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Sample records for aerosol soa generated

  1. A perspective on SOA generated in aerosol water from glyoxal and methylglyoxal and its impacts on climate-relevant aerosol properties

    NASA Astrophysics Data System (ADS)

    Sareen, N.; McNeill, V. F.

    2011-12-01

    In recent years, glyoxal and methylglyoxal have emerged to be potentially important SOA precursors with significant implications for climate-related aerosol properties. Here we will discuss how the chemistry of these and similar organic compounds in aerosol water can affect the aerosol optical and cloud formation properties. Aqueous-phase SOA production from glyoxal and methylglyoxal is a potential source of strongly light-absorbing organics, or "brown carbon". We characterized the kinetics of brown carbon formation from these precursors in mixtures of ammonium sulfate and water using UV-Vis spectrophotometry. This mechanism has been incorporated into a photochemical box model with coupled gas phase-aqueous aerosol chemistry. Methylglyoxal and related compounds also may impact an aerosol's ability to act as a cloud condensation nucleus. We recently showed via pendant drop tensiometry and aerosol chamber studies that uptake of methylglyoxal from the gas phase driven by aqueous-phase oligomerization chemistry is a potentially significant, previously unidentified source of surface-active organic material in aerosols. Results from pendant drop tensiometry showed significantly depressed surface tension in methylglyoxal-ammonium sulfate solutions. We further found that ammonium sulfate particles exposed to gas-phase methylglyoxal in a 3.5 m3 aerosol reaction chamber activate into cloud droplets at sizes up to 15% lower at a given supersaturation than do pure ammonium sulfate particles. The observed enhancement exceeds that predicted based on Henry's Law and our measurements of surface tension depression in bulk solutions, suggesting that surface adsorption of methylglyoxal plays a role in determining CCN activity. Methylglyoxal and similar gas-phase surfactants may be an important and overlooked source of enhanced CCN activity in the atmosphere. To characterize the SOA products formed in these solutions, an Aerosol Chemical Ionization Mass Spectrometer (CIMS) was used

  2. Impact of NOx on secondary organic aerosol (SOA) formation from β-pinene photooxidation

    NASA Astrophysics Data System (ADS)

    Sarrafzadeh, Mehrnaz; Pullinen, Iida; Springer, Monika; Kleist, Einhard; Tillmann, Ralf; Mentel, Thomas F.; Kiendler-Scharr, Astrid; Hastie, Donald R.; Wildt, Jürgen

    2016-04-01

    Secondary organic aerosols (SOA) generated from atmospheric oxidation of volatile organics contributes substantially to the global aerosol load. It has been shown that odd nitrogen (NOx) has a significant influence on the formation of this SOA. In this study, we investigated SOA formation from β-pinene photooxidation in the Jülich Plant Atmosphere Chamber (JPAC) under varying NOx conditions. At higher-NOx levels, the SOA yield was significantly suppressed by increasing the NOx concentration. However at lower-NOx levels the opposite trend, an increase in SOA with increasing NOx concentration, was observed. This increase was likely due to the increased OH concentration in the stirred flow reactor. By holding the OH concentration constant for all experiments we removed the potential effect of OH concentration on SOA mass growth. In this case increasing the NOx concentration only decreased the SOA yield. In addition, the impact of NOx on SOA formation was explored in the presence of ammonium sulfate seed aerosols. This suggested that SOA yield was only slightly suppressed under increasing NOx concentrations when seed aerosol was present.

  3. SOA Aging and Oligomer Content and their Effect on the Volatility and Viscosity of SOA Particles Generated from Different Precursors

    NASA Astrophysics Data System (ADS)

    Wilson, J. M.; Zelenyuk, A.; Imre, D. G.; Beranek, J.

    2013-12-01

    Formation, properties, transformations and temporal evolution of secondary organic aerosol (SOA) particles strongly depend on particle phase and volatility. Our recent studies indicate that laboratory-generated alpha-pinene SOA particles are highly viscous semi-solids with viscosity characteristic of tars, and their evaporation rates are orders of magnitude slower than previously assumed. This is not surprising given that numerous studies provide evidence that SOA particles contain significant amounts of high molecular weight organic compounds (oligomers), which affect SOA phase and volatility. It is well known that oligomers can severely retard diffusion, mixing, and thus evaporation of smaller molecules. One of the most intriguing findings is that SOA fractional evaporation rates are nearly size independent. We begin by presenting our results of evaporation studies of particles composed of hexaethylene glycol (HEG), polyethylene glycols (PEGs) of different polymer chain length, and their mixtures. The data indicate that HEG particles exhibit the size-dependent evaporation expected for liquid droplets, while particles containing polymers with different chain lengths exhibit size-independent evaporation kinetics similar to those of SOA. We will then present the results of evaporation studies of SOA particles generated by oxidation of several different precursors, including alpha-pinene, isoprene, limonene, n-alkenes and cyclo-alkenes, from which we explore the relationship between SOA oligomer content and SOA volatility and viscosity. We, and others, also find that oligomer content in SOA increases with time, and with it we expect corresponding changes in viscosity and volatility. We will present the results of studies aimed at characterizing evaporation kinetics and the viscosity of SOA particles as a function of particle age. We will also present our findings on the effect of hydrophobic organics on SOA oligomer content, its volatility and viscosity.

  4. Organosulfates as Tracers for Secondary Organic Aerosol (SOA) Formation from 2-Methyl-3-Buten-2-ol (MBO) in the Atmosphere

    PubMed Central

    2012-01-01

    2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C5H12O6S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM2.5) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM2.5 collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA. PMID:22849588

  5. Formation of anthropogenic secondary organic aerosol (SOA) and its influence on biogenic SOA properties

    NASA Astrophysics Data System (ADS)

    Emanuelsson, E. U.; Hallquist, M.; Kristensen, K.; Glasius, M.; Bohn, B.; Fuchs, H.; Kammer, B.; Kiendler-Scharr, A.; Nehr, S.; Rubach, F.; Tillmann, R.; Wahner, A.; Wu, H.-C.; Mentel, Th. F.

    2013-03-01

    Secondary organic aerosol (SOA) formation from mixed anthropogenic and biogenic precursors has been studied exposing reaction mixtures to natural sunlight in the SAPHIR chamber in Jülich, Germany. In this study aromatic compounds served as examples of anthropogenic volatile organic compound (VOC) and a mixture of α-pinene and limonene as an example for biogenic VOC. Several experiments with exclusively aromatic precursors were performed to establish a relationship between yield and organic aerosol mass loading for the atmospheric relevant range of aerosol loads of 0.01 to 10 μg m-3. The yields (0.5 to 9%) were comparable to previous data and further used for the detailed evaluation of the mixed biogenic and anthropogenic experiments. For the mixed experiments a number of different oxidation schemes were addressed. The reactivity, the sequence of addition, and the amount of the precursors influenced the SOA properties. Monoterpene oxidation products, including carboxylic acids and dimer esters were identified in the aged aerosol at levels comparable to ambient air. OH radicals were measured by Laser Induced Fluorescence, which allowed for establishing relations of aerosol properties and composition to the experimental OH dose. Furthermore, the OH measurements in combination with the derived yields for aromatic SOA enabled application of a simplified model to calculate the chemical turnover of the aromatic precursor and corresponding anthropogenic contribution to the mixed aerosol. The estimated anthropogenic contributions were ranging from small (≈8%) up to significant fraction (>50%) providing a suitable range to study the effect of aerosol composition on the aerosol volatility (volume fraction remaining (VFR) at 343 K: 0.86-0.94). The aromatic aerosol had higher oxygen to carbon ratio O/C and was less volatile than the biogenic fraction. However, in order to produce significant amount of aromatic SOA the reaction mixtures needed a higher OH dose that also

  6. Improving the representation of secondary organic aerosol (SOA) in the MOZART-4 global chemical transport model

    NASA Astrophysics Data System (ADS)

    Mahmud, A.; Barsanti, K. C.

    2012-12-01

    The secondary organic aerosol (SOA) module in the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4) has been updated by replacing existing two-product (2p) parameters with those obtained from two-product volatility basis set (2p-VBS) fits, and by treating SOA formation from the following volatile organic compounds (VOCs): isoprene, propene and lumped alkenes. Strong seasonal and spatial variations in global SOA distributions were demonstrated, with significant differences in the predicted concentrations between the base-case and updated model versions. The base-case MOZART-4 predicted annual average SOA of 0.36 ± 0.50 μg m-3 in South America, 0.31 ± 0.38 μg m-3 in Indonesia, 0.09 ± 0.05 μg m-3 in the USA, and 0.12 ± 0.07 μg m-3 in Europe. Concentrations from the updated versions of the model showed a~marked increase in annual average SOA. Using the updated set of parameters alone (MZ4-v1) increased annual average SOA by ~8%, ~16%, ~56%, and ~108% from the base-case in South America, Indonesia, USA, and Europe, respectively. Treatment of additional parent VOCs (MZ4-v2) resulted in an even more dramatic increase of ~178-406% in annual average SOA for these regions over the base-case. The increases in predicted SOA concentrations further resulted in increases in corresponding SOA contributions to annual average total aerosol optical depth (AOD) by <1% for MZ4-v1 and ~1-6% for MZ4-v2. Estimated global SOA production was ~6.6 Tg yr-1 and ~19.1 Tg yr-1 with corresponding burdens of ~0.24 Tg and ~0.59 Tg using MZ4-v1 and MZ4-v2, respectively. The SOA budgets predicted in the current study fall well within reported ranges for similar modeling studies, 6.7 to 96 Tg yr-1, but are lower than recently reported observationally-constrained values, 50 to 380 Tg yr-1. With MZ4-v2, simulated SOA concentrations at the surface were also in reasonable agreement with comparable modeling studies and observations. Concentrations of estimated organic aerosol (OA

  7. Wavelength and NOx dependent complex refractive index of SOAs generated from the photooxidation of toluene

    NASA Astrophysics Data System (ADS)

    Nakayama, T.; Sato, K.; Matsumi, Y.; Imamura, T.; Yamazaki, A.; Uchiyama, A.

    2012-06-01

    Recently, secondary organic aerosols (SOAs) generated from anthropogenic volatile organic compounds have been proposed as a possible source of lightabsorbing organic compounds "brown carbon" in the urban atmosphere. However, the atmospheric importance of these SOAs remains unclear due to limited information about their optical properties. In this study, the complex refractive index (RI, m=n - ki) values at 405, 532, and 781 nm of the SOAs generated during the photooxidation of toluene (toluene-SOAs) under a variety of initial nitrogen oxide (NOx= NO + NO2) conditions were examined by photoacoustic spectroscopy (PAS) and cavity ring down spectroscopy (CRDS). The complex RI values obtained in the present study and reported in the literature indicate that the k value, which represents the light absorption of the toluene-SOAs steeply increased to shorter wavelengths at <405 nm, while the n value gradually increased to shorter wavelengths from 781 to 355 nm. The k values at 405 nm were found to increase from 1.8 × 10-3 to 7.2 × 10-3 with increasing initial NOx concentration from 109 to 571 ppbv. The nitrate to organics ratio of the SOAs determined using a highresolution time-of-flight aerosol mass spectrometer (H-ToF-AMS) also increased with increasing initial NOx concentration. The RI values of the SOAs generated during the photooxidation of 1,3,5-trimethylbenzene in the presence of NOx (1,3,5-TMB-SOAs) were also determined to investigate the influence of the chemical structure of the precursor on the optical properties of the SOAs, and it was found that the light absorption of the 1,3,5-TMB-SOAs is negligible at all of the wavelengths investigated (405, 532, and 781 nm). These results can be reasonably explained by the hypothesis that nitro-aromatic compounds such as nitro-cresols are the major contributors to the light absorption of the toluene-SOAs. Using the obtained RI values, mass absorption cross sections of the toluene-SOAs at 405 and 532 nm were estimated to

  8. Wavelength and NOx dependent complex refractive index of SOAs generated from the photooxidation of toluene

    NASA Astrophysics Data System (ADS)

    Nakayama, T.; Sato, K.; Matsumi, Y.; Imamura, T.; Yamazaki, A.; Uchiyama, A.

    2013-01-01

    Recently, secondary organic aerosols (SOAs) generated from anthropogenic volatile organic compounds have been proposed as a possible source of light-absorbing organic compounds, "brown carbon," in the urban atmosphere. However, the atmospheric importance of these SOAs remains unclear due to limited information about their optical properties. In this study, the complex refractive index (RI, m = n-ki values at 405, 532, and 781 nm of the SOAs generated during the photooxidation of toluene (toluene-SOAs) under a variety of initial nitrogen oxide (NOx = NO + NO2) conditions were examined by photoacoustic spectroscopy (PAS) and cavity ring-down spectroscopy (CRDS). The complex RI-values obtained in the present study and reported in the literature indicate that the k-value, which represents the light absorption of the toluene-SOAs, increased to shorter wavelengths at <532 nm, and the n-value also increased to shorter wavelengths from 781 to 355 nm. The k-values at 405 nm were found to increase from 0.0018 to 0.0072 with increasing initial NOx concentration from 109 to 571 ppbv. The nitrate to organics ratio of the SOAs determined using a high-resolution time-of-flight aerosol mass spectrometer (H-ToF-AMS) also increased with increasing initial NOx concentration. The RI-values of the SOAs generated during the photooxidation of 1,3,5-trimethylbenzene in the presence of NOx (1,3,5-TMB-SOAs) were also determined to investigate the influence of the chemical structure of the precursor on the optical properties of the SOAs, and it was found that the light absorption of the 1,3,5-TMB-SOAs is negligible at all of the wavelengths investigated (405, 532, and 781 nm). These results can be reasonably explained by the hypothesis that nitroaromatic compounds, such as nitrocresols, are the major contributors to the light absorption of the toluene-SOAs. Using the obtained RI-values, mass absorption cross sections of the toluene-SOAs at 405 nm were estimated to be 0.08-0.52 m2g-1 under

  9. Secondary Organic Aerosol (SOA) formation from hydroxyl radical oxidation and ozonolysis of monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, D. F.; Kaminski, M.; Schlag, P.; Fuchs, H.; Acir, I.-H.; Bohn, B.; Häseler, R.; Kiendler-Scharr, A.; Rohrer, F.; Tillmann, R.; Wang, M. J.; Wegener, R.; Wildt, J.; Wahner, A.; Mentel, T. F.

    2014-05-01

    Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compounds (VOCs) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene, and limonene) by OH dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR chamber in Jülich, Germany, at low NOx (0.01-1 ppbV) and low ozone (O3) concentration. OH concentration and OH reactivity were measured directly so that the overall reaction rates of organic compounds with OH were quantified. Multi-generation reaction process, particle growth, new particle formation, particle yield, and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction of OH with organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to be dominant after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates of monoterpene with OH or O3 indicates that generally, OH oxidation and ozonolysis had similar efficiency in particle growth. The SOA yield of

  10. Ice Formation Potential of Laboratory Generated Biogenic and Anthropogenic-Biogenic SOA Particles

    NASA Astrophysics Data System (ADS)

    Knopf, D. A.; Alpert, P. A.; Charnawskas, J. C.; Lambe, A. T.; Massoli, P.; Onasch, T. B.; Davidovits, P.; Worsnop, D. R.

    2014-12-01

    Secondary organic aerosol (SOA) is ubiquitous in the atmosphere and may play an important role in cloud glaciation processes. We investigated several laboratory generated SOA particles systems for their initial water uptake and ice formation propensity as a function of temperature, T, relative humidity with respect to water, RH, relative humidity with respect to ice, RHice, and for different humidification rates, cRHice. This includes pure SOA particles formed from α-pinene, isoprene, and longifolene volatile organic compound precursors with and without the presence of sulfate seed particles as well as oxidized soot and soot-coated α-pinene and naphthalene SOA with varying O/C ratios and coating thicknesses. Micro-spectroscopic chemical imaging using scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) is used to characterize SOA, SOA-sulfate, SOA-soot particles generated in the Boston College potential aerosol mass (PAM) flow reactor in relation to their ice nucleation behavior. Water uptake is consistently observed on SOA particles at RH=75% and 95% for 262 and 228 K, respectively, followed by homogeneous ice nucleation applying atmospherically relevant cRHice=1 % min-1. When cRHice=25 % min-1, ice nucleation is delayed by about 30-40% RHice and cannot be explained by homogeneous ice nucleation. This implies diffusion limitation of water into these potentially glassy or semi-solid organic particles resulting in non-equilibrium between ambient RH and particle water activity. These data will aid in our understanding of the role of organic particle phase states in response to changes in T and RH which is crucial information for prediction of atmospheric ice nucleation.

  11. Present-day to 21st century projections of secondary organic aerosol (SOA) from a global climate-aerosol model with an explicit SOA formation scheme

    NASA Astrophysics Data System (ADS)

    Lin, G.; Penner, J. E.; Zhou, C.

    2014-12-01

    Secondary organic aerosol (SOA) has been shown to be an important component of non-refractory submicron aerosol in the atmosphere. The presence of SOA can influence the earth's radiative balance by contributing to the absorption and scattering of radiation and by altering the properties of clouds. Globally, a large fraction of SOA originates from biogenic volatile organic compounds (BVOCs), emissions of which depend on vegetation cover and climate. Temperature, CO2 concentration, and land use and land cover change have been shown to be major drivers of global isoprene emission changes in future climates. Additionally, the SOA concentration in the atmosphere not only depends on BVOC emissions, but is also controlled by anthropogenic emissions, temperature, precipitation and the oxidative capacity of the atmosphere. To project the change in SOA concentrations in the future requires a model that fully couples a BVOC emission model that represents these BVOC emission drivers, together with a sophisticated atmospheric model of SOA formation and properties. Recent studies have suggested that traditional parameterized SOA formation mechanisms that are tuned to fit smog chamber data do not fully account for the complexity and dynamics of real SOA system, calling into the question of the validity and completeness of previous SOA projections. In this study, we investigate the response of SOA mass to future physical climate change, to land cover and land use change, to changes in BVOCs emissions, and to changes in anthropogenic aerosol and gas species emissions for the year 2100, utilizing a global climate-aerosol model (CAM5-IMPACT): the NCAR Community Atmospheric Model (CAM5) coupled with a global aerosol model (IMPACT). The IMPACT model has sophisticated detailed process-based mechanisms describing aerosol microphysics and SOA formation through both gas phase and multiphase reactions. We perform sensitivity tests to isolate the relative roles of individual global change

  12. Secondary Organic Aerosol (SOA) Formation from Hydroxyl Radical Oxidation and Ozonolysis of Monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, Defeng; Kaminski, Martin; Schlag, Patrick; Fuchs, Hendrik; Acir, Ismail-Hakki; Bohn, Birger; Haeseler, Rolf; Kiendler-Scharr, Astrid; Rohrer, Franz; Tillmann, Ralf; Wang, Mingjin; Wegner, Robert; Wahner, Andreas; Mentel, Thomas

    2014-05-01

    Hydroxyl radical (OH) oxidation and ozonolysis are the two major pathways of daytime biogenic volatile organic compounds (VOCs) oxidation and secondary organic aerosol (SOA) formation. The pure OH oxidation of monoterpenes, an important biogenic VOC class, has seldom been investigated. In order to elucidate the importance of the reaction pathyways of the OH oxidation and ozonolysis and their roles in particle formation and growth, we investigated the particle formation of several common monoterpenes (alpha-pinene, beta-pinene, and limonene) in the large atmosphere simulation chamber SAPHIR in Juelich, Germany. The experiments were conducted for both OH dominant and pure ozonolysis case (in the presence of CO as OH scavenger) at ambient relevant conditions (low OA, low VOC and low NOx concentration). OH and ozone (O3) concentrations were measured so that the oxidation rates of OH and O3 with precursors were quantified. The particle formation and growth, aerosol yield, multi-generation reaction process and aerosol composition were analyzed. Pure ozonolysis generated a large amount of particles indicating ozonolysis plays an important role in particle formation as well as OH oxidation. In individual experiments, particle growth rates did not necessarily correlate with OH or O3 oxidation rates. However, comparing the growth rates at similar OH or O3 oxidation rates shows that generally, OH oxidation and ozonolysis have similar efficiency in particle growth. Multi-generation products are shown to be important in the OH oxidation experiment based on aerosol yield "growth curve" (Ng et al., 2006). The reaction process of OH oxidation experiments was analyzed as a function of OH dose to elucidate the role of functionalization and fragmentation. A novel analysis was developed to link the particle formation with the reaction with OH, which was also used to examine the role of functionalization and fragmentation in the particle formation by OH oxidation. These analyses show

  13. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, R. L.; Jang, M.

    2015-11-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+]) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of the photooxidation products and the sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (8 groups) and aerosol phase reactivity (6 groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid catalyzed reactions, and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx. The model is validated using isoprene photooxidation experiments performed in the dual, outdoor UF APHOR chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total OM formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC, and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H+] but is dynamically related to all three parameters. For VOC / NOx > 10, with increasing NOx both experimental and

  14. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, Ross L.; Jang, Myoseon

    2016-05-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+], mol L-1) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of photooxidation products and sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (eight groups) and aerosol phase reactivity (six groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid-catalyzed reactions and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx (VOC - volatile organic compound). The model is validated using isoprene photooxidation experiments performed in the dual, outdoor University of Florida Atmospheric PHotochemical Outdoor Reactor (UF APHOR) chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total organic mass formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H

  15. Effect of NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes

    NASA Astrophysics Data System (ADS)

    Ng, N. L.; Chhabra, P. S.; Chan, A. W. H.; Surratt, J. D.; Kroll, J. H.; Kwan, A. J.; McCabe, D. C.; Wennberg, P. O.; Sorooshian, A.; Murphy, S. M.; Dalleska, N. F.; Flagan, R. C.; Seinfeld, J. H.

    2007-10-01

    Secondary organic aerosol (SOA) formation from the photooxidation of one monoterpene (α-pinene) and two sesquiterpenes (longifolene and aromadendrene) is investigated in the Caltech environmental chambers. The effect of NOx on SOA formation for these biogenic hydrocarbons is evaluated by performing photooxidation experiments under varying NOx conditions. The NOx dependence of α-pinene SOA formation follows the same trend as that observed previously for a number of SOA precursors, including isoprene, in which SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) decreases as NOx level increases. The NOx dependence of SOA yield for the sesquiterpenes, longifolene and aromadendrene, however, differs from that determined for isoprene and α-pinene; the aerosol yield under high-NOx conditions substantially exceeds that under low-NOx conditions. The reversal of the NOx dependence of SOA formation for the sesquiterpenes is consistent with formation of relatively low-volatility organic nitrates, and/or the isomerization of large alkoxy radicals leading to less volatile products. Analysis of the aerosol chemical composition for longifolene confirms the presence of organic nitrates under high-NOx conditions. Consequently the formation of SOA from certain biogenic hydrocarbons such as sesquiterpenes (and possibly large anthropogenic hydrocarbons as well) may be more efficient in polluted air.

  16. Volatility of Secondary Organic Aerosol (SOA) Formed from Photooxidation of Isoprene

    NASA Astrophysics Data System (ADS)

    Ng, N. L.; Kollman, M.; Xu, L.; Shilling, J. E.

    2012-12-01

    Isoprene is the most abundant non-methane hydrocarbon, so even a small aerosol yield may have a large effect on both local and global secondary organic aerosol (SOA) production. Previous studies have shown that isoprene SOA yields are higher under low-NOx conditions, and that volatility of isoprene SOA under low-NOx conditions is similar to a-pinene SOA. In this study, the volatility of SOA formed from the photooxidation of isoprene under different NOx conditions is investigated with a thermodenuder. Laboratory chamber experiments are performed under different NOx conditions at low RH (RH<5%) and without seed. H2O2 and HONO is used as OH precursor for low-NOx and high-NOx experiments, respectively. During each experiment, isoprene and selected gas-phase oxidation products are monitored with a Proton Transfer Reaction Mass Spectrometry (PTRMS).Particle-phase composition, mass, size distribution are measured with a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a Scanning Mobility Particle Sizer (SMPS). The thermodenuder is upstream of the the HR-ToF-AMS and SMPS, modulating the aerosol composition with temperatures ranging from 30 to 200 oC. In general, the volatility of SOA decreases after peak SOA growth, indicating the formation of highly oxidized, low-volatility species with increased photochemical aging. The SOA yields obtained are in agreement with previous studies, with more SOA formed under low-NOx conditions. However, it is found that SOA formed under low-NOx conditions are more volatile. Preliminary results show that about 60% of low-NOx isoprene SOA and <40% of high-NOx isoprene SOA evaporates at 100 oC. Under high-NOx conditions, there is still 10% of aerosol mass remaining at 200 oC, suggesting that there are some very non-volatiles species in high-NOx isoprene SOA. The mass fraction of isoprene SOA remaining as a function of NOx and temperature will be presented. The mass spectra features of SOA at these conditions will also

  17. 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

  18. A comparison of secondary organic aerosol (SOA) yields and composition from ozonolysis of monoterpenes at varying concentrations of NO2

    NASA Astrophysics Data System (ADS)

    Draper, D. C.; Farmer, D. K.; Desyaterik, Y.; Fry, J. L.

    2015-05-01

    The effect of NO2 on secondary organic aerosol (SOA) formation from ozonolysis of α-pinene, β-pinene, Δ3-carene, and limonene was investigated using a dark flow-through reaction chamber. SOA mass yields were calculated for each monoterpene from ozonolysis with varying NO2 concentrations. Kinetics modeling of the first generation gas-phase chemistry suggests that differences in observed aerosol yields for different NO2 concentrations are consistent with NO3 formation and subsequent competition between O3 and NO3 to oxidize each monoterpene. α-pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. β-pinene and Δ3-carene produced fewer particles at higher [NO2], but both retained moderate mass yields. Limonene exhibited both higher number concentrations and greater mass concentrations at higher [NO2]. SOA from each experiment was collected and analyzed by HPLC-ESI-MS, enabling comparisons between product distributions for each system. In general, the systems influenced by NO3 oxidation contained more high molecular weight products (MW >400 amu), suggesting the importance of oligomerization mechanisms in NO3-initiated SOA formation. α-pinene, which showed anomalously low aerosol mass yields in the presence of NO2, showed no increase in these oligomer peaks, suggesting that lack of oligomer formation is a likely cause of α-pinene's near 0% yields with NO3. Through direct comparisons of mixed-oxidant systems, this work suggests that NO3 is likely to dominate nighttime oxidation pathways in most regions with both biogenic and anthropogenic influences. Therefore, accurately constraining SOA yields from NO3 oxidation, which vary substantially with the VOC precursor, is essential in predicting nighttime aerosol production.

  19. Modeling Gas-Particle Partitioning of SOA: Effects of Aerosol Physical State and RH

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Seinfeld, J.

    2011-12-01

    Aged tropospheric aerosol particles contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. In liquid aerosol particles non-ideal mixing of all species determines whether the condensed phase undergoes liquid-liquid phase separation or whether it is stable in a single mixed phase, and whether it contains solid salts in equilibrium with their saturated solution. The extended thermodynamic model AIOMFAC is able to predict such phase states by representing the variety of organic components using functional groups within a group-contribution concept. The number and composition of different condensed phases impacts the diversity of reaction media for multiphase chemistry and the gas-particle partitioning of semivolatile species. Recent studies show that under certain conditions biogenic and other organic-rich particles can be present in a highly viscous, semisolid or amorphous solid physical state, with consequences regarding reaction kinetics and mass transfer limitations. We present results of new gas-particle partitioning computations for aerosol chamber data using a model based on AIOMFAC activity coefficients and state-of-the-art vapor pressure estimation methods. Different environmental conditions in terms of temperature, relative humidity (RH), salt content, amount of precursor VOCs, and physical state of the particles are considered. We show how modifications of absorptive and adsorptive gas-particle mass transfer affects the total aerosol mass in the calculations and how the results of these modeling approaches compare to data of aerosol chamber experiments, such as alpha-pinene oxidation SOA. For a condensed phase in a mixed liquid state containing ammonium sulfate, the model predicts liquid-liquid phase separation up to high RH in case of, on average, moderately hydrophilic organic compounds, such as first generation oxidation products of alpha-pinene. The computations also reveal that treating liquid phases as ideal

  20. Rethinking the global secondary organic aerosol (SOA) budget: stronger production, faster removal, shorter lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, Alma; Kasibhatla, Prasad S.; Jo, Duseong S.; Cappa, Christopher D.; Jimenez, Jose L.; Madronich, Sasha; Park, Rokjin J.

    2016-06-01

    Recent laboratory studies suggest that secondary organic aerosol (SOA) formation rates are higher than assumed in current models. There is also evidence that SOA removal by dry and wet deposition occurs more efficiently than some current models suggest and that photolysis and heterogeneous oxidation may be important (but currently ignored) SOA sinks. Here, we have updated the global GEOS-Chem model to include this new information on formation (i.e., wall-corrected yields and emissions of semi-volatile and intermediate volatility organic compounds) and on removal processes (photolysis and heterogeneous oxidation). We compare simulated SOA from various model configurations against ground, aircraft and satellite measurements to assess the extent to which these improved representations of SOA formation and removal processes are consistent with observed characteristics of the SOA distribution. The updated model presents a more dynamic picture of the life cycle of atmospheric SOA, with production rates 3.9 times higher and sinks a factor of 3.6 more efficient than in the base model. In particular, the updated model predicts larger SOA concentrations in the boundary layer and lower concentrations in the upper troposphere, leading to better agreement with surface and aircraft measurements of organic aerosol compared to the base model. Our analysis thus suggests that the long-standing discrepancy in model predictions of the vertical SOA distribution can now be resolved, at least in part, by a stronger source and stronger sinks leading to a shorter lifetime. The predicted global SOA burden in the updated model is 0.88 Tg and the corresponding direct radiative effect at top of the atmosphere is -0.33 W m-2, which is comparable to recent model estimates constrained by observations. The updated model predicts a population-weighed global mean surface SOA concentration that is a factor of 2 higher than in the base model, suggesting the need for a reanalysis of the contribution of

  1. Rethinking the global secondary organic aerosol (SOA) budget: stronger production, faster removal, shorter lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Kasibhatla, P. S.; Jo, D. S.; Cappa, C.; Jimenez, J. L.; Madronich, S.; Park, R. J.

