytosine 75, in the intact ribozyme, acts as a general acid-base catalyst.

  6. Wintertime aerosol chemical composition, volatility, and spatial variability in the greater London area

    NASA Astrophysics Data System (ADS)

    Xu, L.; Williams, L. R.; Young, D. E.; Allan, J. D.; Coe, H.; Massoli, P.; Fortner, E.; Chhabra, P.; Herndon, S.; Brooks, W. A.; Jayne, J. T.; Worsnop, D. R.; Aiken, A. C.; Liu, S.; Gorkowski, K.; Dubey, M. K.; Fleming, Z. L.; Visser, S.; Prevot, A. S. H.; Ng, N. L.

    2015-08-01

    The composition of PM1 (particulate matter with diameter less than 1 μm) in the greater London area was characterized during the Clean Air for London (ClearfLo) project in winter 2012. Two High-Resolution Time-of-Flight Aerosol Mass Spectrometers (HR-ToF-AMS) were deployed at a rural site (Detling, Kent) and an urban site (North Kensington, London). The simultaneous and high-temporal resolution measurements at the two sites provide a unique opportunity to investigate the spatial distribution of PM1. We find that the organic aerosol (OA) concentration is comparable between the rural and urban sites, but the sources of OA are distinctly different. The concentration of solid fuel OA at the urban site is about twice as high as at the rural site, due to elevated domestic heating in the urban area. While the concentrations of oxygenated OA (OOA) are well-correlated between the two sites, the OOA concentration at the rural site is almost twice that of the urban site. At the rural site, more than 70 % of the carbon in OOA is estimated to be non-fossil, which suggests that OOA is likely related to aged biomass burning considering the small amount of biogenic SOA in winter. Thus, it is possible that the biomass burning OA contributes a larger fraction of ambient OA in wintertime than what previous field studies have suggested. A suite of instruments was deployed downstream of a thermal denuder (TD) to investigate the volatility of PM1 species at the rural Detling site. After heating at 250 °C in the TD, 40 % of the residual mass is OA, indicating the presence of non-volatile organics in the aerosol. Although the OA associated with refractory black carbon (rBC, measured by a soot-particle aerosol mass spectrometer) only accounts for < 10 % of the total OA (measured by a HR-ToF-AMS) at 250 °C, the two measurements are well-correlated, suggesting that the non-volatile organics have similar sources or have undergone similar chemical processing as rBC in the atmosphere

  7. Development and application of a three-dimensional aerosol chemical transport model, PMCAMx

    NASA Astrophysics Data System (ADS)

    Gaydos, Timothy M.; Pinder, Rob; Koo, Bonyoung; Fahey, Kathleen M.; Yarwood, Gregory; Pandis, Spyros N.

    A three-dimensional chemical transport model (PMCAMx) is used to simulate PM mass and composition in the eastern United States for a July 2001 pollution episode. The performance of the model in this region is evaluated, taking advantage of the highly time and size-resolved PM and gas-phase data collected during the Pittsburgh Air Quality Study (PAQS). PMCAMx uses the framework of CAMx and detailed aerosol modules to simulate inorganic aerosol growth, aqueous-phase chemistry, secondary organic aerosol formation, nucleation, and coagulation. The model predictions are compared to hourly measurements of PM 2.5 mass and composition at Pittsburgh, as well as to measurements from the AIRS and IMPROVE networks. The performance of the model for the major PM 2.5 components (sulfate, ammonium, and organic carbon) is encouraging (fractional errors are in general smaller than 50%). Additional improvements are possible if the rainfall measurements are used instead of the meteorological model predictions. The modest errors in ammonium predictions and the lack of bias for the total (gas and particulate) ammonium suggest that the improved ammonia inventory used is reasonable. The significant errors in aerosol nitrate predictions are mainly due to difficulties in simulating the nighttime formation of nitric acid. The concentrations of elemental carbon (EC) in the urban areas are significantly overpredicted. This is a problem related to both the emission inventory but also the different EC measurement methods that have been used in the two measurement networks (AIRS and IMPROVE) and the actual development of the inventory. While the ability of the model to reproduce OC levels is encouraging, additional work is necessary to confirm that that this is due to the right reasons and not offsetting errors in the primary emissions and the secondary formation. The model performance against the semi-continuous measurements in Pittsburgh appears to be quite similar to its performance against

  8. Field Measurements Of Ammonia Fluxes Above A Douglas-fir Forest In Speuld, Holland Using Chemical Ionization Mass Spectrometry (CIMS)

    NASA Astrophysics Data System (ADS)

    McGillen, M. R.; Gallagher, M. W.; Flynn, M. J.; Percival, C. J.

    2009-12-01

    Ammonia (NH3) is an important component of the atmospheric nitrogenous species on regional scales and is a major contributor to the nitrogen budget across the UK and Western Europe. It represents the major atmospheric alkaline gas and in its interaction with acidic gases such as nitric acid, leads to the formation of particulate matter (e.g., Asman, 1998). As sulphur emissions decline across Western Europe, regions of excess ammonia are becoming more widespread and ammonium nitrate aerosol is becoming a significant component of atmospheric nitrogen . NH3 is efficiently lost to the semi-natural vegetation, typical of many natural ecosystems prevalent in Western Europe. Deposition of atmospheric NH3 to ecosystems can lead to deleterious effects such as eutrophication and acidification of soils, contributing to forest decline and a decrease in biological diversity (e.g., Fangmeier et al., 1994). Ammonia measurements were performed using chemical ionization mass spectrometry (CIMS) utilizing the protonated acetone dimer as the precursor ion. NH3 flux measurements were evaluated using the eddy covariance technique at a height of 46m above ground at Speuld forest. The Speuld fieldsite is a mature plantation of Douglas-fir (Pseudotsuga menziesii), located in the centre of the Netherlands (52°13'N, 5 ° 39'E). Data was collected over a two week period (June 25th - July 8th 2009), and fluxes will be determined using the eddy covariance technique. To the authors’ knowledge, these measurements represent the only NH3 flux measurements using CIMS, indeed few studies exist that directly determine fluxes using the this technique. Eddy covariance flux measurements are the most direct way to estimate NH3 removal near the surface. Preliminary data will be presented and compared with the GRadient Ammonia High Accuracy Monitor (GRAHAM) method. References: Asman, W. A. H., Sutton, M. A., and Schjorring, J. K.: Ammonia: emission, atmospheric transport and deposition, New Phytol., 139

  9. Pattern of aerosol mass loading and chemical composition over the atmospheric environment of an urban coastal station

    NASA Astrophysics Data System (ADS)

    Bindu, G.; Nair, Prabha R.; Aryasree, S.; Hegde, Prashant; Jacob, Salu

    2016-02-01

    Aerosol sampling was carried out at four locations in and around Cochin (9°58‧ N, 76°17‧ E), an urban area, located on the southwest coast of India. The gravimetric estimates of aerosol mass loading showed wide range from 78 μg m-3 to >450 μg m-3, occasionally reaching values >500 μg m-3, associated with regional source characteristics. Most of the values were above the air quality standard. Both boundary layer and synoptic scale airflow pattern play role in the temporal features in aerosol mass loading and chemical composition. Chemical analysis of the aerosol samples were done for anionic species viz; F-, Cl-, Br-, NO2-,   NO3-,   PO43-,   SO42- and metallic/cationic species viz; Na, Ca, K, Mg, NH4+, Fe, Al, Cu, Mg, Pb, etc using Ion Chromatography, Atomic Absorption Spectroscopy (AAS) and Inductively Coupled Plasma- Atomic Emission Spectroscopy (ICP-AES). At all the locations, extremely high mass concentration of SO42- was observed with the mean value of 13±6.4 μg m-3 indicating the strong anthropogenic influence. Statistical analysis of the chemical composition data was carried out and the principal factors presented. Seasonal variation of these chemical species along with their percentage contributions and regional variations were also examined. Increase in level of Na in aerosol samples indicated the influence of monsoonal activity. Most of the species showed mass concentrations well above those measured over another coastal site Thiruvananthapuram (8°29‧ N, 76°57‧ E) situated ~220 km south of Cochin revealing the highly localized aerosol features.

  10. Preliminary Results of Aerosol Chemical Composition Measurements in the Gulf of Maine with an Aerosol Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Middlebrook, A. M.; Canagaratna, M. R.; Worsnop, D. R.

    2002-12-01

    The New England Air Quality Study is a multi-institutional research project to improve understanding of the atmospheric processes that control the production and distribution of air pollutants in the New England region. During July-August, 2002 a large, collaborative, intensive period of atmospheric measurement and model comparisons took place. As part of this study, an Aerosol Mass Spectrometer (AMS) was deployed aboard the NOAA ship RONALD H. BROWN in the Gulf of Maine. The AMS measures semi-volatile components of aerosol particles with aerodynamic diameters between roughly 40 and 1500 nm. During this study, the AMS collected 2-minute averaged particle mass spectra as well as speciated organic, sulfate, and nitrate size distributions. Sodium chloride, sodium sulfate, and sodium nitrate components of the aerosol, which are relatively non-volatile at the AMS heater temperature, were not detected with the AMS. A wide variety of air masses were sampled during the intensive period, including clean marine, clean continental, and polluted continental air masses. In general, the volatile particle composition was mostly organic and sulfate with lesser amounts of nitrate. Furthermore, particle mass loadings typically peaked around 400-600 nm in aerodynamic diameter. Several events with high aerosol organic, sulfate, and/or nitrate mass loadings were observed and the atmospheric processes that cause them will be discussed.

  11. Single-particle aerosol mass spectrometry for the detection and identification of chemical warfare agent simulants.

    PubMed

    Martin, Audrey N; Farquar, George R; Frank, Matthias; Gard, Eric E; Fergenson, David P

    2007-08-15

    Single-particle aerosol mass spectrometry (SPAMS) was used for the real-time detection of liquid nerve agent simulants. A total of 1000 dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles each of dimethyl methyl phosphonate, diethyl ethyl phosphonate, diethyl phosphoramidate, and diethyl phthalate using laser fluences between 0.58 and 7.83 nJ/microm2, and mass spectral variation with laser fluence was studied. The mass spectra obtained allowed identification of single particles of the chemical warfare agent (CWA) simulants at each laser fluence used although lower laser fluences allowed more facile identification. SPAMS is presented as a promising real-time detection system for the presence of CWAs. PMID:17630721

  12. Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols.

    PubMed

    McNeill, V Faye

    2015-02-01

    Over the past decade, it has become clear that aqueous chemical processes occurring in cloud droplets and wet atmospheric particles are an important source of organic atmospheric particulate matter. Reactions of water-soluble volatile (or semivolatile) organic gases (VOCs or SVOCs) in these aqueous media lead to the formation of highly oxidized organic particulate matter (secondary organic aerosol; SOA) and key tracer species, such as organosulfates. These processes are often driven by a combination of anthropogenic and biogenic emissions, and therefore their accurate representation in models is important for effective air quality management. Despite considerable progress, mechanistic understanding of some key aqueous processes is still lacking, and these pathways are incompletely represented in 3D atmospheric chemistry and air quality models. In this article, the concepts, historical context, and current state of the science of aqueous pathways of SOA formation are discussed.

  13. Single-particle aerosol mass spectrometry for the detection and identification of chemical warfare agent simulants.

    PubMed

    Martin, Audrey N; Farquar, George R; Frank, Matthias; Gard, Eric E; Fergenson, David P

    2007-08-15

    Single-particle aerosol mass spectrometry (SPAMS) was used for the real-time detection of liquid nerve agent simulants. A total of 1000 dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles each of dimethyl methyl phosphonate, diethyl ethyl phosphonate, diethyl phosphoramidate, and diethyl phthalate using laser fluences between 0.58 and 7.83 nJ/microm2, and mass spectral variation with laser fluence was studied. The mass spectra obtained allowed identification of single particles of the chemical warfare agent (CWA) simulants at each laser fluence used although lower laser fluences allowed more facile identification. SPAMS is presented as a promising real-time detection system for the presence of CWAs.

  14. Chemical composition, sources, and aging process of submicron aerosols in Beijing: Contrast between summer and winter

    NASA Astrophysics Data System (ADS)

    Hu, Weiwei; Hu, Min; Hu, Wei; Jimenez, Jose L.; Yuan, Bin; Chen, Wentai; Wang, Ming; Wu, Yusheng; Chen, Chen; Wang, Zhibin; Peng, Jianfei; Zeng, Limin; Shao, Min

    2016-02-01

    To investigate the seasonal characteristics of submicron aerosol (PM1) in Beijing urban areas, a high-resolution time-of-flight aerosol-mass-spectrometer (HR-ToF-AMS) was utilized at an urban site in summer (August to September 2011) and winter (November to December 2010), coupled with multiple state of the art online instruments. The average mass concentrations of PM1 (60-84 µg m-3) and its chemical compositions in different campaigns of Beijing were relatively consistent in recent years. In summer, the daily variations of PM1 mass concentrations were stable and repeatable. Eighty-two percent of the PM1 mass concentration on average was composed of secondary species, where 62% is secondary inorganic aerosol and 20% secondary organic aerosol (SOA). In winter, PM1 mass concentrations changed dramatically because of the different meteorological conditions. The high average fraction (58%) of primary species in PM1 including primary organic aerosol (POA), black carbon, and chloride indicates primary emissions usually played a more important role in the winter. However, aqueous chemistry resulting in efficient secondary formation during occasional periods with high relative humidity may also contribute substantially to haze in winter. Results of past OA source apportionment studies in Beijing show 45-67% of OA in summer and 22-50% of OA in winter can be composed of SOA. Based on the source apportionment results, we found 45% POA in winter and 61% POA in summer are from nonfossil sources, contributed by cooking OA in both seasons and biomass burning OA (BBOA) in winter. Cooking OA, accounting for 13-24% of OA, is an important nonfossil carbon source in all years of Beijing and should not be neglected. The fossil sources of POA include hydrocarbon-like OA from vehicle emissions in both seasons and coal combustion OA (CCOA) in winter. The CCOA and BBOA were the two main contributors (57% of OA) for the highest OA concentrations (>100 µg m-3) in winter. The POA

  15. Superhydrophobic photocatalytic surfaces through direct incorporation of titania nanoparticles into a polymer matrix by aerosol assisted chemical vapor deposition.