    2015-11-01

    Recent laboratory studies suggest that secondary organic aerosol (SOA) formation rates are higher than assumed in current models. There is also evidence that SOA removal by dry and wet deposition occurs more efficiently than some current models suggest, and that photolysis and heterogeneous oxidation may be important (but currently ignored) SOA sinks. Here, we have updated the global GEOS-Chem model to include this new information on formation (i.e. wall-corrected yields and emissions of semi-volatile and intermediate volatility organic compounds) and on removal processes (photolysis and heterogeneous oxidation). We compare simulated SOA from various model configurations against ground, aircraft and satellite measurements to assess the extent to which these improved representations of SOA formation and removal processes are consistent with observed characteristics of the SOA distribution. The updated model presents a more dynamic picture of the lifecycle of atmospheric SOA, with production rates 4 times higher and sinks a factor of 3.7 more efficient than in the base model. In particular, the updated model predicts larger SOA concentrations in the boundary layer and lower concentrations in the upper troposphere, leading to better agreement with surface and aircraft measurements of organic aerosol compared to the base model. Our analysis thus suggests that the long-standing discrepancy in model predictions of the vertical SOA distribution can now be resolved, at least in part, by a stronger source and stronger sinks leading to a shorter lifetime. The predicted global SOA burden in the updated model is 0.95 Tg and the corresponding direct radiative forcing at top of the atmosphere is -0.35 W m-2, which is comparable to recent model estimates constrained by observations. The updated model predicts a population-weighed global mean surface SOA concentration that is a factor of 2 higher than in the base model, suggesting the need for a reanalysis of the contribution of

  2. Monoterpene SOA - Contribution of first-generation oxidation products to formation and chemical composition

    NASA Astrophysics Data System (ADS)

    Mutzel, Anke; Rodigast, Maria; Iinuma, Yoshiteru; Böge, Olaf; Herrmann, Hartmut

    2016-04-01

    Investigation of the consecutive reactions of first-generation terpene oxidation products provides insight into the formation of secondary organic aerosol (SOA). To this end, OH radical reactions with α-pinene, β-pinene, and limonene were examined along with the OH-oxidation of nopinone as a β-pinene oxidation product and pinonaldehyde and myrtenal as α-pinene oxidation products. The SOA yield of β-pinene (0.50) was much higher than that of α-pinene (0.35) and the limonene/OH system (0.30). This is opposite to the ozonolysis SOA yields described in the literature. The growth curve of SOA from β-pinene shows the contribution of secondary reactions, such as further reaction of nopinone. This contribution (17%) and the high SOA yield of nopinone (0.24) might lead to the high SOA formation potential observed for β-pinene. The majority of the C9 oxidation products observed from β-pinene can be attributed to the consecutive reaction of nopinone, whereas in the case of pinonaldehyde, only a few α-pinene oxidation products were identified. Nopinone contributes significantly to the formation of pinic acid (51%), homoterpenylic acid (74%), and 3-methyl-1,2,3-butane-tricarboxylic acid (MBTCA, 88%) during β-pinene oxidation. The oxidation of pinonaldehyde was expected to produce important SOA markers, but only negligible amounts were identified. This indicates that their formation by oxidation of α-pinene must proceed via different pathways from the further oxidation of pinonaldehyde. Only pinonic acid and MBTCA were found in considerable amounts and were formed in α-pinene oxidation with 57% yield, while that for the pinonaldehyde/OH reaction was 33%. The lack of important SOA marker compounds might cause the low SOA yield (0.07) observed for pinonaldehyde. Based on the low SOA yield, pinonaldehyde contributes only 4.5% to α-pinene SOA. Myrtenal was identified among the gas-phase products of α-pinene oxidation. A majority of α-pinene SOA marker compounds was

  3. Is dry deposition of semi-volatile organic gases a significant loss of secondary organic aerosols (SOA)?

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Aumont, B.; Knote, C. J.; Lee-Taylor, J. M.; Madronich, S.

    2013-12-01

    Dry deposition removal of semi-volatile organic compounds from the atmosphere and its impact on organic aerosol mass is currently under-explored and not well represented in chemistry-climate models, especially for the many complex partly oxidized organics involved in particle formation. The main reason for this omission is that current models use simplified SOA mechanisms that lump precursors and their products into volatility bins, therefore losing information on important properties of individual molecules (or groups) that are needed to calculate dry deposition. In this study, we apply the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to simulate SOA formation and estimate the influence of dry deposition of gas-phase organics on SOA concentrations downwind of an urban area (Mexico City), as well as over a pine forest. SOA precursors considered here include short- and long-chain alkanes (C3-25), alkenes, light aromatics, isoprene and monoterpenes. We show that dry deposition of oxidized gases is not an efficient sink for anthropogenic SOA, as it removes <5% of SOA within the city's boundary layer and ~15% downwind. The effect on biogenic SOA is however significantly larger. We discuss reasons for these differences, and investigate separately the impacts on short and long-chain species. We show that the dry deposition is competing with the uptake of gases to the aerosol phase. In the absence of this condensation, ~50% of the regionally produced mass downwind of Mexico City would have been dry-deposited. However, because dry deposition of submicron aerosols is slow, condensation onto particles protects organic gases from deposition and therefore increases their atmospheric burden and lifetime. We use the explicit GECKO-A model to build an empirical parameterization for use in 3D models. Removal (dry and wet) of organic vapors depends on their solubility, and required Henry's law solubility coefficients were estimated for

  4. Solid aerosol generator

    DOEpatents

    Prescott, D.S.; Schober, R.K.; Beller, J.

    1992-03-17

    An improved solid aerosol generator used to produce a gas borne stream of dry, solid particles of predetermined size and concentration is disclosed. The improved solid aerosol generator nebulizes a feed solution of known concentration with a flow of preheated gas and dries the resultant wet heated aerosol in a grounded, conical heating chamber, achieving high recovery and flow rates. 2 figs.

  5. Improved solid aerosol generator

    DOEpatents

    Prescott, D.S.; Schober, R.K.; Beller, J.

    1988-07-19

    An improved solid aerosol generator used to produce a gas borne stream of dry, solid particles of predetermined size and concentration. The improved solid aerosol generator nebulizes a feed solution of known concentration with a flow of preheated gas and dries the resultant wet heated aerosol in a grounded, conical heating chamber, achieving high recovery and flow rates. 2 figs.

  6. Solid aerosol generator

    DOEpatents

    Prescott, Donald S.; Schober, Robert K.; Beller, John

    1992-01-01

    An improved solid aerosol generator used to produce a gas borne stream of dry, solid particles of predetermined size and concentration. The improved solid aerosol generator nebulizes a feed solution of known concentration with a flow of preheated gas and dries the resultant wet heated aerosol in a grounded, conical heating chamber, achieving high recovery and flow rates.

  7. In situ Measurements of Gas- and Particle-Phase Organic Compounds: Insights for SOA Formation Mechanisms and Contributions of SOA to Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Zhao, Y.; Kreisberg, N. M.; Worton, D. R.; Isaacman, G. A.; Weber, R.; Liu, S.; Day, D. A.; Markovic, M. Z.; VandenBoer, T. C.; Russell, L. M.; Murphy, J. G.; Hering, S. V.; Goldstein, A. H.

    2011-12-01

    To investigate formation of secondary organic aerosol (SOA) and the contribution of SOA to organic aerosols, semi-volatile and intermediate-volatile organic compounds (SVOCs/IVOCs) in both gas and particle phases were measured using a modified Thermal Desorption Gas Chromatograph (TAG) instrument in Bakersfield, CA during the CALifornia at the NEXus between air quality and climate (CALNEX) campaign from 31 May through 27 June, 2010. More than 150 organic compounds were identified, spanning a wide range of volatility and functionality. Quantified compounds included organic tracers for primary and secondary organic sources, such as alkanes, PAHs, acids, hopanes and ketones. Hourly gas/particle partitioning was determined by a denuder difference method where the sample flow alternated every other sample through an active charcoal multi-channel denuder that efficiently removed gas-phase components. Gas/particle partitioning of three SOA tracers (phthalic acid, pinonaldehyde and 6, 10, 14-trimethyl-2-pentadecanone) was investigated to understand the formation mechanisms of SOA for different functional group classes in the ambient atmosphere. Comparison with Pankow gas/particle partitioning theory, observed particle-phase phthalic acid and pinonaldehyde, suggests formation by other mechanisms than gas-to-particle condensation. Source attribution is performed using Positive Matrix Factorization (PMF) analysis of speciated particle-phase TAG data along with total submicron organic aerosol (OA) measured by an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). SOA accounts for a major component of OA and the contribution of biogenic SOA to total SOA is comparable to anthropogenic SOA during nights.

  8. Influence of dry deposition of semi-volatile organic compounds (VOC) on secondary organic aerosol (SOA) formation in the Mexico City plume

    NASA Astrophysics Data System (ADS)

    Hodzic, Alma; Madronich, Sasha; Aumont, Bernard; Lee-Taylor, Julia; Karl, Thomas

    2013-04-01

    The dry deposition removal of organic compounds from the atmosphere and its impact on organic aerosol mass is currently unexplored and unaccounted for in chemistry-climate models. The main reason for this omission is that current models use simplified SOA mechanisms that lump precursors and their products into volatility bins, therefore losing information on other important properties of individual molecules (or groups) that are needed to calculate dry deposition. In this study, we apply the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to simulate SOA formation and estimate the influence of dry deposition of VOCs on SOA concentrations downwind of Mexico City. SOA precursors considered here include short- and long-chain alkanes (C3-25), alkenes, and light aromatics. The results suggest that 90% of SOA produced in Mexico City originates from the oxidation and partitioning of long-chain (C>12) alkanes, while the regionally exported SOA is almost equally produced from long-chain alkanes and from shorter alkanes and light aromatics. We show that dry deposition of oxidized gases is not an efficient sink for SOA, as it removes <5% of SOA within the city's boundary layer and ~15% downwind. We discuss reasons for this limited influence, and investigate separately the impacts on short and long-chain species. We show that the dry deposition is competing with the uptake of gases to the aerosol phase, and because dry deposition of submicron aerosols is slow, condensation onto particles protects organic gases from deposition and therefore increases their atmospheric burden and lifetime. In the absence of this condensation, ~50% of the regionally produced mass would have been dry-deposited.

  9. Microspectroscopic Analysis of Anthropogenic- and Biogenic-Influenced Aerosol Particles during the SOAS Field Campaign

    NASA Astrophysics Data System (ADS)

    Ault, A. P.; Bondy, A. L.; Nhliziyo, M. V.; Bertman, S. B.; Pratt, K.; Shepson, P. B.

    2013-12-01

    During the summer, the southeastern United States experiences a cooling haze due to the interaction of anthropogenic and biogenic aerosol sources. An objective of the summer 2013 Southern Oxidant and Aerosol Study (SOAS) was to improve our understanding of how trace gases and aerosols are contributing to this relative cooling through light scattering and absorption. To improve understanding of biogenic-anthropogenic interactions through secondary organic aerosol (SOA) formation on primary aerosol cores requires detailed physicochemical characterization of the particles after uptake and processing. Our measurements focus on single particle analysis of aerosols in the accumulation mode (300-1000 nm) collected using a multi orifice uniform deposition impactor (MOUDI) at the Centreville, Alabama SEARCH site. Particles were characterized using an array of microscopic and spectroscopic techniques, including: scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and Raman microspectroscopy. These analyses provide detailed information on particle size, morphology, elemental composition, and functional groups. This information is combined with mapping capabilities to explore individual particle spatial patterns and how that impacts structural characteristics. The improved understanding will be used to explore how sources and processing (such as SOA coating of soot) change particle structure (i.e. core shell) and how the altered optical properties impact air quality/climate effects on a regional scale.

  10. Key parameters controlling OH-initiated formation of secondary organic aerosol in the aqueous phase (aqSOA)

    NASA Astrophysics Data System (ADS)

    Ervens, Barbara; Sorooshian, Armin; Lim, Yong B.; Turpin, Barbara J.

    2014-04-01

    Secondary organic aerosol formation in the aqueous phase of cloud droplets and aerosol particles (aqSOA) might contribute substantially to the total SOA burden and help to explain discrepancies between observed and predicted SOA properties. In order to implement aqSOA formation in models, key processes controlling formation within the multiphase system have to be identified. We explore parameters affecting phase transfer and OH(aq)-initiated aqSOA formation as a function of OH(aq) availability. Box model results suggest OH(aq)-limited photochemical aqSOA formation in cloud water even if aqueous OH(aq) sources are present. This limitation manifests itself as an apparent surface dependence of aqSOA formation. We estimate chemical OH(aq) production fluxes, necessary to establish thermodynamic equilibrium between the phases (based on Henry's law constants) for both cloud and aqueous particles. Estimates show that no (currently known) OH(aq) source in cloud water can remove this limitation, whereas in aerosol water, it might be feasible. Ambient organic mass (oxalate) measurements in stratocumulus clouds as a function of cloud drop surface area and liquid water content exhibit trends similar to model results. These findings support the use of parameterizations of cloud-aqSOA using effective droplet radius rather than liquid water volume or drop surface area. Sensitivity studies suggest that future laboratory studies should explore aqSOA yields in multiphase systems as a function of these parameters and at atmospherically relevant OH(aq) levels. Since aerosol-aqSOA formation significantly depends on OH(aq) availability, parameterizations might be less straightforward, and oxidant (OH) sources within aerosol water emerge as one of the major uncertainties in aerosol-aqSOA formation.

  11. Aqueous secondary organic aerosol (SOA) production from the oxidation of phenols by triplet excited state organics

    NASA Astrophysics Data System (ADS)

    Smith, J.; Yu, L.; Zhang, Q.; Anastasio, C.

    2011-12-01

    Recent literature has shown that atmospheric condensed-phase chemistry can play a significant role in the evolution of organic aerosols, including the formation of secondary organic aerosol (SOA). SOA formation from the oxidation of volatile organic compounds (VOCs) in the aqueous phase has largely focused on oxidations involving the hydroxyl radical and other oxidants, such as photochemically created triplet excited states, have not been fully investigated. Phenolic compounds are one of the primary carbon emission classes from biomass and wood combustion and have significant water solubility. Once in the aqueous phase, phenolic compounds can react with the triplet excited states of non-phenolic aromatic carbonyls (NPCs), particle-bound organics that are also emitted in large quantities from wood combustion. The oxidation of phenolic species in the condensed phase by triplet excited states can result in the production of SOA. A main goal of this study was to investigate bulk solution reaction kinetics under atmospherically relevant conditions in order to ascertain how these reactions can impact aqueous-phase SOA production. In our experiments, we studied the reactions of five phenols (phenol, guaiacol, syringol, catechol, and resorcinol) with the triplet state of 3,4-dimethoxybenzaldehyde (34-DMB) during simulated solar radiation. We have characterized the impacts of pH, ionic strength and reactant concentrations on the reaction behavior of this system. In addition, we analyzed the SOA formed using high-resolution aerosol mass spectrometry, ion chromatography, and liquid chromatography-mass spectrometry to infer the reaction mechanisms. Our evidence suggests that under atmospherically relevant conditions, triplet excited states can be the dominant oxidant of phenolics and contribute significantly to the total SOA budget.

  12. Surface-active and Light-absorbing Secondary Organic Aerosol (SOA) Material

    NASA Astrophysics Data System (ADS)

    McNeill, V. F.; Sareen, N.; Schwier, A. N.; Shapiro, E. L.

    2009-12-01

    We have observed the formation of light-absorbing, high-molecular-weight, and surface-active organics from methylgyloxal interacting with ammonium salts in aqueous aerosol mimics. Mixtures of methylglyoxal and glyoxal also form light-absorbing products and exhibit surface tension depression with a Langmuir-like dependence on initial methylglyoxal concentration. We used chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS) to characterize the product species. The results are consistent with aldol condensation products, carbon-nitrogen species, sulfur-containing compounds, and oligomeric species up to 759 amu. These observations have potentially significant implications for our understanding of the effects of SOA on climate, since a) SOA are typically treated as non-absorbing in climate models, and b) surface tension depression in aqueous aerosols by SOA material may result in increased cloud condensation nucleus (CCN) activity. Furthermore, surface film formation could affect aerosol heterogeneous chemistry. We will also discuss aerosol flow tube O3 oxidation experiments designed to determine the atmospheric lifetimes of the observed product compounds.

  13. Secondary Organic Aerosol Formation in the Captive Aerosol Growth and Evolution (CAGE) Chambers during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL

    NASA Astrophysics Data System (ADS)

    Leong, Y.; Karakurt Cevik, B.; Hernandez, C.; Griffin, R. J.; Taylor, N.; Matus, J.; Collins, D. R.

    2013-12-01

    Secondary organic aerosol (SOA) represents a large portion of sub-micron particulate matter on a global scale. The composition of SOA and its formation processes are heavily influenced by anthropogenic and biogenic activity. Volatile organic compounds (VOCs) that are emitted naturally from forests or from human activity serve as precursors to SOA formation. Biogenic SOA (BSOA) is formed from biogenic VOCs and is prevalent in forested regions like the Southeastern United States. The formation and enhancement of BSOA under anthropogenic influences such as nitrogen oxides (NOx), sulfur dioxide (SO2), and oxygen radicals are still not well understood. The lack of information on anthropogenic BSOA enhancement and the reversibility of SOA formation could explain the underprediction of SOA in current models. To address some of these gaps in knowledge, this study was conducted as part of the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL during the summer of 2013. SOA growth experiments were conducted in two Captive Aerosol Growth and Evolution (CAGE) outdoor chambers located at the SEARCH site. Ambient trace gas concentrations were maintained in these chambers using semi-permeable gas-exchange membranes, while studying the growth of injected monodisperse seed aerosol. The control chamber was operated under ambient conditions; the relative humidity and oxidant and NOx levels were perturbed in the second chamber. This design allows experiments to capture the natural BSOA formation processes in the southeastern atmosphere and to study the influence of anthropogenic activity on aerosol chemistry. Chamber experiments were periodically monitored with physical and chemical instrumentation including a scanning mobility particle sizer (SMPS), a cloud condensation nuclei counter (CCNC), a humidified tandem differential mobility analyzer (H-TDMA), and an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The CAGE experiments focused on SOA

  14. Molecular markers of biomass burning, fungal spores and biogenic SOA in the Taklimakan desert aerosols

    NASA Astrophysics Data System (ADS)

    Fu, Pingqing; Zhuang, Guoshun; Sun, Yele; Wang, Qiongzhen; Chen, Jing; Ren, Lujie; Yang, Fan; Wang, Zifa; Pan, Xiaole; Li, Xiangdong; Kawamura, Kimitaka

    2016-04-01

    Biogenic primary organic aerosols (POA) and secondary organic aerosols (SOA) are important organic constituents of atmospheric particulate matter (PM). In order to better understand the atmospheric abundances, molecular compositions and sources of the desert aerosols, biomass-burning tracers (e.g. levoglucosan), primary saccharides including fungal spore tracers, and SOA tracers from the oxidation of biogenic volatile organic compounds (e.g. isoprene, monoterpenes and sesquiterpene) have been studied in ambient aerosols from the Taklimakan desert, using gas chromatography-mass spectrometry. Results showed that the total concentrations of biomass-burning tracers at Hetian (177-359 ng m-3, mean 233 ng m-3 in PM2.5) in the south rim of the desert were much higher than those at Tazhong (1.9-8.8 ng m-3 in PM2.5 and 5.9-32 ng m-3 in TSP) in the central Taklimakan desert. Molecular markers of fungal spores were also detected in all the desert aerosols, highlighting the importance of primary bioaerosols in the Asian dust particles. A specific pattern of the dominance of 2-methylglyceric acid over 2-methyltetrols and C5-alkene triols was found in the Taklimakan desert aerosols, especially during the dust storm events, which is different from the 2-methyltetrols-dominated pattern in other ambient aerosols. Our results provide direct evidence on the biogenic POA and SOA tracers in the Taklimakan desert region, which help to better understand their impact on the aerosol chemistry in the down-wind regions.

  15. Secondary Organic Aerosol (SOA) production from the Aqueous Reactions of Phenols and Triplet Aromatic Carbonyls

    NASA Astrophysics Data System (ADS)

    Smith, J.; Sun, Y.; Lu, Y.; Zhang, Q.; Anastasio, C.

    2010-12-01

    The phenolic compounds guaiacol, syringol and phenol have recently been shown to produce secondary organic aerosol (SOA) at high yields in the aqueous phase upon exposure to simulated sunlight and hydroxyl radical. These phenols are significant products from wood combustion that can readily enter atmospheric waters, such as aqueous aerosol particles and cloud/fog droplets. Once in the aqueous phase, phenols can react with the triplet excited states of non-phenolic aromatic carbonyls (NPCs), particle-bound organics that are also emitted from wood combustion. In this study, we examined the aqueous-phase production of SOA from the reaction of phenolic compounds with triplet excited state organics. These aqueous phase reactions were tested by illuminating solutions containing a phenolic compound and NPC under simulated sunlight at various concentrations and pH values. The phenolic compound is consumed during these reactions, following a first-order decay that varies with phenol concentration, phenol identity, and pH. The non-volatile product mass formed in our illuminated solutions was determined gravimetrically and by analysis with High Resolution Time of Flight Aerosol Mass Spectrometry (HR-AMS). The SOA mass yield was determined as the mass of non-volatile product formed per mass of phenolic consumed during illumination. We also used HR-AMS to analyze for elemental composition, carbon oxidation state, and oligomers in the SOA produced. Our results to date indicate that phenols can be rapidly oxidized by triplet excited states under environmentally relevant conditions and that the accompanying SOA mass yields are very high.

  16. Secondary Organic Aerosol Formation from Glyoxal: photochemical versus dark uptake and reversible versus irreversible SOA formation

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Slowik, J.; Kampf, C.; Timkovsky, J.; Noziere, B.; Praplan, A.; Pffafenberger, L.; Holzinger, R.; Hoffmann, T.; Dommen, J.; Prevot, A.; Baltensperger, U.; Volkamer, R.

    2012-04-01

    Glyoxal forms secondary organic aerosol (SOA) by partitioning to the aerosol aqueous phase according to Henry's law. The subsequent processing by heterogeneous and multiphase reactions shifts the partitioning towards aerosols. Currently it is not well understood whether these reactions result in reversible or irreversible SOA formation, and what parameters influence the rate limiting step of multiphase processing. We conducted a series of simulation chamber experiments at PSI in April and May 2011 to investigate processing under dark conditions, UV and/or visible light irradiated conditions, and in the presence and absence of OH radicals. Experiments used ammonium sulfate or ammonium sulfate/fulvic acid mixtures as seed aerosols, and were conducted between 50% and 85% relative humidity at approximately constant RH over the course of any given experiment. Glyoxal was produced photochemically from acetylene, using HONO photolysis as the OH radical source. Gas-phase glyoxal was measured by the CU LED-Cavity Enhanced-DOAS. The Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS) and Ion Chromatography Mass Spectrometer (IC-MS) monitored both gas and aerosol-phase organic reaction products. Particle composition was monitored by High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS), and HPLC-ESI MS/MS and LC-MS analysis of filter samples.

  17. Secondary Organic Aerosol Formation from Glyoxal: photochemical versus dark uptake and reversible versus irreversible SOA formation

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Slowik, J. G.; Kampf, C. J.; Timkovsky, J.; Noziere, B.; Praplan, A. P.; Pfaffenberger, L.; Holzinger, R.; Hoffmann, T.; Dommen, J.; Prevot, A. S.; Baltensperger, U.; Volkamer, R.

    2011-12-01

    Glyoxal forms secondary organic aerosol (SOA) by partitioning to the aerosol aqueous phase according to Henry's law. The subsequent processing by heterogeneous and multiphase reactions shifts the partitioning towards aerosols. Currently it is not well understood whether these reactions result in reversible or irreversible SOA formation, and what parameters influence the rate limiting step of multiphase processing. We conducted a series of simulation chamber experiments at PSI in April and May 2011 to investigate processing under dark conditions, UV and/or visible light irradiated conditions, and in the presence and absence of OH radicals. Experiments used ammonium sulfate or ammonium sulfate/fulvic acid mixtures as seed aerosols, and were conducted between 50% and 85% relative humidity at approximately constant RH over the course of any given experiment. Glyoxal was produced photochemically from acetylene, using HONO photolysis as the OH radical source. Gas-phase glyoxal was measured by the CU LED-Cavity Enhanced-DOAS. The Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS) and Ion Chromatography Mass Spectrometer (IC-MS) monitored both gas and aerosol-phase organic reaction products. Particle composition was monitored by High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS), and HPLC-ESI MS/MS and LC-MS analysis of filter samples.

  18. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2016-02-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas-wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas-wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.

  19. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2015-09-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool which explicitly represents SOA formation and gas/wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas/wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up to 0.35 yield unit due to the loss of organic vapors to chamber walls.

  20. Simulation of semi-explicit mechanisms of SOA formation from glyoxal in aerosol in a 3-D model

    NASA Astrophysics Data System (ADS)

    Knote, C.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J.; Fast, J.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R.; Tyndall, G.; Washenfelder, R.; Waxman, E.; Zhang, Q.

    2014-06-01

    New pathways to form secondary organic aerosol (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous phase of cloud droplets and deliquesced particles where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aerosol aqueous-phase. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. A month-long simulation over the continental United States (US) enables us to extend our results to the continental scale. In all simulations over California, the Los Angeles (LA) basin was found to be the hot spot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a reactive (surface limited) uptake coefficient leads to higher SOA yields from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to give the highest SOA mass yields compared to a volume process and reversible formation. We find that the yields of the latter are limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A time dependence in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume

  1. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    NASA Astrophysics Data System (ADS)

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; McKinney, K.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Brito, J.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Alexander, M. L.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

    2015-10-01

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40 ‰) but varies substantially between locations, which is shown to reflect

  2. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    DOE PAGESBeta

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; et al

    2015-10-23

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accountedmore » by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown

  3. 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

  4. Monodisperse aerosol generator

    DOEpatents

    Ortiz, Lawrence W.; Soderholm, Sidney C.

    1990-01-01

    An aerosol generator is described which is capable of producing a monodisperse aerosol within narrow limits utilizing an aqueous solution capable of providing a high population of seed nuclei and an organic solution having a low vapor pressure. The two solutions are cold nebulized, mixed, vaporized, and cooled. During cooling, particles of the organic vapor condense onto the excess seed nuclei, and grow to a uniform particle size.

  5. Secondary Organic Aerosol (SOA) Formation From the NO3 Radical Oxidation of Alpha- pinene

    NASA Astrophysics Data System (ADS)

    Perraud, V.; Yu, Y.; Bruns, E.; Ezell, M. J.; Johnson, S. N.; Alexander, M.; Zelenyuk, A.; Imre, D.; Finlayson-Pitts, B. J.

    2008-12-01

    Terpenes such as alpha-pinene, emitted in large quantities from vegetation into the troposphere, are well known to react with O3, OH and NO3 radicals leading to the formation of secondary organic aerosol, SOA. While particle formation and growth from the NO3 reaction with alpha-pinene have been reported by a number of groups, as have the gas phase products of this reaction, little is known about the chemical composition of the particles. We report studies of the composition of particles formed in the NO3 - alpha- pinene reaction using two reactors, a flow tube and a static chamber. Nitrate radicals were generated in the flow tube by the reaction of NO2 with O3 and in the static chamber by the thermal decomposition of N2O5. Particle formation and growth was monitored using SMPS and APS. A variety of analytical techniques were applied to measure the chemical composition, including FTIR of particles collected on ZnSe impactor discs, and GC-MS, ESI-MS, APCI-MS, HPLC-MS and HPLC-UV of samples collected on quartz fiber filters. In addition, particle mass spectrometer techniques including AMS and SPLAT provided real-time analysis. A number of organic nitrates were observed in the particles, along with carbonyl compounds and organic acids. Gas phase products measured using DNPH coated-cartridges included pinonaldehyde, formaldehyde, acetaldehyde and acetone. Results of studies in which concentrations of the reactants were varied will be presented and possible mechanisms and the atmospheric implications will be discussed.

  6. Phase, Viscosity, Morphology, and Room Temperature Evaporation Rates of SOA Particles Generated from Different Precursors, at Low and High Relative Humidities, and their Interaction with Hydrophobic Organics

    NASA Astrophysics Data System (ADS)

    Wilson, J. M.; Zelenyuk, A.; Imre, D. G.; Beranek, J.; Abramson, E.; Shrivastava, M.

    2012-12-01

    Formation, properties, transformations, and temporal evolution of secondary organic aerosol (SOA) particles strongly depend on particle phase. Semi-volatile molecules that comprise SOA particles were assumed to form a low viscosity solution that maintains equilibrium with the evolving gas phase by rapid evaporation condensation. However, studies by our group indicate that laboratory-generated alpha-pinene SOA particles and ambient SOA characterized in a recent field campaign are in a semi-solid, highly viscous phase, and their evaporation rates are orders of magnitude slower than predicted. We present the results of recent studies in which we have extended our work to include SOA particles generated by oxidation of a number of precursors including limonene, n-alkenes, cyclo-alkenes and isoprene. The resulting particles are characterized by their phase, morphology and room temperature evaporation rates. We conclude that, while the detailed properties of SOA particles depend of their precursor, all studied SOA particles are highly viscous semi-solids that exhibit very slow evaporation rates. Given that atmospheric relative humidity (RH) can change particle phase, it is important to investigate the effect of RH on the phase and evaporation kinetics of SOA particles. To this end SOA particles were generated at low and high (~90%) RH, and their evaporation kinetics and phase were characterized as a function of RH. In the ambient atmosphere SOA particles form in the presence of a mixture of different organic compounds, which are present at or below their equilibrium vapor pressure, and thus have been ignored. However, our data show that these compounds can adsorb to the surface of particles during SOA formation, becoming trapped in the highly viscous SOA, and affect particle properties. We examine the interaction between SOA particles and different hydrophobic organics representing typical anthropogenic emissions by making SOA in the presence of the vapors of these

  7. 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.