    PubMed

    Crick, Colin R; Bear, Joseph C; Kafizas, Andreas; Parkin, Ivan P

    2012-07-10

    A new class of superhydrophobic photocatalytic surfaces that are self-cleaning through light-induced photodegradation and the Lotus effect are presented. The films are formed in a single-step aerosol-assisted chemical vapor deposition (AACVD) process. The films are durable and show no degradation on continuous exposure to UV-C radiation. PMID:22706974

  16. Long-term Measurements of Submicrometer Aerosol Chemistry at the Southern Great Plains (SGP) Using an Aerosol Chemical Speciation Monitor (ACSM)

    SciTech Connect

    Parworth, Caroline; Fast, Jerome D.; Mei, Fan; Shippert, Timothy R.; Sivaraman, Chitra; Tilp, Alison; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the U.S. Department of Energy’s Southern Great Plains (SGP) site are discussed. Over the period of 19 months (Nov. 20, 2010 – June 2012) highly time resolved (~30 min.) NR-PM1 data was recorded. Using this dataset the value-added product (VAP) of deriving organic aerosol components (OACOMP) is introduced. With this VAP, multivariate analysis of the measured organic mass spectral matrix can be performed on long term data to return organic aerosol (OA) factors that are associated with distinct sources, evolution processes, and physiochemical properties. Three factors were obtained from this VAP including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when nitrate increased due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations showed little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increased and were mainly associated with local fires. Isoprene and carbon monoxide emission rates were computed by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) to represent the spatial distribution of biogenic and anthropogenic sources, respectively. From this model there is evidence to support that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.

  17. Determination of the passing efficiency for aerosol chemical species through a typical aircraft-mounted, diffuser-type aerosol inlet system

    NASA Astrophysics Data System (ADS)

    Sheridan, Patrick J.; Norton, Richard B.

    1998-04-01

    To assess the particle transmission efficiency of a conventional aircraft-mounted, diffuser-type inlet (CI), a new design inlet containing an internal filter basket assembly (aerosol filter inlet, or AFI) was constructed. All interior surfaces of the AFI were covered with filter material, and air was actively pulled through these filter walls during aerosol sampling. The AFI was demonstrated in the laboratory to trap nearly all particles entering its nozzle orifice, so it was considered usable as a baseline to judge the performance of other inlets. Wind tunnel studies were conducted at three different wind velocities that approximated typical research aircraft speeds. As wind velocity increased, particle transmission through the CI relative to the AFI decreased, as evidenced by chemical analysis of the filter deposits. Aircraft studies of the two inlets showed that particle transmission varied significantly with the measured species. Typical coarse-particle species such as Ca++, Mg++, Na+ and K+ showed 50-90% mass losses through a conventional diffuser-type inlet/curved intake tube system. Predominantly fine particle species such as SO4= and NH4+ passed the CI system with much higher efficiencies, with aerosol mass losses of 0-26% for most flights. Since the AFI traps nearly all particles aspirated into its nozzle orifice, these values indicate that on average, 80-90% of the SO4= and NH4+ aerosol mass passes through the CI and curved intake tube during airborne sampling. This finding suggests that the capability to sample fine (i.e., submicrometer) aerosols from aircraft is perhaps not as bad as has been previously reported, given that adequate attention is paid to inlet design, location, and orientation issues.

  18. Sources of atmospheric aerosol from long-term measurements (5 years) of chemical composition in Athens, Greece.

    PubMed

    Paraskevopoulou, D; Liakakou, E; Gerasopoulos, E; Mihalopoulos, N

    2015-09-15

    To identify the sources of aerosols in Greater Athens Area (GAA), a total of 1510 daily samples of fine (PM 2.5) and coarse (PM 10-2,5) aerosols were collected at a suburban site (Penteli), during a five year period (May 2008-April 2013) corresponding to the period before and during the financial crisis. In addition, aerosol sampling was also conducted in parallel at an urban site (Thissio), during specific, short-term campaigns during all seasons. In all these samples mass and chemical composition measurements were performed, the latest only at the fine fraction. Particulate organic matter (POM) and ionic masses (IM) are the main contributors of aerosol mass, equally contributing by accounting for about 24% of the fine aerosol mass. In the IM, nss-SO4(-2) is the prevailing specie followed by NO3(-) and NH4(+) and shows a decreasing trend during the 2008-2013 period similar to that observed for PM masses. The contribution of water in fine aerosol is equally significant (21 ± 2%), while during dust transport, the contribution of dust increases from 7 ± 2% to 31 ± 9%. Source apportionment (PCA and PMF) and mass closure exercises identified the presence of six sources of fine aerosols: secondary photochemistry, primary combustion, soil, biomass burning, sea salt and traffic. Finally, from winter 2012 to winter 2013 the contribution of POM to the urban aerosol mass is increased by almost 30%, reflecting the impact of wood combustion (dominant fuel for domestic heating) to air quality in Athens, which massively started in winter 2013.

  19. Sources of atmospheric aerosol from long-term measurements (5 years) of chemical composition in Athens, Greece.

    PubMed

    Paraskevopoulou, D; Liakakou, E; Gerasopoulos, E; Mihalopoulos, N

    2015-09-15

    To identify the sources of aerosols in Greater Athens Area (GAA), a total of 1510 daily samples of fine (PM 2.5) and coarse (PM 10-2,5) aerosols were collected at a suburban site (Penteli), during a five year period (May 2008-April 2013) corresponding to the period before and during the financial crisis. In addition, aerosol sampling was also conducted in parallel at an urban site (Thissio), during specific, short-term campaigns during all seasons. In all these samples mass and chemical composition measurements were performed, the latest only at the fine fraction. Particulate organic matter (POM) and ionic masses (IM) are the main contributors of aerosol mass, equally contributing by accounting for about 24% of the fine aerosol mass. In the IM, nss-SO4(-2) is the prevailing specie followed by NO3(-) and NH4(+) and shows a decreasing trend during the 2008-2013 period similar to that observed for PM masses. The contribution of water in fine aerosol is equally significant (21 ± 2%), while during dust transport, the contribution of dust increases from 7 ± 2% to 31 ± 9%. Source apportionment (PCA and PMF) and mass closure exercises identified the presence of six sources of fine aerosols: secondary photochemistry, primary combustion, soil, biomass burning, sea salt and traffic. Finally, from winter 2012 to winter 2013 the contribution of POM to the urban aerosol mass is increased by almost 30%, reflecting the impact of wood combustion (dominant fuel for domestic heating) to air quality in Athens, which massively started in winter 2013. PMID:25958364

  20. Handheld hyperspectral imager for standoff detection of chemical and biological aerosols

    NASA Astrophysics Data System (ADS)

    Hinnrichs, Michele; Jensen, James O.; McAnally, Gerard

    2004-02-01

    Pacific Advanced Technology has developed a small hand held imaging spectrometer, Sherlock, for gas leak and aerosol detection and imaging. The system is based on a patent technique that uses diffractive optics and image processing algorithms to detect spectral information about objects in the scene of the camera (IMSS Image Multi-spectral Sensing). This camera has been tested at Dugway Proving Ground and Dstl Porton Down facility looking at Chemical and Biological agent simulants. The camera has been used to investigate surfaces contaminated with chemical agent simulants. In addition to Chemical and Biological detection the camera has been used for environmental monitoring of green house gases and is currently undergoing extensive laboratory and field testing by the Gas Technology Institute, British Petroleum and Shell Oil for applications for gas leak detection and repair. The camera contains an embedded Power PC and a real time image processor for performing image processing algorithms to assist in the detection and identification of gas phase species in real time. In this paper we will present an over view of the technology and show how it has performed for different applications, such as gas leak detection, surface contamination, remote sensing and surveillance applications. In addition a sampling of the results form TRE field testing at Dugway in July of 2002 and Dstl at Porton Down in September of 2002 will be given.

  1. The Pasadena Aerosol Characterization Observatory (PACO): chemical and physical analysis of the Western Los Angeles Basin aerosol

    NASA Astrophysics Data System (ADS)

    Hersey, S. P.; Craven, J. S.; Schilling, K. A.; Metcalf, A. R.; Sorooshian, A.; Chan, M. N.; Flagan, R. C.; Seinfeld, J. H.

    2011-02-01

    The Pasadena Aerosol Characterization Observatory (PACO) represents the first major aerosol characterization experiment centered in the Western/Central Los Angeles Basin. The sampling site, located on the campus of the California Institute of Technology in Pasadena, was positioned to sample a continuous afternoon influx of transported urban aerosol with a photochemical age of 1-2 h and generally free from major local contributions. Sampling spanned 5 months during the summer of 2009, which were broken into 3 regimes on the basis of distinct meteorological conditions. Regime I was characterized by a series of low pressure systems, resulting in high humidity and rainy periods with clean conditions. Regime II typified early summer meteorology, with significant morning marine layers and warm, sunny afternoons. Regime III was characterized by hot, dry conditions with little marine layer influence. Organic aerosol (OA) is the most significant constituent of Los Angeles aerosol (42, 43, and 55% of total submicron mass in regimes I, II, and III, respectively), and that the overall oxidation state remains relatively constant on timescales of days to weeks (O:C = 0.44 ± 0.08, 0.55 ± 0.05, and 0.48 ± 0.08 during regimes I, II, and III, respectively), with no difference in O:C between morning and afternoon periods. Periods characterized by significant morning marine layer influence followed by photochemically favorable afternoons displayed significantly higher aerosol mass and O:C ratio, suggesting that aqueous processes may be important in the generation of secondary aerosol and oxidized organic aerosol (OOA) in Los Angeles. Water soluble organic mass (WSOM) reaches maxima near 14:00-15:00 local time (LT), but the percentage of AMS organic mass contributed by WSOM remains relatively constant throughout the day. Sulfate and nitrate reside predominantly in accumulation mode aerosol, while afternoon SOA production coincides with the appearance of a distinct fine mode

  2. Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

    NASA Astrophysics Data System (ADS)

    Parworth, Caroline; Fast, Jerome; Mei, Fan; Shippert, Tim; Sivaraman, Chitra; Tilp, Alison; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ∼30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations of the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.

  3. Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

    SciTech Connect

    Parworth, Caroline; Tilp, Alison; Fast, Jerome; Mei, Fan; Shippert, Tim; Sivaraman, Chitra; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ~30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations of the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.

  4. Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

    DOE PAGES

    Parworth, Caroline; Tilp, Alison; Fast, Jerome; Mei, Fan; Shippert, Tim; Sivaraman, Chitra; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ~30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations ofmore » the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.« less

  5. Aerosol Types using Passive Remote Sensing: Global Distribution, Consistency Check, Total-Column Investigation and Translation into Composition Derived from Climate and Chemical Transport Model

    NASA Astrophysics Data System (ADS)

    Kacenelenbogen, M. S.; Dawson, K. W.; Johnson, M. S.; Burton, S. P.; Redemann, J.; Hasekamp, O. P.; Hair, J. W.; Ferrare, R. A.; Butler, C. F.; Holben, B. N.; Beyersdorf, A. J.; Ziemba, L. D.; Froyd, K. D.; Dibb, J. E.; Shingler, T.; Sorooshian, A.; Jimenez, J. L.; Campuzano Jost, P.; Jacob, D. J.

    2015-12-01

    To improve the predictions of aerosol composition in chemical transport models (CTMs) and global climate models (GCMs), we have developed an aerosol classification algorithm (called Specified Clustering and Mahalanobis Classification, SCMC) that assigns an aerosol type to multi-parameter retrievals by spaceborne, airborne or ground based passive remote sensing instruments [Russell et al., 2014]. The aerosol types identified by our scheme are pure dust, polluted dust, urban-industrial/developed economy, urban-industrial/developing economy, dark biomass smoke, light biomass smoke and pure marine. We apply the SCMC method to two different total-column datasets of aerosol optical properties: inversions from the ground-based AErosol RObotic NETwork (AERONET) and retrievals from the space-borne POLDER (Polarization and Directionality of Earth's Reflectances) instrument. The POLDER retrievals that we use differ from the standard POLDER retrievals [Deuzé et al., 2001] as they make full use of multi-angle, multispectral polarimetric data [Hasekamp et al., 2011]. We analyze agreement in the aerosol types inferred from both AERONET and POLDER globally. Then, we investigate how our total-column "effective" SCMC aerosol types relate to different aerosol types within the column (i.e. either a mixture of different types within one layer in the vertical or the stacking of different aerosol types within the vertical column). For that, we compare AERONET-SCMC aerosol types to collocated NASA LaRC HSRL vertically resolved aerosol types [Burton et al., 2012] during the SEAC4RS and DISCOVER-AQ airborne field experiments, mostly over Texas in Aug-Sept 2013. Finally, in order to evaluate the GEOS-Chem CTM aerosol types, we translate each of our SCMC aerosol type into a unique distribution of GEOS-Chem aerosol composition (e.g. biomass burning, dust, sulfate, sea salt). We bridge the gap between remote sensing and model-inferred aerosol types by using multiple years of collocated AERONET

  6. Direct quantification of chemical warfare agents and related compounds at low ppt levels: comparing active capillary dielectric barrier discharge plasma ionization and secondary electrospray ionization mass spectrometry.

    PubMed

    Wolf, Jan-Christoph; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

    2015-01-01

    A novel active capillary dielectric barrier discharge plasma ionization (DBDI) technique for mass spectrometry is applied to the direct detection of 13 chemical warfare related compounds, including sarin, and compared to secondary electrospray ionization (SESI) in terms of selectivity and sensitivity. The investigated compounds include an intact chemical warfare agent and structurally related molecules, hydrolysis products and/or precursors of highly toxic nerve agents (G-series, V-series, and "new" nerve agents), and blistering and incapacitating warfare agents. Well-defined analyte gas phase concentrations were generated by a pressure-assisted nanospray with consecutive thermal evaporation and dilution. Identification was achieved by selected reaction monitoring (SRM). The most abundant fragment ion intensity of each compound was used for quantification. For DBDI and SESI, absolute gas phase detection limits in the low ppt range (in MS/MS mode) were achieved for all compounds investigated. Although the sensitivity of both methods was comparable, the active capillary DBDI sensitivity was found to be dependent on the applied AC voltage, thus enabling direct tuning of the sensitivity and the in-source fragmentation, which may become a key feature in terms of field applicability. Our findings underline the applicability of DBDI and SESI for the direct, sensitive detection and quantification of several CWA types and their degradation products. Furthermore, they suggest the use of DBDI in combination with hand-held instruments for CWAs on-site monitoring.

  7. Selectivity of negative ion chemical ionization mass spectrometry for benzo(a)pyrene

    SciTech Connect

    Hilpert, L.R.; Byrd, G.D.; Vogt, C.R.

    1984-09-01

    Gas chromatography/negative ion chemical ionization mass spectrometry (GC/NICIMS) was used as a selective and sensitive technique for the detection of benzo(a)pyrene (BaP). Under optimized conditions, the molecular anion, M/sup -/, of BaP was more than 3 orders of magnitude more abundant than that of its isomer benzo(e)pyrene (BeP) using methane as the reagent gas. Quantities of BaP as low as 1 pg can easily be detected in the selected ion monitoring mode and the response vs. concentration was linear over a range of 3 orders of magnitude. The absolute sensitivity and the selectivity for detection were found to depend on the pressure and temperature in the ion source of the mass spectrometer. NICIMS was used for the quantitative determination of BaP, indeno(1,2,3-cd)pyrene, and benzo(ghl)perylene in a sample of petroleum crude oil as part of the process of certifying the oil as a Standard Reference Material.

  8. Chemical ionization mass spectrometry using carbon nanotube field emission electron sources.

    PubMed

    Radauscher, Erich J; Keil, Adam D; Wells, Mitch; Amsden, Jason J; Piascik, Jeffrey R; Parker, Charles B; Stoner, Brian R; Glass, Jeffrey T

    2015-11-01

    A novel chemical ionization (CI) source has been developed based on a carbon nanotube (CNT) field emission electron source. The CNT-based electron source was evaluated and compared with a standard filament thermionic electron source in a commercial explosives trace detection desktop mass spectrometer. This work demonstrates the first reported use of a CNT-based ion source capable of collecting CI mass spectra. Both positive and negative modes were investigated. Spectra were collected for a standard mass spectrometer calibration compound, perfluorotributylamine (PFTBA), as well as trace explosives including trinitrotoluene (TNT), Research Department explosive (RDX), and pentaerythritol tetranitrate (PETN). The electrical characteristics, lifetime at operating pressure, and power requirements of the CNT-based electron source are reported. The CNT field emission electron sources demonstrated an average lifetime of 320 h when operated in constant emission mode under elevated CI pressures. The ability of the CNT field emission source to cycle on and off can provide enhanced lifetime and reduced power consumption without sacrificing performance and detection capabilities. Graphical Abstract ᅟ. PMID:26133527

  9. Chemical Ionization Mass Spectrometry Using Carbon Nanotube Field Emission Electron Sources

    NASA Astrophysics Data System (ADS)

    Radauscher, Erich J.; Keil, Adam D.; Wells, Mitch; Amsden, Jason J.; Piascik, Jeffrey R.; Parker, Charles B.; Stoner, Brian R.; Glass, Jeffrey T.

    2015-11-01

    A novel chemical ionization (CI) source has been developed based on a carbon nanotube (CNT) field emission electron source. The CNT-based electron source was evaluated and compared with a standard filament thermionic electron source in a commercial explosives trace detection desktop mass spectrometer. This work demonstrates the first reported use of a CNT-based ion source capable of collecting CI mass spectra. Both positive and negative modes were investigated. Spectra were collected for a standard mass spectrometer calibration compound, perfluorotributylamine (PFTBA), as well as trace explosives including trinitrotoluene (TNT), Research Department explosive (RDX), and pentaerythritol tetranitrate (PETN). The electrical characteristics, lifetime at operating pressure, and power requirements of the CNT-based electron source are reported. The CNT field emission electron sources demonstrated an average lifetime of 320 h when operated in constant emission mode under elevated CI pressures. The ability of the CNT field emission source to cycle on and off can provide enhanced lifetime and reduced power consumption without sacrificing performance and detection capabilities.

  10. Real-time flavor release from French fries using atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    van Loon, Wil A M; Linssen, Jozef P H; Boelrijk, Alexandra E M; Burgering, Maurits J M; Voragen, Alphons G J

    2005-08-10

    Flavor release from French fries was measured with atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) using both assessors (in vivo) and a mouth model system (in vitro). Several volatiles measured with APCI were identified with MS-MS. The effect of frying time, salt addition, and an alternative process using superheated steam was determined on I(max) (maximum intensity of compounds) and on t(max) (time of maximum intensity). In vitro a "chewing" frequency of 0.60 Hz caused an increased t(max) for low molecular weight compounds compared to the other frequencies tested. Above 0.93 Hz further increase in the frequency did not affect t(max). Trends observed with in vivo experiments could be verified with in vitro experiments. I(max) correlated well with frying time. Addition of salt resulted in a decreased t(max), suggesting a salting-out effect. The alternative process caused a layer of oil on the surface, and this resulted in a higher t(max), but no effect on I(max) was found. This phenomenon may be critical for the sensory quality and would not have been observed with static volatile measurements, demonstrating the value of flavor release measurements.

  11. A chemical ionization mass spectrometry technique for airborne measurements of ammonia

    NASA Astrophysics Data System (ADS)

    Nowak, J. B.; Neuman, J. A.; Kozai, K.; Huey, L. G.; Tanner, D. J.; Holloway, J. S.; Ryerson, T. B.; Frost, G. J.; McKeen, S. A.; Fehsenfeld, F. C.

    2007-05-01

    A chemical ionization mass spectrometer (CIMS) utilizing protonated acetone dimer ion chemistry to measure gas-phase ammonia (NH3) from the NOAA WP-3D aircraft is described. The average sensitivity determined from in-flight standard addition calibrations ranged from 2.6 to 5 ion counts s-1 pptv-1, depending on flow conditions, for 1 MHz of reagent ion signal. The instrument time response was determined to be 5 s from the 2 e-folding signal decay time after removal of a standard addition calibration. The instrumental background varied from flight to flight ranging from 0.5 to 1.3 ppbv. The variability between successive background measurements ranged from 50 pptv to 100 pptv. Total uncertainty for the 5 s data was conservatively estimated to be ±(30% + 125 pptv). Two NH3 sources were sampled during the New England Air Quality Study-Intercontinental Transport and Chemical Transformation (NEAQS-ITCT) 2004 campaign, one urban and one agricultural. During the 25 July flight, enhancements in NH3 mixing ratios were coincident with enhancements in CO, NOx, and SO2 mixing ratios downwind of New York City. The NH3 mixing ratios in the urban outflow plume ranged from 0.4 to 1 ppbv, or enhancements of 0.2 to 0.8 ppbv above local background. During the 15 August flight, NH3 mixing ratios were enhanced 0.3 to 0.45 ppbv above local background directly downwind of an agricultural area northeast of Atlanta, Georgia. The NH3 CIMS instrument has shown the ability to measure sub-ppbv NH3 levels at high time resolution from an aircraft.

  12. Chemical composition of emissions from urban sources of fine organic aerosol

    SciTech Connect

    Hildemann, L.M.; Markowski, G.R.; Cass, G.R. )

    1991-04-01

    A dilution source sampling system was used to collect primary fine aerosol emissions from important sources of urban organic aerosol, including a boiler burning No. 2 fuel oil, a home fireplace, a fleet of catalyst-equipped and noncatalyst automobiles, heavy-duty diesel trucks, natural gas home appliances, and meat cooking operations. Alternative dilution sampling techniques were used to collect emissions from cigarette smoking and a roofing tar pot, and grab sample techniques were employed to characterize paved road dust, brake lining wear, and vegetative detritus. Organic aerosol constituted the majority of the fine aerosol mass emitted from many of the sources tested. Fine primary organic aerosol emissions within the heavily urbanized western portion of the Los Angeles Basin were determined to total 29.8 metric ton/day. Over 40% of these organic aerosol emissions are from anthropogenic pollution sources that are expected to emit contemporary (nonfossil) aerosol carbon, in good agreement with the available ambient monitoring data.

  13. The ambient organic aerosol soluble in water: Measurements, chemical characterization, and an investigation of sources

    NASA Astrophysics Data System (ADS)

    Sullivan, Amy P.

    This thesis characterizes the ambient fine organic carbon (OC) aerosol and investigates its sources through the development and deployment of new analytical measurement techniques. Recognizing that OC is highly chemically complex, the approach was to develop methods capable of quantitatively measuring a large chemical fraction of the aerosol instead of specific chemical speciation. The focus is on organic compounds that are soluble in water (WSOC) since little is known about its chemical nature. The results from this thesis show that WSOC has mainly two sources: biomass burning and secondary organic aerosol (SOA). In urban areas, WSOC increases with plume age, and tracks other photochemically produced compounds. Chemical analysis of WSOC suggests that in urban Atlanta, the SOA is mainly small-chain aliphatic compounds indirectly linked to vehicle emissions. A method was first developed for quantitative on-line measurements of WSOC by extending the application of the Particle-into-Liquid Sampler (PILS) from inorganic to organic aerosol measurements. In this approach a PILS captures ambient particles into a flow of purified water, which is then forced through a liquid filter and the carbonaceous content quantified on-line by a Total Organic Carbon (TOC) analyzer. An instrument was first developed for ground-based measurements and then modified for airborne deployment. Ground-based measurements at the St. Louis - Midwest Supersite during the summer of 2003 showed that the fraction of OC that is water-soluble can have a highly diurnal pattern with WSOC to OC ratios reaching 0.80 during the day and lows of 0.40 during the night. During extended periods under stagnation pollution events, this pattern was well correlated with ozone concentrations. The results are consistent with formation of SOA. Airborne PILS-TOC measurements from the NOAA WP-3D during the New England Air Quality Study/Intercontinental Transport and Chemical Transformation (NEAQS/ITCT) 2004 program

  14. The Pasadena Aerosol Characterization Observatory (PACO): chemical and physical analysis of the Western Los Angeles basin aerosol

    NASA Astrophysics Data System (ADS)

    Hersey, S. P.; Craven, J. S.; Schilling, K. A.; Metcalf, A. R.; Sorooshian, A.; Chan, M. N.; Flagan, R. C.; Seinfeld, J. H.

    2011-08-01

    The Pasadena Aerosol Characterization Observatory (PACO) represents the first major aerosol characterization experiment centered in the Western/Central Los Angeles Basin. The sampling site, located on the campus of the California Institute of Technology in Pasadena, was positioned to sample a continuous afternoon influx of transported urban aerosol with a photochemical age of 1-2 h and generally free from major local contributions. Sampling spanned 5 months during the summer of 2009, which were broken into 3 regimes on the basis of distinct meteorological conditions. Regime I was characterized by a series of low pressure systems, resulting in high humidity and rainy periods with clean conditions. Regime II typified early summer meteorology, with significant morning marine layers and warm, sunny afternoons. Regime III was characterized by hot, dry conditions with little marine layer influence. Regardless of regime, organic aerosol (OA) is the most significant constituent of nonrefractory submicron Los Angeles aerosol (42, 43, and 55 % of total submicron mass in regimes I, II, and III, respectively). The overall oxidation state remains relatively constant on timescales of days to weeks (O:C = 0.44 ± 0.08, 0.55 ± 0.05, and 0.48 ± 0.08 during regimes I, II, and III, respectively), with no difference in O:C between morning and afternoon periods. Periods characterized by significant morning marine layer influence followed by photochemically favorable afternoons displayed significantly higher aerosol mass and O:C ratio, suggesting that aqueous processes may be important in the generation of secondary aerosol and oxidized organic aerosol (OOA) in Los Angeles. Online analysis of water soluble organic carbon (WSOC) indicates that water soluble organic mass (WSOM) reaches maxima near 14:00-15:00 local time (LT), but the percentage of AMS organic mass contributed by WSOM remains relatively constant throughout the day. Sulfate and nitrate reside predominantly in accumulation

  15. The chemical composition of fine ambient aerosol particles in the Beijing area

    NASA Astrophysics Data System (ADS)

    Nekat, Bettina; van Pinxteren, Dominik; Iinuma, Yoshiteru; Gnauk, Thomas; Müller, Konrad; Herrmann, Hartmut

    2010-05-01

    The strong economical growth in China during the last few decades led to heavy air pollution caused by significantly increased particle emissions. The aerosol particles affect not only the regional air quality and visibility, but can also influence cloud formation processes and the radiative balance of the atmosphere by their optical and microphysical properties. The ability to act as Cloud Condensation Nuclei (CCN) is related to microphysical properties like the hygroscopic growth or the cloud droplet activation. The chemical composition of CCN plays an important role on these properties and varies strongly with the particle size and the time of day. Hygroscopic or surface active substances can increase the hygroscopicity and lower the surface tension of the particle liquid phase, respectively. The presence of such compounds may result in faster cloud droplet activation by faster water uptake. The DFG project HaChi (Haze in China) aimed at studying physical and chemical parameters of urban aerosol particles in the Beijing area in order to associate the chemical composition of aerosol particles with their ability to act as CCN. To this end, two measurement campaigns were performed at the Wuqing National Ordinary Meteorological Observing Station, which is a background site near Beijing. The winter campaign was realized in March 2009 and the summer campaign took place from mid July 2009 to mid August 2009. Fine particles with an aerodynamic diameter smaller than or equal 1 μm were continuously sampled for 24h over the two campaigns using a DIGITEL high volume sampler (DHA-80). The present contribution presents and discusses the results of the chemical characterization of the DIGITEL filters samples. The filters were analyzed for the mass concentration, inorganic ions and carbon sum parameters like elemental (EC), organic (OC) and water soluble organic carbon (WSOC). The WSOC fraction was further characterized for hygroscopic substances like low molecular