  8. Characterization of a real-time tracer for Isoprene Epoxydiols-derived Secondary Organic Aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    NASA Astrophysics Data System (ADS)

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

    2015-04-01

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene low-NO oxidation pathways, was quantified by applying Positive Matrix Factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of OA in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the SOAS study, 78% of IEPOX-SOA is accounted for the measured molecular tracers, making it the highest level of molecular identification of an ambient SOA component to our knowledge. Enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O ( fC5H6O = C5H6O+/OA) across multiple field, chamber and source datasets. A background of ~ 1.7 ± 0.1‰ is observed in studies strongly influenced by urban, biomass-burning and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.8‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7‰). Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3‰) observed in non IEPOX-derived isoprene-SOA indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from

  9. Characterization of a real-time tracer for Isoprene Epoxydiols-derived Secondary Organic Aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    DOE PAGESBeta

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; et al

    2015-04-16

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene low-NO oxidation pathways, was quantified by applying Positive Matrix Factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of OA in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the SOAS study, 78% of IEPOX-SOA is accounted for the measured molecular tracers, making itmore » the highest level of molecular identification of an ambient SOA component to our knowledge. Enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O ( fC5H6O = C5H6O+/OA) across multiple field, chamber and source datasets. A background of ~ 1.7 ± 0.1‰ is observed in studies strongly influenced by urban, biomass-burning and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.8‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7‰). Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3‰) observed in non IEPOX-derived isoprene-SOA indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA

  10. Land cover maps, BVOC emissions, and SOA burden in a global aerosol-climate model

    NASA Astrophysics Data System (ADS)

    Stanelle, Tanja; Henrot, Alexandra; Bey, Isaelle

    2015-04-01

    It has been reported that different land cover representations influence the emission of biogenic volatile organic compounds (BVOC) (e.g. Guenther et al., 2006). But the land cover forcing used in model simulations is quite uncertain (e.g. Jung et al., 2006). As a consequence the simulated emission of BVOCs depends on the applied land cover map. To test the sensitivity of global and regional estimates of BVOC emissions on the applied land cover map we applied 3 different land cover maps into our global aerosol-climate model ECHAM6-HAM2.2. We found a high sensitivity for tropical regions. BVOCs are a very prominent precursor for the production of Secondary Organic Aerosols (SOA). Therefore the sensitivity of BVOC emissions on land cover maps impacts the SOA burden in the atmosphere. With our model system we are able to quantify that impact. References: Guenther et al. (2006), Estimates of global terrestrial isoprene emissions using MEGAN, Atmos. Chem. Phys., 6, 3181-3210, doi:10.5194/acp-6-3181-2006. Jung et al. (2006), Exploiting synergies of global land cover products for carbon cycle modeling, Rem. Sens. Environm., 101, 534-553, doi:10.1016/j.rse.2006.01.020.

  11. Radiative forcing of organic aerosol in the atmosphere and on snow: incorporation of SOA and brown carbon

    NASA Astrophysics Data System (ADS)

    Lin, G.; Flanner, M.; Penner, J. E.

    2013-12-01

    Organic aerosols (OA) play an important role in climate change through their radiative forcing. Secondary organic aerosol (SOA) contributes a large portion of total organic aerosol, especially in remote regions. Organic aerosol has been shown to be an important source of solar-light absorption. However, very few global model calculations of the radiative forcing due to organic aerosol include SOA or the light-absorbing part of OA (brown carbon). Here, we use a global chemical transport model with a detailed SOA formation mechanism to investigate the change in SOA between present day and pre-industrial conditions. We employ a radiative transfer model to assess the radiative forcing associated with the change in SOA. We also reassess the radiative forcing of total OA by considering previously neglected brown carbon. In addition to the OA in the atmosphere, we examine for the first time the radiative forcing of OA deposited in snow and sea-ice by using the NCAR Community Land Model 4 (CLM4) for the land snow simulation and the Community Ice CodE 4 (CICE) for the sea-ice simulation. Anthropogenic emissions of NOx, CO, sulfate, biomass burning and fossil fuel organic aerosol are shown to influence the formation rate of SOA substantially, causing it to increase by 35 Tg/yr (41%) since pre-industrial times. The increase of SOA results in a direct forcing ranging from -0.12 to -0.34 Wm-2 and a first indirect forcing in warm phase clouds ranging from -0.24 to -0.32 Wm-2, with the range due to different assumed size distributions for SOA and different refractive indices. The global burden of primary organic aerosol (POA) is estimated to increase by 0.53 Tg since pre-industrial times. Based on different refractive indices assumed for brown carbon, the increase of POA leads to a direct forcing varying from -0.07 to -0.12 Wm-2. The change in total OA exerts a direct radiative forcing ranging from -0.17 to -0.46 Wm-2. Atmospheric absorption from brown carbon ranges from +0.13 to

  12. Highly stable aerosol generator

    DOEpatents

    DeFord, H.S.; Clark, M.L.

    1981-11-03

    An improved compressed air nebulizer has been developed such that a uniform aerosol particle size and concentration may be produced over long time periods. This result is achieved by applying a vacuum pressure to the makeup assembly and by use of a vent tube between the atmosphere and the makeup solution. By applying appropriate vacuum pressures to the makeup solution container and by proper positioning of the vent tube, a constant level of aspirating solution may be maintained within the aspirating assembly with aspirating solution continuously replaced from the makeup solution supply. This device may also be adapted to have a plurality of aerosol generators and only one central makeup assembly. 2 figs.

  13. Highly stable aerosol generator

    DOEpatents

    DeFord, Henry S.; Clark, Mark L.

    1981-01-01

    An improved compressed air nebulizer has been developed such that a uniform aerosol particle size and concentration may be produced over long time periods. This result is achieved by applying a vacuum pressure to the makeup assembly and by use of a vent tube between the atmosphere and the makeup solution. By applying appropriate vacuum pressures to the makeup solution container and by proper positioning of the vent tube, a constant level of aspirating solution may be maintained within the aspirating assembly with aspirating solution continuously replaced from the makeup solution supply. This device may also be adapted to have a plurality of aerosol generators and only one central makeup assembly.

  14. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: Explicit modeling of SOA formation from alkane and alkene oxidation

    DOE PAGESBeta

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2016-02-08

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas–wall partitioning. The model was compared with 41 smog chambermore » experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas–wall mass transfer, the vapor pressure of the species and the duration of the experiments. Furthermore, this work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.« less

  15. Organosulfates as Tracers for Secondary Organic Aerosol (SOA) Formation from 2-Methyl-3-Buten-2 ol (MBO) in the Atmosphere

    EPA Science Inventory

    2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was exa...

  16. Secondary Organic Aerosol Formation and Aging in a Flow Reactor in the Forested Southeast US during SOAS

    NASA Astrophysics Data System (ADS)

    Hu, W.; Palm, B. B.; Hacker, L.; Campuzano Jost, P.; Day, D. A.; Simoes de Sa, S.; Fry, J.; Ayres, B. R.; Draper, D. C.; Ortega, A. M.; Kiendler-Scharr, A.; Panujoka, A.; Virtanen, A.; Miettinen, P.; Krechmer, J.; Canagaratna, M. R.; Thompson, S.; Yatavelli, L. R.; Stark, H.; Worsnop, D. R.; Lechner, M.; Martin, S. T.; Farmer, D.; Brown, S. S.; Jimenez, J. L.

    2013-12-01

    A major field campaign (Southern Oxidant and Aerosol Study, SOAS) was conducted in summer 2013 in a forested area (Centreville Supersite) in the southeast U.S. To investigate secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (BVOCs), 3 flow reactors (potential aerosol mass, PAM) were used to expose ambient air to oxidants and their output was analyzed by state-of-art gas and aerosol instruments including a High-Resolution Aerosol Mass Spectrometer (HR-AMS), a High-Resolution Proton-Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOFMS), and for the first time, two different High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometers (HRToF-CIMS), and an SMPS. Ambient air was exposed 24/7 to variable concentrations of each of the 3 main atmospheric oxidants (OH, O3 and NO3) to investigate SOA formation and aging. The OH exposure was estimated by 3 different methods (empirical parameterization, carbon monoxide consumption, and chemical box model). Effective OH exposures up to 7e12 molec cm-3 s were achieved, which is equivalent to over a month of aging in the atmosphere. High SOA formation of up to 12 μg m-3 above ambient concentrations of 5 μg m-3 was observed under intermediate OH exposures, while very high OH exposures led to destruction of ambient OA by ≈ 30%, indicating shifting contributions of functionalization vs. fragmentation, which is similar to previous results from urban and terpene-dominated environments. The highest SOA enhancements were 3-4 times higher than the ambient OA. More SOA is typically formed during nighttime when terpenes are higher and lower during daytime when isoprene is higher. SOA formation is also observed after exposure of ambient air to O3 or NO3, although the amount and oxidation was lower than for OH exposure. Formation of organic nitrates in the NO3 reaction will be discussed. High SOA formation (above 40 μg m-3) and a large number of CIMS ions, indicating many different

  17. Organic Aerosol Formation in the Humid, Photochemically-Active Southeastern US: SOAS Experiments and Simulations

    NASA Astrophysics Data System (ADS)

    Sareen, N.; Lim, Y. B.; Carlton, A. G.; Turpin, B. J.

    2013-12-01

    Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized low volatility organic aerosol and, in some cases, light absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, health, and the environment. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols) leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify other precursors that are atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere at Brent, Alabama during the Southern Oxidant and Aerosol Study (SOAS). Four mist chambers in parallel collected ambient gases in a DI water medium at 20-25 LPM with a 4 hr collection time. Total organic carbon (TOC) values in daily composited samples were 64-180 μM. Aqueous OH radical oxidation experiments were conducted with these mixtures in a newly designed cuvette chamber to understand the formation of SOA through gas followed by aqueous chemistry. OH radicals (3.5E-2 μM [OH] s-1) were formed in-situ in the chamber, continuously by H2O2 photolysis. Precursors and products of these aqueous OH experiments were characterized using ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. ESI-MS results from a June 12th, 2013 sample showed precursors to be primarily odd, positive mode ions, indicative of the presence of non-nitrogen containing alcohols, aldehydes, organic peroxides, or epoxides. Products were seen in the negative mode and included organic acid ions like pyruvate

  18. Chemical characterization of biogenic SOA generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

    NASA Astrophysics Data System (ADS)

    Faiola, C. L.; Wen, M.; VanReken, T. M.

    2014-10-01

    The largest global source of secondary organic aerosol in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic VOC profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate, a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six different coniferous plant types. VOCs emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA particle size distribution and chemical composition were measured using a scanning mobility particle sizer (SMPS) and Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS), respectively. The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+) m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, methyl jasmonate, is also presented. Elemental analysis results demonstrated an O:C range of baseline biogenic SOA between 0.3-0.47. The O:C of standard methyl jasmonate SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient datasets collected in forest environments.

  19. Chemical characterization of biogenic SOA generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

    DOE PAGESBeta

    Faiola, C. L.; Wen, M.; VanReken, T. M.

    2014-10-01

    The largest global source of secondary organic aerosol in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic VOC profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate, a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six differentmore » coniferous plant types. VOCs emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA particle size distribution and chemical composition were measured using a scanning mobility particle sizer (SMPS) and Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS), respectively. The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+) m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, methyl jasmonate, is also presented. Elemental analysis results demonstrated an O:C range of baseline biogenic SOA between 0.3–0.47. The O:C of standard methyl jasmonate SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient datasets collected in forest environments.« less

  20. Potential Aerosol Mass (PAM) flow reactor measurements of SOA formation in a Ponderosa Pine forest in the southern Rocky Mountains during BEACHON-RoMBAS

    NASA Astrophysics Data System (ADS)

    Palm, B. B.; Ortega, A. M.; Campuzano Jost, P.; Day, D. A.; Kaser, L.; Karl, T.; Jud, W.; Hansel, A.; Fry, J.; Brown, S. S.; Zarzana, K. J.; Dube, W. P.; Wagner, N.; Draper, D.; Brune, W. H.; Jimenez, J. L.

    2012-12-01

    A Potential Aerosol Mass (PAM) photooxidation flow reactor was used in combination with an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer to characterize biogenic secondary organic aerosol (SOA) formation in a terpene-dominated forest during the July-August 2011 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) field campaign at the U.S. Forest Service Manitou Forest Observatory, Colorado, as well as in corresponding laboratory experiments. In the PAM reactor, a chosen oxidant (OH, O3, or NO3) was generated and controlled over a range of values up to 10,000 times ambient levels. High oxidant concentrations accelerated the gas-phase, heterogeneous, and possibly aqueous oxidative aging of volatile organic compounds (VOCs), inorganic gases, and existing aerosol, which led to repartitioning into the aerosol phase. PAM oxidative processing represented from a few hours up to ~20 days of equivalent atmospheric aging during the ~3 minute reactor residence time. During BEACHON-RoMBAS, PAM photooxidation enhanced SOA at intermediate OH exposure (1-10 equivalent days) but resulted in net loss of OA at long OH exposure (10-20 equivalent days), demonstrating the competing effects of functionalization vs. fragmentation (and possibly photolysis) as aging increased. PAM oxidation also resulted in f44 vs. f43 and Van Krevelen diagram (H/C vs. O/C) slopes similar to ambient oxidation, suggesting the PAM reactor employs oxidation pathways similar to ambient air. Single precursor aerosol yields were measured using the PAM reactor in the laboratory as a function of organic aerosol concentration and reacted hydrocarbon amounts. When applying the laboratory PAM yields with complete consumption of the most abundant VOCs measured at the forest site (monoterpenes, sesquiterpenes, MBO, and toluene), a simple model underpredicted the amount of SOA formed in the PAM reactor in the

  1. Examining the Effects of Anthropogenic Emissions on Isoprene-Derived Secondary Organic Aerosol Formation During the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, Ground Site

    EPA Science Inventory

    A suite of offline and real-time gas- and particle-phase measurements was deployed atLook Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formatio...

  2. Aged Organic Aerosol in the Upper Troposphere: Aging of boundary layer aerosol during and after convective transport and in-situ SOA formation during DC3. (Invited)

    NASA Astrophysics Data System (ADS)

    Campuzano Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Jimenez, J. L.; Hodzic, A.; Bela, M. M.; Barth, M. C.; Olson, J. R.; Crawford, J. H.; Brune, W. H.; Pollack, I. B.; Ryerson, T. B.; Blake, D. R.; Wisthaler, A.; Mikoviny, T.

    2013-12-01

    While aerosol scavenging in deep convection is efficient (comparable to soluble species like formaldehyde), significant transport of submicron aerosol was observed repeatedly during storms targeted in the course of the DC3 (Deep Convective Clouds and Chemistry ) campaign. The lofted aerosol was mostly organic, and even in fresh outflow was significantly more oxidized than the aerosol sampled in the source region of the convection. Organic aerosol (OA) sampled in both day-old outflow as well as in the background continental UT was in general significantly more oxidized than OA observed both in the fresh outflow, and in most lower tropospheric aerosol. This suggests either fast oxidative chemistry, and/or long residence times in the UT. Some of the potential factors contributing to this fast oxidation will be explored in this talk. A second source of UT OA was observed during several flights where gas-phase organics in the presence of NOx lead to the formation of secondary OA (SOA), including particulate organic nitrate. Most observations of this UT SOA during DC3 were made in fresh outflow. However, a unique opportunity to study the chemistry of this SOA formation in more detail with a box model presented itself in the flight on July 21st, 2012; here an initially near-particle-free UT airmass originating in the wake of a dissolving nighttime mesoscale convective system (MCS) was observed over several hours until new particle growth dominated by OA and particulate nitrate was measured.

  3. Influence of humidity, temperature, and radicals on the formation and thermal properties of secondary organic aerosol (SOA) from ozonolysis of β-pinene.

    PubMed

    Emanuelsson, Eva U; Watne, Ågot K; Lutz, Anna; Ljungström, Evert; Hallquist, Mattias

    2013-10-10

    The influence of water and radicals on SOAs produced by β-pinene ozonolysis was investigated at 298 and 288 K using a laminar flow reactor. A volatility tandem differential mobility analyzer (VTDMA) was used to measure the evaporation of the SOA, enabling the parametrization of its volatility properties. The parameters extracted included the temperature at which 50% of the aerosol had evaporated (T(VFR0.5)) and the slope factor (S(VFR)). An increase in S(VFR) indicates a broader distribution of vapor pressures for the aerosol constituents. Reducing the reaction temperature increased S(VFR) and decreased T(VFR0.5) under humid conditions but had less effect on T(VFR0.5) under dry conditions. In general, higher water concentrations gave lower T(VFR0.5) values, more negative S(VFR) values, and a reduction in total SOA production. The radical conditions were changed by introducing OH scavengers to generate systems with and without OH radicals and with different [HO2]/[RO2] ratios. The presence of a scavenger and lower [HO2]/[RO2] ratio reduced SOA production. Observed changes in S(VFR) values could be linked to the more complex chemistry that occurs in the absence of a scavenger and indicated that additional HO2 chemistry gives products with a wider range of vapor pressures. Updates to existing ozonolysis mechanisms with routes that describe the observed responses to water and radical conditions for monoterpenes with endocyclic and exocyclic double bonds are discussed. PMID:24001129

  4. Oligomerization as a potential mechanism for Secondary Organic Aerosol (SOA) formation in clouds

    NASA Astrophysics Data System (ADS)

    Yasmeen, F.; Sauret, N.; Claeys, M.; Maria, P. C.; Massi, L.

    2009-04-01

    Electrospray ionization - mass spectrometry (ESI-MS) has been used to investigate oligomer formation in dark chamber experiments designed to study the polymerization conditions of common atmospheric photooxidation products without photochemical action. Methylglyoxal has been selected as the monomer considering, it is a gas-phase product from the atmospheric oxidation of isoprene and terpenes (biogenic sources) as well as of aromatic compounds (anthropogenic sources). Aqueous-phase oligomer formation of methylglyoxal has been investigated in a simulated cloud matrix, under dark conditions in view of its short life time (~1.6 hrs). A mechanistic pathway for the growth of oligomers via aldol condensation under cloud conditions and in the absence of UV-light and the OH radical is proposed here for the first time. Soluble oligomers (n=1-12) formed in the course of acid-catalyzed aldol condensation have been detected and identified by positive and negative ion ESI-MS, while their relative abundance is estimated from the full-scan mass spectra. In particular, oligomer abundances and their adduct formation was considered with special emphasis on the structural elucidation of these oligomers and their corresponding adduct products. The oligomer series starts with a β-hydroxy ketone via aldol condensation and oligomers are formed by multiple addition of C3H4O2 units (72 Da) to the parent β-hydroxy ketone. MS2 ion trap experiments have been performed to structurally characterize the oligomers. Oligomers could form under conditions encountered in clouds even at micromolar concentrations and thus could significantly result in secondary organic aerosol (SOA) after cloud droplet evaporation. Therefore, it is proposed that oligomer formation does not only occur during droplet evaporation when the concentrations of products increase but could as well be an in-cloud process and substantially enhance in-cloud SOA yields.

  5. On the chemical nature of the oxygenated organic aerosol: implication in the formation and aging of α-pinene SOA in a Mediterranean environment, Marseille

    NASA Astrophysics Data System (ADS)

    El Haddad, I.; D'Anna, B.; Temime-Roussel, B.; Nicolas, M.; Boreave, A.; Favez, O.; Voisin, D.; Sciare, J.; George, C.; Jaffrezo, J.-L.; Wortham, H.; Marchand, N.

    2012-08-01

    Organic Aerosol (OA) measurements were conducted during summer 2008 at an urban background site, in Marseille, France's second city and the largest port in the Mediterranean, an urban industrialized environment known for its active photochemistry. PM2.5 was collected using high volume samplers and analyzed for elemental and organic carbon, major ions (NH4+, NO3- and SO42-), humic-like-substances, organic markers (i.e. primary tracers and α-pinene oxidation products), elemental composition and radiocarbon content (14C). The real-time chemical characterization of submicron particles was also achieved using a compact time of flight aerosol mass spectrometer. Positive matrix factorization conducted on the organic aerosol mass spectra matrix revealed four factors, including traffic emissions (hydrocarbon-like OA, HOA), industrial emissions, semi-volatile (SV-OOA) and low-volatile (LV-OOA) oxygenated organic aerosol (OOA) related to oxidation processes. The results obtained were in excellent agreement with chemical mass balance source apportionments conducted in conjunction with organic markers and elements. It appears that while primary emissions contributed only 22% to the total OA (of which 23% was associated with industrial processes), OOA constituted the overwhelming fraction. Radiocarbon measurements suggest that about 80% of this fraction was of non-fossil origin, assigned predominantly to biogenic secondary organic aerosol. Non-fossil carbon appears to especially dominate the LV-OOA fraction, an aged long-range-transported OOA, marginally affected by local anthropogenic SOA. We also examined the relation between OOA and α-pinene SOA obtained based on the levels of α-pinene oxidation products. α-pinene SOA showed good correlation with SV-OOA, suggesting that the compounds used for estimating α-pinene SOA appear to pertain mainly to the moderately oxidized fraction. In contrast, LV-OOA was found to be intimately related to HUmic LIke substances (HULIS

  6. SOA Formation from Glyoxal in the Aerosol Aqueous Phase: A case study from Mexico City using an explicit laboratory-based model

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Dzepina, K.; Lee-Taylor, J.; Ervens, B.; Volkamer, R.

    2012-04-01

    Glyoxal is an important contributor to secondary organic aerosol (SOA) formation via aerosol aqueous phase processing. This work takes a glyoxal-SOA model parameterization based on laboratory data and applies the box model to ambient measurements. For the Mexico City Metropolitan Area (MCMA) case study on April 9, 2003 the aerosol uptake and processing of glyoxal in aerosol water is investigated, and found able to rationalize the previously observed gas phase glyoxal imbalance (Volkamer et al., 2007) for the first time based on laboratory data. Our aerosol size distribution resolving model is constrained with time resolved distributions of aerosol chemical composition, and supports a surface limited uptake mechanism of glyoxal in Mexico City. We compare the AMS-measured OOA to SOA predictions using our glyoxal model combined with background aerosol, traditional VOC precursor (e.g., aromatics) SOA, and three parameterizations for SOA formation from S/IVOC, i.e., based on (1) Robinson et al., 2007, (2) Grieshop et al., 2009, and (3) GECKO-A (Lee-Taylor et al., 2011), which account for the bulk of SOA mass, but give very different results for the O/C ratio of predicted SOA. This presents to our knowledge the first comparison of a molecular perspective of S/IVOC ageing with empirical parameterizations. We compare the mass weighted O/C ratio from these different SOA sources to AMS-measured O/C ratios, in an attempt to use the rapidly increasing O/C to test for closure, and advance our understanding of aerosol ageing in Mexico City.

  7. Aqueous Secondary Organic Aerosol (aqSOA) Formation By Radical Reactions: Model Studies Comparing the Role of OH Versus Organic Radicals

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Renard, P.; Reed Harris, A.; Vaida, V.; Monod, A.

    2014-12-01

    Chemical reactions in the aqueous phase are thought to significantly contribute to ambient aerosol mass under specific conditions. Results from many laboratory studies suggest that these reactions are efficiently initiated by the OH radical and lead to high molecular weight compounds (oligomers). Recent laboratory experiments have shown that methyl vinyl ketone (MVK) can form oligomers in high yield in aqueous solutions similar to aerosol water. Additional experiments have shown that the direct photolysis of pyruvic acid can generate organic radicals that initiate similar oligomer products upon oxidation of MVK (Renard et al., submitted). Sources of the OH radical in the aerosol aqueous phase include the direct uptake from the gas phase, Fenton reactions and, to a smaller extent, direct photolyses of hydrogen peroxide and nitrate. Recent model studies imply that under many conditions, aqSOA formation might be oxidant-limited since these OH(aq) sources are not sufficient to provide a continuous OH supply. This limitation can be (partially) removed if additional radical sources in the multiphase system are considered. Exemplary, we include the direct photolysis of aqueous pyruvic acid as a proxy for possible other radical sources. Model results will be shown and consequences for aqSOA formation and processing under ambient conditions will be discussed.

  8. Preliminary aerosol generator design studies

    NASA Technical Reports Server (NTRS)

    Stampfer, J. F., Jr.

    1976-01-01

    The design and construction of a prototype vaporization generator for highly dispersed sodium chloride aerosols is described. The aerosol generating system is to be used in the Science Simulator of the Cloud Physics Laboratory Project and as part of the Cloud Physics Laboratory payload to be flown on the shuttle/spacelab.

  9. Cloud condensation nuclei activity, droplet growth kinetics, and hygroscopicity of biogenic and anthropogenic secondary organic aerosol (SOA)

    NASA Astrophysics Data System (ADS)

    Zhao, D. F.; Buchholz, A.; Kortner, B.; Schlag, P.; Rubach, F.; Fuchs, H.; Kiendler-Scharr, A.; Tillmann, R.; Wahner, A.; Watne, Å. K.; Hallquist, M.; Flores, J. M.; Rudich, Y.; Kristensen, K.; Hansen, A. M. K.; Glasius, M.; Kourtchev, I.; Kalberer, M.; Mentel, Th. F.

    2016-02-01

    Interaction of biogenic volatile organic compounds (VOCs) with Anthropogenic VOC (AVOC) affects the physicochemical properties of secondary organic aerosol (SOA). We investigated cloud droplet activation (CCN activity), droplet growth kinetics, and hygroscopicity of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Selected monoterpenes and aromatics were used as representative precursors of BSOA and ASOA, respectively.

    We found that BSOA, ASOA, and ABSOA had similar CCN activity despite the higher oxygen to carbon ratio (O/C) of ASOA compared to BSOA and ABSOA. For individual reaction systems, CCN activity increased with the degree of oxidation. Yet, when considering all different types of SOA together, the hygroscopicity parameter, κCCN, did not correlate with O/C. Droplet growth kinetics of BSOA, ASOA, and ABSOA were comparable to that of (NH4)2SO4, which indicates that there was no delay in the water uptake for these SOA in supersaturated conditions.

    In contrast to CCN activity, the hygroscopicity parameter from a hygroscopic tandem differential mobility analyzer (HTDMA) measurement, κHTDMA, of ASOA was distinctively higher (0.09-0.10) than that of BSOA (0.03-0.06), which was attributed to the higher degree of oxidation of ASOA. The ASOA components in mixed ABSOA enhanced aerosol hygroscopicity. Changing the ASOA fraction by adding biogenic VOC (BVOC) to ASOA or vice versa (AVOC to BSOA) changed the hygroscopicity of aerosol, in line with the change in the degree of oxidation of aerosol. However, the hygroscopicity of ABSOA cannot be described by a simple linear combination of pure BSOA and ASOA systems. This indicates that additional processes, possibly oligomerization, affected the hygroscopicity.

    Closure analysis of CCN and HTDMA data showed κHTDMA was lower than κCCN by 30-70 %. Better closure was achieved for ASOA compared to BSOA. This

  10. Secondary Organic Aerosol (SOA) formation from the β-pinene + NO3 system: effect of humidity and peroxy radical fate

    NASA Astrophysics Data System (ADS)

    Boyd, C. M.; Sanchez, J.; Xu, L.; Eugene, A. J.; Nah, T.; Tuet, W. Y.; Guzman, M. I.; Ng, N. L.

    2015-01-01

    The formation of secondary organic aerosol (SOA) from the oxidation of β-pinene via nitrate radicals is investigated in the Georgia Tech Environmental Chamber facility (GTEC). Aerosol yields are determined for experiments performed under both dry (RH < 2%) and humid (RH = 50% and RH = 70%) conditions. To probe the effects of peroxy radical (RO2) fate on aerosol formation, "RO2 + NO3 dominant" and "RO2 + HO2 dominant" experiments are performed. Gas-phase organic nitrate species (with molecular weights of 215, 229, 231 and 245 amu) are detected by chemical ionization mass spectrometry and their formation mechanisms are proposed. The ions at m/z 30 (NO+) and m/z 46 (NO2+) contribute about 11% to the total organics signal in the typical aerosol mass spectrum, with NO+ : NO2+ ratio ranging from 6 to 9 in all experiments conducted. The SOA yields in the "RO2 + NO3 dominant" and "RO2 + HO2 dominant" experiments are comparable. For a wide range of organic mass loadings (5.1-216.1 μg m-3), the aerosol mass yield is calculated to be 27.0-104.1%. Although humidity does not appear to affect SOA yields, there is evidence of particle-phase hydrolysis of organic nitrates, which are estimated to compose 45-74% of the organic aerosol. The extent of organic nitrate hydrolysis is significantly lower than that observed in previous studies on photooxidation of volatile organic compounds in the presence of NOx. It is estimated that about 90 and 10% of the organic nitrates formed from the β-pinene + NO3 reaction are primary organic nitrates and tertiary organic nitrates, respectively. While the primary organic nitrates do not appear to hydrolyze, the tertiary organic nitrates undergo hydrolysis with a lifetime of 3-4.5 h. Results from this laboratory chamber study provide the fundamental data to evaluate the contributions of monoterpene + NO3 reaction to ambient organic aerosol measured in the southeastern United States, including the Southern Oxidant and Aerosol Study (SOAS) and the

  11. Secondary Organic Aerosol Formation and Aging in a Flow Reactor in the Forested Southeast US during SOAS

    NASA Astrophysics Data System (ADS)

    Hu, W.; Palm, B. B.; Hacker, L.; Campuzano Jost, P.; Day, D. A.; de Sá, S. S.; Ayres, B. R.; Draper, D.; Fry, J.; Ortega, A. M.; Kiendler-Scharr, A.; Pajunoja, A.; Virtanen, A.; Krechmer, J.; Canagaratna, M. R.; Thompson, S.; Yatavelli, R. L. N.; Stark, H.; Worsnop, D. R.; Martin, S. T.; Farmer, D.; Brown, S. S.; Jimenez, J. L.