  16. The Chemical and Microphysical Properties of Secondary Organic Aerosols from Holm Oak Emissions

    NASA Astrophysics Data System (ADS)

    Lang-Yona, Naama; Rudich, Yinon; Thomas, Mentel; Angela, Buchholz; Astrid, Kiendler-Scharr; Einhard, Kleist; Christian, Spindler; Ralf, Tillmann; Jürgen, Wildt

    2010-05-01

    Plant-emitted volatile organic compounds (VOC) undergo atmospheric oxidation, which leads to the formation of secondary organic aerosols (SOA). Large uncertainties exist about possible climatic effects on SOA formation from biogenic sources. Therefore it is important to investigate the impact of environmental conditions on the plants' emissions, on the formation of biogenic SOA, and on SOA properties in order to understand possible climatic impacts. The Mediterranean region is expected to experience substantial climatic change in the next 50 years and the possible effects on biogenic emissions are yet unexplored. To address such issues, the effects of temperature and light intensity on Mediterranean Holm Oak VOC emissions, as well as on microphysical properties and chemical composition of the resulting SOA have been studied in the Jülich plant aerosol atmosphere chamber. We studied SOA formation from Holm Oak under conditions possibly simulating future climate warming. Monoterpenes dominate the VOC emissions from Holm Oak (97.5%) and temperature increase enhanced the emission strength and changed the emission pattern. Enhanced emissions lead to linearly enhanced SOA formation with a fractional mass yield of SOA (5.7±1%) independent of the detailed emission pattern. The particles are highly scattering with no absorption abilities. Their average hygroscopic growth factor was 1.13±0.03 at 90% RH with a critical diameter of droplet activation was 100±4 nm at a supersaturation of 0.4%. All microphysical properties were not dependent on the detailed emission pattern, in accordance with an invariant O/C ratio (0.57(+0.03/-0.1)) of the SOA as derived from high resolution aerosol mass spectrometry. The temperature increase for the plants essentially led to stronger VOC emissions with the SOA mass being linearly related to the VOC concentrations. However, the increase of Holm oak emissions with temperature (≈ 20 % per degree) was stronger than for Boreal tree species

  17. Formation of Metal-Adducted Analyte Ions by Flame-Induced Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Cheng, Sy-Chyi; Wang, Chin-Hsiung; Shiea, Jentaie

    2016-05-17

    A flame-induced atmospheric pressure chemical ionization (FAPCI) source, consisting of a miniflame, nebulizer, and heated tube, was developed to ionize analytes. The ionization was performed by reacting analytes with a charged species generated in a flame. A stainless steel needle deposited with saturated alkali chloride solution was introduced into the mini oxyacetylene flame to generate alkali ions, which were reacted with analytes (M) generated in a heated nebulizer. The alkali-adducted 18-crown-6 ether ions, including (M + Li)(+), (M + Na)(+), (M + K)(+), (M + Rb)(+), and (M + Cs)(+), were successfully detected on the FAPCI mass spectra when the corresponding alkali chloride solutions were separately introduced to the flame. When an alkali chloride mixture was introduced, all alkali-adducted analyte ions were simultaneously detected. Their intensity order was as follows: (M + Cs)(+) > (M + Rb)(+) > (M + K)(+) > (M + Na)(+) > (M + Li)(+), and this trend agreed with the lattice energies of alkali chlorides. Besides alkali ions, other transition metal ions such as Ni(+), Cu(+), and Ag(+) were generated in a flame for analyte ionization. Other than metal ions, the reactive species generated in the fossil fuel flame could also be used to ionize analytes, which formed protonated analyte ions (M + H)(+) in positive ion mode and deprotonated analyte ions (M - H)(-) in negative ion mode.

  18. Size-segregated aerosol chemical composition at a boreal site in southern Finland, during the QUEST project

    NASA Astrophysics Data System (ADS)

    Cavalli, F.; Facchini, M. C.; Decesari, S.; Emblico, L.; Mircea, M.; Jensen, N. R.; Fuzzi, S.

    2006-03-01

    Size-segregated aerosol samples were collected during the QUEST field campaign at Hyytiää;, a boreal forest site in Southern Finland, during spring 2003. Aerosol samples were selectively collected during both particle formation events and periods in which no particle formation occurred.

    A comprehensive characterisation of the aerosol chemical properties (water-soluble inorganic and organic fraction) and an analysis of the relevant meteorological parameters revealed how aerosol chemistry and meteorology combine to determine a favorable "environment" for new particle formation. The results indicated that all events, typically favored during northerly air mass advection, were background aerosols (total mass concentrations range between 1.97 and 4.31 µg m-3), with an increasingly pronounced marine character as the northerly air flow arrived progressively from the west and, in contrast, with a moderate SO2-pollution influence as the air arrived from more easterly directions. Conversely, the non-event aerosol, transported from the south, exhibited the chemical features of European continental sites, with a marked increase in the concentrations of all major anthropogenic aerosol constituents. The higher non-event mass concentration (total mass concentrations range between 6.88 and 16.30 µg m-3) and, thus, a larger surface area, tended to suppress new particle formation, more efficiently depleting potential gaseous precursors for nucleation. The analysis of water-soluble organic compounds showed that clean nucleation episodes were dominated by aliphatic biogenic species, while non-events were characterised by a large abundance of anthropogenic oxygenated species. Interestingly, a significant content of α-pinene photo-oxidation products was observed in the events aerosol, accounting for, on average, 72% of their WSOC; while only moderate amounts of these species were found in the non-event aerosol. If the organic vapors condensing onto

  19. Size-segregated aerosol chemical composition at a boreal site in southern Finland, during the QUEST project

    NASA Astrophysics Data System (ADS)

    Cavalli, F.; Facchini, M. C.; Decesari, S.; Emblico, L.; Mircea, M.; Jensen, N. R.; Fuzzi, S.

    2005-09-01

    Size-segregated aerosol samples were collected during the QUEST field campaign at Hyytiälä, a boreal forest site in Southern Finland, during spring 2003. Aerosol samples were selectively collected during both particle formation events and periods in which no particle formation occurred. A comprehensive characterisation of the aerosol chemical properties (water-soluble inorganic and organic fraction) and an analysis of the relevant meteorological parameters revealed how aerosol chemistry and meteorology combine to determine a favorable "environment" for new particle formation. The results indicated that all events, typically favored during northerly air mass advection, were background aerosols (total mass concentrations range between 1.97 and 4.31 μg m-3), with an increasingly pronounced marine character as the northerly air flow arrived progressively from the west and, in contrast, with a moderate SO2-pollution influence as the air arrived from more easterly directions. Conversely, the non-event aerosol, transported from the south, exhibited the chemical features of European continental sites, with a marked increase in the concentrations of all major anthropogenic aerosol constituents. The higher non-event mass concentration (total mass concentrations range between 6.88 and 16.30 μg m-3) and, thus, a larger surface area, tended to suppress new particle formation, more efficiently depleting potential gaseous precursors for nucleation. The analysis of water-soluble organic compounds showed that clean nucleation episodes were dominated by aliphatic biogenic species, while non-events were characterised by a large abundance of anthropogenic oxygenated species. Interestingly, a significant content of α-pinene photo-oxidation products was observed in the events aerosol, accounting for, on average, 72% of their WSOC; while only moderate amounts of these species were found in the non-event aerosol. If the organic vapors condensing onto accumulation mode particles are

  20. Latitudinal Variation of Chemical Composition in Marine Aerosol Over the Central North Pacific in the Summer

    NASA Astrophysics Data System (ADS)

    Uematsu, M.; Narita, Y.; Mano, Y.; Iguchi, H.; Yoshida, K.; Iwamoto, Y.; Miura, K.

    2006-12-01

    Aeolian dust and gaseous and particulate pollutants from the Asian continent are transported eastward over the North Pacific. These natural and anthropogenic materials in the atmosphere can influence regional and global climate by altering the Earth's radiative balance. From the view of biogeochemical cycles, the atmospheric deposition of aerosols containing iron and other essential trace elements may contribute in sustaining primary productivity of phytoplankton, food web structure and chemical properties of marine atmosphere in the central North Pacific region. During the South-North cross-section cruise from 8 August to 21 September 2005, we conducted atmospheric sampling of aerosol and gaseous components on board R/V Hakuho Maru. Results from 10S to 53N along 160E revealed high nitrate concentration in the high latitude zone corresponded with back-air trajectories to subarctic North Pacific from the Asian continent during the summer. The atmospheric supply of nitrogen compounds may affect the primary production of stratified surface layer in the region. Non-sea-salt sulfate concentration was also high over the subarctic region, and downwind of the Hawaii islands. Volcanic and anthropogenic sulfur are suspected to be the sources of nss-sulfate. However, as an indicator of marine biogenic sulfate, methane sulfonic acid (MSA) is also correlated well with the concentration peaks of nss-sulfate both the vicinity of Hawaii islands and subarctic region. We will attempt to separate nss-sulfate into two fractions, marine biogenic and anthropogenic by using the relation between trace metals and sulfate over the source regions.

  1. Morphological and chemical changes of aerosolized E. coli treated with a dielectric barrier discharge

    DOE PAGES

    Romero-Mangado, Jaione; Nordlund, Dennis; Soberon, Felipe; Deane, Graham; Maughan, Kevin; Sainio, Sami; Singh, Gurusharan; Daniels, Stephen; Saunders, Ian T.; Loftus, David; et al

    2016-02-12

    This paper presents the morphological and chemical modification of the cell structure of aerosolized Escherichia coli treated with a dielectric barrier discharge (DBD). Exposure to DBD results in severe oxidation of the bacteria, leading to the formation of hydroxyl groups and carbonyl groups and a significant reduction in amine functionalities and phosphate groups. Near edge x-ray absorption fine structure(NEXAFS) measurements confirm the presence of additional oxide bonds upon DBD treatment, suggesting oxidation of the outer layer of the cell wall. Electron microscopy images show that the bacteria undergo physical distortion to varying degrees, resulting in deformation of the bacterial structure.more » The electromagnetic field around the DBD coil causes severe damage to the cell structure, possibly resulting in leakage of vital cellular materials. The oxidation and chemical modification of the bacterial components are evident from the Fourier transform infrared spectroscopy and NEXAFS results. The bacterial reculture experiments confirm inactivation of airborne E. coli upon treating with DBD.« less

  2. Uptake of Organic Vapors by Sulfate Aerosols: Physical and Chemical Processes

    NASA Technical Reports Server (NTRS)

    Michelsen, R. R.; Ashbourn, S. F. M.; Iraci, L.T.; Staton, S. J. R.

    2003-01-01

    While it is known that upper tropospheric sulfate particles contain a significant amount of organic matter, both the source of the organic fraction and its form in solution are unknown. These studies explore how the chemical characteristics of the molecules and surfaces in question affect heterogeneous interactions. The solubilities of acetaldehyde [CH3CHO] and ethanol [CH3CH20H] in cold, aqueous sulfuric acid solutions have been measured by Knudsen cell studies. Henry's law solubility coefficients range from 10(exp 2) to 10(exp 5) M/atm for acetaldehyde, and from 10(exp 4) to 10(exp 9) M/atm for ethanol under upper tropospheric conditions (210-240 K, 40-80 wt. % H2S04). The multiple solvation pathways (protonation, enolization, etc.) available to these compounds in acidic aqueous environments will be discussed. Preliminary results from the interaction of acetaldehyde with solutions of formaldehyde in sulfuric acid will be presented as well. The physical and chemical processes that affect organic uptake by aqueous aerosols will be explored, with the aim of evaluating organic species not yet studied in low temperature aqueous sulfuric acid.

  3. Handheld hyperspectral imager for standoff detection of chemical and biological aerosols

    NASA Astrophysics Data System (ADS)

    Hinnrichs, Michele; Jensen, James O.; McAnally, Gerard

    2004-08-01

    Pacific Advanced Technology has developed a small hand held imaging spectrometer, Sherlock, for gas leak and aerosol detection and imaging. The system is based on a patented technique, (IMSS Image Multi-spectral Sensing), that uses diffractive optics and image processing algorithms to detect spectral information about objects in the scene of the camera. This cameras technology has been tested at Dugway Proving Ground and Dstl Porton Down facilities looking at Chemical and Biological agent simulants. In addition to Chemical and Biological detection, the camera has been used for environmental monitoring of green house gases and is currently undergoing extensive laboratory and field testing by the Gas Technology Institute, British Petroleum and Shell Oil for applications for gas leak detection and repair. In this paper we will present some of the results from the data collection at the TRE test at Dugway Proving Ground during the summer of 2002 and laboratory testing at the Dstl facility at Porton Down in the UK in the fall of 2002.

  4. Correlations between Optical, Chemical and Physical Properties ofBiomass Burn Aerosols

    SciTech Connect

    Hopkins, Rebecca J.; Lewis, K.; Desyaterik, Yury; Wang, Z.; Tivanski, Alexei V.; Arnott, W.P.; Laskin, Alexander; Gilles, M.K.

    2008-01-29

    Aerosols generated from burning different plant fuels were characterized to determine relationships between chemical, optical and physical properties. Single scattering albedo ({omega}) and Angstrom absorption coefficients ({alpha}{sub ap}) were measured using a photoacoustic technique combined with a reciprocal nephelometer. Carbon-to-oxygen atomic ratios, sp{sup 2} hybridization, elemental composition and morphology of individual particles were measured using scanning transmission X-ray microscopy coupled with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) and scanning electron microscopy with energy dispersion of X-rays (SEM/EDX). Particles were grouped into three categories based on sp2 hybridization and chemical composition. Measured {omega} (0.4-1.0 at 405 nm) and {alpha}{sub ap} (1.0-3.5) values displayed a fuel dependence. The category with sp{sup 2} hybridization >80% had values of {omega} (<0.5) and {alpha}{sub ap} ({approx}1.25) characteristic of light absorbing soot. Other categories with lower sp2 hybridization (20 to 60%) exhibited higher {omega} (>0.8) and {alpha}{sub ap} (1.0 to 3.5) values, indicating increased absorption spectral selectivity.