    2015-12-01

    A major field campaign (Southern Oxidant and Aerosol Study, SOAS) was conducted in summer 2013 in a forested area in Centreville Supersite, AL (SEARCH network) in the southeast U.S. To investigate secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (BVOCs), 3 oxidation flow reactors (OFR) were used to expose ambient air to oxidants and their output was analyzed by state-of-the-art gas and aerosol instruments including a High-Resolution Aerosol Mass Spectrometer (HR-AMS), a HR Proton-Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOFMS), and Two HR-TOF Chemical Ionization Mass Spectrometers (HRToF-CIMS). Ambient air was exposed 24/7 to variable concentrations of each of the 3 main atmospheric oxidants (OH, NO3 radicals and O3) to investigate the oxidation of BVOCs (including isoprene derived epoxydiols, IEPOX) and SOA formation and aging. Effective OH exposures up to 1×1013 molec cm-3 s were achieved, equivalent to over a month of aging in the atmosphere. Multiple oxidation products from isoprene and monoterpenes including small gas-phase acids were observed in OH OFR. High SOA formation of up to 12 μg m-3 above ambient concentrations of 5 μg m-3 was observed under intermediate OH exposures, while very high OH exposures led to destruction of ~30% of ambient OA, indicating shifting contributions of functionalization vs. fragmentation, consistent with results from urban and terpene-dominated environments. The highest SOA enhancements were 3-4 times higher than ambient OA. More SOA is typically formed during nighttime when terpenes are higher and photochemistry is absent, and less during daytime when isoprene is higher, although the IEPOX pathway is suppressed in the OFR. SOA is also observed after exposure of ambient air to O3 or NO3, although the amounts and oxidation levels were lower than for OH. Formation of organic nitrates in the NO3 reaction will also be discussed.A major field campaign (Southern Oxidant and Aerosol

  12. Secondary organic aerosol (SOA) derived from isoprene epoxydiols: Insights into formation, aging and distribution over the continental US from the DC3 and SEAC4RS campaigns

    NASA Astrophysics Data System (ADS)

    Campuzano Jost, P.; Palm, B. B.; Day, D. A.; Hu, W.; Ortega, A. M.; Jimenez, J. L.; Liao, J.; Froyd, K. D.; Pollack, I. B.; Peischl, J.; Ryerson, T. B.; St Clair, J. M.; Crounse, J.; Wennberg, P. O.; Mikoviny, T.; Wisthaler, A.; Ziemba, L. D.; Anderson, B. E.

    2014-12-01

    Isoprene-derived SOA formation has been studied extensively in the laboratory. However, it is still unclear to what extent isoprene contributes to the overall SOA burden over the southeastern US, an area with both strong isoprene emissions as well as large discrepancies between modeled and observed aerosol optical depth. For the low-NO isoprene oxidation pathway, the key gas-phase intermediate is believed to be isoprene epoxide (IEPOX), which can be incorporated into the aerosol phase by either sulfate ester formation (IEPOX sulfate) or direct hydrolysis. As first suggested by Robinson et al, the SOA formed by this mechanism (IEPOX-SOA) has a characteristic fragmentation pattern when analyzed by an Aerodyne Aerosol Mass Spectrometer (AMS) with enhanced relative abundances of the C5H6O+ ion (fC5H6O). Based on data from previous ground campaigns and chamber studies, we have developed a empirical method to quantify IEPOX-SOA and have applied it to the data from the DC3 and SEAC4RS aircraft campaigns that sampled the SE US during the Spring of 2012 and the Summer of 2013. We used Positive Matrix Factorization (PMF) to extract IEPOX-SOA factors that show good correlation with inside or downwind of high isoprene emitting areas and in general agree well with the IEPOX-SOA mass predicted by the empirical expression. According to this analysis, the empirical method performs well regardless of (at times very strong) BBOA or urban OA influences. On average 17% of SOA in the SE US boundary layer was IEPOX-SOA. Overall, the highest concentrations of IEPOX-SOA were typically found around 1-2 km AGL, several hours downwind of the isoprene source areas with high gas-phase IEPOX present. IEPOX-SOA was also detected up to altitudes of 6 km, with a clear trend towards more aged aerosol at altitude, likely a combination of chemical aging and physical airmass mixing. The unique instrument package aboard the NASA-DC8 allows us to examine the influence of multiple factors (aerosol

  13. Characterization of Isoprene-Derived Secondary Organic Aerosol Formation at the Look Rock Site during the 2013 Southern Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S.; Li, X.; Bairai, S. T.; Hicks, W.; Renfro, J.; Corrigan, A. L.; Guzman, J. M.; Russell, L. M.; Liu, Y.; McKinney, K. A.; Zhang, X.; Cappa, C. D.; Zimmermann, K.; Bertram, T. H.; Canagaratna, M. R.; Croteau, D.; Worsnop, D. R.; Jayne, J. T.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2013-12-01

    Although isoprene is considered as the single largest source of secondary organic aerosol (SOA), the exact manner in which it forms remains unclear. Improving our fundamental understanding of isoprene-derived SOA will be key to improving existing air quality models, especially in the southeastern U.S. where models currently underestimate observations. Reactive epoxides, which include methacrylic acid epoxide (MAE) and isomeric isoprene epoxydiols (IEPOX), produced from the oxidation of isoprene have recently been demonstrated to lead to SOA through heterogeneous chemistry. Anthropogenic pollutants (NOx and SO2) have been shown to enhance isoprene-derived epoxides as a source of SOA. One of the major aims during SOAS was to examine how anthropogenic pollutants impact isoprene SOA formation and its climate-relevant properties. To address this aim, we deployed both an Aerodyne aerosol chemical speciation monitor (ACSM) and a chemical ionization high-resolution time-of-flight mass spectrometer (CI-HR-TOFMS) at the Look Rock (LRK) site in the Great Smoky Mountains National Park, TN, from June 1 to July 15, 2013. In addition, high-volume PM2.5 samplers collected daily (8AM-7AM), day (8AM-7PM), and night (8PM-7AM) samples onto quartz filters. On days that LRK was forecasted to have high isoprene, SO4 (sulfate), and NOx levels, PM2.5 were collected more frequently (8AM-11AM, 12PM-3PM, 4PM-7PM, and 8PM-7AM). Filters were analyzed for known isoprene-derived SOA tracers (2-methyltetrols, 2-methylglyceric acid, C5-alkene triols, 3-methyltetrahydrofuran-3,4-diols, and organosulfates) by gas chromatography/mass spectrometry and ultra performance liquid chromatography coupled to diode array detection and electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry. The average non-refractory PM1 mass measured by the ACSM was 3.87 μg m-3, with organic, sulfate, ammonium, nitrate and chloride contributing 64.4%, 24.1%, 7.6%, 3.8%, and 0.1%, respectively

  14. Physical Properties of Ambient and Laboratory-Generated Secondary Organic Aerosol

    SciTech Connect

    O'Brien, Rachel E.; Neu, Alexander; Epstein, Scott A.; MacMillan, Amanda; Wang, Bingbing; Kelly, Stephen T.; Nizkorodov, Sergey; Laskin, Alexander; Moffet, Ryan C.; Gilles, Mary K.

    2014-06-17

    The size and thickness of organic aerosol particles collected by impaction in five field campaigns were compared to those of laboratory generated secondary organic aerosols (SOA). Scanning transmission x-ray microscopy (STXM) was used to measure the total carbon absorbance (TCA) by individual particles as a function of their projection areas on the substrate. Because they flatten less upon impaction, particles with higher viscosity and surface tension can be identified by a steeper slope on a plot of TCA vs. size. The slopes of the ambient data are statistically similar indicating a small range of average viscosities and surface tensions across five field campaigns. Steeper slopes were observed for the plots corresponding to ambient particles, while smaller slopes were indicative of the laboratory generated SOA. This comparison indicates that ambient organic particles have higher viscosities and surface tensions than those typically generated in laboratory SOA studies.

  15. Multi-generational oxidation model to simulate secondary organic aerosol in a 3-D air quality model

    NASA Astrophysics Data System (ADS)

    Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

    2015-08-01

    Multi-generational gas-phase oxidation of organic vapors can influence the abundance, composition and properties of secondary organic aerosol (SOA). Only recently have SOA models been developed that explicitly represent multi-generational SOA formation. In this work, we integrated the statistical oxidation model (SOM) into SAPRC-11 to simulate the multi-generational oxidation and gas/particle partitioning of SOA in the regional UCD/CIT (University of California, Davis/California Institute of Technology) air quality model. In the SOM, evolution of organic vapors by reaction with the hydroxyl radical is defined by (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the organic molecule. These SOM parameter values were fit to laboratory smog chamber data for each precursor/compound class. SOM was installed in the UCD/CIT model, which simulated air quality over 2-week periods in the South Coast Air Basin of California and the eastern United States. For the regions and episodes tested, the two-product SOA model and SOM produce similar SOA concentrations but a modestly different SOA chemical composition. Predictions of the oxygen-to-carbon ratio qualitatively agree with those measured globally using aerosol mass spectrometers. Overall, the implementation of the SOM in a 3-D model provides a comprehensive framework to simulate the atmospheric evolution of organic aerosol.

  16. Wind Power Charged Aerosol Generator

    SciTech Connect

    Marks, A.M.

    1980-07-01

    This describes experimental results on a Charged Aerosol Wind/Electric Power Generator, using Induction Electric Charging with a water jet issuing under water pressure from a small diameter (25-100 ..mu..m) orifice.

  17. Modeling SOA production from the oxidation of intermediate volatility alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-12-01

    Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapour pressure. This process was investigated using the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). Results for the C8-C24 n-alkane series show the expected trends, i.e. (i) SOA yield grows with the carbon backbone of the parent hydrocarbon, (ii) SOA yields decreases with the decreasing pre-existing organic aerosol concentration, (iii) the number of generations required to describe SOA production increases when the pre-existing organic aerosol concentration decreases. Most SOA contributors were found to be not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA). Branched alkanes are more prone to fragment in the early stage of the oxidation than their corresponding linear analogues. Fragmentation is expected to alter both the yield and the mean oxidation state of the SOA. Here, GECKO-A is applied to generate highly detailed oxidation schemes for various series of branched and cyclised alkanes. Branching and cyclisation effects on SOA yields and oxidation states will be examined.

  18. Optical properties of secondary organic aerosols generated by photooxidation of aromatic hydrocarbons

    PubMed Central

    Li, Kun; Wang, Weigang; Ge, Maofa; Li, Jiangjun; Wang, Dong

    2014-01-01

    The refractive index (RI) is the fundamental characteristic that affects the optical properties of aerosols, which could be some of the most important factors influencing direct radiative forcing. The secondary organic aerosols (SOAs) generated by the photooxidation of benzene, toluene, ethylbenzene and m-xylene (BTEX) under low-NOx and high-NOx conditions are explored in this study. The particles generated in our experiments are considered to be spherical, based on atomic force microscopy (AFM) images, and nonabsorbent at a wavelength of 532 nm, as determined by ultraviolet-visible light (UV-Vis) spectroscopy. The retrieved RIs at 532 nm for the SOAs range from 1.38–1.59, depending on several factors, such as different precursors and NOx levels. The RIs of the SOAs are altered differently as the NOx concentration increases as follows: the RIs of the SOAs derived from benzene and toluene increase, whereas those of the SOAs derived from ethylbenzene and m-xylene decrease. Finally, by comparing the experimental data with the model values, we demonstrate that the models likely overestimate the RI values of the SOA particles to a certain extent, which in turn overestimates the global direct radiative forcing of the organic particles. PMID:24815734

  19. Improving the simulation of organic aerosols from anthropogenic and burning sources: a simplified SOA formation mechanism and the impact of trash burning

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Wiedinmyer, C.; Jimenez, J. L.

    2011-12-01

    Organic aerosols (OA) are an major component of fine aerosols, but their sources are poorly understood. We present results of two methods to improve OA predictions in anthropogenic pollution and biomass-burning impacted regions. (1) An empirical parameterization for secondary organic aerosol (SOA) formation in polluted air and biomass burning smoke is implemented into community chemistry-transport models (WRF/Chem and CHIMERE) and tested in this work, towards the goal of a computationally inexpensive method to calculate pollution and biomass burning SOA. This approach is based on the observed proportionality of SOA concentrations to excess CO and photochemical age of the airmass, as described in Hodzic and Jimenez (GMDD, 2011). The oxygen to carbon ratio in organic aerosols is also parameterizated vs. photochemical aged based on the ambient observations, and is used to estimate the aerosol hygroscopicity and CCN activity. The predicted SOA is assessed against observations from the Mexico City metropolitan area during the MILAGRO 2006 field experiment, and compared to previous model results using the more complex volatility basis approach (VBS) of Robinson et al.. The results suggest that the simplified approach reproduces the observed average SOA mass within 30% in the urban area and downwind, and gives better results than the original VBS. In addition to being much less computationally expensive than VBS-type methods, the empirical approach can also be used in regions where the emissions of SOA precursors are not yet available. (2) The contribution of trash burning emissions to primary and secondary organic aerosols in Mexico City are estimated, using a recently-developed emission inventory. Submicron antimony (Sb) is used as a garbage-burning tracer following the results of Christian et al. (ACP 2010), which allows evaluation of the emissions inventory. Results suggests that trash burning may be an appreciable source of organic aerosols in the Mexico City

  20. AEROSOL OPTICAL PROPERTIES AND BIOGENIC SOA: EFFECT ON HYGROSCOPIC PROPERTIES AND LIGHT ABSORPTION

    EPA Science Inventory

    This study will provide a comprehensive characterization of optical properties of biogenic SOA and their sensitivity to anthropogenic influence. Several parameters critical for climate modeling, such as absorption cross-section, single scattering albedo and sensitivity to R...

  1. Reactive uptake of Isoprene-derived epoxydiols to submicron aerosol particles: implications for IEPOX lifetime and SOA formation

    NASA Astrophysics Data System (ADS)

    Thornton, J. A.; Gaston, C.; Riedel, T.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2014-12-01

    The reactive uptake of isoprene-derived epoxydiols (IEPOX) is thought to be a significant source of atmospheric secondary organic aerosol (SOA). However, the IEPOX reaction probability (γIEPOX) and its dependence upon particle composition remain poorly constrained. We report measurements of γIEPOX for trans-b-IEPOX, the predominant IEPOX isomer, on submicron particles as a function of composition, acidity, and relative humidity (RH). Particle acidity had the strongest effect. γIEPOX is more than 500 times larger on ammonium bisulfate (γ ~ 0.05) than on ammonium sulfate (γ ≤ 1 x 10-4). We could accurately predict γIEPOX using an acid-catalyzed, epoxide ring-opening mechanism and a high Henry's law coefficient (1.6 x 108 M/atm). Suppression of γIEPOX was observed in particles containing both ammonium bisulfate and polyethylene glycol (PEG-300), likely due to diffusion and solubility limitations within a PEG-300 coating, suggesting that IEPOX uptake could be self-limiting. Using the measured uptake kinetics, the predicted atmospheric lifetime of IEPOX is a few hours in the presence of highly acidic particles (pH < 0), but is greater than a day on less acidic particles (pH > 3). We connect these net reactive uptake measurements to chamber studies of the SOA yield from IEPOX multiphase chemistry and discuss the implications of these findings for modeling the anthropogenic influence upon SOA formation from isoprene.

  2. Development of a Carbon Number Polarity Grid SOA Model with the use of Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Chung, S. H.; Lee-Taylor, J.; Asher, W.; Hodzic, A.; Madronich, S.; Aumont, B.; Pankow, J. F.; Barsanti, K. C.

    2012-12-01

    A major weakness in current air quality and climate models is the ability to simulate secondary organic aerosol (SOA) levels and physiochemical properties accurately. A new approach to model SOA formation is the carbon number (nc) polarity grid (CNPG) framework. The CNPG framework makes use of a nc vs. polarity grid for representing relevant organic compounds and their time-dependent concentrations. The nc vs polarity grid is well suited for modeling SOA because nc together with some suitable measure of total molecular polarity provides the minimum yet sufficient formation for estimating the parameters required to calculate partitioning coefficients. Furthermore, CNPG allows consideration of the effects of variation in the activity coefficients of the partitioning compounds, variation in the mean molecular weight of the absorbing organic phase, water uptake, and the possibility of phase separation in the organic aerosol phase. In this work, we use the GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) chemistry mechanism to produce the chemical structures of SOA precursor oxidization products and their time-dependent concentrations. The SIMPOL group contribution method is used to calculate the enthalpy of vaporization ΔHvap for each product. The total molecular polarity is then calculated as ΔHvap,diff, the difference between each compound's ΔHvap and that of its carbon-number equivalent straight-chain hydrocarbon. The gas- and particle-phase concentrations of each compound are mapped onto the nc vs polarity grid as a function of time to evaluate the time evolution of SOA-relevant oxidation products and to help guide lumping strategies for reducing complexity. In addition to using ΔHvap,diff, use of other measures of polarity will also be explored. Initial SOA precursor studies include toluene (C7) + n-heptadecane (C17) and α-pinene, under atmospherically relevant conditions. Results will be discussed in the context of the

  3. Evaporation kinetics of laboratory-generated secondary organic aerosols at elevated relative humidity.

    PubMed

    Wilson, Jacqueline; Imre, Dan; Beránek, Josef; Shrivastava, Manish; Zelenyuk, Alla

    2015-01-01

    Secondary organic aerosols (SOA) dominate atmospheric organic aerosols that affect climate, air quality, and health. Recent studies indicate that, contrary to previously held assumptions, at low relative humidity (RH) these particles are semisolid and evaporate orders of magnitude slower than expected. Elevated relative humidity has the potential to affect significantly formation, properties, and atmospheric evolution of SOA particles. Here we present a study of the effect of RH on the room-temperature evaporation kinetics of SOA particles formed by ozonolysis of α-pinene and limonene. Experiments were carried out on α-pinene SOA particles generated, evaporated, and aged at <5%, 50 and 90% RH, and on limonene SOA particles at <5% and 90% RH. We find that in all cases evaporation begins with a relatively fast phase, during which 30-70% of the particle mass evaporates in 2 h, followed by a much slower evaporation rate. Evaporation kinetics at <5% and 50% RH are nearly the same, while at 90% RH a slightly larger fraction evaporates. In all cases, aging the particles prior to inducing evaporation reduces the evaporative losses; with aging at elevated RH leading to a more significant effect. In all cases, the observed SOA evaporation is nearly size-independent. PMID:25494490

  4. Probing Molecular Associations of Field-Collected and Laboratory-Generated SOA with Nano-DESI High-Resolution Mass Spectrometry

    SciTech Connect

    O'Brien, Rachel E.; Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia; Hayes, Patrick L.; Liu, Shang; Jimenez, Jose L.; Russell, Lynn M.; Nizkorodov, Sergey; Goldstein, Allen H.

    2013-01-30

    Aerosol samples from the 2010 CalNex field study in Bakersfield (BF) and Los Angeles (LA) were analyzed using positive mode nanospray-desorption electrospray ionization mass spectrometry (nano-DESI-MS). Secondary organic aerosol (SOA) produced in a photochemical chamber by photooxidation of diesel (DSL) fuel and isoprene (ISO) under humid, high-NOx conditions, was analyzed for comparison. Three groups of organic compounds with zero, one, or two nitrogen atoms in their molecular formulas (0N, 1N, 2N) were compared in detail. The composition of ambient SOA exhibited greater overlap with DSL than with ISO. The overlap of the chamber experiments with the BF data was relatively consistent throughout the day while the overlap with LA data increased significantly in the noon-6pm sample, consistent with the SOA plume arriving from downtown Los Angeles. BF samples were more oxidized, contained more organic nitrogen, and had more overlap with the chamber data compared to LA samples. The addition of gaseous ammonia (NH3) to the DSL experiment was necessary to generate many of the 2N compounds observed in BF. This analysis demonstrates that DSL and ISO were important sources but cannot account for all of the observed ambient compounds indicating that other sources of organics were also likely important.

  5. Wintertime Secondary Organic Aerosol (SOA) Formation from Oxidation of Volatile Organic Compounds (VOCs) Associated with Oil and Gas Extraction

    NASA Astrophysics Data System (ADS)

    Murphy, S. M.; Soltis, J.; Field, R. A.; Bates, T. S.; Quinn, P.; De Gouw, J. A.; Veres, P. R.; Warneke, C.; Graus, M.; Gilman, J.; Lerner, B. M.; Koss, A.

    2013-12-01

    The Uintah Basin is located in a lightly populated area of Northeastern Utah near Dinosaur National Monument. Oil and gas extraction activities in the basin have dramatically increased in recent years due to the application of hydraulic fracturing. The Uintah Basin has experienced numerous high-ozone events during the past several winters with concentrations often exceeding 100 ppb. PM 2.5 monitoring by the city of Vernal, located at the edge of the basin, have shown wintertime concentrations in excess of the EPA 8-hour national standard, though the source and composition of particulates during these events is unclear. The Energy and Environment - Uintah Basin Winter Ozone Study (E&E UBWOS) was conducted during the winters of 2012 and 2013. During the study, intensive measurements of aerosol composition and speciated VOCs were made at a monitoring site near oil and gas extraction activities. Organic aerosol was found to be a major component of PM 2.5 and organic aerosol formation was highly correlated with the production of secondary VOC's. This correlation suggests that the organic aerosol is secondary in nature even though O:C ratios suggest a less oxidized aerosol than often observed in summertime SOA. The ozone levels and organic aerosol mass during 2012 were much lower than those observed in 2013. Calculations of the aerosol yield during both years will be presented along with an analysis of how well observed yields match predictions based on smog-chamber data. The potential for additional aerosol formation in the system will also be discussed.

  6. In-Situ Measurements of Aerosol Optical and Hygroscopic Properties at the Look Rock Site during SOAS 2013

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Zimmermann, K.; Bertram, T. H.; Corrigan, A. L.; Guzman, J. M.; Russell, L. M.; Budisulistiorini, S.; Li, X.; Surratt, J. D.; Hicks, W.; Bairai, S. T.; Cappa, C. D.

    2013-12-01

    One of the main goals of the Southern Oxidant and Aerosol Study (SOAS) is to characterize the climate-relevant properties of aerosols over the southeastern United States at the interface of biogenic and anthropogenic emissions. As part of the SOAS campaign, the UCD cavity ringdown/photoacoustic spectrometer was deployed to make in-situ measurements of aerosol light extinction, absorption and sub-saturated hygroscopicity at the Look Rock site (LRK) in the Great Smoky Mountains National Park, TN from June 1 to July 15, 2013. The site is influenced by substantial biogenic emissions with varying impacts from anthropogenic pollutants, allowing for direct examination of the optical and hygroscopic properties of anthropogenic-influenced biogenic secondary organic aerosols (SOA). During the experiment period, the average dry aerosol extinction (Bext), absorption (Babs) coefficients and single scattering albedo (SSA) at 532 nm were 30.3 × 16.5 Mm-1, 1.12 × 0.78 Mm-1 and 0.96 × 0.06. The Babs at 532 nm was well correlated (r2 = 0.79) with the refractory black carbon (rBC) number concentration determined by a single particle soot spectrometer (SP2). The absorption by black carbon (BC), brown carbon (BrC) and the absorption enhancement due to the 'lensing' effect were quantified by comparing the Babs of ambient and thermo-denuded aerosols at 405 nm and 532 nm. The optical sub-saturated hygroscopic growth factor was derived from extinction and particle size distribution measurements at dry and elevated relative humidity. In addition, to explore the extent to which ammonia mediated chemistry leads to BrC formation, as suggested in recent laboratory studies(1,2), we performed an NH3 perturbation experiment in-situ for 1 week during the study, in which ambient aerosols were exposed to approximately 100 ppb NH3 with a residence time of ~ 3hr. The broader implications of these observational data at LRK will be discussed in the context of the concurrent gas and aerosol chemical

  7. Multi-generational oxidation model to simulate secondary organic aerosol in a 3-D air quality model

    NASA Astrophysics Data System (ADS)

    Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

    2015-02-01

    Multi-generational gas-phase oxidation of organic vapors can influence the abundance, composition and properties of secondary organic aerosol (SOA). Only recently have SOA models been developed that explicitly represent multi-generational SOA formation. In this work, we integrated the statistical oxidation model (SOM) into SAPRC-11 to simulate the multi-generational oxidation and gas/particle partitioning of SOA in the regional UCD/CIT air quality model. In SOM, evolution of organic vapors by reaction with the hydroxyl radical is defined by (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the organic molecule. These SOM parameter values were fit to laboratory "smog chamber" data for each precursor/compound class. The UCD/CIT model was used to simulate air quality over two-week periods in the South Coast Air Basin of California and the eastern United States. For the regions and episodes tested, the traditional two-product SOA model and SOM produce similar SOA concentrations but a modestly different SOA chemical composition. Predictions of the oxygen-to-carbon ratio qualitatively agree with those measured globally using aerosol mass spectrometers. Overall, the implementation of the SOM in a 3-D model provides a comprehensive framework to simulate the atmospheric evolution of OA.

  8. Generation of a monodispersed aerosol

    NASA Technical Reports Server (NTRS)

    Schenck, H.; Mikasa, M.; Devicariis, R.

    1974-01-01

    The identity and laboratory test methods for the generation of a monodispersed aerosol are reported on, and are subjected to the following constraints and parameters; (1) size distribution; (2) specific gravity; (3) scattering properties; (4) costs; (5) production. The procedure called for the collection of information from the literature, commercial available products, and experts working in the field. The following topics were investigated: (1) aerosols; (2) air pollution -- analysis; (3) atomizers; (4) dispersion; (5) particles -- optics, size analysis; (6) smoke -- generators, density measurements; (7) sprays; (8) wind tunnels -- visualization.

  9. ORGANIC AEROSOL FORMATION IN THE HUMID, PHOTOCHEMICALLY-ACTIVE SOUTHEASTERN US: SOAS EXPERIMENTS AND SIMULATIONS

    EPA Science Inventory

    A better understanding of SOA formation, properties and behavior in the humid eastern U.S. including dependence on anthropogenic emissions (RFA Q #1, 2). More accurate air quality prediction enabling more accurate air quality management (EPA Goal #1). Scientific insights co...

  10. 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.

  11. Characterization of secondary organic aerosol generated from ozonolysis of α-pinene mixtures

    NASA Astrophysics Data System (ADS)

    Amin, Hardik S.; Hatfield, Meagan L.; Huff Hartz, Kara E.

    2013-03-01

    In the atmosphere, multiple volatile organic compounds (VOCs) co-exist, and they can be oxidized concurrently and generate secondary organic aerosol (SOA). In this work, SOA is formed by the oxidation (in presence of excess ozone) of mixtures containing α-pinene and other VOCs. The VOC mixtures were made so their composition approached a commercially-available α-pinene-based essential oil, Siberian fir needle oil. The SOA products were sampled using filters, solvent extracted and analyzed by gas chromatography/mass spectrometry with trimethylsilyl derivatization. The individual product yields for SOA generated from α-pinene changed upon the addition of other VOCs. An increase in concentration of non-reactive VOCs (bornyl acetate, camphene, and borneol) lead to a decrease in individual product yields of characteristic α-pinene SOA products. Although these experiments were carried out under higher VOC and ozone concentrations in comparison to the atmosphere, this work suggests that the role of non-reactive VOCs should be explored in SOA products formation.

  12. Self-stabilizing optical clock pulse-train generator using SOA and saturable absorber for asynchronous optical packet processing.

    PubMed

    Nakahara, Tatsushi; Takahashi, Ryo

    2013-05-01

    We propose a novel, self-stabilizing optical clock pulse-train generator for processing preamble-free, asynchronous optical packets with variable lengths. The generator is based on an optical loop that includes a semiconductor optical amplifier (SOA) and a high-extinction spin-polarized saturable absorber (SA), with the loop being self-stabilized by balancing out the gain and absorption provided by the SOA and SA, respectively. The optical pulse train is generated by tapping out a small portion of a circulating seed pulse. The convergence of the generated pulse energy is enabled by the loop round-trip gain function that has a negative slope due to gain saturation in the SOA. The amplified spontaneous emission (ASE) of the SOA is effectively suppressed by the SA, and a backward optical pulse launched into the SOA enables overcoming the carrier-recovery speed mismatch between the SOA and SA. Without external control for the loop gain, a stable optical pulse train consisting of more than 50 pulses with low jitter is generated from a single 10-ps seed optical pulse even with a variation of 10 dB in the seed pulse intensity. PMID:23669927

  13. SOA multiday growth: Model artifact or reality?

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J. M.; Madronich, S.; Aumont, B.; Hodzic, A.; Camredon, M.; Valorso, R.

    2013-12-01

    Simulations of SOA gas-particle partitioning with the explicit gas-phase chemical mechanism generator GECKO-A show significant SOA mass growth continuing for several days, even as the initial air parcel is diluted into the regional atmosphere. This result is a robust feature of our model and occurs with both anthropogenic and biogenic precursors. The growth originates from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase. This result implies that sources of aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over a wider region than previously imagined, and that SOA measurements near precursor sources may routinely underestimate this influence. It highlights the need to better understand the sink terms in the SOA budget.

  14. Molecular-level Analysis of Size Resolved Secondary Organic Aerosol (SOA) Samples from CALNEX Bakersfield Using High Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    O'Brien, R. E.; Laskin, A.; Laskin, J.; Weber, R.; Goldstein, A. H.