  5. Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry

    SciTech Connect

    Tao, Shikang; Lu, Xiaohui; Levac, Nicole; Bateman, Adam P.; Nguyen, Tran B.; Bones, David L.; Nizkorodov, Sergey A.; Laskin, Julia; Laskin, Alexander; Yang, Xin

    2014-09-16

    Aerosol samples collected in the urban areas of Shanghai and Los Angeles were analyzed by nanospray-desorption electrospray ionization mass spectrometry (nano-DESI MS) with high mass resolution (m/Δm=100,000). Solvent mixtures of acetonitrile/water and acetonitrile/toluene were used to extract and ionize polar and non-polar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. Majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates in the two samples have distinctly different molecular characteristics. Specifically, organosulfates in the Los Angeles sample were dominated by isoprene- or monoterpene-derived products, while organosulfates of yet unknown origin in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degree of oxidation and unsaturation. The use of acetonitrile/toluene solvent facilitated identification of this type of organosulfates, suggesting they could be missed in previous studies relying on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the organosulfates detected in the Shanghai sample suggest that they may act as surfactants, and plausibly affect the surface tension and hygroscopicity of the atmospheric particulate matter. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in liquid phase could be the formation pathway of these special organosulfates. Finally, long-chain alkanes from vehicle emissions might be their precursors.

  6. Physical and Chemical Characterization of Particles in the Upper Troposphere and Lower Stratosphere: Microanalysis of Aerosol Impactor Samples

    NASA Technical Reports Server (NTRS)

    Sheridan, Patrick J.

    1999-01-01

    Herein is reported activities to support the characterization of the aerosol in the upper troposphere (UT) and lower stratosphere (LS) collected during the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA) missions in 1994. Through a companion proposal, another group was to measure the size distribution of aerosols in the 0.008 to 2 micrometer diameter range and to collect for us impactor samples of particles larger than about 0.02 gm. In the first year, we conducted laboratory studies related to particulate deposition patterns on our collection substrates, and have performed the analysis of many ASHOE/MAESA aerosol samples from 1994 using analytical electron microscopy (AEM). We have been building an "aerosol climatology" with these data that documents the types and relative abundances of particles observed at different latitudes and altitudes. The second year (and non-funded extension periods) saw continued analyses of impactor aerosol samples, including more ASHOE/MAESA samples, some northern hemisphere samples from the NASA Stratospheric Photochemistry Aerosols and Dynamics Expedition (SPADE) program for comparison, and a few aerosol samples from the NASA Stratospheric TRacers of Atmospheric Transport (STRAT) program. A high-resolution field emission microscope was used for the analysis and re-analysis of a number of samples to determine if this instrument was superior in performance to our conventional electron microscope. In addition, some basic laboratory studies were conducted to determine the minimum detectable and analyzable particle size for different types of aerosols. In all, 61 aerosol samples were analyzed, with a total of over 30,000 individual particle analyses. In all analyzed samples, sulfate particles comprised the major aerosol number fraction. It must be stressed that particles composed of more than one species, for example sulfate and organic carbon, were classified

  7. Seasonal characterization of submicron aerosol chemical composition and organic aerosol sources in the southeastern United States: Atlanta, Georgia,and Look Rock, Tennessee

    NASA Astrophysics Data System (ADS)

    Hapsari Budisulistiorini, Sri; Baumann, Karsten; Edgerton, Eric S.; Bairai, Solomon T.; Mueller, Stephen; Shaw, Stephanie L.; Knipping, Eladio M.; Gold, Avram; Surratt, Jason D.

    2016-04-01

    A year-long near-real-time characterization of non-refractory submicron aerosol (NR-PM1) was conducted at an urban (Atlanta, Georgia, in 2012) and rural (Look Rock, Tennessee, in 2013) site in the southeastern US using the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA) and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (up to 76 %) and sulfate (up to 31 %). Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the 1 year of near-continuous measurements at each site: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), semi-volatile oxygenated OA (SV-OOA), low-volatility oxygenated OA (LV-OOA), isoprene-derived epoxydiols (IEPOX) OA (IEPOX-OA) and 91Fac (a factor dominated by a distinct ion at m/z 91 fragment ion previously observed in biogenic influenced areas). LV-OOA was observed throughout the year at both sites and contributed up to 66 % of total OA mass. HOA was observed during the entire year only at the urban site (on average 21 % of OA mass). BBOA (15-33 % of OA mass) was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly ( ˜ 27 %), it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27-41 %) of OA at both sites, particularly in spring and summer. An ion fragment at m/z 75 is well correlated with the m/z 82 ion associated with the aerosol mass spectrum of IEPOX-derived secondary organic aerosol (SOA). The

  8. Microstructural, chemical and textural characterization of ZnO nanorods synthesized by aerosol assisted chemical vapor deposition

    SciTech Connect

    Sáenz-Trevizo, A.; Amézaga-Madrid, P.; Fuentes-Cobas, L.; Pizá-Ruiz, P.; Antúnez-Flores, W.; Ornelas-Gutiérrez, C.; Pérez-García, S.A.; Miki-Yoshida, M.

    2014-12-15

    ZnO nanorods were synthesized by aerosol assisted chemical vapor deposition onto TiO{sub 2} covered borosilicate glass substrates. Deposition parameters were optimized and kept constant. Solely the effect of different nozzle velocities on the growth of ZnO nanorods was evaluated in order to develop a dense and uniform structure. The crystalline structure was characterized by conventional X-ray diffraction in grazing incidence and Bragg–Brentano configurations. In addition, two-dimensional grazing incidence synchrotron radiation diffraction was employed to determine the preferred growth direction of the nanorods. Morphology and growth characteristics analyzed by electron microscopy were correlated with diffraction outcomes. Chemical composition was established by X-ray photoelectron spectroscopy. X-ray diffraction results and X-ray photoelectron spectroscopy showed the presence of wurtzite ZnO and anatase TiO{sub 2} phases. Morphological changes noticed when the deposition velocity was lowered to the minimum, indicated the formation of relatively vertically oriented nanorods evenly distributed onto the TiO{sub 2} buffer film. By coupling two-dimensional X-ray diffraction and computational modeling with ANAELU it was proved that a successful texture determination was achieved and confirmed by scanning electron microscopy analysis. Texture analysis led to the conclusion of a preferred growth direction in [001] having a distribution width Ω = 20° ± 2°. - Highlights: • Uniform and pure single-crystal ZnO nanorods were obtained by AACVD technique. • Longitudinal and transversal axis parallel to the [001] and [110] directions, respectively. • Texture was determined by 2D synchrotron diffraction and electron microscopy analysis. • Nanorods have its [001] direction distributed close to the normal of the substrate. • Angular spread about the preferred orientation is 20° ± 2°.

  9. Automated Measurements of Ambient Aerosol Chemical Composition and its Dry and Wet Size Distributions at Pittsburgh Supersite

    NASA Astrophysics Data System (ADS)

    Khlystov, A. Y.; Stanier, C.; Chun, W.; Vayenas, D.; Mandiro, M.; Pandis, S. N.

    2001-12-01

    Ambient aerosol particles change size with changes in ambient relative humidity. The magnitude of the size change depends on the hygroscopic properties of the particles, which is determined by their chemical composition. Hygroscopic properties of particles influence many environmentally important aerosol qualities, such as light scattering and partitioning between the gas and particle phases of semivolitile compounds. Studying the hygroscopic growth of ambient particles is thus of paramount importance. The highroscopic growth of ambient particles and their chemical composition are measured continuously within the Pittsburgh Air Quality Study (EPA supersite program). The hygroscopic size changes are measured using an automated system built for this study. The system consists of two Scanning Mobility Particle Sizers (SMPS, TSI Inc.) and an Aerodynamic Particle Sizer (APS, TSI Inc.). The three instruments measure aerosol size distribution between 5 nanometers and 10 micrometers in diameter. The inlets of the instruments and the sheath air lines of the SMPS systems are equipped with computer controlled valves that direct air through Nafion dryers (PermaPure Inc.) or bypass them. The Nafion dryers are drying the air stream below 40% RH at which point ambient particles are expected to lose most or all water and thus be virtually dry. To avoid changes in relative humidity and evaporation of volatile particles due to temperature differences the system is kept at ambient temperature. The system measures alternatively dry (below 40% RH) and wet (actual ambient RH) aerosol size distributions every 6 minutes. The hygroscopic growth observed with the size-spectrometer system is compared with theoretic predictions based on the chemical composition of aerosol particles. A modified semi-continuous Steam-Jet Aerosol Collector provides the total available budget (particles and gas) of water-soluble species, which is used as an input to the thermodynamic model. The model calculates

  10. Analysis of the Effects of Chemical Composition and Humidity on Visibility using Highly Time Resolved Aerosol Data

    NASA Astrophysics Data System (ADS)

    Lunden, M. M.; Brown, N. J.; Liu, D.; Tonse, S.

    2005-12-01

    Transported aerosols from populated and industrial areas result in regional haze that causes visibility degradation in areas valued for their scenic beauty, such as the National Parks. These areas are designated as Class I Areas in the United States, and there are specific visibility goals put forth to ultimately return these areas to natural conditions. To both understand current conditions and chart progress towards meeting these goals requires measurement of important aerosol species and an understanding of how these different aerosol species affect light attenuation to allow for predictive modeling capabilities. The current investigation seeks to understand if more highly time resolved measurements of chemically speciated particle mass, relative humidity, scattering, and absorption would enable a better estimation of extinction as the relationship between these variables is non-linear. Our particular objective is to explore the contributions of the aerosol species mentioned above to visibility degradation, and the role played by relative humidity. We performed analyses on a data set collected in Central California from the intensive ambient aerosol sampling campaign conducted from 2000 summer-2001 winter1. The data include PM-2.5 mass concentrations of nitrate, sulfate, organic carbon and black carbon aerosol, as well as simultaneous measurements on light scattering, ambient temperature and relative humidity. The dataset is highly time-resolved, allowing the affect of temporal variations of particle chemical composition and meteorological features to be considered. The final results provide response curves that allow calculation of light scattering given aerosol concentrations and relative humidity. Our results are compared with those obtained using formulae suggested for analysis of IMPROVE (a regional haze monitoring network2) data collected under lower temporal resolution to understand the effects of temporal resolution on the characteristics of the

  11. Chemical composition of aerosol particles and light extinction apportionment before and during the heating season in Beijing, China

    NASA Astrophysics Data System (ADS)

    Wang, Qingqing; Sun, Yele; Jiang, Qi; Du, Wei; Sun, Chengzhu; Fu, Pingqing; Wang, Zifa

    2015-12-01

    Despite extensive efforts into characterization of the sources and formation mechanisms of severe haze pollution in the megacity of Beijing, the response of aerosol composition and optical properties to coal combustion emissions in the heating season remain poorly understood. Here we conducted a 3 month real-time measurement of submicron aerosol (PM1) composition by an Aerosol Chemical Speciation Monitor and particle light extinction by a Cavity Attenuated Phase Shift extinction monitor in Beijing, China, from 1 October to 31 December 2012. The average (±σ) PM1 concentration was 82.4 (±73.1) µg/m3 during the heating period (HP, 15 November to 31 December), which was nearly 50% higher than that before HP (1 October to 14 November). While nitrate and secondary organic aerosol (SOA) showed relatively small changes, organics, sulfate, and chloride were observed to have significant increases during HP, indicating the dominant impacts of coal combustion sources on these three species. The relative humidity-dependent composition further illustrated an important role of aqueous-phase processing for the sulfate enhancement during HP. We also observed great increases of hydrocarbon-like OA (HOA) and coal combustion OA (CCOA) during HP, which was attributed to higher emissions at lower temperatures and coal combustion emissions, respectively. The relationship between light extinction and chemical composition was investigated using a multiple linear regression model. Our results showed that the largest contributors to particle extinction were ammonium nitrate (32%) and ammonium sulfate (28%) before and during HP, respectively. In addition, the contributions of SOA and primary OA to particle light extinction were quantified. The results showed that the OA extinction was mainly caused by SOA before HP and by SOA and CCOA during HP, yet with small contributions from HOA and cooking aerosol for the entire study period. Our results elucidate substantial changes of aerosol

  12. Urban aerosol in Oporto, Portugal: Chemical characterization of PM10 and PM2.5

    NASA Astrophysics Data System (ADS)

    Custódio, Danilo; Ferreira, Catarina; Alves, Célia; Duarte, Mácio; Nunes, Teresa; Cerqueira, Mário; Pio, Casimiro; Frosini, Daniele; Colombi, Cristina; Gianelle, Vorne; Karanasiou, Angeliki; Querol, Xavier

    2014-05-01

    Several urban and industrial areas in Southern Europe are not capable of meeting the implemented EU standards for particulate matter. Efficient air quality management is required in order to ensure that the legal limits are not exceeded and that the consequences of poor air quality are controlled and minimized. Many aspects of the direct and indirect effects of suspended particulate matter on climate and public health are not well understood. The temporal variation of the chemical composition is still demanded, since it enables to adopt off-set strategies and to better estimate the magnitude of anthropogenic forcing on climate. This study aims to provide detailed information on concentrations and chemical composition of aerosol from Oporto city, an urban center in Southern Europe. This city is located near the coast line in the North of Portugal, being the country's second largest urban area. Moreover, Oporto city economic prospects depend heavily on a diversified industrial park, which contribute to air quality degradation. Another strong source of air pollution is traffic. The main objectives of this study are: 1) to characterize the chemical composition of PM10 and PM2.5 by setting up an orchestra of aerosol sampling devices in a strategic place in Oporto; 2) to identify the sources of particles exploring parameters such as organic and inorganic markers (e.g. sugars as tracers for biomass burning; metals and elemental carbon for industrial and vehicular emissions); 3) to evaluate long range transport of pollutants using back trajectory analysis. Here we present data obtained between January 2013 and January 2014 in a heavy traffic roadside sampling site located in the city center. Different PM10 and PM2.5 samplers were operated simultaneously in order to collect enough mass on different filter matrixes and to fulfill the requirements of analytical methodologies. More than 100 aerosol samples were collected and then analysed for their mass concentration and

  13. The optical, physical and chemical properties of the products of glyoxal uptake on ammonium sulfate seed aerosols

    NASA Astrophysics Data System (ADS)

    Trainic, M.; Abo Riziq, A.; Lavi, A.; Flores, J. M.; Rudich, Y.