    2011-12-01

    This project focuses on analyzing the identities of molecules that comprise oligomers in size resolved aerosol fractions. Since oligomers are generally too large and polar to be measured by typical GC/MS analysis, soft ionization with high resolution mass spectrometry is used to extend the range of observable compounds. Samples collected with a microorifice uniform deposition impactor (MOUDI) during CALNEX Bakersfield in June 2010 have been analyzed with nanospray desorption electrospray ionization (nano-DESI) and an Orbitrap mass spectrometer. The nano-DESI is a soft ionization technique that allows molecular ions to be observed and the Orbitrap has sufficient resolution to determine the elemental composition of almost all species above the detection limit. A large fraction of SOA is made up of high molecular weight oligomers which are thought to form through acid catalyzed reactions of photo-chemically processed volatile organic compounds (VOC). The formation of oligomers must be influenced by the VOCs available, the amount of atmospheric sulfate and nitrate, and the magnitude of photo-chemical processing, among other potential influences. We present the elemental composition of chemical species in SOA in the 0.18 to 0.32 micron size range, providing the first multi-day data set for the study of these oligomers in atmospheric samples. Possible formation pathways and sources of observed compounds will be examined by comparison to other concurrent measurements at the site.

  15. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-08-01

    The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

  16. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-06-01

    The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

  17. Evaporation Kinetics of Laboratory Generated Secondary Organic Aerosols at Elevated Relative Humidity

    SciTech Connect

    Wilson, Jacqueline M.; Imre, D.; Beranek, Josef; Shrivastava, ManishKumar B.; Zelenyuk, Alla

    2015-01-06

    Secondary organic aerosols (SOA) dominate atmospheric organic aerosols that affect climate, air quality, and health. Recent studies indicate that, contrary to previously held assumptions, at low relative humidity (RH) these particles are semi-solid and evaporate orders of magnitude slower than expected. Elevated relative humidity has the potential to affect significantly formation, properties, and atmospheric evolution of SOA particles. Here we present a study of the effect of RH on the room-temperature evaporation kinetics of SOA particles formed by ozonolysis of α-pinene and limonene. Experiments were carried out on SOA particles generated, evaporated, and aged at 0%, 50% and 90% RH. We find that in all cases evaporation begins with a relatively fast phase, during which 30% to 70% of the particle mass evaporates in 2 hours, followed by a much slower evaporation rate. Evaporation kinetics at 0% and 50% RH are nearly the same, while at 90% RH a slightly larger fraction evaporates. In all cases, aging the particles prior to inducing evaporation reduces the evaporative losses, with aging at elevated RH leading to more significant effect. In all cases, SOA evaporation is nearly size-independent, providing direct evidence that oligomers play a crucial role in determining the evaporation kinetics.

  18. Complex refractive index of secondary organic aerosol generated from isoprene/NOx photooxidation in the presence and absence of SO2

    NASA Astrophysics Data System (ADS)

    Nakayama, Tomoki; Sato, Kei; Tsuge, Masashi; Imamura, Takashi; Matsumi, Yutaka

    2015-08-01

    We report the first measurements of the complex refractive index (RI) at 375, 405, 532, and 781 nm for secondary organic aerosol (SOA) generated from isoprene/NOx photooxidation. At all wavelengths studied, slightly greater real components of the RI were observed for the SOA generated in the absence of SO2 compared with those generated in its presence. Considering the chemical properties, the differences in the oxidation state and/or ratio of particle density to molecular weight of compounds in the SOA are considered to be the main factors determining the real components. The imaginary components at ≤532 nm were found to increase with increasing initial SO2 concentration. The highly conjugated oligomers are suggested to be plausible chromophore candidates. This study suggests that when large amounts of SOA are generated after mixing of isoprene with NOx and SOx, light absorption of these SOAs may compete with that of black carbon, especially at ultraviolet wavelengths.

  19. Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2015-08-01

    A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 > 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black

  20. Gas-particle partitioning of organic acids during the Southern Oxidant and Aerosol Study (SOAS): measurements and modeling

    NASA Astrophysics Data System (ADS)

    Thompson, S.; Yatavelli, R.; Stark, H.; Kimmel, J.; Krechmer, J.; Day, D. A.; Isaacman, G. A.; Goldstein, A. H.; Khan, M. A. H.; Holzinger, R.; Lopez-Hilfiker, F.; Mohr, C.; Thornton, J. A.; Jayne, J. T.; Worsnop, D. R.; Jimenez, J. L.

    2014-12-01

    Gas-Particle partitioning measurements of organic acids were carried out during the Southern Oxidant and Aerosol Study (SOAS, June-July 2013) at the Centerville, AL Supersite in the Southeast US, a region with significant isoprene and terpene emissions. Organic acid measurements were made with a Chemical Ionization High Resolution Time-of-Flight Mass Spectrometer (HRToF-CIMS) with a Filter Inlet for Gases and AEROsols (FIGAERO) and acetate (CH3COO-) as the reagent ion. We investigate both individual species and bulk organic acids and partitioning to organic and water phases in the aerosol. Measured partitioning is compared to data from three other instruments that can also quantify gas-particle partitioning with high time resolution: another HRToF-CIMS using iodide (I-) as the reagent ion to ionize acids and other highly oxidized compounds, a Semivolatile Thermal Desorption Aerosol GC/MS (SV-TAG), and a Thermal Desorption Proton Transfer Time-of-Flight Mass Spectrometer (TD-PTRMS The partitioning measurements for three of the instruments are generally consistent, with results in the same range for most species and following similar temporal trends and diurnal cycles. The TD-PTRMS measures on average ½ the partitioning to the particle phase of the acetate CIMS. Both the measurements and the model of partitioning to the organic phase respond quickly to temperature, and the model agrees with the measured partitioning within the error of the measurement for multiple compounds, although many compounds do not match the modeled partitioning, especially at lower m/z. This discrepancy may be due to thermal decomposition of larger molecules into smaller ones when heated.

  1. Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, ground site

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2015-03-01

    A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~9% (up to 26%) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~97% of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2>0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~25% (up to 47%) of the IEPOX-OA factor mass, which accounted for 32% of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO~0.03ppb), carbon monoxide (CO~116 ppb), and black carbon (BC~0

  2. Light absorption coefficient measurement of SOA using a UV-Visible spectrometer connected with an integrating sphere

    NASA Astrophysics Data System (ADS)

    Zhong, Min; Jang, Myoseon

    2011-08-01

    A method for measuring an aerosol light absorption coefficient ( B a) has been developed using a conventional UV-visible spectrometer equipped with an integrating sphere covering a wide range of wavelengths (280-800 nm). The feasibility of the proposed method was evaluated in both the transmittance mode (TUV-IS) and the reflective mode (RUV-IS) using the reference aerosol known for the cross-sectional area. The aerosol was collected on a conventional filter and measured for B a values. The resulting RUV-IS method was applied to measure light absorption of secondary organic aerosol (SOA). SOA was produced through photooxidation of different precursor hydrocarbons such as toluene, d-limonene and α-pinene in the presence of NO x (60-70 ppb) and inorganic seed aerosol using a 2-m 3 indoor Teflon film chamber. Of the three precursor hydrocarbons, the B a value of toluene SOA (0.574 m 2 g -1 at 350 nm) was the highest compared with B a values for α-pinene SOA (0.029 m 2 g -1) and d-limonene SOA (0.038 m 2 g -1). When d-limonene SOA or toluene SOA was internally mixed with neutral [(NH 4) 2SO 4] or acidic inorganic seed (NH 4HSO 4:H 2SO 4 = 1:1 by mole), the SOA showed 2-3 times greater B a values at 350 nm than the SOA with no seed. Aerosol aging with a light source for this study reduced B a values of SOA (e.g., on average 10% for toluene SOA and 30% for d-limonene SOA within 4 h). Overall, weak absorption appeared for chamber-generated SOA over wavelengths ranging from 280 to 550 nm, which fall into the sunlight spectrum.

  3. Effect of Vapor Pressure Scheme on Multiday Evolution of SOA in an Explicit Model

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Madronich, S.; Aumont, B.; Camredon, M.; Emmons, L. K.; Tyndall, G. S.; Valorso, R.

    2011-12-01

    Recent modeling of the evolution of Secondary Organic Aerosol (SOA) has led to the critically important prediction that SOA mass continues to increase for several days after emission of primary pollutants. This growth of organic aerosol in dispersing plumes originating from urban point sources has direct implications for regional aerosol radiative forcing. We investigate the robustness of predicted SOA mass growth downwind of Mexico City in the model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), by assessing its sensitivity to the choice of vapor pressure prediction scheme. We also explore the implications for multi-day SOA mass growth of glassification / solidification of SOA constituents during aging. Finally we use output from the MOZART-4 chemical transport model to evaluate our results in the regional and global context.

  4. ATI TDA 5A aerosol generator evaluation

    SciTech Connect

    Gilles, D.A.

    1998-07-27

    Oil based aerosol ``Smoke`` commonly used for testing the efficiency and penetration of High Efficiency Particulate Air filters (HEPA) and HEPA systems can produce flammability hazards that may not have been previously considered. A combustion incident involving an aerosol generator has caused an investigation into the hazards of the aerosol used to test HEPA systems at Hanford.

  5. Test-Aerosol Generator For Calibrating Particle Counters

    NASA Technical Reports Server (NTRS)

    Mogan, Paul A.; Adams, Alois J.; Schwindt, Christian J.; Hodge, Timothy R.; Mallow, Tim J.; Duong, Anh A.; Bukauskas, Vyto V.

    1996-01-01

    Apparatus generates clean, stable aerosol stream for use in testing and calibrating laser-based aerosol-particle counter. Size and concentration of aerosol particles controlled to ensure accurate calibration. Cheap, widely available medical nebulizers used to generate aerosols.

  6. Submicron aerosol organic functional groups, ions, and water content at the Centreville SEARCH site (Alabama), during SOAS campaign

    NASA Astrophysics Data System (ADS)

    Ruggeri, G.; Ergin, G.; Modini, R. L.; Takahama, S.

    2013-12-01

    The SOAS campaign was conducted from June 1 to July 15 of 2013 in order to understand the relationship between biogenic and anthropogenic emissions in the South East US1,2. In this study, the organic and inorganic composition of submicron aerosol in the Centreville SEARCH site was measured by Fourier Transform Infrared Spectroscopy (FTIR) and the Ambient Ion Monitor (AIM; URG Corporation), whereas the aerosol water content was measured with a Dry Ambient Aerosol Size Spectrometer (DAASS)3. Organic functional group analysis was performed on PM1 aerosol selected by cyclone and collected on teflon filters with a time resolution of 4-12 hours, using one inlet heated to 50 °C and the other operated either at ambient temperature or 70 °C 4. The AIM measured both condensed and gas phase composition with a time resolution of 1 hour, providing partitioning behavior of inorganic species such as NH3/NH4+, HNO3/NO3-. These measurements collectively permit calculation of pure-component vapor pressures of candidate organic compounds and activity coefficients of interacting components in the condensed phase, using models such as SIMPOL.15, E-AIM6, and AIOMFAC7. From these results, the water content of the aerosol is predicted, and a comparison between modeled and measured partitioning of inorganic compounds and water vapor are discussed, in addition to organic aerosol volatility prediction based on functional group analysis. [1]- Goldstein, A.H., et al., Biogenic carbon and anthropogenic pollutants combine to form a cooling haze over the southeastern United States. Proceedings of the National Academy of Sciences of the United States of America, 2009. 106(22), 8835-8840. [2]- Carlton, A.G., Turpin, B.J., 2013. Particle partitioning potential of organic compounds is highest in the Eastern US and driven by anthropogenic water. Atmospheric Chemistry and Physics Discussions 13, 12743-12770. [3]- Khlystov, A., Stanier, C.O., Takahama, S., Pandis, S.N., 2005. Water content of ambient

  7. Aerosol generation by raindrop impact on soil

    NASA Astrophysics Data System (ADS)

    Joung, Young Soo; Buie, Cullen R.

    2015-01-01

    Aerosols are investigated because of their significant impact on the environment and human health. To date, windblown dust and sea salt from sea spray through bursting bubbles have been considered the chief mechanisms of environmental aerosol dispersion. Here we investigate aerosol generation from droplets hitting wettable porous surfaces including various classifications of soil. We demonstrate that droplets can release aerosols when they influence porous surfaces, and these aerosols can deliver elements of the porous medium to the environment. Experiments on various porous media including soil and engineering materials reveal that knowledge of the surface properties and impact conditions can be used to predict when frenzied aerosol generation will occur. This study highlights new phenomena associated with droplets on porous media that could have implications for the investigation of aerosol generation in the environment.

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

    SciTech Connect

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

    2010-02-01

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

  9. Molecular distributions and isotopic compositions of marine aerosols over the western North Atlantic: Dicarboxylic acids, ketoacids, α-dicarbonyls (glyoxal and methylglyoxal), fatty acids, sugars, and SOA tracers

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Ono, K.; Tachibana, E.; Quinn, P.; Bates, T. S.

    2013-12-01

    Marine aerosols were collected over the western North Atlantic from off the coast of Boston to Bermuda during the WACS (Western Atlantic Climate Study) cruise of R/V Ronald H. Brown in August 2012 using a high volume air sampler and pre-combusted quartz fiber filters. Aerosol filter samples (n=5) were analyzed for OC/EC, major inorganic ions, low molecular weight dicarboxylic acids and various secondary organic aerosol (SOA) tracers using carbon analyzer, ion chromatograph, GC/FID and GC/MS, respectively. Homologous series (C2-C12) of dicarboxylic acids (31-335 ng m-3) were detected with a predominance of oxalic acid. Total carbon and nitrogen and their stable isotope ratios were determined as well as stable carbon isotopic compositions of individual diacids using IRMS. Diacids were found to be the most abundant compound class followed by monoterpene-SOA tracers > isoprene-SOA tracers > sugar compounds > ketoacids > fatty alcohols > fatty acids > α-dicarbonyls > aromatic acids > n-alkanes. The concentrations of these compounds were higher in the coastal site and decreased in the open ocean. However, diacids stayed relatively high even in the remote ocean. Interestingly, contributions of oxalic acid to total aerosol carbon increased from the coast (2.3%) to the remote ocean (5.6%) during long-range atmospheric transport. Stable carbon isotopic composition of oxalic acid increased from the coast (-17.5‰) to open ocean (-12.4‰), suggesting that photochemical aging of organic aerosols occurred during the atmospheric transport over the ocean. Stable carbon isotope ratios of bulk aerosol carbon also increased from the coast near Boston to the open ocean near Bermuda.

  10. Aging of secondary organic aerosol generated from the ozonolysis of α-pinene: effects of ozone, light and temperature

    NASA Astrophysics Data System (ADS)

    Denjean, C.; Formenti, P.; Picquet-Varrault, B.; Camredon, M.; Pangui, E.; Zapf, P.; Katrib, Y.; Giorio, C.; Tapparo, A.; Temime-Roussel, B.; Monod, A.; Aumont, B.; Doussin, J. F.

    2014-09-01

    A series of experiments was conducted in the CESAM simulation chamber to investigate the evolution of the physical and chemical properties of secondary organic aerosol (SOA) during different forcing. The present experiments represent a first attempt to comprehensively investigate the influence of oxidative processing, photochemistry, and diurnal temperature cycling upon SOA properties. SOA generated from the ozonolysis of α-pinene were exposed to (1) elevated ozone concentrations, (2) light (under controlled temperature conditions), or (3) light and heat (6 °C light-induced temperature increase), and the resultant changes in SOA optical properties (i.e. absorption and scattering), hygroscopicity and chemical composition were measured using a suite of instrumentation interfaced to the CESAM chamber. The complex refractive index (CRI) was derived from integrated nephelometer measurements at 525 nm wavelength, using Mie scattering calculations and measured number size distributions. The particle size growth factor (GF) was measured with a hygroscopic tandem differential mobility analyzer (H-TDMA). An aerosol mass spectrometer (AMS) was used for the determination of the f44 / f43 and O : C ratio of the particles bulk. No change in SOA size or chemical composition was observed during O3 and light exposure at constant temperature; in addition, GF and CRI of the SOA remained constant with forcing. By contrast, illumination of the SOA in the absence of temperature control led to an increase in the real part of the CRI from 1.35 (±0.03) to 1.49 (±0.03), an increase of the GF from 1.04 (±0.02) to 1.14 (±0.02) and an increase of the f44 / f43 ratio from 1.73 (±0.03) to 2.23 (±0.03). These surprising results suggest that SOA properties may be governed more by local temperature fluctuations than by oxidative processing and photochemistry.

  11. Temperature Effects on Secondary Organic Aerosol (SOA) from the Dark Ozonolysis and Photo-Oxidation of Isoprene.

    PubMed

    Clark, Christopher H; Kacarab, Mary; Nakao, Shunsuke; Asa-Awuku, Akua; Sato, Kei; Cocker, David R

    2016-06-01

    Isoprene is globally the most ubiquitous nonmethane hydrocarbon. The biogenic emission is found in abundance and has a propensity for SOA formation in diverse climates. It is important to characterize isoprene SOA formation with varying reaction temperature. In this work, the effect of temperature on SOA formation, physical properties, and chemical nature is probed. Three experimental systems are probed for temperature effects on SOA formation from isoprene, NO + H2O2 photo-oxidation, H2O2 only photo-oxidation, and dark ozonolysis. These experiments show that isoprene readily forms SOA in unseeded chamber experiments, even during dark ozonolysis, and also reveal that temperature affects SOA yield, volatility, and density formed from isoprene. As temperature increases SOA yield is shown to generally decrease, particle density is shown to be stable (or increase slightly), and formed SOA is shown to be less volatile. Chemical characterization is shown to have a complex trend with both temperature and oxidant, but extensive chemical speciation are provided. PMID:27175613

  12. Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions on SOA Loadings and their Spatial and Temporal Evolution in the Atmosphere

    SciTech Connect

    Shrivastava, ManishKumar B.; Zelenyuk, Alla; Imre, Dan; Easter, Richard C.; Beranek, Josef; Zaveri, Rahul A.; Fast, Jerome D.

    2013-04-27

    Recent laboratory and field measurements by a number of groups show that secondary organic aerosol (SOA) evaporates orders of magnitude slower than traditional models assume. In addition, chemical transport models using volatility basis set (VBS) SOA schemes neglect gas-phase fragmentation reactions, which are known to be extremely important. In this work, we present modeling studies to investigate the implications of non-evaporating SOA and gas-phase fragmentation reactions. Using the 3-D chemical transport model, WRF-Chem, we show that previous parameterizations, which neglect fragmentation during multi-generational gas-phase chemistry of semi-volatile/inter-mediate volatility organics ("aging SIVOC"), significantly over-predict SOA as compared to aircraft measurements downwind of Mexico City. In sharp contrast, the revised models, which include gas-phase fragmentation, show much better agreement with measurements downwind of Mexico City. We also demonstrate complex differences in spatial SOA distributions when we transform SOA to non-volatile secondary organic aerosol (NVSOA) to account for experimental observations. Using a simple box model, we show that for same amount of SOA precursors, earlier models that do not employ multi-generation gas-phase chemistry of precursors ("non-aging SIVOC"), produce orders of magnitude lower SOA than "aging SIVOC" parameterizations both with and without fragmentation. In addition, traditional absorptive partitioning models predict almost complete SOA evaporation at farther downwind locations for both "non-aging SIVOC" and "aging SIVOC" with fragmentation. In contrast, in our revised approach, SOA transformed to NVSOA implies significantly higher background concentrations as it remains in particle phase even under highly dilute conditions. This work has significant implications on understanding the role of multi-generational chemistry and NVSOA formation on SOA evolution in the atmosphere.

  13. Probing Molecular Associations of Secondary Organic Aerosol (SOA) Samples from CalNex 2010 with Nano-DESI High-Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    O'Brien, R. E.; Nguyen, T. B.; Laskin, A.; Laskin, J.; Hayes, P. L.; Liu, S.; Jimenez, J. L.; Russell, L. M.; Nizkorodov, S.; Goldstein, A. H.

    2012-12-01

    This project focuses on analyzing the identities of molecules that comprise oligomers in size resolved aerosol fractions. Since oligomers are generally too large and polar to be measured by typical GC/MS analysis, soft ionization with high resolution mass spectrometry is used to extend the range of observable compounds. Samples collected during CalNex 2010 in Bakersfield and Los Angeles and secondary organic aerosol (SOA) produced in a photochemical chamber by photooxidation of diesel (DSL) fuel and isoprene (ISO) under humid, high-NOx conditions have been analyzed with nanospray desorption electrospray ionization (nano-DESI) and a high-resolution Orbitrap mass spectrometer. The nano-DESI is a soft ionization technique that allows molecular ions to be observed and the Orbitrap has sufficient resolution to determine the elemental composition of almost all species above the detection limit. A large fraction of SOA is made up of high molecular weight oligomers which are thought to form through acid catalyzed reactions of photo-chemically processed volatile organic compounds (VOC). The formation of oligomers is influenced by the VOCs available, the amount of atmospheric sulfate and nitrate, and the magnitude of photo-chemical processing, among other potential influences. We present the elemental composition of chemical species in size resolved SOA samples with six-hour time resolution, providing the first time resolved data set for the study of these oligomers in atmospheric samples. We present a comparison of the degree of overlap between the ambient and chamber experiments as a novel method to examine sources for this fraction of SOA. Possible formation pathways and sources of observed compounds are analyzed by comparison to other concurrent measurements at the site.

  14. Ozone reactivity of biogenic volatile organic compound (BVOC) emissions during the Southeast Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Park, J.; Guenther, A. B.; Helmig, D.

    2013-12-01

    Recent studies on atmospheric chemistry in the forest environment showed that the total reactivity by biogenic volatile organic compound (BVOC) emission is still not well understood. During summer 2013, an intensive field campaign (Southeast Oxidant and Aerosol Study - SOAS) took place in Alabama, U.S.A. In this study, an ozone reactivity measurement system (ORMS) was deployed for the direct determination of the reactivity of foliage emissions. The ORMS is a newly developed measurement approach, in which a known amount of ozone is added to the ozone-free air sample stream, with the ORMS measuring ozone concentration difference between before and after a glass flask flow tube reaction vessel (2-3 minutes of residence time). Emissions were also collected onto adsorbent cartridges to investigate the discrepancy between total ozone reactivity observation and reactivity calculated from identified BVOC. Leaf and canopy level experiments were conducted by deploying branch enclosures on the three dominant tree species at the site (i.e. liquidambar, white oak, loblolly pine) and by sampling ambient air above the forest canopy. For the branch enclosure experiments, BVOC emissions were sampled from a 70 L Teflon bag enclosure, purged with air scrubbed for ozone, nitrogen oxides. Each branch experiment was performed for 3-5 days to collect at least two full diurnal cycle data. In addition, BVOCs were sampled using glass tube cartridges for 2 hours during daytime and 3 - 4 hours at night. During the last week of campaign, the inlet for the ORMS was installed on the top of scaffolding tower (~30m height). The ozone loss in the reactor showed distinct diurnal cycle for all three tree species investigated, and ozone reactivity followed patterns of temperature and light intensity.

  15. High speed all-optical PRBS generation using binary phase shift keyed signal based on QD-SOA

    NASA Astrophysics Data System (ADS)

    Li, Wenbo; Hu, Hongyu; Dutta, Niloy K.

    2014-09-01

    A scheme to generate return-to-zero on-off keying (RZ-OOK) high speed all-optical pseudo random bit sequence (PRBS) using binary phase shift keyed (BPSK) signal based on quantum-dot semiconductor optical amplifiers (QD-SOA) has been designed and studied. The PRBS is generated by a linear feedback shift register (LFSR) composed of all-optical logic XOR and AND gates. The XOR gate is composed of a pair of QD SOA Mach-Zehnder interferometers, which can generate BSPK signal to realize all-optical logic XOR gate. Results show that this scheme can mitigate the patterning effects and increase the operation speed to ~250Gb/s.

  16. Characterization of ambient aerosols during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL with a high-resolution time-of-flight aerosol mass spectrometer Basak Karakurt Cevik1, Yu Jun Leong1, Carlos Hernandez1, Robert Griffin1 1 Rice University, CEE Department, 6100 Main St., Houston, TX 77005, USA

    NASA Astrophysics Data System (ADS)

    Karakurt Cevik, B.; Leong, Y.; Hernandez, C.; Griffin, R. J.

    2013-12-01

    An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a Brechtel Manufacturing, Inc. particle-into-liquid sampler (PILS) were deployed at a rural location in Centreville, AL, from 1 June to 15 July 2013 as a part of the Southern Oxidant and Aerosol Study (SOAS). PILS samples were analyzed with Dionex ion chromatographs. The data will allow us to characterize the temporal characteristics of the concentrations and size distributions of non-refractory (NR) chemical species in the ambient submicron particles. Preliminary analysis of the data indicates that the sub-micron particulate matter is highly dominated by organic matter with a relatively high state of oxidation and it is followed by smaller contributions from sulfate and ammonium. In order to investigate the processes and sources that lead to observed aerosol concentrations at the site, the time series will be analyzed in conjunction with additional trace gas, aerosol, and meteorological measurements. The region is known to have high biogenic volatile organic compounds (VOCs) emissions and many of these biogenic VOCs (BVOCs) are important secondary organic aerosol (SOA) precursors. Preliminary data from the HR-ToF-AMS indicates the importance of oxidized organic aerosol during SOAS. The study will also focus on the importance of the SOA in the total organic fraction and the effect of atmospheric processing on the chemical composition of the organic fraction.

  17. Aging of secondary organic aerosol generated from the ozonolysis of α-pinene: effects of ozone, light and temperature

    NASA Astrophysics Data System (ADS)

    Denjean, C.; Formenti, P.; Picquet-Varrault, B.; Camredon, M.; Pangui, E.; Zapf, P.; Katrib, Y.; Giorio, C.; Tapparo, A.; Temime-Roussel, B.; Monod, A.; Aumont, B.; Doussin, J. F.

    2015-01-01

    A series of experiments was conducted in the CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) simulation chamber to investigate the evolution of the physical and chemical properties of secondary organic aerosols (SOAs) during different forcings. The present experiments represent a first attempt to comprehensively investigate the influence of oxidative processing, photochemistry, and diurnal temperature cycling upon SOA properties. SOAs generated from the ozonolysis of α-pinene were exposed under dry conditions (< 1% relative humidity) to (1) elevated ozone concentrations, (2) light (under controlled temperature conditions) or (3) light and heat (6 °C light-induced temperature increase), and the resultant changes in SOA optical properties (i.e. absorption and scattering), hygroscopicity and chemical composition were measured using a suite of instrumentation interfaced to the CESAM chamber. The complex refractive index (CRI) was derived from integrated nephelometer measurements of 525 nm wavelength, using Mie scattering calculations and measured number size distributions. The particle size growth factor (GF) was measured with a hygroscopic tandem differential mobility analyzer (H-TDMA). An aerosol mass spectrometer (AMS) was used for the determination of the f44 / f43 and O : C ratio of the particles bulk. No change in SOA size or chemical composition was observed during O3 and light exposure at constant temperature; in addition, GF and CRI of the SOA remained constant with forcing. On the contrary, illumination of SOAs in the absence of temperature control led to an increase in the real part of the CRI from 1.35 (±0.03) to 1.49 (±0.03), an increase of the GF from 1.04 (±0.02) to 1.14 (±0.02) and an increase of the f44 / f43 ratio from 1.73 (±0.03) to 2.23 (±0.03). The simulation of the experiments using the master chemical mechanism (MCM) and the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere

  18. How will SOA change in the future?

    NASA Astrophysics Data System (ADS)

    Lin, Guangxing; Penner, Joyce E.; Zhou, Cheng

    2016-02-01

    Secondary organic aerosol (SOA) plays a significant role in the Earth system by altering its radiative balance. Here we use an Earth system model coupled with an explicit SOA formation module to estimate the response of SOA concentrations to changes in climate, anthropogenic emissions, and human land use in the future. We find that climate change is the major driver for SOA change under the representative concentration pathways for the 8.5 future scenario. Climate change increases isoprene emission rate by 18% with the effect of temperature increases outweighing that of the CO2 inhibition effect. Annual mean global SOA mass is increased by 25% as a result of climate change. However, anthropogenic emissions and land use change decrease SOA. The net effect is that future global SOA burden in 2100 is nearly the same as that of the present day. The SOA concentrations over the Northern Hemisphere are predicted to decline in the future due to the control of sulfur emissions.

  19. Organosulfate Formation in Biogenic Secondary Organic Aerosol

    EPA Science Inventory

    Organosulfates of isoprene, α-pinene, and β-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive seri...

  20. Molecular Characterization of Brown Carbon (BrC) Chromophores in Secondary Organic Aerosol Generated From Photo-Oxidation of Toluene

    SciTech Connect

    Lin, Peng; Liu, Jiumeng; Shilling, John E.; Kathmann, Shawn M.; Laskin, Julia; Laskin, Alexander

    2015-09-28

    Atmospheric Brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365nm = 0.78 m2 g-1) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the atmosphere.

  1. Molecular characterization of brown carbon (BrC) chromophores in secondary organic aerosol generated from photo-oxidation of toluene.

    PubMed

    Lin, Peng; Liu, Jiumeng; Shilling, John E; Kathmann, Shawn M; Laskin, Julia; Laskin, Alexander

    2015-09-28

    Atmospheric brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365 nm = 0.78 m(2) g(-1)) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/Vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the

  2. Chemical characterization of biogenic secondary organic aerosol generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

    NASA Astrophysics Data System (ADS)

    Faiola, C. L.; Wen, M.; VanReken, T. M.

    2015-04-01

    The largest global source of secondary organic aerosol (SOA) in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic volatile organic compound (BVOC) profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate (MeJA), a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six different coniferous plant types. Volatile organic compounds (VOCs) emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA chemical composition was measured using a Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS). The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+), m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, MeJA, is also presented. Elemental analysis results demonstrated an O : C range of baseline biogenic SOA between 0.3 and 0.47. The O : C of standard MeJA SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient data sets collected in forest environments.