    2011-09-01

    The heterogeneous reaction between gas phase glyoxal and ammonium sulfate (AS) aerosols, a proxy for inorganic atmospheric aerosol, was studied in terms of the dependence of the optical, physical and chemical properties of the product aerosols on initial particle size and ambient relative humidity (RH). Our experiments imitate an atmospheric scenario of a dry particle hydration at ambient RH conditions in the presence of glyoxal gas followed by efflorescence due to decrease of the ambient RH. The reactions were studied under different RH conditions, starting from dry conditions (~20% RH) and up to 90% RH, covering conditions prevalent in many atmospheric environments, and followed by consequent drying of the reacted particles before their analysis by the aerosol mass spectrometer (AMS), cavity ring down (CRD) and scanning mobility particle sizer (SMPS) systems. At λ = 355 nm, the reacted aerosols demonstrate a substantial growth in optical extinction cross section, as well as in mobility diameter under a broad range of RH values (35-90%). The ratio of the product aerosol to seed aerosol geometric cross section reached up to ~3.5, and the optical extinction cross-section up to ~250. The reactions show a trend of increasing physical and optical growth with decreasing seed aerosol size, from 100 nm to 300 nm, as well as with decreasing RH values from 90% to ~40%. Optically inactive aerosols, at the limit of the Mie range (100 nm diameter) become optically active as they grow due to the reaction. AMS analyses of the reaction of 300 nm AS at RH values of 50%, 75% and 90% show that the main products of the reaction are glyoxal oligomers, formed by acetal formation in the presence of AS. In addition, imidazole formation, which is a minor channel, is observed for all reactions, yielding a product which absorbs at λ = 290 nm, with possible implications on the radiative properties of the product aerosols. The ratio of absorbing substances (C-N compounds, including

  14. AEROSOL CHEMICAL CHARACTERISTION ON BOARD THE DOE G1 AIRCRAFT USING A PARTICLE INTO LIQUID SAMPLER DURING THE TEXAQS 2000 EXPERIMENT.

    SciTech Connect

    LEE,Y.N.; SONG,Z.; LIU,Y.; DAUM,P.; WEBER,R.; ORSINI,D.; LAULAINEN,N.; HUBBE,J.; MORRIS,V.

    2001-01-13

    Knowledge of aerosol chemical composition is key to understanding a number of properties of ambient aerosol particles including sources, size/number distribution, chemical evolution, optical properties and human health effects. Although filter based techniques have been widely used to determine aerosol chemical constituents, they generally cannot provide sufficiently fast time resolution needed to investigate sources and chemical evolution that effect aerosol chemical, size and number changes. In order to gain an ability to describe and predict the life cycles of ambient aerosols as a basis for ambient air quality control, fast and sensitive determination of the aerosol chemical composition must be made available. To help to achieve this goal, we deployed a newly developed technique, referred to as PILS (particle-into-liquid-sampler), on the DOE G1 aircraft during the 2000 Texas Air Quality Study (TexAQS 2000) to characterize the major ionic species of aerosol particles with aerodynamic size smaller than 2.5 {micro}m (PM 2.5). The results obtained are examined in the context of other simultaneously collected data for insights into the measurement capability of the PILS system.

  15. Temporal variability in Chemical and Stable isotopic characteristics of ambient bulk aerosols over a coastal environment of India

    NASA Astrophysics Data System (ADS)

    Agnihotri, R.; Karapurkar, S. G.; Sarma, V. V.; Praveen, P.; Kumar, M. D.

    2012-12-01

    Atmospheric carbonaceous aerosols are known to influence regional biogeochemical cycles of carbon (C) and nitrogen (N) in addition to regional radiation budgets. Owing to multiplicity of primary sources of natural and anthropogenic origin, their detailed chemical and isotopic characterization can greatly help in source apportionment and identifying secondary processes. From the roof of NIO-Goa (India) [15.46οN, 73.8oE; at ~55.8 MASL], atmospheric bulk aerosols (n=22) were collected on Quartz filters, from 2009 December to January 2011 covering entire 2010 (except monsoon period) to investigate temporal variability in their chemical and isotopic characteristics of the carbonaceous fraction i.e. TC, TOC and TN mass concentrations and their stable isotopic ratios (δ13CTC, δ13CTOC and δ15NTN). Both δ13CTC and δ13CTOC varied in narrow ranges (-24.9±1.1‰, -25.7±0.9‰ respectively), but significant differences were observed between the two during pre-monsoon months (as high as 2.3‰), possibly due to mixing of inorganic mineral dust. δ15NTN values showed a wide range of variability (average = 13.6±7.2‰), with significantly lower values (~2-5‰; as reported earlier by Agnihotri et al. 2011) during pre-monsoon period compared to those during winter (as high as ~26‰). Using δ13CTC values and two end-member mixing model (assuming δ13C of marine and continental carbon as -21 and -27‰ respectively), the average marine carbon fraction for Goa aerosols was estimated as 36±18.5%, significantly higher than reported for Chennai aerosols (~19%) (Pavuluri et al., 2011), but close to the reported average for marine aerosols at Bermuda (38%) (Turekian et al., 2003). Chemical and isotopic characteristics of ambient aerosols over Goa along with contemporaneous meteorological data indicate that winter aerosols contain significant proportion of carbonaceous fraction originated from biomass burning and other anthropogenic activities carried out in northern parts of

  16. Wintertime aerosol chemical composition, volatility, and spatial variability in the greater London area

    DOE PAGES

    Xu, L.; Williams, L. R.; Young, D. E.; Allan, J. D.; Coe, H.; Massoli, P.; Fortner, E.; Chhabra, P.; Herndon, S.; Brooks, W. A.; et al

    2016-02-02

    The composition of PM1 (particulate matter with diameter less than 1 µm) in the greater London area was characterized during the Clean Air for London (ClearfLo) project in winter 2012. Two high-resolution time-of-flight aerosol mass spectrometers (HR-ToF-AMS) were deployed at a rural site (Detling, Kent) and an urban site (North Kensington, London). The simultaneous and high-temporal resolution measurements at the two sites provide a unique opportunity to investigate the spatial distribution of PM1. We find that the organic aerosol (OA) concentration is comparable between the rural and urban sites, but the contribution from different sources is distinctly different between the two sites.more » The concentration of solid fuel OA at the urban site is about twice as high as at the rural site, due to elevated domestic heating in the urban area. While the concentrations of oxygenated OA (OOA) are well-correlated between the two sites, the OOA concentration at the rural site is almost twice that of the urban site. At the rural site, more than 70 % of the carbon in OOA is estimated to be non-fossil, which suggests that OOA is likely related to aged biomass burning considering the small amount of biogenic SOA in winter. Thus, it is possible that the biomass burning OA contributes a larger fraction of ambient OA in wintertime than what previous field studies have suggested. A suite of instruments was deployed downstream of a thermal denuder (TD) to investigate the volatility of PM1 species at the rural Detling site. After heating at 250 °C in the TD, 40 % of the residual mass is OA, indicating the presence of non-volatile organics in the aerosol. Although the OA associated with refractory black carbon (rBC; measured by a soot-particle aerosol mass spectrometer) only accounts for < 10 % of the total OA (measured by a HR-ToF-AMS) at 250 °C, the two measurements are well-correlated, suggesting that the non-volatile organics have similar sources or have

  17. Wintertime aerosol chemical composition, volatility, and spatial variability in the greater London area

    NASA Astrophysics Data System (ADS)

    Xu, L.; Williams, L. R.; Young, D. E.; Allan, J. D.; Coe, H.; Massoli, P.; Fortner, E.; Chhabra, P.; Herndon, S.; Brooks, W. A.; Jayne, J. T.; Worsnop, D. R.; Aiken, A. C.; Liu, S.; Gorkowski, K.; Dubey, M. K.; Fleming, Z. L.; Visser, S.; Prévôt, A. S. H.; Ng, N. L.

    2016-02-01

    The composition of PM1 (particulate matter with diameter less than 1 µm) in the greater London area was characterized during the Clean Air for London (ClearfLo) project in winter 2012. Two high-resolution time-of-flight aerosol mass spectrometers (HR-ToF-AMS) were deployed at a rural site (Detling, Kent) and an urban site (North Kensington, London). The simultaneous and high-temporal resolution measurements at the two sites provide a unique opportunity to investigate the spatial distribution of PM1. We find that the organic aerosol (OA) concentration is comparable between the rural and urban sites, but the contribution from different sources is distinctly different between the two sites. The concentration of solid fuel OA at the urban site is about twice as high as at the rural site, due to elevated domestic heating in the urban area. While the concentrations of oxygenated OA (OOA) are well-correlated between the two sites, the OOA concentration at the rural site is almost twice that of the urban site. At the rural site, more than 70 % of the carbon in OOA is estimated to be non-fossil, which suggests that OOA is likely related to aged biomass burning considering the small amount of biogenic SOA in winter. Thus, it is possible that the biomass burning OA contributes a larger fraction of ambient OA in wintertime than what previous field studies have suggested. A suite of instruments was deployed downstream of a thermal denuder (TD) to investigate the volatility of PM1 species at the rural Detling site. After heating at 250 °C in the TD, 40 % of the residual mass is OA, indicating the presence of non-volatile organics in the aerosol. Although the OA associated with refractory black carbon (rBC; measured by a soot-particle aerosol mass spectrometer) only accounts for < 10 % of the total OA (measured by a HR-ToF-AMS) at 250 °C, the two measurements are well-correlated, suggesting that the non-volatile organics have similar sources or have undergone similar chemical

  18. Chemical composition of size-segregated aerosols in Lhasa city, Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Wan, Xin; Kang, Shichang; Xin, Jinyuan; Liu, Bin; Wen, Tianxue; Wang, Pengling; Wang, Yuesi; Cong, Zhiyuan

    2016-06-01

    To reveal the chemical characteristics of size-segregated aerosols in the high-altitude city of Tibetan Plateau, eight-size aerosol samples were collected in Lhasa from March 2013 to February 2014. The annual mean of online PM2.5 was 25.0 ± 16.0 μg m- 3, which was much lower than Asian cities but similar with some European cities. The annual mean concentrations of organic carbon (OC, 7.92 μg m- 3 in PM2.1 and 12.66 μg m- 3 in PM9.0) and elemental carbon (EC, 1.00 μg m- 3 in PM2.1 and 1.21 μg m- 3 in PM9.0) in Lhasa aerosols were considerably lower than those heavily polluted cities such as Beijing and Xi'an, China and Kathmandu, Nepal. Sulfate, NO3-, NH4+ and Ca2 + were 0.75 ± 0.31, 0.82 ± 0.35, 0.38 ± 0.34 and 0.57 ± 0.29 μg m- 3 in fine particles while in coarse particles they were 0.57 ± 0.37, 0.73 ± 0.23, 0.07 ± 0.03 and 2.52 ± 1.37 μg m- 3, respectively. Secondary water-soluble ions composed 35.8% of the total ionic components in fine particles according to the established electroneutrality, while in coarse particles they took up only 9.3%. Ca2 + (40.6%) was the major component of the coarse particles. For seasonality, the concentrations of OC, EC, SO42 -, NH4+, K+, Ca2 +, Mg2 +, Cl- and Na+ presented higher values during late autumn and winter but were relatively lower in spring and summer. Nevertheless, NO3- was considerably higher in summer and autumn, presumably due to increased tourist-vehicle emissions. During winter and spring, [Ca2 +]/[NO3-+ SO42 -] ratios in coarse particles showed higher values of 7.31 and 6.17, respectively, emphasizing the dust influence. [NO3-]/[SO42 -] ratios in fine particles during spring, summer and autumn exceeding 1 indicated that the currently predominant vehicle exhaust makes a greater contribution to the aerosols. While more stationary sources such as coal and biomass burning existed in winter since the [NO3-]/[SO42 -] ratio was less than 1. Different sources and formation processes lead to a bimodal size

  19. The effect of local sources on particle size and chemical composition and their role in aerosol-cloud interactions

    NASA Astrophysics Data System (ADS)

    Portin, H.; Leskinen, A.; Hao, L.; Kortelainen, A.; Miettinen, P.; Jaatinen, A.; Laaksonen, A.; Lehtinen, K. E. J.; Romakkaniemi, S.; Komppula, M.

    2013-12-01

    The effects of local pollutant sources and particle chemical composition on aerosol-cloud interactions were investigated by measuring cloud interstitial and total aerosol size distributions, particle chemical composition and hygroscopic growth factors and cloud droplet size distributions on an observation tower, with a special focus on comparing clean air masses with those affected by local sources. The polluted air masses contained more particles than the clean air masses in all size classes, excluding the accumulation mode. This was caused by cloud processing, which was also observed for the polluted air but to a lesser extent. Some, mostly minor, differences in the particle chemical composition between the air masses were observed. The average size and number concentration of activating particles were quite similar for both air masses, producing average droplet populations with only minor distinctions. As a case study, a long cloud event was analyzed in detail regarding emissions from local sources, including a paper mill and a heating plant. Clear differences in the total and accumulation mode particle concentrations, particle hygroscopicity and chemical composition during the cloud event were observed. Particularly, larger particles, higher hygroscopicities and elevated amounts of inorganic constituents, especially SO4, were linked with the pollutant plumes. In the air masses affected by traffic and domestic wood combustion, a bimodal particle hygroscopicity distribution was observed, indicating externally mixed aerosol. The variable conditions during the event had a clear impact on cloud droplet formation.

  20. 2014 iAREA campaign on aerosol in Spitsbergen - Part 1: Study of physical and chemical properties

    NASA Astrophysics Data System (ADS)

    Lisok, J.; Markowicz, K. M.; Ritter, C.; Makuch, P.; Petelski, T.; Chilinski, M.; Kaminski, J. W.; Becagli, S.; Traversi, R.; Udisti, R.; Rozwadowska, A.; Jefimow, M.; Markuszewski, P.; Neuber, R.; Pakszys, P.; Stachlewska, I. S.; Struzewska, J.; Zielinski, T.

    2016-09-01

    This paper presents the results of measurements of aerosol physical and chemical properties during iAREA2014 campaign that took place on Svalbard between 15th of Mar and 4th of May 2014. With respect to field area, the experiment consisted of two sites: Ny-Ålesund (78°55‧N, 11°56‧E) and Longyearbyen (78°13‧N, 15°33‧E) with further integration of Aerosol Robotic Network (AERONET) station in Hornsund (77°00‧N, 15°33‧E). The subject of this study is to investigate the in-situ, passive and active remote sensing observations as well as numerical simulations to describe the temporal variability of aerosol single-scattering properties during spring season on Spitsbergen. The retrieval of the data indicates several event days with enhanced single-scattering properties due to the existence of sulphate and additional sea-salt load in the atmosphere which is possibly caused by relatively high wind speed. Optical results were confirmed by numerical simulations made by the GEM-AQ model and by chemical observations that indicated up to 45% contribution of the sea-salt to a PM10 total aerosol mass concentration. An agreement between the in-situ optical and microphysical properties was found, namely: the positive correlation between aerosol scattering coefficient measured by the nephelometer and effective radius obtained from laser aerosol spectrometer as well as negative correlation between aerosol scattering coefficient and the Ångstrom exponent indicated that slightly larger particles dominated during special events. The in-situ surface observations do not show any significant enhancement of the absorption coefficient as well as the black carbon concentration which might occur during spring. All of extensive single-scattering properties indicate a diurnal cycle in Longyearbyen, where 21:00-5:00 data stays at the background level, however increasing during the day by the factor of 3-4. It is considered to be highly connected with local emissions originating

  1. Aerosol assisted chemical vapour deposition of Cu-ZnO composite from single source precursors.

    PubMed

    Shahid, Muhammad; Mazhar, Muhammad; Hamid, Mazhar; O'Brien, Paul; Malik, Mohammad A; Helliwell, Madeleine; Raftery, James

    2009-07-28

    Two heterobimetallic precursors [Zn(TFA)3(micro-OH)Cu3(dmae)3Cl].THF (1) and [Zn(TFA)4Cu3(dmae)4] (2) [dmae=N,N-dimethylaminoethanolate and TFA=trifluoroacetate], have been synthesized and characterized by their melting points, elemental analysis, FT-IR spectroscopy, mass spectrometry, TGA and single crystal X-ray diffraction methods. Both complexes were used to deposit thin films of Cu-ZnO composite on glass substrates by aerosol assisted chemical vapor deposition (AACVD) method. The films were characterized by "scotch tape" test for adhesion, thickness measurement as a function of temperature, EDX for composition, SEM for surface morphology and XRD for crystalline phases. Thin film deposition studies at 250, 325, 400, 475 degrees C indicated the increase in thickness with temperature reaching a maximum at 400 degrees C and then decreasing. EDX and PXRD results showed the uniform distribution of cubic metallic copper and hexagonal zinc oxide phases which make them useful for nanocatalysis on structured surfaces. PMID:19587992

  2. Simplified route to multi-walled carbon nanotube synthesis by aerosol assisted chemical vapor deposition.

    PubMed

    Antúnez-Flores, W; Valenzuela-Muñiz, A M; Amézaga-Madrid, P; Alonso-Nuñez, G; Verde, Y; Martínez-Sánchez, R; Miki-Yoshida, M

    2008-12-01

    Uniform multi-walled carbon nanotubes (MWCNTs) were obtained decomposing toluene inside of fused silica tubing previously covered with Co oxide thin film. The two-step process, ruled successively in the same aerosol assisted chemical vapor deposition (AACVD) set up, constitutes a simplified route to the synthesis of MWCNTs. First, Co oxide thin film was deposited inside of fused silica tubing at 723 K, using a precursor solution of Co acetate in absolute methanol. After Co oxide deposition, the covered tubing was heated up to 1173 K under Ar flow, then a mist of toluene was injected inside the tubing, using also Ar as carrier gas, consequently MWCNTs were obtained in the internal wall of the tubing. The Co oxide film and the MWCNTs were analyzed by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM). Uniform and very long MWCNTs (several tens of microm) with diameters around 20 to 100 nm were observed, with the advantage that the content of Co particles inside the nanotube was very low. PMID:19205220

  3. Aerosol-assisted chemical vapor deposition (AACVD) of binary alloy films: Studies of film composition

    SciTech Connect

    Xu, C.; Hampden-Smith, M.J.; Kodas, T.T.

    1995-08-01

    The chemical vapor deposition (CVD) of Cu-Ag and Cu-Pd alloys using aerosol precursor delivery over a range of preheating temperatures, 70 {approximately} 80 C and substrate temperatures, 250 {approximately} 300 C is described. The precursors used include Cu(hfac){sub 2}, (hfac)Ag(SEt{sub 2}) and Pd(hfac){sub 2} dissolved in toluene and 10% H{sub 2} in Ar as carrier gas. The films were characterized by SEM, EDS and X-ray diffraction (XRD). The X-ray diffraction results showed the Cu/Ag films were composed of {alpha}- and {beta}-phases of Cu-Ag alloys, the Cu/Pd films were Cu-Pd and Pd-Ag alloy, solid solutions, under these conditions. Compositional variation studies in Cu-Pd and Pd-Ag alloy systems were also conducted by mixing Cu(hfac){sub 2}/Pd(hfac){sub 2} and (hfac) Ag(SEt{sub 2})/Pd(hfac){sub 2} in toluene solution in different ratios. The films were characterized by X-ray diffraction and the results showed the composition of films was affected by the solution stoichiometry.

  4. Sensitive monitoring of volatile chemical warfare agents in air by atmospheric pressure chemical ionization mass spectrometry with counter-flow introduction.

    PubMed

    Seto, Yasuo; Kanamori-Kataoka, Mieko; Tsuge, Koichiro; Ohsawa, Isaac; Iura, Kazumitsu; Itoi, Teruo; Sekiguchi, Hiroyuki; Matsushita, Koji; Yamashiro, Shigeharu; Sano, Yasuhiro; Sekiguchi, Hiroshi; Maruko, Hisashi; Takayama, Yasuo; Sekioka, Ryoji; Okumura, Akihiko; Takada, Yasuaki; Nagano, Hisashi; Waki, Izumi; Ezawa, Naoya; Tanimoto, Hiroyuki; Honjo, Shigeru; Fukano, Masumi; Okada, Hidehiro

    2013-03-01

    A new method for sensitively and selectively detecting chemical warfare agents (CWAs) in air was developed using counter-flow introduction atmospheric pressure chemical ionization mass spectrometry (MS). Four volatile and highly toxic CWAs were examined, including the nerve gases sarin and tabun, and the blister agents mustard gas (HD) and Lewisite 1 (L1). Soft ionization was performed using corona discharge to form reactant ions, and the ions were sent in the direction opposite to the airflow by an electric field to eliminate the interfering neutral molecules such as ozone and nitrogen oxide. This resulted in efficient ionization of the target CWAs, especially in the negative ionization mode. Quadrupole MS (QMS) and ion trap tandem MS (ITMS) instruments were developed and investigated, which were movable on the building floor. For sarin, tabun, and HD, the protonated molecular ions and their fragment ions were observed in the positive ion mode. For L1, the chloride adduct ions of L1 hydrolysis products were observed in negative ion mode. The limit of detection (LOD) values in real-time or for a 1 s measurement monitoring the characteristic ions were between 1 and 8 μg/m(3) in QMS instrument. Collision-induced fragmentation patterns for the CWAs were observed in an ITMS instrument, and optimized combinations of the parent and daughter ion pairs were selected to achieve real-time detection with LOD values of around 1 μg/m(3). This is a first demonstration of sensitive and specific real-time detection of both positively and negatively ionizable CWAs by MS instruments used for field monitoring. PMID:23339735

  5. Chemical Composition, Seasonal Variation and Size distribution of Atmospheric Aerosols at an Alpine Site in Guanzhong Plain, China

    NASA Astrophysics Data System (ADS)

    Li, J.

    2015-12-01

    PM10 and size-segregated aerosol samples were collected at Mt. Hua (2065 a.s.m) in central China, and determined for carbonaceous fraction, ions and organic composition. The concentration of most chemical compositions in summer are lower than those in winter, due to decreased emissions of biomass and coal burning for house heating. High temperature and relative humidity (RH) conditions are favorable for secondary aerosol formation, resulting in higher concentrations of SO42- and NH4+ in summer. Non-dehydrated sugars are increased in summer because of the enhanced metabolism. Carbon preference index results indicate that n-alkanes at Mt. Hua are derived mostly by plant wax. Low Benzo(a)pyrene/Benzo(a)pyrene ratios indicate that mountain aerosols are more aged. Concentrations of biogenic (BSOA, the isoprene/pinene/caryophyllene oxidation products) and anthropogenic (ASOA, mainly aromatic acids) SOA positively correlated with temperature . However, a decreasing trend of BSOA concentration with an increase in RH was observed during the sampling period, although a clear trend between ASOA and RH was not found. Based on the AIM Model calculation, we found that during the sampling period an increase in RH resulted in a decrease in the aerosol acidity and thus reduced the effect of acid-catalysis on BSOA formation. Size distributions of K+ and NH4+ present as an accumulation mode, in contrast to Ca2+ and Mg2+, which are mainly existed in coarse particles. SO42- and NO3- show a bimodal pattern. Dehydrated sugars, fossil fuel derived n-alkanes and PAHs presented unimode size distribution, whereas non-dehydrated sugars and plant wax derived n-alkanes showed bimodal pattern. Most of the determined BSOA are formed in the aerosol phase and enriched in the fine mode except for cis-pinonic acid, which is formed in the gas phase and subsequently partitioned into aerosol phase and thus presents a bimodal pattern with a major peak in the coarse mode.

  6. Chemical composition, sources and evolution processes of aerosol at an urban site in Yangtze River Delta, China during wintertime

    NASA Astrophysics Data System (ADS)

    Zhang, Yunjiang; Tang, Lili; Yu, Hongxia; Wang, Zhuang; Sun, Yele; Qin, Wei; Chen, Wentai; Chen, Changhong; Ding, Aijun; Wu, Jing; Ge, Shun; Chen, Cheng; Zhou, Hong-cang

    2015-12-01

    To investigate the composition, sources and evolution processes of submicron aerosol during wintertime, a field experiment was conducted during December 1-31, 2013 in urban Nanjing, a megacity in Yangtze River Delta of China. Non-refractory submicron aerosol (NR-PM1) species were measured with an Aerodyne Aerosol Chemical Speciation Monitor. NR-PM1 is dominated by secondary inorganic aerosol (55%) and organic aerosol (OA, 42%) during haze periods. Six OA components were identified by positive matrix factorization of the OA mass spectra. The hydrocarbon-like OA and cooking-related OA represent the local traffic and cooking sources, respectively. A highly oxidized factor related to biomass burning OA accounted for 15% of the total OA mass during haze periods. Three types of oxygenated OA (OOA), i.e., a less-oxidized OOA (LO-OOA), a more-oxidized OOA (MO-OOA), and a low-volatility OOA (LV-OOA), were identified. LO-OOA is likely associated with fresh urban secondary OA. MO-OOA likely represents photochemical products showing a similar diurnal cycle to nitrate with a pronounced noon peak. LV-OOA appears to be a more oxidized factor with a pronounced noon peak. The OA composition is dominated by secondary species, especially during haze events. LO-OOA, MO-OOA and LV-OOA on average account for 11%, (18%), 24% (21%) and 23% (18%) of the total OA mass for the haze (clean) periods respectively. Analysis of meteorological influence suggested that regional transport from the northern and southeastern areas of the city is responsible for large secondary and low-volatility aerosol formation.

  7. Potential of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry for screening and quantification of hexabromocyclododecane.

    PubMed

    Sales, Carlos; Portolés, Tania; Sancho, Juan Vicente; Abad, Esteban; Ábalos, Manuela; Sauló, Jordi; Fiedler, Heidelore; Gómara, Belén; Beltrán, Joaquim

    2016-01-01

    A fast method for the screening and quantification of hexabromocyclododecane (sum of all isomers) by gas chromatography using a triple quadrupole mass spectrometer with atmospheric pressure chemical ionization (GC-APCI-QqQ) is proposed. This novel procedure makes use of the soft atmospheric pressure chemical ionization source, which results in less fragmentation of the analyte than by conventional electron impact (EI) and chemical ionization (CI) sources, favoring the formation of the [M - Br](+) ion and, thus, enhancing sensitivity and selectivity. Detection was based on the consecutive loses of HBr from the [M - Br](+) ion to form the specific [M - H5Br6](+) and [M - H4Br5](+) ions, which were selected as quantitation (Q) and qualification (q) transitions, respectively. Parameters affecting ionization and MS/MS detection were studied. Method performance was also evaluated; calibration curves were found linear from 1 pg/μL to 100 pg/μL for the total HBCD concentration; instrumental detection limit was estimated to be 0.10 pg/μL; repeatability and reproducibility, expressed as relative standard deviation, were better than 7% in both cases. The application to different real samples [polyurethane foam disks (PUFs), food, and marine samples] pointed out a rapid way to identify and allow quantification of this compound together with a number of polybrominated diphenyl ethers (BDE congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two other novel brominated flame retardants [i.e., decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)] because of their presence in the same fraction when performing the usual sample treatment.