  3. Chemical characterization of biogenic secondary organic aerosol generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

    DOE PAGESBeta

    Faiola, C. L.; Wen, M.; VanReken, T. M.

    2015-04-01

    The largest global source of secondary organic aerosol (SOA) in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic volatile organic compound (BVOC) profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate (MeJA), a proxy compound. Experiments were repeated under pre- andmore » post-treatment conditions for six different coniferous plant types. Volatile organic compounds (VOCs) emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA chemical composition was measured using a Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS). The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+), m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, MeJA, is also presented. Elemental analysis results demonstrated an O : C range of baseline biogenic SOA between 0.3 and 0.47. The O : C of standard MeJA SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient data sets collected in forest environments.« less

  4. Copper oxide aerosol: generation and characterization.

    PubMed

    Peoples, S M; McCarthy, J F; Chen, L C; Eppelsheimer, D; Amdur, M O

    1988-06-01

    Effluent gases from high temperature systems such as fossil fuel combustion and pyrometallurgical processes contain inorganic material which has the potential to interact with sulfur dioxide (SO2) on the surface of particles to form an irritant aerosol. The submicron fraction of this inorganic material is especially important as the fine particles may penetrate deep into the lung and cause serious health effects. A laboratory furnace was designed to produce a submicrometer copper oxide aerosol to stimulate emissions from copper smelters and other pyrometallurgical operations. The ultimate aim of this research is to investigate the interaction of SO2 and the copper oxide aerosol at different temperatures and humidities in order to determine the reaction products and their potential health effects upon inhalation. The initial work, as presented in this paper, was to reproducibly generate a submicrometer copper oxide aerosol and to characterize it in terms of size, morphology and composition. Two experimental regimes were set up. One admitted filtered air, without water vapor, into the furnace, and the other admitted filtered air and water vapor. The size and morphology of the aerosols were determined using an electrical aerosol analyzer and transmission electron microscopy. The particles appear as chain aggregates with a count median diameter of 0.026 micron when no water vapor was added and 0.031 micron when water vapor was added into the furnace. Composition of the aerosol was determined using x-ray photoelectron spectroscopy. The aerosol, with or without water in the furnace, consists of a mixture of copper(I) oxide and copper(II) hydroxide. PMID:3400592

  5. SOA Production From Cloud Processing of Glycolaldehyde

    NASA Astrophysics Data System (ADS)

    Perri, M. J.; Seitzinger, S. P.; Tan, Y.; Turpin, B. J.

    2007-12-01

    Recent studies suggest that aqueous cloud chemistry contributes to secondary organic aerosol (SOA) production. Gas phase primary precursors, such as ethene and isoprene, can oxidize in the interstitial spaces of clouds to form water-soluble species, including glycolaldehyde. These water-soluble products can partition into cloud droplets and undergo further oxidation (e.g., via hydroxyl radicals). If low-volatility products (e.g., oxalate) are formed, these products can remain in the particle phase following droplet evaporation, forming organic aerosol. Organic aerosol plays an important role in cloud microphysics, visibility, and human health, yet little is known about aqueous phase reaction pathways and products that contribute to SOA. The kinetics of aqueous phase glycolaldehyde oxidation were studied and products were identified. Hydroxyl radical was generated via continuous UV photolysis of hydrogen peroxide inside a glass photochemical vessel. The reaction of glycolaldehyde and hydroxyl radical was monitored in real-time via continuous electrospray ionization mass spectrometry (ESI-MS). Organic products (acids and aldehydes) formed and destroyed during the reaction were identified and quantified via negative and positive mode ionization. Based on ESI-MS data obtained, glycolaldehyde is oxidized via hydroxyl radical to glycolic acid, glyoxylic acid, and ultimately oxalic acid, as previously suggested. In addition, several unexpected higher molecular weight compounds were produced, and identification of these reaction products is currently underway. The results obtained from this study serve to validate and refine the aqueous SOA-producing pathway for glycolaldehyde in cloud chemistry models and can be used to increase the accuracy of SOA prediction in atmospheric air quality and climate models.

  6. Fast onset medications through thermally generated aerosols.

    PubMed

    Rabinowitz, Joshua D; Wensley, Martin; Lloyd, Peter; Myers, Daniel; Shen, William; Lu, Amy; Hodges, Craig; Hale, Ron; Mufson, Daniel; Zaffaroni, Alejandro

    2004-05-01

    Smoking involves heating a drug to form a mixture of drug vapor and gaseous degradation products. These gases subsequently cool and condense into aerosol particles that are inhaled. Here, we demonstrate rapid and reliable systemic delivery of pure pharmaceutical compounds without degradation products through a related process that also involves inhalation of thermally generated aerosol. Drug is coated as a thin film on a metallic substrate and vaporized by heating the metal. The thin nature of the drug coating minimizes the length of time during which the drug is exposed to elevated temperatures, thereby preventing its thermal decomposition. The vaporized, gas-phase drug rapidly condenses and coagulates into micrometer-sized aerosol particles. For the commonly prescribed antimigraine drug rizatriptan, inhalation of these particles results in nearly instantaneous systemic drug action. PMID:14752061

  7. Generating monodisperse pharmacological aerosols using the spinning-top aerosol generator.

    PubMed

    Biddiscombe, Martyn F; Barnes, Peter J; Usmani, Omar S

    2006-01-01

    Pharmacological aerosols of precisely controlled particle size and narrow dispersity can be generated using the spinning-top aerosol generator (STAG). The ability of the STAG to generate monodisperse aerosols from solutions of raw drug compounds makes it a valuable research instrument. In this paper, the versatility of this instrument has been further demonstrated by aerosolizing a range of commercially available nebulized pulmonary therapy preparations. Nebules of Flixotide (fluticasone propionate), Pulmicort (budesonide), Combivent (salbutamol sulphate and ipratropium bromide), Bricanyl (terbutaline sulphate), Atrovent(ipratropium bromide), and Salamol (salbutamol sulphate) were each mixed with ethanol and delivered to the STAG. Monodisperse drug aerosol distributions were generated with MMADs of 0.95-6.7 microm. To achieve larger particle sizes from the nebulizer drug suspensions, the STAG formed compound particle agglomerates derived from the smaller insoluble drug particles. These compound agglomerates behaved aerodynamically as a single particle, and this was verified using an aerodynamic particle sizer and an Andersen Cascade Impactor. Scanning electron microscope images demonstrated their physical structure. On the other hand using the nebulizer drug solutions, spherical particles proportional to the original droplet diameter were generated. The aerosols generated by the STAG can allow investigators to study the scientific principles of inhaled drug deposition and lung physiology for a range of therapeutic agents. PMID:17034300

  8. SOA Pragmatism

    NASA Astrophysics Data System (ADS)

    Shan, Tony C.

    This paper presents a pragmatic approach composed of Methodology, Automation, Patterns, and Strategy (MAPS), to effectively manage the architecture design practices and solution development lifecycle of information systems in a service-oriented paradigm. The key challenges in SOA are discussed, such as architecture complexity, evolving technologies, immature governance, fragmented specification efforts, and disparate visual notations. This comprehensive framework aims to provide a mature integration of appropriate knowledge and capabilities to filter the inessential from the essential. In the Methodology dimension, a hybrid method, SOA philosophy, and a methodical approach are the key components. The Automation dimension covers tools, service lifecycle, and COTS mapping. The prominent elements of the Patterns dimension are data caching patterns, reference model, and open source reference implementation. Finally, the Strategy dimension addresses the strategy metamodel, technology architecture planning, and strategy roadmapping. In addition, a 9-point list of SOA wisdom is articulated, which gives best-practice guidelines to adopt and implement SOA pragmatically in large organizations from a practitioner's perspeoctive.

  9. Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

    NASA Astrophysics Data System (ADS)

    Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

    2016-02-01

    Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the statistical oxidation model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional University of California at Davis / California Institute of Technology (UCD/CIT) air quality model and applied to air quality episodes in California and the eastern USA. The mass, composition and properties of SOA predicted using SOM were compared to SOA predictions generated by a traditional two-product model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation.Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions

  10. Formation of brown carbon via reactions of ammonia with secondary organic aerosols from biogenic and anthropogenic precursors

    NASA Astrophysics Data System (ADS)

    Updyke, Katelyn M.; Nguyen, Tran B.; Nizkorodov, Sergey A.

    2012-12-01

    Filter samples of secondary organic aerosols (SOA) generated from the ozone (O3)- and hydroxyl radical (OH)-initiated oxidation of various biogenic (isoprene, α-pinene, limonene, α-cedrene, α-humulene, farnesene, pine leaf essential oils, cedar leaf essential oils) and anthropogenic (tetradecane, 1,3,5-trimethylbenzene, naphthalene) precursors were exposed to humid air containing approximately 100 ppb of gaseous ammonia (NH3). Reactions of SOA compounds with NH3 resulted in production of light-absorbing "brown carbon" compounds, with the extent of browning ranging from no observable change (isoprene SOA) to visible change in color (limonene SOA). The aqueous phase reactions with dissolved ammonium (NH4+) salts, such as ammonium sulfate, were equally efficient in producing brown carbon. Wavelength-dependent mass absorption coefficients (MAC) of the aged SOA were quantified by extracting known amounts of SOA material in methanol and recording its UV/Vis absorption spectra. For a given precursor, the OH-generated SOA had systematically lower MAC compared to the O3-generated SOA. The highest MAC values, for brown carbon from SOA resulting from O3 oxidation of limonene and sesquiterpenes, were comparable to MAC values for biomass burning particles but considerably smaller than MAC values for black carbon aerosols. The NH3/NH4+ + SOA brown carbon aerosol may contribute to aerosol optical density in regions with elevated concentrations of NH3 or ammonium sulfate and high photochemical activity.

  11. SOA Precursors: A Comparison of Semi-Volatile and Water Soluble Organic Gases During SOAS

    NASA Astrophysics Data System (ADS)

    Carlton, A. M. G.; Sareen, N.; Turpin, B. J.

    2014-12-01

    It is well-established that a major pathway for secondary organic aerosol (SOA) formation is via the partitioning of semi-volatile products of gas-phase photochemical reactions into preexisting organic particulate matter. Semi-volatile partitioning theory is widely used while modeling SOA. Despite its significance, parameterizations based solely on this formation pathway are unable to reproduce trends in SOA mass, particularly high atmospheric O/C ratios and enrichment of organic aerosol aloft. Recent studies have also highlighted the importance of formation of SOA through reactions of water-soluble organic gases (WSOG) in atmospheric waters (clouds, fogs, and wet aerosols). In order to understand the relative magnitude of potential precursors to SOA via both formation pathways, we modeled semi-volatile and WSOG concentrations during the Secondary Organic and Aerosol Study (SOAS) conducted in Brent, Alabama during June-July 2013. CMAQ 5.0.1 is used to predict mixing ratios of semi-volatile gases and WSOG over the continental US for a 10 day time period during SOAS. Our modeling results indicate that WSOG concentrations are an order of magnitude greater, on average, than the sum of semi-volatile gases. Interestingly, concentrations of semi-volatile gases increase aloft, unlike concentrations of WSOG. These results suggest that the potential for SOA formation from WSOG was high, and provide support for efforts to accurately model that multiphase chemistry in order to develop more effective air quality management strategies.

  12. Examining the role of NOx and acidity on organic aerosol formation through predictions of key isoprene aerosol species in the United States

    EPA Science Inventory

    Isoprene is a significant contributor to organic aerosol in the Southeastern United States. Later generation isoprene products, specifically isoprene epoxydiols (IEPOX) and methacryloylperoxynitrate (MPAN), have been identified as SOA precursors. The contribution of each pathway ...

  13. Generation and characterization of aerosols and vapors for inhalation experiments.

    PubMed Central

    Tillery, M I; Wood, G O; Ettinger, H J

    1976-01-01

    Control of aerosol and vapor characteristics that affect the toxicity of inhaled contaminants often determines the methods of generating exposure atmospheres. Generation methods for aerosols and vapors are presented. The characteristics of the resulting exposure atmosphere and the limitations of the various generation methods are discussed. Methods and instruments for measuring the airborne contaminant with respect to various charcteristics are also described. PMID:797565

  14. Photodegradation of SOA Prepared by Oxidation of d-Limonene by Ozone and NO3

    NASA Astrophysics Data System (ADS)

    Pan, X.; Xing, J.; Underwood, J. S.; Nizkorodov, S. A.

    2008-12-01

    Terpenes account for over 50% of biogenically emitted volatile organic compounds (VOC). Terpenes including limonene react with gas phase oxidants in the air such as NO3, ozone and OH. Secondary organic aerosol (SOA) is formed when low vapor pressure products spontaneously condense into particles. While in the atmosphere, SOA age via heterogeneous atmospheric chemistry, often with profound effects on the physical and chemical properties of the particles. The primary goal of this research is to study the photochemical aging of monoterpene-derived aerosol particles. SOA particles are generated in the lab by reacting limonene and oxidants including ozone and NO3 in a Teflon reaction chamber. The concentrations of limonene and oxidants were set to different levels in experiments. The particles are collected on filters and irradiated with light in the actinic region (>290 nm). The gas-phase photolysis products were studied using chemical ionization mass spectrometry (CIMS) in real time. The results show that the photodegradation of limonene SOA strongly depends on radiation wavelengths. SOA photodegradation mechanisms and their implications for photochemical aging of organic aerosols will be discussed.

  15. Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of α-pinene

    NASA Astrophysics Data System (ADS)

    Denjean, C.; Formenti, P.; Picquet-Varrault, B.; Pangui, E.; Zapf, P.; Katrib, Y.; Giorio, C.; Tapparo, A.; Monod, A.; Temime-Roussel, B.; Decorse, P.; Mangeney, C.; Doussin, J. F.

    2015-03-01

    Secondary organic aerosol (SOA) were generated from the ozonolysis of α-pinene in the CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) simulation chamber. The SOA formation and aging were studied by following their optical, hygroscopic and chemical properties. The optical properties were investigated by determining the particle complex refractive index (CRI). The hygroscopicity was quantified by measuring the effect of relative humidity (RH) on the particle size (size growth factor, GF) and on the scattering coefficient (scattering growth factor, f(RH)). The oxygen to carbon atomic ratios (O : C) of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition during their formation and aging in CESAM. The real CRI at 525 nm wavelength decreased from 1.43-1.60 (±0.02) to 1.32-1.38 (±0.02) during the SOA formation. The decrease in the real CRI correlated to the O : C decrease from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF remained roughly constant over the reaction time, with values of 1.02-1.07 (±0.02) at 90% (±4.2%) RH. Simultaneous measurements of O : C of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but contained less oxidised species at the surface which may limit water absorption. In addition, an apparent change in both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 14 h of reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state.

  16. 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).

  17. Photochemical aging of secondary organic aerosols generated from the photooxidation of polycyclic aromatic hydrocarbons in the gas-phase.

    PubMed

    Riva, Matthieu; Robinson, Ellis S; Perraudin, Emilie; Donahue, Neil M; Villenave, Eric

    2015-05-01

    Aging processes of secondary organic aerosol (SOA) may be a source of oxygenated organic aerosols; however, the chemical processes involved remain unclear. In this study, we investigate photochemical aging of SOA produced by the gas-phase oxidation of naphthalene by hydroxyl radicals and acenaphthylene by ozone. We monitored the SOA composition using a high-resolution time-of-flight aerosol mass spectrometer. We initiated SOA aging with UV photolysis alone and with OH radicals in the presence or absence of light and at different NOx levels. For naphthalene, the organic composition of the particulate phase seems to be dominated by highly oxidized compounds such as carboxylic acids, and aging data may be consistent with diffusion limitations. For acenaphthylene, the fate of oxidized products and the moderately oxidized aerosol seem to indicate that functionalization reactions might be the main aging process were initiated by the cumulative effect of light and OH radicals. PMID:25856309

  18. Photo-oxidation of pinonaldehyde at low NOx: from chemistry to organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Chacon-Madrid, H. J.; Henry, K. M.; Donahue, N. M.

    2013-03-01

    Pinonaldehyde oxidation by OH radicals under low-NOx conditions produces significant secondary organic aerosol (SOA) mass yields. Under concurrent UV illumination, mass yields are lower than high-NOx yields published earlier by our group. However, when OH radicals are produced via dark ozonolysis the SOA mass yields are comparable at high and low NOx. Because pinonaldehyde is a major first-generation gas-phase product of α-pinene oxidation by either ozone or OH radicals, its potential to form SOA serves as a molecular counterpoint to bulk SOA aging experiments involving SOA formed from α-pinene. Both the general tendency for aging reactions to produce more SOA and the sensitivity of the low-NOx products to UV photolysis observed in the bulk clearly occur for this single species as well. Photochemical oxidation of pinonaldehye and analogous first-generation terpene oxidation products are potentially a significant source of additional SOA in biogenically influenced air masses.

  19. Generation and characterization of biological aerosols for laser measurements

    SciTech Connect

    Cheng, Yung-Sung; Barr, E.B.

    1995-12-01

    Concerns for proliferation of biological weapons including bacteria, fungi, and viruses have prompted research and development on methods for the rapid detection of biological aerosols in the field. Real-time instruments that can distinguish biological aerosols from background dust would be especially useful. Sandia National Laboratories (SNL) is developing a laser-based, real-time instrument for rapid detection of biological aerosols, and ITRI is working with SNL scientists and engineers to evaluate this technology for a wide range of biological aerosols. This paper describes methods being used to generate the characterize the biological aerosols for these tests. In summary, a biosafe system has been developed for generating and characterizing biological aerosols and using those aerosols to test the SNL laser-based real-time instrument. Such tests are essential in studying methods for rapid detection of airborne biological materials.

  20. Exposure of BALB/c Mice to Diesel Engine Exhaust Origin Secondary Organic Aerosol (DE-SOA) during the Developmental Stages Impairs the Social Behavior in Adult Life of the Males

    PubMed Central

    Win-Shwe, Tin-Tin; Kyi-Tha-Thu, Chaw; Moe, Yadanar; Fujitani, Yuji; Tsukahara, Shinji; Hirano, Seishiro

    2016-01-01

    Secondary organic aerosol (SOA) is a component of particulate matter (PM) 2.5 and formed in the atmosphere by oxidation of volatile organic compounds. Recently, we have reported that inhalation exposure to diesel engine exhaust (DE) originated SOA (DE-SOA) affect novel object recognition ability and impair maternal behavior in adult mice. However, it is not clear whether early life exposure to SOA during the developmental stages affect social behavior in adult life or not. In the present study, to investigate the effects of early life exposure to DE-SOA during the gestational and lactation stages on the social behavior in the adult life, BALB/c mice were exposed to clean air (control), DE, DE-SOA and gas without any PM in the inhalation chambers from gestational day 14 to postnatal day 21 for 5 h a day and 5 days per week. Then adult mice were examined for changes in their social behavior at the age of 13 week by a sociability and social novelty preference, social interaction with a juvenile mouse and light-dark transition test, hypothalamic mRNA expression levels of social behavior-related genes, estrogen receptor-alpha and oxytocin receptor as well as of the oxidative stress marker gene, heme oxygenase (HO)-1 by real-time RT-PCR method. In addition, hypothalamic level of neuronal excitatory marker, glutamate was determined by ELISA method. We observed that sociability and social novelty preference as well as social interaction were remarkably impaired, expression levels of estrogen receptor-alpha, oxytocin receptor mRNAs were significantly decreased, expression levels of HO-1 mRNAs and glutamate levels were significantly increased in adult male mice exposed to DE-SOA compared to the control ones. Findings of this study indicate early life exposure of BALB/c mice to DE-SOA may affect their late-onset hypothalamic expression of social behavior related genes, trigger neurotoxicity and impair social behavior in the males. PMID:26834549

  1. Exposure of BALB/c Mice to Diesel Engine Exhaust Origin Secondary Organic Aerosol (DE-SOA) during the Developmental Stages Impairs the Social Behavior in Adult Life of the Males.

    PubMed

    Win-Shwe, Tin-Tin; Kyi-Tha-Thu, Chaw; Moe, Yadanar; Fujitani, Yuji; Tsukahara, Shinji; Hirano, Seishiro

    2015-01-01

    Secondary organic aerosol (SOA) is a component of particulate matter (PM) 2.5 and formed in the atmosphere by oxidation of volatile organic compounds. Recently, we have reported that inhalation exposure to diesel engine exhaust (DE) originated SOA (DE-SOA) affect novel object recognition ability and impair maternal behavior in adult mice. However, it is not clear whether early life exposure to SOA during the developmental stages affect social behavior in adult life or not. In the present study, to investigate the effects of early life exposure to DE-SOA during the gestational and lactation stages on the social behavior in the adult life, BALB/c mice were exposed to clean air (control), DE, DE-SOA and gas without any PM in the inhalation chambers from gestational day 14 to postnatal day 21 for 5 h a day and 5 days per week. Then adult mice were examined for changes in their social behavior at the age of 13 week by a sociability and social novelty preference, social interaction with a juvenile mouse and light-dark transition test, hypothalamic mRNA expression levels of social behavior-related genes, estrogen receptor-alpha and oxytocin receptor as well as of the oxidative stress marker gene, heme oxygenase (HO)-1 by real-time RT-PCR method. In addition, hypothalamic level of neuronal excitatory marker, glutamate was determined by ELISA method. We observed that sociability and social novelty preference as well as social interaction were remarkably impaired, expression levels of estrogen receptor-alpha, oxytocin receptor mRNAs were significantly decreased, expression levels of HO-1 mRNAs and glutamate levels were significantly increased in adult male mice exposed to DE-SOA compared to the control ones. Findings of this study indicate early life exposure of BALB/c mice to DE-SOA may affect their late-onset hypothalamic expression of social behavior related genes, trigger neurotoxicity and impair social behavior in the males. PMID:26834549

  2. Relationship between Oxidation Level and Optical Properties of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Lambe, A. T.; Cappa, C. D.; Massoli, P.; Onasch, T. B.; Forestieri, S.; Martin, A. T.; Cummings, M. J.; Croasdale, D. R.; Brune, W. H.; Worsnop, D. R.; Davidovits, P.

    2013-12-01

    Brown carbon (BrC), which may include secondary organic aerosol (SOA), can be a significant climate-forcing agent via its optical absorption properties. However, the overall contribution of SOA to BrC remains poorly understood. Here, correlations between oxidation level and optical properties of SOA are examined. SOA was generated in a flow reactor in the absence of NOx by OH oxidation of gas-phase precursors used as surrogates for anthropogenic (naphthalene, tricyclo-[5.2.1.02,6]decane), biomass burning (guaiacol), and biogenic (α-pinene) emissions. SOA chemical composition was characterized with a time-of-flight aerosol mass spectrometer. SOA mass-specific absorption cross sections (MAC) and refractive indices were calculated from real-time cavity ring-down photoacoustic spectrometry measurements at 405 and 532 nm and from UV-vis spectrometry measurements of methanol extracts of filter-collected particles (300 to 600 nm). At 405 nm, SOA MAC values and imaginary refractive indices increased with increasing oxidation level and decreased with increasing wavelength, leading to negligible absorption at 532 nm. Real refractive indices of SOA decreased with increasing oxidation level. Comparison with literature studies suggests that under typical polluted conditions the effect of NOx on SOA absorption is small. SOA may contribute significantly to atmospheric BrC, with the magnitude dependent on both precursor type and oxidation level. Mass-specific absorption cross sections (MAC) of SOA at λ = 405 nm as a function of the O/C ratio

  3. Characterization of Highly Oxidized Molecules in Fresh and Aged Biogenic Secondary Organic Aerosol.

    PubMed

    Tu, Peijun; Hall, Wiley A; Johnston, Murray V

    2016-04-19

    In this work, highly oxidized multifunctional molecules (HOMs) in fresh and aged secondary organic aerosol (SOA) derived from biogenic precursors are characterized with high-resolution mass spectrometry. Fresh SOA was generated by mixing ozone with a biogenic precursor (β-pinene, limonene, α-pinene) in a flow tube reactor. Aging was performed by passing the fresh SOA through a photochemical reactor where it reacted with hydroxyl radicals. Although these aerosols were as a whole not highly oxidized, molecular analysis identified a significant number of HOMs embedded within it. HOMs in fresh SOA consisted mostly of monomers and dimers, which is consistent with condensation of extremely low-volatility organic compounds (ELVOCs) that have been detected in the gas phase in previous studies and linked to SOA particle formation. Aging caused an increase in the average number of carbon atoms per molecule of the HOMs, which is consistent with particle phase oxidation of (less oxidized) oligomers already existing in fresh SOA. HOMs having different combinations of oxygen-to-carbon ratio, hydrogen-to-carbon ratio and average carbon oxidation state are discussed and compared to low volatility oxygenated organic aerosol (LVOOA), which has been identified in ambient aerosol based on average elemental composition but not fully understood at a molecular level. For the biogenic precursors and experimental conditions studied, HOMs in fresh biogenic SOA have molecular formulas more closely resembling LVOOA than HOMs in aged SOA, suggesting that aging of biogenic SOA is not a good surrogate for ambient LVOOA. PMID:27000653

  4. 10 GHz pulses generated across a ~100 nm tuning range using a gain-shifted mode-locked SOA ring laser

    NASA Astrophysics Data System (ADS)

    Tang, W. W.; Fok, M.; Shu, Chester

    2006-03-01

    Widely-tunable picosecond pulses have been generated from a harmonically mode-locked semiconductor optical amplifier (SOA) ring laser with a center wavelength spanning from 1491 to 1588 nm. An intra-cavity birefringence loop mirror filter is used to define a 1.6 nm comb that governs the wavelength spacing of the tunable output pulses. The filter also serves to control the spectral gain profile of the laser cavity and thus extends the tuning range. By exploiting the spectral shift of the SOA gain with different amount of optical feedback, the output can be obtained over a wid wavelength range. Applying mode-locking together with the dispersion tuning approach, 10 GHz picosecond pulses have been successfully generated over a tuning range of 97 nm.

  5. Radiative impact of aerosols generated from biomass burning

    NASA Technical Reports Server (NTRS)

    Christopher, Sundar A.; Vulcan, Donna V.; Welch, Ronald M.

    1995-01-01

    Atmospheric aerosol particles play a vital role in the Earth's radiative energy budget. They exert a net cooling influence on climate by directly reflecting the solar radiation to space and by modifying the shortwave reflective properties of clouds. Each year, increasing amounts of aerosol particles are released into the atmosphere due to biomass burning, dust storms, forest fires, and volcanic activity. These particles significantly perturb the radiative balance on local, regional, and global scales. While the detection of aerosols over water is a well established procedure, the detection of aerosols over land is often difficult due to the poor contrast between the aerosols and the underlying terrain. In this study, we use textural measures in order to detect aerosols generated from biomass burning over South America, using AVHRR data. The regional radiative effects are then examined using ERBE data. Preliminary results show that the net radiative forcing of aerosols is about -36 W/sq m.

  6. Relationship between fluid bed aerosol generator operation and the aerosol produced

    SciTech Connect

    Carpenter, R.L.; Yerkes, K.

    1980-12-01

    The relationships between bed operation in a fluid bed aerosol generator and aerosol output were studied. A two-inch diameter fluid bed aerosol generator (FBG) was constructed using stainless steel powder as a fluidizing medium. Fly ash from coal combustion was aerosolized and the influence of FBG operating parameters on aerosol mass median aerodynamic diameter (MMAD), geometric standard deviation (sigma/sub g/) and concentration was examined. In an effort to extend observations on large fluid beds to small beds using fine bed particles, minimum fluidizing velocities and elutriation constant were computed. Although FBG minimum fluidizing velocity agreed well with calculations, FBG elutriation constant did not. The results of this study show that the properties of aerosols produced by a FBG depend on fluid bed height and air flow through the bed after the minimum fluidizing velocity is exceeded.

  7. Generation, behavior, and toxicity of ammonium sulfite aerosols

    SciTech Connect

    Rothenberg, S.J.; Dahl, A.R.; Barr, E.B.; Wolff, R.K.

    1986-01-01

    Ammonium sulfite aerosols were continuously generated for periods up to 6 h by gas phase reaction of sulfur dioxide, ammonia, and water vapor in nitrogen carrier gas. Concentrations from 1 to 500 mg/m/sup 3/ were obtained. Aerosol leaving the generator was greater than 90% sulfite, but when diluted with air preparatory to animal exposures, the aerosol was rapidly oxidized. Sulfite concentrations in a large exposure chamber with a long residence time were consistently less than 25 percent of the aerosol mass. Sulfite concentrations in a nose-only or head-only inhalation chamber 1 ft downstream from a radial air injection system ranged from 10 to 80 percent sulfite. The latter system, with a short residence time, was used to expose animals to aerosols. Effects of the mixed sulfite/sulfate aerosol on acute mortality of guinea pigs and tracheal mucous clearance of dogs were measured and no effects were observed.

  8. Photochemistry of limonene secondary organic aerosol studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, Xiang

    Limonene is one of the most abundant monoterpenes in the atmosphere. Limonene easily reacts with gas-phase oxidants in air such as NO3, ozone and OH. Secondary organic aerosol (SOA) is formed when low vapor pressure products condense into particles. Chemicals in SOA particles can undergo further reactions with oxidants and with solar radiation that significantly change SOA composition over the course of several days. The goal of this work was to characterize radiation induced reaction in SOA. To perform experiments, we have designed and constructed an Atmospheric Pressure Chemical Ionization Mass Spectrometer (APCIMS) coupled to a photochemical cell containing SOA samples. In APCIMS, (H2O)nH 3O+ clusters are generated in a 63Ni source and react with gaseous organic analytes. Most organic chemicals are not fragmented by the ionization process. We have focused our attention on limonene SOA prepared in two different ways. The first type of SOA is produced by oxidation of limonene by ozone; and the second type of SOA is formed by the NO3-induced oxidation of limonene. They model the SOA formed under daytime and nighttime conditions, respectively. Ozone initiated oxidation is the most important chemical sink for limonene both indoors, where it is used for cleaning purposes, and outdoors. Terpenes are primarily oxidized by reactions with NO3 at night time. We generated limonene SOA under different ozone and limonene concentrations. The resulting SOA samples were exposed to wavelength-tunable radiation in the UV-Visible range between 270 nm and 630 nm. The results show that the photodegradation rates strongly depend on radiation wavelengths. Gas phase photodegradation products such as acetone, formaldehyde, acetaldehyde, and acetic acid were shown to have different production rates for SOA formed in different concentration conditions. Even for SOA prepared under the lowest concentrations, the SOA photodegradation was efficient. The conclusion is that exposure of SOA to

  9. Secondary Organic Aerosol formation from isoprene photooxidation during cloud condensation-evaporation cycles

    NASA Astrophysics Data System (ADS)

    Brégonzio-Rozier, L.; Giorio, C.; Siekmann, F.; Pangui, E.; Morales, S. B.; Temime-Roussel, B.; Gratien, A.; Michoud, V.; Cazaunau, M.; DeWitt, H. L.; Tapparo, A.; Monod, A.; Doussin, J.-F.

    2015-07-01

    The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene/NOx/light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are two and four times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of two or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to water soluble volatile organic compounds (VOCs) dissolution in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.

  10. Secondary organic aerosol formation from isoprene photooxidation during cloud condensation-evaporation cycles

    NASA Astrophysics Data System (ADS)

    Brégonzio-Rozier, L.; Giorio, C.; Siekmann, F.; Pangui, E.; Morales, S. B.; Temime-Roussel, B.; Gratien, A.; Michoud, V.; Cazaunau, M.; DeWitt, H. L.; Tapparo, A.; Monod, A.; Doussin, J.-F.

    2016-02-01

    The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene / NOx / light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are 2 and 4 times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of 2 or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to the dissolution of water soluble volatile organic compounds (VOCs) in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.

  11. Lessons Learned About Organic Aerosol Formation in the Southeast U.S. Using Observations and Modeling

    EPA Science Inventory

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA). In this work, modeling of isoprene SOA via heterogeneous uptake is explored and compared to observations from the Southern Oxidant and Aerosol Study (SOAS).

  12. Insight into the numerical challenges of implementing 2-dimensional SOA models in atmospheric chemical transport models

    NASA Astrophysics Data System (ADS)

    Napier, W. J.; Ensberg, J. J.; Seinfeld, J. H.

    2014-10-01

    The new generation of secondary organic aerosol (SOA) models that represent gas- and particle-phase chemistry and thermodynamic partitioning using discrete two-dimensional grids (e.g. SOM, 2D-VBS) cannot be efficiently implemented into three-dimensional atmospheric chemical transport models (CTMs) due to the large number of bins (tracers) required. In this study, we introduce a novel mathematical framework, termed the Oxidation State/Volatility Moment Method, that is designed to address these computational burdens so as to allow the new generation of SOA models to be implemented into CTMs. This is accomplished by mapping the two-dimensional grids onto probability distributions that conserve carbon and oxygen mass. Assessment of the Moment Method strengths (speed, carbon and oxygen conservation) and weaknesses (numerical drift) provide valuable insight that can guide future development of SOA modules for atmospheric CTMs.

  13. Capstone Depleted Uranium Aerosols: Generation and Characterization

    SciTech Connect

    Parkhurst, MaryAnn; Szrom, Fran; Guilmette, Ray; Holmes, Tom; Cheng, Yung-Sung; Kenoyer, Judson L.; Collins, John W.; Sanderson, T. Ellory; Fliszar, Richard W.; Gold, Kenneth; Beckman, John C.; Long, Julie

    2004-10-19

    In a study designed to provide an improved scientific basis for assessing possible health effects from inhaling depleted uranium (DU) aerosols, a series of DU penetrators was fired at an Abrams tank and a Bradley fighting vehicle. A robust sampling system was designed to collect aerosols in this difficult environment and continuously monitor the sampler flow rates. Aerosols collected were analyzed for uranium concentration and particle size distribution as a function of time. They were also analyzed for uranium oxide phases, particle morphology, and dissolution in vitro. The resulting data provide input useful in human health risk assessments.

  14. Multiphase, Multigeneration SOA Formation from Terpenes

    NASA Astrophysics Data System (ADS)

    Donahue, N. M.; Zhang, J.; Tischuk, J. E.; Macsymiuk, C.

    2006-12-01

    Traditional representations of Secondary Organic Aerosol (SOA) formation typically focus on prompt products from the gas-phase reaction of a precursor with an oxidant. A well-studied example is that of terpenes, especially α-pinene, reacting with ozone. Typically, aerosol mass is measured as a function of the precursor consumed, and the mass fraction (yield) can be fit to an expression describing semi-volatile partitioning. Often an `Odum 2-product model' is used, with parameters fed directly into chemical transport models. Here we present chamber data for the reaction of ozone with limonene, which has 2 double bonds and thus 2 obvious generations of oxidation. We can represent the oxidation of limonene through two generations by using a volatility basis set, which describes the distribution of organic volatilities in the atmosphere over a range of 9 orders of magnitude. We represent the complete volatility distribution of oxidation products using the basis set, developing `volatility operators' for each step of the limonene oxidation. The conclusions are supported by data for ozonolysis of limonaketone as well as NMR analysis of SOA from limonene obtained in excess limonene vs excess ozone conditions. While ozone + terpene reactions make good laboratory models, a pressing question is how to constrain and represent multiple-generation oxidation of semivolatile vapors, which are mostly saturated. Given the enormous range of individual compounds comprising semivolatile organics, a condensed representation is essential. The volatility basis set and operators meet that need; we suggest preliminary gas-phase volatility operators for oxidation by OH radicals, depending on the O:C ratio of the organics. At low O:C, OH oxidation drives volatility downward, but as O:C approaches some limit (roughly 1), oxidation sharply increases volatility because the carbon backbone breaks, making light, volatile products. Operators are required for gas-phase, heterogeneous, and

  15. Relationship between oxidation level and optical properties of secondary organic aerosol.

    PubMed

    Lambe, Andrew T; Cappa, Christopher D; Massoli, Paola; Onasch, Timothy B; Forestieri, Sara D; Martin, Alexander T; Cummings, Molly J; Croasdale, David R; Brune, William H; Worsnop, Douglas R; Davidovits, Paul

    2013-06-18

    Brown carbon (BrC), which may include secondary organic aerosol (SOA), can be a significant climate-forcing agent via its optical absorption properties. However, the overall contribution of SOA to BrC remains poorly understood. Here, correlations between oxidation level and optical properties of SOA are examined. SOA was generated in a flow reactor in the absence of NOx by OH oxidation of gas-phase precursors used as surrogates for anthropogenic (naphthalene, tricyclo[5.2.1.0(2,6)]decane), biomass burning (guaiacol), and biogenic (α-pinene) emissions. SOA chemical composition was characterized with a time-of-flight aerosol mass spectrometer. SOA mass-specific absorption cross sections (MAC) and refractive indices were calculated from real-time cavity ring-down photoacoustic spectrometry measurements at 405 and 532 nm and from UV-vis spectrometry measurements of methanol extracts of filter-collected particles (300 to 600 nm). At 405 nm, SOA MAC values and imaginary refractive indices increased with increasing oxidation level and decreased with increasing wavelength, leading to negligible absorption at 532 nm. Real refractive indices of SOA decreased with increasing oxidation level. Comparison with literature studies suggests that under typical polluted conditions the effect of NOx on SOA absorption is small. SOA may contribute significantly to atmospheric BrC, with the magnitude dependent on both precursor type and oxidation level. PMID:23701291

  16. Modeling the formation and aging of secondary organic aerosols during CalNex 2010

    NASA Astrophysics Data System (ADS)

    Hayes, P. L.; Ortega, A. M.; Ahmadov, R.; McKeen, S. A.; Washenfelder, R. A.; Alvarez, S.; Rappenglueck, B.; Holloway, J. S.; Gilman, J. B.; Kuster, W. C.; De Gouw, J. A.; Zotter, P.; Prevot, A. S.; Kleindienst, T. E.; Offenberg, J. H.; Jimenez, J. L.

    2012-12-01

    Several traditional and recently proposed models are applied to predict the concentrations and properties of secondary organic aerosols (SOA) and organic gases at the Pasadena ground site during the CalNex campaign. The models are constrained with and compared against results from available observations. The CalNex campaign and specifically the Pasadena ground site featured a large and sophisticated suite of aerosol and gas phase instrumentation, and thus, it provides a unique opportunity to test SOA models under conditions of strong urban emissions at a range of low photochemical ages. The oxidation of volatile organic compounds (VOCs) using an updated traditional model cannot explain the observed ambient SOA, and under-predicts the measurements by a factor of ~40. Similarly, after accounting for the multi-generation oxidation of VOCs using a volatility basis set (VBS) approach as described by Tsimpidi et al. (2010), SOA is still under-predicted by a factor of ~8. For SOA formed from VOCs (V-SOA) the dominant precursors are aromatics (xylenes, toluene, and trimethylbenzenes). The model SOA formed from the oxidation of primary semivolatile and intermediate volatility organic compounds (P-S/IVOCs, producing SI-SOA) is also predicted using the parameterizations of Robinson et al. (2007) and Grieshop et al. (2009), and the properties of V-SOA + SI-SOA are compared against the measured O:C and volatility. We also compare the results of the different models against fossil/non-fossil carbon measurements as well as tracers of different SOA precursors. Potential Aerosol Mass (PAM) measurements of the SOA forming potential of the Pasadena air masses are also compared against that predicted by the models. The PAM analysis allows for model/measurement comparisons of SOA properties over a range of photochemical ages spanning almost two weeks. Using the V-SOA model, at low photochemical ages (< 1 day) the modeled PAM V-SOA is less than the measured PAM SOA, similar to the

  17. 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

  18. Modeling SOA formation from alkanes and alkenes in chamber experiments: effect of gas/wall partitioning of organic vapors.

    NASA Astrophysics Data System (ADS)

    Stéphanie La, Yuyi; Camredon, Marie; Ziemann, Paul; Ouzebidour, Farida; Valorso, Richard; Madronich, Sasha; Lee-Taylor, Julia; Hodzic, Alma; Aumont, Bernard

    2014-05-01

    Oxidation products of Intermediate Volatility Organic Compounds (IVOC) are expected to be the major precursors of secondary organic aerosols (SOA). Laboratory experiments were conducted this last decade in the Riverside APRC chamber to study IVOC oxidative mechanisms and SOA formation processes for a large set of linear, branched and cyclic aliphatic hydrocarbons (Ziemann, 2011). This dataset are used here to assess the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) (Aumont et al., 2005). The simulated SOA yields agree with the general trends observed in the chamber experiments. They are (i) increasing with the increasing carbon number; (ii) decreasing with increasing methyl branch number; and (iii) increasing for cyclic compounds compared to their corresponding linear analogues. However, simulated SOA yields are systematically overestimated regardless of the precursors, suggesting missing processes in the model. In this study, we assess whether gas-to-wall partitioning of organic vapors can explain these model/observation mismatches (Matsunaga and Ziemann, 2010). First results show that GECKO-A outputs better match the observations when wall uptake of organic vapors is taken into account. Effects of gas/wall partitioning on SOA yields and composition will be presented. Preliminary results suggest that wall uptake is a major process influencing SOA production in the Teflon chambers. References Aumont, B., Szopa, S., Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach. Atmos.Chem.Phys., 5, 2497-2517 (2005). P. J. Ziemann: Effects of molecular structure on the chemistry of aerosol formation from the OH-radical-initiated oxidation of alkanes and alkenes, Int. Rev.Phys.Chem., 30:2, 161-195 (2011). Matsunaga, A., Ziemann, P. J.: Gas-wall partitioning of organic compounds in a Teflon film

  19. ANALYSIS OF SECONDARY ORGANIC AEROSOL COMPOUNDS FROM THE PHOTOOXIDATION OF D-LIMONENE IN THE PRESENCE OF NO X AND THEIR DETECTION IN AMBIENT PM 2.5

    EPA Science Inventory

    Chemical analysis of secondary organic aerosol (SOA) from the photooxidation of a d-limonene/NOx/air mixture was carried out. SOA, generated in a smog chamber, was collected on Zefluor filters. To determine the structural characteristics of the compounds, the filter sample...

  20. Photochemical Aging of Organic Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Nizkorodov, S. A.; Bateman, A. P.; Dailo, M.; Do, T.; Mang, S. A.; Pan, X.; Underwood, J. S.; Walser, M. L.

    2007-05-01

    Secondary Organic Aerosol (SOA) particles are produced in the atmosphere as a result of oxidation of volatile organic compounds (VOC). Primary Organic Aerosol (POA) particles are directly emitted in the atmosphere by their sources. This research focuses on the mechanisms of direct photochemical processes taking place in model SOA and POA particles, the role of such processes in aging of organic aerosol particles, and the effect of photochemistry on particles' physicochemical properties. To address these questions, artificial SOA and POA particles are investigated with several laboratory-based approaches relying on cavity ring-down spectroscopy and mass-spectrometry. SOA particles generated by dark oxidation of d-Limonene, alpha-Pinene, and beta-Pinene by ozone are all found to absorb radiation in the tropospheric actinic window. The UV absorption photolyzes SOA constituents resulting in a release of small VOC molecules back in the gas-phase, and considerable change in SOA chemical composition. For terpenes featuring a terminal double bond, the main SOA photolysis products are invariably found to be formaldehyde and formic acid. Similar observations are obtained for products of ozonolysis of thin films of unsaturated fatty acids and self-assembled monolayers of unsaturated alkenes. For the case of fatty acids, a very detailed mechanism of ozonolysis and subsequent photolysis is proposed. The photolytic activity is primarily attributed to organic peroxides and aldehydes. These results convincingly demonstrate that photochemical processes occurring inside SOA and POA particles age the particles on time scales that are shorter than typical lifetimes of aerosol particles in the atmosphere.

  1. Wired/wireless access integrated RoF-PON with scalable generation of multi-frequency MMWs enabled by polarization multiplexed FWM in SOA.

    PubMed

    Xiang, Yu; Chen, Chen; Zhang, Chongfu; Qiu, Kun

    2013-01-14

    In this paper, we propose and demonstrate a novel integrated radio-over-fiber passive optical network (RoF-PON) system for both wired and wireless access. By utilizing the polarization multiplexed four-wave mixing (FWM) effect in a semiconductor optical amplifier (SOA), scalable generation of multi-frequency millimeter-waves (MMWs) can be provided so as to assist the configuration of multi-frequency wireless access for the wire/wireless access integrated ROF-PON system. In order to obtain a better performance, the polarization multiplexed FWM effect is investigated in detail. Simulation results successfully verify the feasibility of our proposed scheme. PMID:23389014

  2. SOA from BVOCs in the Southeastern United States

    EPA Science Inventory

    Biogenic hydrocarbons contribute to organic aerosol in the southeast United States. In this work, we represent aerosol formation from the oxidation of isoprene and monoterpenes in CMAQ and compare to data from the Southeast Oxidants and Aerosol Study (SOAS). Sensitivity simulatio...

  3. To What Extent Can Biogenic SOA Be Controlled?

    EPA Science Inventory

    Anthropogenic pollution facilitates transformation of naturally emitted volatile organic compounds (VOCs) to the particle phase, enhancing the ambient concentrations of material commonly referred to as biogenic secondary organic aerosol (SOA). It is therefore conceivable that som...

  4. SOA FROM ISOPRENE OXIDATION PRODUCTS: MODEL SIMULATION OF CLOUD CHEMISTRY

    EPA Science Inventory

    Recent laboratory evidence supports the hypothesis that secondary organic aerosol (SOA) is formed in the atmosphere through aqueous-phase reactions in clouds. The results of batch photochemical reactions of glyoxal, methylglyoxal and hydrogen peroxide are presented. These labor...

  5. Secondary Aerosol Formation from Oxidation of Aromatics Hydrocarbons by Cl atoms

    NASA Astrophysics Data System (ADS)

    Cai, X.; Griffin, R.

    2006-12-01

    Aerosol Formation From the Oxidation of Aromatic Hydrocarbons by Chlorine Atmospheric secondary organic aerosol (SOA) affects regional and global air quality. The formation mechanisms of SOA via the oxidation of volatile organic compounds by hydroxyl radicals, ozone, and nitrate radicals have been studied intensively during the last decade. Chlorine atoms (Cl) also have been hypothesized to be effective oxidants in marine and industrially influenced areas. Recent work by the authors has indicated that significant amounts of SOA are formed from the oxidation of monoterpenes by Cl. Aromatic hydrocarbons are important for generation of both SOA and ozone in urban areas because of their large emission rates and high reactivity. The goal of this work was to quantify the SOA formation potentials of two representative aromatic hydrocarbons through laboratory chamber experiments in which oxidation was initiated by Cl. The system constructed for this study includes an experimental chamber, a gas chromatograph for quantification of aromatic mixing ratios, a Scanning Mobility Particle Spectrometer to measure SOA size distributions, a zero air generator, and an illuminating system. The model aromatic hydrocarbons chosen for this study are toluene and m-xylene. Aerosol yields are estimated based on measured aerosol volume concentration, the concentration of consumed hydrocarbon, and estimation of wall loss of the newly formed aerosol. Toluene and m-xylene exhibit similar SOA yields from the oxidation initiated by Cl. The toluene SOA yield from Cl-initiated oxidation, however, depends on the ratio between the mixing ratios of the initial chlorine source and toluene in the chamber. For toluene experiments with higher such ratios, SOA yields vary from 0.05 to 0.079 for generated aerosol ranging from 4.2 to12.0 micrograms per cubic meter. In the lower ratio experiments, SOA yields are from 0.033 to 0.064, corresponding to generated aerosol from 3.0 to 11.0 micrograms per cubic

  6. Significant Contributions of Isoprene to Summertime Secondary Organic Aerosol in Eastern United States.

    PubMed

    Ying, Qi; Li, Jingyi; Kota, Sri Harsha

    2015-07-01

    A modified SAPRC-11 (S11) photochemical mechanism with more detailed treatment of isoprene oxidation chemistry and additional secondary organic aerosol (SOA) formation through surface-controlled reactive uptake of dicarbonyls, isoprene epoxydiol and methacrylic acid epoxide was incorporated in the Community Multiscale Air Quality Model (CMAQ) to quantitatively determine contributions of isoprene to summertime ambient SOA concentrations in the eastern United States. The modified model utilizes a precursor-origin resolved approach to determine secondary glyoxal and methylglyoxal produced by oxidation of isoprene and other major volatile organic compounds (VOCs). Predicted OC concentrations show good agreement with field measurements without significant bias (MFB ∼ 0.07 and MFE ∼ 0.50), and predicted SOA reproduces observed day-to-day and diurnal variation of Oxygenated Organic Aerosol (OOA) determined by an aerosol mass spectrometer (AMS) at two locations in Houston, Texas. On average, isoprene SOA accounts for 55.5% of total predicted near-surface SOA in the eastern U.S., followed by aromatic compounds (13.2%), sesquiterpenes (13.0%) and monoterpenes (10.9%). Aerosol surface uptake of isoprene-generated glyoxal, methylglyoxal and epoxydiol accounts for approximately 83% of total isoprene SOA or more than 45% of total SOA. A domain wide reduction of NOx emissions by 40% leads to a slight decrease of domain average SOA by 3.6% and isoprene SOA by approximately 2.6%. Although most of the isoprene SOA component concentrations are decreased, SOA from isoprene epoxydiol is increased by ∼16%. PMID:26029963

  7. UNDERSTANDING REGIONAL OXIDATION CAPACITY BY COMPREHENSIVE OBSERVATIONS TO CONSTRAIN HYDROXYL RADICAL SOURCES AND SINKS DURING THE SOUTHERN OXIDANT AEROSOL STUDY (SOAS)

    EPA Science Inventory

    The proposed field measurements and data analysis will provide an important constraint to understand oxidation capacity in the Southeastern U.S. that determines SOA and photochemical ozone formation. Unexpectedly high levels of OH determining oxidation capacity have been co...

  8. Enhanced Deep Blue aerosol retrieval algorithm: The second generation

    NASA Astrophysics Data System (ADS)

    Hsu, N. C.; Jeong, M.-J.; Bettenhausen, C.; Sayer, A. M.; Hansell, R.; Seftor, C. S.; Huang, J.; Tsay, S.-C.

    2013-08-01

    The aerosol products retrieved using the Moderate Resolution Imaging Spectroradiometer (MODIS) collection 5.1 Deep Blue algorithm have provided useful information about aerosol properties over bright-reflecting land surfaces, such as desert, semiarid, and urban regions. However, many components of the C5.1 retrieval algorithm needed to be improved; for example, the use of a static surface database to estimate surface reflectances. This is particularly important over regions of mixed vegetated and nonvegetated surfaces, which may undergo strong seasonal changes in land cover. In order to address this issue, we develop a hybrid approach, which takes advantage of the combination of precalculated surface reflectance database and normalized difference vegetation index in determining the surface reflectance for aerosol retrievals. As a result, the spatial coverage of aerosol data generated by the enhanced Deep Blue algorithm has been extended from the arid and semiarid regions to the entire land areas. In this paper, the changes made in the enhanced Deep Blue algorithm regarding the surface reflectance estimation, aerosol model selection, and cloud screening schemes for producing the MODIS collection 6 aerosol products are discussed. A similar approach has also been applied to the algorithm that generates the Sea-viewing Wide Field-of-view Sensor (SeaWiFS) Deep Blue products. Based upon our preliminary results of comparing the enhanced Deep Blue aerosol products with the Aerosol Robotic Network (AERONET) measurements, the expected error of the Deep Blue aerosol optical thickness (AOT) is estimated to be better than 0.05 + 20%. Using 10 AERONET sites with long-term time series, 79% of the best quality Deep Blue AOT values are found to fall within this expected error.

  9. Generation and Characterization of Indoor Fungal Aerosols for Inhalation Studies.

    PubMed

    Madsen, Anne Mette; Larsen, Søren T; Koponen, Ismo K; Kling, Kirsten I; Barooni, Afnan; Karottki, Dorina Gabriela; Tendal, Kira; Wolkoff, Peder

    2016-04-01

    In the indoor environment, people are exposed to several fungal species. Evident dampness is associated with increased respiratory symptoms. To examine the immune responses associated with fungal exposure, mice are often exposed to a single species grown on an agar medium. The aim of this study was to develop an inhalation exposure system to be able to examine responses in mice exposed to mixed fungal species aerosolized from fungus-infested building materials. Indoor airborne fungi were sampled and cultivated on gypsum boards. Aerosols were characterized and compared with aerosols in homes. Aerosols containing 10(7)CFU of fungi/m(3)air were generated repeatedly from fungus-infested gypsum boards in a mouse exposure chamber. Aerosols contained Aspergillus nidulans,Aspergillus niger, Aspergillus ustus, Aspergillus versicolor,Chaetomium globosum,Cladosporium herbarum,Penicillium brevicompactum,Penicillium camemberti,Penicillium chrysogenum,Penicillium commune,Penicillium glabrum,Penicillium olsonii,Penicillium rugulosum,Stachybotrys chartarum, and Wallemia sebi They were all among the most abundant airborne species identified in 28 homes. Nine species from gypsum boards and 11 species in the homes are associated with water damage. Most fungi were present as single spores, but chains and clusters of different species and fragments were also present. The variation in exposure level during the 60 min of aerosol generation was similar to the variation measured in homes. Through aerosolization of fungi from the indoor environment, cultured on gypsum boards, it was possible to generate realistic aerosols in terms of species composition, concentration, and particle sizes. The inhalation-exposure system can be used to study responses to indoor fungi associated with water damage and the importance of fungal species composition. PMID:26921421

  10. Generation and Characterization of Indoor Fungal Aerosols for Inhalation Studies

    PubMed Central

    Larsen, Søren T.; Koponen, Ismo K.; Kling, Kirsten I.; Barooni, Afnan; Karottki, Dorina Gabriela; Tendal, Kira; Wolkoff, Peder

    2016-01-01

    In the indoor environment, people are exposed to several fungal species. Evident dampness is associated with increased respiratory symptoms. To examine the immune responses associated with fungal exposure, mice are often exposed to a single species grown on an agar medium. The aim of this study was to develop an inhalation exposure system to be able to examine responses in mice exposed to mixed fungal species aerosolized from fungus-infested building materials. Indoor airborne fungi were sampled and cultivated on gypsum boards. Aerosols were characterized and compared with aerosols in homes. Aerosols containing 107 CFU of fungi/m3 air were generated repeatedly from fungus-infested gypsum boards in a mouse exposure chamber. Aerosols contained Aspergillus nidulans, Aspergillus niger, Aspergillus ustus, Aspergillus versicolor, Chaetomium globosum, Cladosporium herbarum, Penicillium brevicompactum, Penicillium camemberti, Penicillium chrysogenum, Penicillium commune, Penicillium glabrum, Penicillium olsonii, Penicillium rugulosum, Stachybotrys chartarum, and Wallemia sebi. They were all among the most abundant airborne species identified in 28 homes. Nine species from gypsum boards and 11 species in the homes are associated with water damage. Most fungi were present as single spores, but chains and clusters of different species and fragments were also present. The variation in exposure level during the 60 min of aerosol generation was similar to the variation measured in homes. Through aerosolization of fungi from the indoor environment, cultured on gypsum boards, it was possible to generate realistic aerosols in terms of species composition, concentration, and particle sizes. The inhalation-exposure system can be used to study responses to indoor fungi associated with water damage and the importance of fungal species composition. PMID:26921421

  11. Modeling the Explicit Chemistry of Anthropogenic and Biogenic Organic Aerosols

    SciTech Connect

    Madronich, Sasha

    2015-12-09

    The atmospheric burden of Secondary Organic Aerosols (SOA) remains one of the most important yet uncertain aspects of the radiative forcing of climate. This grant focused on improving our quantitative understanding of SOA formation and evolution, by developing, applying, and improving a highly detailed model of atmospheric organic chemistry, the Generation of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model. Eleven (11) publications have resulted from this grant.

  12. Assessing the oxidative potential of isoprene-derived epoxides and secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Kramer, Amanda J.; Rattanavaraha, Weruka; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.; Lin, Ying-Hsuan

    2016-04-01

    Fine particulate matter (PM2.5) is known to contribute to adverse health effects, such as asthma, cardiopulmonary disease, and lung cancer. Secondary organic aerosol (SOA) is a major component of PM2.5 and can be enhanced by atmospheric oxidation of biogenic volatile organic compounds in the presence of anthropogenic pollutants, such as nitrogen oxides (NOx) and sulfur dioxide. However, whether biogenic SOA contributes to adverse health effects remains unclear. The objective of this study was to assess the potential of isoprene-derived epoxides and SOA for generating reactive oxygen species (ROS) in light of the recent recognition that atmospheric oxidation of isoprene in the presence of acidic sulfate aerosol is a major contributor to the global SOA burden. The dithiothreitol (DTT) assay was used to characterize the ROS generation by the isoprene-derived epoxides, trans-β-isoprene epoxydiol (trans-β-IEPOX) and methacrylic acid epoxide (MAE), and their hydrolysis products, the 2-methyltetrol diastereomers (2-MT), 2-methylglyceric acid (2-MG), their organosulfate derivatives, as well as an isoprene-derived hydroxyhydroperoxide (ISOPOOH). In addition, ROS generation potential was evaluated for total SOA produced from photooxidation of isoprene and methacrolein (MACR) as well as from the reactive uptake of trans-β-IEPOX and MAE onto acidified sulfate aerosol. The high-NOx regime, which yields 2-MG-, MAE- and MACR-derived SOA has a higher ROS generation potential than the low-NOx regime, which yields 2-MT, IEPOX- and isoprene-derived SOA. ISOPOOH has an ROS generation potential similar to 1,4-naphthoquinone (1,4-NQ), suggesting a significant contribution of aerosol-phase organic peroxides to PM oxidative potential. MAE- and MACR-derived SOA show equal or greater ROS generation potential than reported in studies on diesel exhaust PM, highlighting the importance of a comprehensive investigation of the toxicity of isoprene-derived SOA.

  13. Enhanced Deep Blue Aerosol Retrieval Algorithm: The Second Generation

    NASA Technical Reports Server (NTRS)

    Hsu, N. C.; Jeong, M.-J.; Bettenhausen, C.; Sayer, A. M.; Hansell, R.; Seftor, C. S.; Huang, J.; Tsay, S.-C.

    2013-01-01

    The aerosol products retrieved using the MODIS collection 5.1 Deep Blue algorithm have provided useful information about aerosol properties over bright-reflecting land surfaces, such as desert, semi-arid, and urban regions. However, many components of the C5.1 retrieval algorithm needed to be improved; for example, the use of a static surface database to estimate surface reflectances. This is particularly important over regions of mixed vegetated and non- vegetated surfaces, which may undergo strong seasonal changes in land cover. In order to address this issue, we develop a hybrid approach, which takes advantage of the combination of pre-calculated surface reflectance database and normalized difference vegetation index in determining the surface reflectance for aerosol retrievals. As a result, the spatial coverage of aerosol data generated by the enhanced Deep Blue algorithm has been extended from the arid and semi-arid regions to the entire land areas.

  14. SOA Formation from the Atmospheric Oxidation of 2-Methyl-3-Buten-2-ol and Its Implications for PM2.5

    EPA Science Inventory

    The formation of secondary organic aerosol (SOA) generated by irradiating 2-methyl-3-buten-2-01 (MBO) in the presence and/or absence of NOx H2O2, and/or SO2 was examined. Experiments were conducted. in smog chambers operated either in dyna....