  8. Potential of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry for screening and quantification of hexabromocyclododecane.

    PubMed

    Sales, Carlos; Portolés, Tania; Sancho, Juan Vicente; Abad, Esteban; Ábalos, Manuela; Sauló, Jordi; Fiedler, Heidelore; Gómara, Belén; Beltrán, Joaquim

    2016-01-01

    A fast method for the screening and quantification of hexabromocyclododecane (sum of all isomers) by gas chromatography using a triple quadrupole mass spectrometer with atmospheric pressure chemical ionization (GC-APCI-QqQ) is proposed. This novel procedure makes use of the soft atmospheric pressure chemical ionization source, which results in less fragmentation of the analyte than by conventional electron impact (EI) and chemical ionization (CI) sources, favoring the formation of the [M - Br](+) ion and, thus, enhancing sensitivity and selectivity. Detection was based on the consecutive loses of HBr from the [M - Br](+) ion to form the specific [M - H5Br6](+) and [M - H4Br5](+) ions, which were selected as quantitation (Q) and qualification (q) transitions, respectively. Parameters affecting ionization and MS/MS detection were studied. Method performance was also evaluated; calibration curves were found linear from 1 pg/μL to 100 pg/μL for the total HBCD concentration; instrumental detection limit was estimated to be 0.10 pg/μL; repeatability and reproducibility, expressed as relative standard deviation, were better than 7% in both cases. The application to different real samples [polyurethane foam disks (PUFs), food, and marine samples] pointed out a rapid way to identify and allow quantification of this compound together with a number of polybrominated diphenyl ethers (BDE congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two other novel brominated flame retardants [i.e., decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)] because of their presence in the same fraction when performing the usual sample treatment. PMID:26554601

  9. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: SOA Yield and Chemical Composition

    NASA Astrophysics Data System (ADS)

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Qi, Li; Kacarab, Mary; Cocker, David

    2016-04-01

    Aromatic hydrocarbons account for 20%-30% of urban atmospheric VOCs and are major contributors to anthropogenic secondary organic aerosol (SOA). However, prediction of SOA from aromatic hydrocarbons as a function of structure, NOx concentration, and OH radical levels remains elusive. Innovative SOA yield and chemical composition evaluation approaches are developed here to investigate SOA formation from aromatic hydrocarbons. SOA yield is redefined in this work by adjusting the molecular weight of all aromatic precursors to the molecular weight of benzene (Yield'= Yieldi×(MWi/MWBenzene); i: aromatic hydrocarbon precursor). Further, SOA elemental ratio is calculated on an aromatic ring basis rather than the classic mole basis. Unified and unique characteristics in SOA formed from aromatic hydrocarbons with different alkyl groups (varying in carbon number and location on aromatic ring) are explored by revisiting fifteen years of UC Riverside/CE-CERT environmental chamber data on 129 experiments from 17 aromatic precursors at urban region relevant low NOx conditions (HC:NO 11.1-171 ppbC:ppb). Traditionally, SOA mass yield of benzene is much greater than that of other aromatic species. However, when adjusting for molecular weight, a similar yield is found across the 17 different aromatic precursors. More importantly, four oxygens per aromatic ring are observed in the resulting SOA regardless of the alkyl substitutes attached to the ring, which majorly affect H/C ratio in SOA. Therefore, resulting SOA bulk composition from aromatic hydrocarbons can be predicted as C6+nH6+2nO4 (n: alkyl substitute carbon number). Further, the dominating role of the aromatic ring carbons is confirmed by studying the chemical composition of SOA formed from the photooxidation of an aromatic hydrocarbon with a 13C isotopically labeled alkyl carbon. Overall, this study unveils the similarity in SOA formation from aromatic hydrocarbons enhancing the understanding of SOA formation from

  10. Detailed Chemical Characterization of Unresolved Complex Mixtures (UCM) inAtmospheric Organics: Insights into Emission Sources, Atmospheric Processing andSecondary Organic Aerosol Formation

    EPA Science Inventory

    Recent studies suggest that semivolatile organic compounds (SVOCs) are important precursors to secondary organic aerosol (SOA) in urban atmospheres. However, knowledge of the chemical composition of SVOCs is limited by current analytical techniques, which are typically unable to...

  11. Sensitivity of thermal infrared sounders to the chemical and micro-physical properties of UTLS secondary sulphate aerosols

    NASA Astrophysics Data System (ADS)

    Sellitto, P.; Legras, B.

    2015-08-01

    Monitoring upper tropospheric-lower stratospheric (UTLS) secondary sulphate aerosols and their chemical and micro-physical properties from satellite nadir observations is crucial to better understand their formation and evolution processes and then to estimate their impact to the UTLS chemistry, and on regional and global radiative balance. Here we present a study aimed at the evaluation of the sensitivity of thermal infrared (TIR) satellite nadir observations to the chemical composition and the size distribution of idealized UTLS sulphate aerosol layers. The extinction properties of sulphuric acid/water droplets, for different sulphuric acid mixing ratios and temperatures, are systematically analysed. The extinction coefficients are derived by means of a Mie code, using refractive indexes taken from the GEISA (Gestion et Étude des Informations Spectroscopiques Atmosphériques: Management and Study of Spectroscopic Information) spectroscopic database and log-normal size distributions with different effective radii and number concentrations. IASI (Infrared Atmospheric Sounding Interferometer) pseudo-observations are generated using forward radiative transfer calculations performed with the 4A (Automatized Atmospheric Absorption Atlas) radiative transfer model, to estimate the impact of the extinction of idealized aerosol layers, at typical UTLS conditions, on the brightness temperature spectra observed by this satellite instrument. We found a marked and typical spectral signature of these aerosol layers between 700 and 1200 cm-1, due to the absorption bands of the sulphate and bi-sulphate ions and the undissociated sulphuric acid, with the main absorption peaks at 1170 and 905 cm-1. The dependence of the aerosol spectral signature to the sulphuric acid mixing ratio, and effective number concentration and radius, as well as the role of interferring parameters like the ozone, sulphur dioxide, carbon dioxide and ash absorption, and temperature and water vapour profile

  12. Optical properties and chemical composition of aerosol particles at an urban location: An estimation of the aerosol mass scattering and absorption efficiencies

    NASA Astrophysics Data System (ADS)

    Titos, G.; Foyo-Moreno, I.; Lyamani, H.; Querol, X.; Alastuey, A.; Alados-Arboledas, L.

    2012-02-01

    We investigated aerosol optical properties, mass concentration and chemical composition over a 1 year period (from March 2006 to February 2007) at an urban site in Southern Spain (Granada, 37.18°N, 3.58°W, 680 m above sea level). Light-scattering and absorption measurements were performed using an integrating nephelometer and a MultiAngle Absorption Photometer (MAAP), respectively, with no aerosol size cut-off and without any conditioning of the sampled air. PM10 and PM1 (ambient air levels of atmospheric particulate matter finer than 10 and 1 microns) were collected with two high volume samplers, and the chemical composition was investigated for all samples. Relative humidity (RH) within the nephelometer was below 50% and the weighting of the filters was also at RH of 50%. PM10 and PM1 mass concentrations showed a mean value of 44 ± 19 μg/m3 and 15 ± 7 μg/m3, respectively. The mineral matter was the major constituent of the PM10-1 fraction (contributing more than 58%) whereas organic matter and elemental carbon (OM+EC) contributed the most to the PM1 fraction (around 43%). The absorption coefficient at 550 nm showed a mean value of 24 ± 9 Mm-1 and the scattering coefficient at 550 nm presented a mean value of 61 ± 25 Mm-1, typical of urban areas. Both the scattering and the absorption coefficients exhibited the highest values during winter and the lowest during summer, due to the increase in the anthropogenic contribution and the lower development of the convective mixing layer during winter. A very low mean value of the single scattering albedo of 0.71 ± 0.07 at 550 nm was calculated, suggesting that urban aerosols in this site contain a large fraction of absorbing material. Mass scattering and absorption efficiencies of PM10 particles exhibited larger values during winter and lower during summer, showing a similar trend to PM1 and opposite to PM10-1. This seasonality is therefore influenced by the variations on PM composition. In addition, the mass

  13. Chemical composition of the atmospheric aerosol in the troposphere over the Hudson Bay lowlands and Quebec-Labrador regions of Canada

    NASA Technical Reports Server (NTRS)

    Gorzelska, K.; Talbot, R. W.; Klemm, K.; Lefer, B.; Klemm, O.; Gregory, G. L.; Anderson, B.; Barrie, L. A.

    1994-01-01

    Atmospheric aerosols were collected in the boundary layer and free troposphere over continental and coastal subarctic regions of Canada during the July - August 1990 joint U.S.-Canadian Arctic Boundary Layer Expedition (ABLE) 3B/Northern Wetlands Study (NOWES). The samples were analyzed for the following water soluble species: sulfate, nitrate, ammonium, potassium, sodium, chloride, oxalate, methylsulfonate, and total amine nitrogen. Ammonium and sulfate were the major water soluble components of these aerosols. The nearly neutral (overall) chemical composition of summertime aerosol particles contrasts their strongly acidic wintertime composition. Aerosol samples were separated into several air mass categories and characterized in terms of chemical composition, associated mixing ratios of gaseous compounds, and meteorological parameters. The fundamental category represented particles associated with 'background' air masses. The summertime atmospheric aerosols in background air over the North American subarctic and Arctic regions were characterized by relatively small and spatially uniform mixing ratios of the measured species. These aerosol particles were aged to the extent that they had lost their primary source signature. The chemical profile of the background air aerosols was frequently modified by additions from biomass fire plumes, aged tropical marine air, and intrusions of upper tropospheric/lower stratospheric air. Aerosols in boundary layer background air over the boreal forest region of Quebec-Labrador had significantly larger mixing ratios of ammonium and sulfate relative to the Hudson Bay region. This may reflect infiltration of anthropogenic pollution or be due to natural emissions from this region.

  14. Chemical composition of the atmospheric aerosol in the troposphere over the Hudson Bay lowlands and Quebec-Labrador regions of Canada

    NASA Astrophysics Data System (ADS)

    Gorzelska, K.; Talbot, R. W.; Klemm, K.; Lefer, B.; Klemm, O.; Gregory, G. L.; Anderson, B.; Barrie, L. A.

    1994-01-01

    Atmospheric aerosols were collected in the boundary layer and free troposphere over continental and coastal subarctic regions of Canada during the July-August 1990 joint U.S.-Canadian Arctic Boundary Layer Expedition (ABLE) SB/Northern Wetlands Study (NOWES). The samples were analyzed for the following water soluble species: sulfate, nitrate, ammonium, potassium, sodium, chloride, oxalate, methylsulfonate, and total amine nitrogen. Ammonium and sulfate were the major water soluble components of these aerosols. The nearly neutral (overall) chemical composition of summertime aerosol particles contrasts their strongly acidic wintertime composition. Aerosol samples were separated into several air mass categories and characterized in terms of chemical composition, associated mixing ratios of gaseous compounds, and meteorological parameters. The fundamental category represented particles associated with"background"air masses. The summertime atmospheric aerosols in background air over the North American subarctic and Arctic regions were characterized by relatively small and spatially uniform mixing ratios of the measured species. These aerosol particles were aged to the extent that they had lost their primary source signature. The chemical profile of the background air aerosols was frequently modified by additions from biomass fire plumes, aged tropical marine air, and intrusions of upper tropospheric/lower stratospheric air. Aerosols in boundary layer background air over the boreal forested region of Quebec-Labrador had significantly larger mixing ratios of ammonium and sulfate relative to the Hudson Bay region. This may reflect infiltration of anthropogenic pollution or be due to natural emissions from this region.

  15. Chemical and Physical Properties of Bulk Aerosols Observed During TRACE-P: Evidence of Nitrate Uptake on Dust Particles

    NASA Astrophysics Data System (ADS)

    Jordan, C.; Anderson, B.; Hudgins, C.; Winstead, E.; Thornhill, L.; Talbot, R.; Russo, R.; Scheuer, E.; Seid, G.; Dibb, J.; Fuelberg, H.

    2002-12-01

    Back trajectories and bulk aerosol chemical properties have been used to group aerosol samples measured on the DC-8 during TRACE-P into five source regions. Each of these source region groups was further subdivided into three altitude bins (< 2 km, 2 - 7 km, and > 7 km). The mean chemical signatures, size distributions, and other physical properties (e.g., volatility, single scatter albedo) will be presented for these groups. By combining chemical and physical measurements, the observed aerosol population for each group may be partitioned between black carbon, sea salts, non-sea salt water soluble ions, and dust. Using this approach, we have found that the bulk of the dust emanating from Asia during TRACE-P came from one region. The highest concentrations of pollution species were also found in this region, including particulate nitrate. The presence of gas phase pollutants such as nitric acid co-located with the dust allows for the uptake of gas-phase nitrogen onto the dust surfaces. Results show that in the dust sector at mid-altitudes (2 - 7 km), where the influence of sea salt is reduced compared to lower altitudes, 50% of the total nitrate is in particulate form. This is in contrast to 15% for sectors with little dust.

  16. Chemical and hygroscopic properties of aerosol organics at Storm Peak Laboratory

    NASA Astrophysics Data System (ADS)

    Hallar, A. Gannet; Lowenthal, Douglas H.; Clegg, Simon L.; Samburova, Vera; Taylor, Nathan; Mazzoleni, Lynn R.; Zielinska, Barbara K.; Kristensen, Thomas B.; Chirokova, Galina; McCubbin, Ian B.; Dodson, Craig; Collins, Don

    2013-05-01

    A combined field and laboratory study was conducted to improve our understanding of the chemical and hygroscopic properties of organ