  15. Aerosol Generation by Modern Flush Toilets

    PubMed Central

    Johnson, David; Lynch, Robert; Marshall, Charles; Mead, Kenneth; Hirst, Deborah

    2015-01-01

    A microbe-contaminated toilet will produce bioaerosols when flushed. We assessed toilet plume aerosol from high efficiency (HET), pressure-assisted high efficiency (PAT), and flushometer (FOM) toilets with similar bowl water and flush volumes. Total and droplet nuclei “bioaerosols” were assessed. Monodisperse 0.25–1.9-μm fluorescent microspheres served as microbe surrogates in separate trials in a mockup 5 m3 water closet (WC). Bowl water seeding was approximately 1012 particles/mL. Droplet nuclei were sampled onto 0.2-μm pore size mixed cellulose ester filters beginning 15 min after the flush using open-face cassettes mounted on the WC walls. Pre- and postflush bowl water concentrations were measured. Filter particle counts were analyzed via fluorescent microscopy. Bowl headspace droplet count size distributions were bimodal and similar for all toilet types and flush conditions, with 95% of droplets <2 μm diameter and >99% <5 μm. Up to 145,000 droplets were produced per flush, with the high-energy flushometer producing over three times as many as the lower energy PAT and over 12 times as many as the lowest energy HET despite similar flush volumes. The mean numbers of fluorescent droplet nuclei particles aerosolized and remaining airborne also increased with flush energy. Fluorescent droplet nuclei per flush decreased with increasing particle size. These findings suggest two concurrent aerosolization mechanisms—splashing for large droplets and bubble bursting for the fine droplets that form droplet nuclei. PMID:26635429

  16. Uncertainties in SOA Formation from the Photooxidation of α-pinene

    NASA Astrophysics Data System (ADS)

    McVay, R.; Zhang, X.; Aumont, B.; Valorso, R.; Camredon, M.; La, S.; Seinfeld, J.

    2015-12-01

    Explicit chemical models such as GECKO-A (the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) enable detailed modeling of gas-phase photooxidation and secondary organic aerosol (SOA) formation. Comparison between these explicit models and chamber experiments can provide insight into processes that are missing or unknown in these models. GECKO-A is used to model seven SOA formation experiments from α-pinene photooxidation conducted at varying seed particle concentrations with varying oxidation rates. We investigate various physical and chemical processes to evaluate the extent of agreement between the experiments and the model predictions. We examine the effect of vapor wall loss on SOA formation and how the importance of this effect changes at different oxidation rates. Proposed gas-phase autoxidation mechanisms are shown to significantly affect SOA predictions. The potential effects of particle-phase dimerization and condensed-phase photolysis are investigated. We demonstrate the extent to which SOA predictions in the α-pinene photooxidation system depend on uncertainties in the chemical mechanism.

  17. SOA Measurements vs. Models: a Status Report

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.; de Gouw, J. A.

    2009-12-01

    The advent of fast and more detailed organic aerosol (OA) and VOC measurements in the last decade has allowed clearer model-measurement comparisons for OA and secondary OA (SOA). Here we summarize the patterns emerging from studies to date.

  18. At least 8 studies have reported a large (x5-10) underestimation of SOA for polluted regions when using traditional models (those developed until ~2006) (Heald GRL05, Volkamer GRL06, Johnson ACP06, Kleinman ACP08, Matsui JGR09, Dzepina ACP09, Hodzic ACP09, Tsimpidi ACP09). This is especially obvious when models are evaluated with the ΔOA/ΔCO ratio.
  19. Close to pollution sources, discrepancies of an order-of-magnitude in SOA lead to smaller discrepancies (often x2-3) for total OA due to the presence of primary OA (de Gouw EST09). Such OA discrepancies have been repeatedly observed (e.g. Vutukuru JGR06, McKeen JGR07&09, Heald JGR07, Fast ACP09, Hodzic ACP09).
  20. The discrepancy is reduced when recently-updated yields for aromatics (Ng ACP07) and SOA from glyoxal (Volkamer GRL07) are used, and is eliminated when using SOA formation from S/IVOC (Robinson Sci07) although with an overprediction of SOA at long aging times (Dzepina ACP09; Hodzic ACP09b). It is not clear whether the urban discrepancy is removed for the right reasons.
  21. 4 evaluations of biogenic SOA formed in unpolluted regions find reasonable agreement between SOA from traditional models and field measurements (Tunved Sci06; Hodzic ACP09; Chen GRL09; Slowik ACPD09). One evaluation reports a significant underprediction (Capes ACP09), although the amount of precursor reacted was difficult to ascertain for that case. The difference with the systematic underprediction observed for anthropogenic SOA may be due to the lack of primary S/IVOC in biogenic emissions, or to other reasons (NOx, SO2, POA, etc.).
  22. Comparisons for biogenic SOA formed in polluted regions are more complex. Several studies have reported a lack of clear influence of biogenic VOCs in SOA

  23. Inkjet aerosol generator as monodisperse particle number standard

    NASA Astrophysics Data System (ADS)

    Iida, Kenjiro; Sakurai, Hiromu; Ehara, Kensei

    2013-05-01

    Inkjet technology can be applied to generate highly monodisperse aerosol particles in micrometer range at a precisely controlled rate. AIST has been developing an inkjet aerosol generator (AIST-IAG), and the device will soon become the secondary measurement standard for aerosol particle number concentration in 0.35 μm to 10 μm range. The AIST-IAG can generate both solid and liquid particles consisting of water-soluble ionic compounds. We first report the characteristics of the particle sizes of the generated particles. The full width half maximum of the particle size distribution is about 2 percent, and the particle diameter of the IAG particles was calibrated as a function of the particle mass within 0.6-10 μm range using polystyrene latex sphere as reference material. Then we report the capability of the AIST-IAG as the particle number standard. The particle generation efficiency ηIAG was defined as the number of aerosol particles exiting from the AIST-IAG divided by the rate of the droplet generation, and the values of ηIAG within 0.35-10 μm is essentially 100%, and the 95% confidence interval of the values is less than 1%. The result strongly supports that the AISTIAG can be used to calibrate the counting efficiency of the optical particle counters in submicrometer to micrometer range.

  24. Development of new parameterizations for SOA production from SVOC and IVOC oxidation

    NASA Astrophysics Data System (ADS)

    Lemaire, Vincent; Coll, Isabelle; Camredon, Marie; Aumont, Bernard; Siour, Guillaume

    2014-05-01

    Recent experimental studies have demonstrated the partially volatile pattern of primary organic aerosol (POA) that is actually associated with organic species of so-called intermediate volatility (IVOCs), and by semi-volatile (SVOCs) species. Indeed, 50% to 75% of the total emitted mass of POA may be present in the atmospheric gas phase in accordance with the thermodynamic properties of its components (Shrivastava et al., 2006). During the processing of the emission plume, this gaseous material will then undergo photochemical oxidation, enhancing the production of secondary organic aerosol (SOA) (Robinson et al., 2007; Hodzic et al., 2010; Lee-Taylor et al., 2011). Considering POA as non volatile in Chemistry Transport Models (CTMs) could thus lead to an underestimation of SOA and an overestimation of POA (Aksoyoglu et al., 2011) and bias the temporal formation of the organic aerosol (Kroll et al., 2007; Presto et al., 2012). However, very rare experimental data exist on the fate of these species and their aerosol yield, but all existing studies have shown a significant SOA production (Presto et al., 2009; Miracolo et al., 2010; Lambe et al., 2012). Our works aims at including and testing in the CHIMERE CTM new parameterizations of SOA formation from the oxidation of IVOCs and SVOCs, arising from explicit 0D-model experiments. Our approach is based on the works of Aumont et al., (2013) who used the GECKO-A tool (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) to generate the explicit chemistry and gas-particle partitioning of superior alkanes and their oxidation products. Using this explicit scheme, Aumont et al., (2013) indeed produced 0D simulations of the oxidation of given SVOCs and IVOCs under different initial conditions of organic aerosol mass. We first focused on the chemistry of n-hexadecane. From the 0D-experiments, we tested the influence of the number of first generation surrogate species and the number of generation taken

  25. Global transformation and fate of SOA: Implications of low-volatility SOA and gas-phase fragmentation reactions

    NASA Astrophysics Data System (ADS)

    Shrivastava, Manish; Easter, Richard C.; Liu, Xiaohong; Zelenyuk, Alla; Singh, Balwinder; Zhang, Kai; Ma, Po-Lun; Chand, Duli; Ghan, Steven; Jimenez, Jose L.; Zhang, Qi; Fast, Jerome; Rasch, Philip J.; Tiitta, Petri

    2015-05-01

    Secondary organic aerosols (SOA) are large contributors to fine-particle loadings and radiative forcing but are often represented crudely in global models. We have implemented three new detailed SOA treatments within the Community Atmosphere Model version 5 (CAM5) that allow us to compare the semivolatile versus nonvolatile SOA treatments (based on some of the latest experimental findings) and to investigate the effects of gas-phase fragmentation reactions. The new treatments also track SOA from biomass burning and biofuel, fossil fuel, and biogenic sources. For semivolatile SOA treatments, fragmentation reactions decrease the simulated annual global SOA burden from 7.5 Tg to 1.8 Tg. For the nonvolatile SOA treatment with fragmentation, the burden is 3.1 Tg. Larger differences between nonvolatile and semivolatile SOA (up to a factor of 5) exist in areas of continental outflow over the oceans. According to comparisons with observations from global surface Aerosol Mass Spectrometer measurements and the U.S. Interagency Monitoring of Protected Visual Environments (IMPROVE) network measurements, the FragNVSOA treatment, which treats SOA as nonvolatile and includes gas-phase fragmentation reactions, agrees best at rural locations. Urban SOA is underpredicted, but this may be due to the coarse model resolution. All three revised treatments show much better agreement with aircraft measurements of organic aerosols (OA) over the North American Arctic and sub-Arctic in spring and summer, compared to the standard CAM5 formulation. This is mainly due to the oxidation of SOA precursor gases from biomass burning, not included in standard CAM5, and long-range transport of biomass burning OA at high altitudes. The revised model configurations that include fragmentation (both semivolatile and nonvolatile SOA) show much better agreement with MODerate resolution Imaging Spectrometers (MODIS) aerosol optical depth data over regions dominated by biomass burning during the summer

  1. A Cough Aerosol Simulator for the Study of Disease Transmission by Human Cough-Generated Aerosols

    PubMed Central

    Lindsley, William G.; Reynolds, Jeffrey S.; Szalajda, Jonathan V.; Noti, John D.; Beezhold, Donald H.

    2015-01-01

    Aerosol particles expelled during human coughs are a potential pathway for infectious disease transmission. However, the importance of airborne transmission is unclear for many diseases. To better understand the role of cough aerosol particles in the spread of disease and the efficacy of different types of protective measures, we constructed a cough aerosol simulator that produces a humanlike cough in a controlled environment. The simulated cough has a 4.2 l volume and is based on coughs recorded from influenza patients. In one configuration, the simulator produces a cough aerosol containing particles from 0.1 to 100 µm in diameter with a volume median diameter (VMD) of 8.5 µm and a geometric standard deviation (GSD) of 2.9. In a second configuration, the cough aerosol has a size range of 0.1–30 µm, a VMD of 3.4 µm, and a GSD of 2.3. The total aerosol volume expelled during each cough is 68 µl. By generating a controlled and reproducible artificial cough, the simulator allows us to test different ventilation, disinfection, and personal protection scenarios. The system can be used with live pathogens, including influenza virus, which allows isolation precautions used in the healthcare field to be tested without risk of exposure for workers or patients. The information gained from tests with the simulator will help to better understand the transmission of infectious diseases, develop improved techniques for infection control, and improve safety for healthcare workers and patients. PMID:26500387

  2. Generation and characterization of large-particle aerosols using a center flow tangential aerosol generator with a nonhuman-primate, head-only aerosol chamber

    PubMed Central

    Bohannon, J. Kyle; Lackemeyer, Matthew G.; Kuhn, Jens H.; Wada, Jiro; Bollinger, Laura; Jahrling, Peter B.; Johnson, Reed F.

    2016-01-01

    Aerosol droplets or particles produced from infected respiratory secretions have the potential to infect another host through inhalation. These respiratory particles can be polydisperse and range from 0.05–500 μm in diameter. Animal models of infection are generally established to facilitate the potential licensure of candidate prophylactics and/or therapeutics. Consequently, aerosol-based animal infection models are needed to properly study and counter airborne infections. Ideally, experimental aerosol exposure should reliably result in animal disease that faithfully reproduces the modelled human disease. Few studies have been performed to explore the relationship between exposure particle size and induced disease course for infectious aerosol particles. The center flow tangential aerosol generator (CenTAG™) produces large-particle aerosols capable of safely delivering a variety of infectious aerosols to nonhuman primates within a Class III Biological Safety Cabinet (BSC) for establishment or refinement of nonhuman primate infectious disease models. Here we report the adaptation of this technology to the Animal Biosafety Level 4 (ABSL-4) environment for the future study of high-consequence viral pathogens and the characterization of CenTAG™-created sham (no animal, no virus) aerosols using a variety of viral growth media and media supplements. PMID:25970823

  3. Generation and characterization of large-particle aerosols using a center flow tangential aerosol generator with a non-human-primate, head-only aerosol chamber.

    PubMed

    Bohannon, J Kyle; Lackemeyer, Matthew G; Kuhn, Jens H; Wada, Jiro; Bollinger, Laura; Jahrling, Peter B; Johnson, Reed F

    2015-01-01

    Aerosol droplets or particles produced from infected respiratory secretions have the potential to infect another host through inhalation. These respiratory particles can be polydisperse and range from 0.05 to 500 µm in diameter. Animal models of infection are generally established to facilitate the potential licensure of candidate prophylactics and/or therapeutics. Consequently, aerosol-based animal infection models are needed to properly study and counter airborne infections. Ideally, experimental aerosol exposure should reliably result in animal disease that faithfully reproduces the modeled human disease. Few studies have been performed to explore the relationship between exposure particle size and induced disease course for infectious aerosol particles. The center flow tangential aerosol generator (CenTAG™) produces large-particle aerosols capable of safely delivering a variety of infectious aerosols to non-human primates (NHPs) within a Class III Biological Safety Cabinet (BSC) for establishment or refinement of NHP infectious disease models. Here, we report the adaptation of this technology to the Animal Biosafety Level 4 (ABSL-4) environment for the future study of high-consequence viral pathogens and the characterization of CenTAG™-created sham (no animal, no virus) aerosols using a variety of viral growth media and media supplements. PMID:25970823

  4. The remarkable effect of FeSO4 seed aerosols on secondary organic aerosol formation from photooxidation of α-pinene/NOx and toluene/NOx

    NASA Astrophysics Data System (ADS)

    Chu, Biwu; Hao, Jiming; Takekawa, Hideto; Li, Junhua; Wang, Kun; Jiang, Jingkun

    2012-08-01

    To investigate the effects of Fe(II) and Fe(III) ions on secondary organic aerosol (SOA) formation, we conducted a series of photooxidation experiments with α-pinene and toluene in the presence of nitric oxides (NOx) with/without FeSO4 or Fe2(SO4)3 seed aerosols. The FeSO4 seed aerosols suppressed SOA formation, while Fe2(SO4)3 seed aerosols did not display a noticeable effect on SOA formation. We did not observe effects of FeSO4 and Fe2(SO4)3 seed aerosols on gas phase compounds, including ozone, NOx, and hydrocarbons (HCs). The negative effect of Fe(II)-containing seed aerosols on SOA formation due to the reduction of condensable compounds (CCs) generated from hydrocarbon oxidation is discussed. The mean molecular weight of CCs reduced by Fe(II) is tentatively estimated to be larger than 300, indicating a possibility that many of the CCs reduced by Fe(II) are oligomers. Reduction of oligomer precursors may interrupt the oligomerization of other aldehyde products. If Fe(II) regeneration from photoreduction of Fe(III) is considered, the estimated mean molecular weight of the CCs reduced would be smaller. However, the negligible effect of Fe(III)-containing seed aerosols on SOA formation indicates that Fe(III) photoreduction is negligible in our experiments.

  5. SOA YIELDS AND ORGANIC PRODUCT DISTRIBUTION FROM NATURAL HYDROCARBON/NOX IRRADIATIONS

    EPA Science Inventory

    Secondary organic aerosol (SOA) typically comprises one-quarter to one-third of the ambient aerosol mass in summertime urban atmospheres. In tropospheric environments, the main precursors of SOA come from aromatic and natural hydrocarbons. Recent work by various investigators...

  6. Indoor transient SOA formation from ozone + α-pinene reactions: Impacts of air exchange and initial product concentrations, and comparison to limonene ozonolysis

    NASA Astrophysics Data System (ADS)

    Youssefi, Somayeh; Waring, Michael S.

    2015-07-01

    The ozonolysis of reactive organic gases (ROG), e.g. terpenes, generates secondary organic aerosol (SOA) indoors. The SOA formation strength of such reactions is parameterized by the aerosol mass fraction (AMF), a.k.a. SOA yield, which is the mass ratio of generated SOA to oxidized ROG. AMFs vary in magnitude both among and for individual ROGs. Here, we quantified dynamic SOA formation from the ozonolysis of α-pinene with 'transient AMFs,' which describe SOA formation due to pulse emission of a ROG in an indoor space with air exchange, as is common when consumer products are intermittently used in ventilated buildings. We performed 19 experiments at low, moderate, and high (0.30, 0.52, and 0.94 h-1, respectively) air exchange rates (AER) at varying concentrations of initial reactants. Transient AMFs as a function of peak SOA concentrations ranged from 0.071 to 0.25, and they tended to increase as the AER and product of the initial reactant concentrations increased. Compared to our similar research on limonene ozonolysis (Youssefi and Waring, 2014), for which formation strength was driven by secondary ozone reactions, the AER impact for α-pinene was opposite in direction and weaker, while the initial reactant product impact was in the same direction but stronger for α-pinene than for limonene. Linear fits of AMFs for α-pinene ozonolysis as a function of the AER and initial reactant concentrations are provided so that future indoor models can predict SOA formation strength.

  7. Ultraviolet Absorption by Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Madronich, S.; Lee-Taylor, J. M.; Hodzic, A.; Aumont, B.

    2014-12-01

    Secondary organic aerosols (SOA) are typically formed in the atmosphere by the condensation of a myriad of intermediates from the photo-oxidation of volatile organic compounds (VOCs). Many of these partly oxidized molecules have functional groups (chromophores) that absorb at the ultraviolet (UV) wavelengths available in the troposphere (λ ≳ 290 nm). We used the explicit chemical model GECKO-A (Generator of Explicit Chemistry and Kinetics for Organics in the Atmosphere) to estimate UV absorption cross sections for the gaseous and particulate components of SOA from different precursors (biogenic and anthropogenic) and formed in different environments (low and high NOx, day and night). Model predictions are evaluated with laboratory and field measurements of SOA UV optical properties (esp. mass absorption coefficients and single scattering albedo), and implications are presented for surface UV radiation trends, urban actinic flux modification, and SOA lifetimes.

  8. Secondary Organic Aerosol Formation from 2-Methyl-3-Buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

    SciTech Connect

    Zhang, Haofei; Zhang, Zhenfa; Cui, Tianqu; Lin, Ying-Hsuan; Bhathela, Neil A.; Ortega, John; Worton, David; Goldstein, Allen H.; Guenther, Alex B.; Jimenez, Jose L.; Gold, Avram; Surratt, Jason D.

    2014-04-08

    Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to isoprene, MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide) was synthesized and tentatively proposed here to explain this enhancement. In the present study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosols. Major SOA constituents, 2,3-dihydroxyisopentanol (DHIP) and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and in ambient fine aerosols collected from the BEACHON-RoMBAS field campaign during summer 2011, where MBO emissions are substantial. Our results support epoxides as potential products of MBO photooxidation leading to formation of atmospheric SOA and suggest that reactive uptake of epoxides may generally explain acid enhancement of SOA observed from other biogenic hydrocarbons.

  9. Impacts of Sulfate Seed Acidity and Water Content on Isoprene Secondary Organic Aerosol Formation.

    PubMed

    Wong, Jenny P S; Lee, Alex K Y; Abbatt, Jonathan P D

    2015-11-17

    The effects of particle-phase water and the acidity of pre-existing sulfate seed particles on the formation of isoprene secondary organic aerosol (SOA) was investigated. SOA was generated from the photo-oxidation of isoprene in a flow tube reactor at 70% relative humidity (RH) and room temperature in the presence of three different sulfate seeds (effloresced and deliquesced ammonium sulfate and ammonium bisulfate) under low NOx conditions. High OH exposure conditions lead to little isoprene epoxydiol (IEPOX) SOA being generated. The primary result is that particle-phase water had the largest effect on the amount of SOA formed, with 60% more SOA formation occurring with deliquesced ammonium sulfate seeds as compared to that on effloresced ones. The additional organic material was highly oxidized. Although the amount of SOA formed did not exhibit a dependence on the range of seed particle acidity examined, perhaps because of the low amount of IEPOX SOA, the levels of high-molecular-weight material increased with acidity. While the uptake of organics was partially reversible under drying, the results nevertheless indicate that particle-phase water enhanced the amount of organic aerosol material formed and that the RH cycling of sulfate particles may mediate the extent of isoprene SOA formation in the atmosphere. PMID:26460477

  10. Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols

    SciTech Connect

    Lee, Hyun Ji; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A.

    2013-05-10

    Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of SOA generated from two monoterpenes, limonene and a-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ~100 ppb ammonia vapor in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (~0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for excitation = 420+- 50 nm and emission = 475 +- 38 nm. The window of the strongest fluorescence shifted to excitation = 320 +- 25 nm and emission = 425 +- 38 nm for the a-pinene-derived SOA. Both regions overlap with the excitation-emission matrix (EEM) spectra of some of the fluorophores found in primary biological aerosols. Our study suggests that, despite the low quantum yield, the aged SOA particles should have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

  11. An aerosol generator for the resuspension of cotton dust.

    PubMed

    Weyel, D A; Ellakkani, M; Alarie, Y; Karol, M

    1984-12-01

    An aerosol generator, the Pitt 3 model, was designed, fabricated, and characterized for the resuspension of inhalable particles from bulk cotton dust. The generator was constructed around a loudspeaker whose energy is transferred into an air column through latex rubber dams. This action tumbles the bulk dust, and small particles are loosened which can then be carried out of the column with the air passing through it. Thirty to forty grams of bulk cotton dust produced a stable aerosol concentration for at least 90 min. The maximum output of about 100 mg/m3 can be reduced to lower concentrations by adding dilution air. In one application, the generator produced a stable aerosol cloud in the range of 2 to 30 mg/m3 with a mass median aerodynamic diameter (MMAD) of about 3 microns and a geometric standard deviation (sigma g) of about 1.5. In another application the concentration in an animal exposure chamber was kept at 20.8 mg/m3 with an MMAD = 2.5 microns and a sigma g = 1.8 for over 6 months. The Pitt 3 generator proved to be trouble-free and produced large amounts of inhalable particles from bulk cotton dust. The generator was also used to generate dust clouds from silica powder, fly ash, and cellulose dust. The only requirement for successful resuspension of any dust with this generator is the presence of small particles in the bulk feed dust. PMID:6506079

  12. Secondary Organic Aerosol Formation from Glyoxal: Effects of Seed Aerosol on Particle Composition

    NASA Astrophysics Data System (ADS)

    Slowik, Jay; Waxman, Eleanor; Coburn, Sean; Klein, Felix; Koenig, Theodore; Krapf, Manuel; Kumar, Nivedita; Wang, Siyuan; Baltensperger, Urs; Dommen, Josef; Prévôt, Andre; Volkamer, Rainer

    2014-05-01

    Conventional models of secondary organic aerosol (SOA) production neglect aqueous-phase processing mechanisms, thereby excluding potentially important SOA formation pathways. These missing pathways may be an important factor in the inability of current models to fully explain SOA yields and oxidation states. Molecules identified as important precursors to SOA generated through aqueous-phase include glyoxal, which is an oxidation product of numerous organic gases. Glyoxal SOA formation experiments were conducted in the PSI smog chamber as a function of seed composition, relative humidity (RH, 60 to 85%), and the presence/absence of gaseous ammonia, affecting particle acidity. In a typical experiment, the chamber was filled with the selected seed aerosol (NaCl, (NH4)2SO4, NaNO3, or K2SO4), after which glyoxal was generated by the brief (i.e. a few minutes) exposure of acetylene to UV light. The experiment was then allowed to proceed undisturbed for several hours. Each experiment consisted of several UV exposures, followed by a dilution phase at constant RH to investigate the gas/particle partitioning behavior of the generated SOA. Gas-phase glyoxal was monitored by an LED-CE-DOAS system, while the particle composition was measured using online aerosol mass spectrometry (Aerodyne HR-ToF-AMS) and offline analysis of collected filter samples. SOA composition was observed to depend strongly on seed type, with increased imidazole formation evident during experiments with (NH4)2SO¬4 and K2SO4 seeds relative to those with NaCl and NaNO3. Additionally, experiments conducted in the presence of ammonia showed large enhancements in both imidazole content and total SOA yield. Analysis of mass spectral markers indicates reversible uptake of glyoxal but irreversible particle-phase production of the imidazole-containing SOA. Positive matrix factorization (PMF) using the Multilinear Engine (ME-2) was applied to the AMS mass spectral time series to quantify factors related to

  13. Aerosol generation by blower motors as a bias in assessing aerosol penetration into cabin filtration systems.

    PubMed

    Heitbrink, William A; Collingwood, Scott

    2005-01-01

    In cabin filtration systems, blower motors pressurize a vehicle cabin with clean filtered air and recirculate air through an air-conditioning evaporator coil and a heater core. The exposure reduction offered by these cabins is evaluated by optical particle counters that measure size-dependent aerosol concentration inside and outside the cabin. The ratio of the inside-to-outside concentration is termed penetration. Blower motors use stationary carbon brushes to transmit an electrical current through a rotating armature that abrades the carbon brushes. This creates airborne dust that may affect experimental evaluations of aerosol penetration. To evaluate the magnitude of these dust emissions, blower motors were placed in a test chamber and operated at 12 and 13.5 volts DC. A vacuum cleaner drew 76 m3/hour (45 cfm) of air through HEPA filters, the test chamber, and through a 5 cm diameter pipe. An optical particle counter drew air through an isokinetic sampling probe and measured the size-dependent particle concentrations from 0.3 to 15 microm. The concentration of blower motor aerosol was between 2 x 10(5) and 1.8 x 10(6) particles/m3. Aerosol penetration into three stationary vehicles, two pesticide application vehicles and one tractor were measured at two conditions: low concentration (outside in the winter) and high concentration (inside repair shops and burning incense sticks used as a supplemental aerosol source). For particles smaller than 1 microm, the in-cabin concentrations can be explained by the blower motor emissions. For particles larger than 1 microm, other aerosol sources, such as resuspended dirt, are present. Aerosol generated by the operation of the blower motor and by other sources can bias the exposure reduction measured by optical particle counters. PMID:15764523

  14. A method for generating pulmonary neutrophilia using aerosolized lipopolysaccharide.

    PubMed

    Roos, Abraham B; Berg, Tove; Ahlgren, Kerstin M; Grunewald, Johan; Nord, Magnus

    2014-01-01

    Acute lung injury (ALI) is a severe disease characterized by alveolar neutrophilia, with limited treatment options and high mortality. Experimental models of ALI are key in enhancing our understanding of disease pathogenesis. Lipopolysaccharide (LPS) derived from gram positive bacteria induces neutrophilic inflammation in the airways and lung parenchyma of mice. Efficient pulmonary delivery of compounds such as LPS is, however, difficult to achieve. In the approach described here, pulmonary delivery in mice is achieved by challenge to aerosolized Pseudomonas aeruginosa LPS. Dissolved LPS was aerosolized by a nebulizer connected to compressed air. Mice were exposed to a continuous flow of LPS aerosol in a Plexiglas box for 10 min, followed by 2 min conditioning after the aerosol was discontinued. Tracheal intubation and subsequent bronchoalveolar lavage, followed by formalin perfusion was next performed, which allows for characterization of the sterile pulmonary inflammation. Aerosolized LPS generates a pulmonary inflammation characterized by alveolar neutrophilia, detected in bronchoalveolar lavage and by histological assessment. This technique can be set up at a small cost with few appliances, and requires minimal training and expertise. The exposure system can thus be routinely performed at any laboratory, with the potential to enhance our understanding of lung pathology. PMID:25548888

  15. Unspeciated Organic Emissions From Combustion Sources And Their Influence On The Secondary Organic Aerosol Budget In The United States

    NASA Astrophysics Data System (ADS)

    Jathar, S.; Gordon, T.; Hennigan, C. J.; Pye, H. O.; Donahue, N. M.; Adams, P. J.; Robinson, A. L.

    2012-12-01

    Combustion sources are a major source of organic emissions and therefore a potentially important source for secondary organic aerosol (SOA) formation in the atmosphere. Although speciated organic emissions from combustion sources are considered in models to form SOA, a large fraction of the organics are unspeciated. In this work, we analyze data from numerous smog chamber experiments, which photo-oxidized dilute emissions from different combustion sources (on-road gasoline vehicles, aircraft, on-road diesel vehicles, wood burning and open biomass burning), to determine the contribution that unspeciated emissions make to SOA formation. An SOA model based on speciated organics is able to explain, on average, 8-31% of the SOA measured in the experiments. We hypothesize that the remainder results from the gas-phase oxidation of unspeciated emissions, which account on average for 25-75% of the non-methane organic gas (NMOG) emissions. Using the SOA data, we develop, for the first time, source-specific parameterizations to model SOA from unspeciated emissions; all sources seem to have median SOA yields similar to large n-alkanes (C12+). To assess the influence of unspeciated emissions on SOA formation regionally, we use the parameterization to predict SOA production in the United States. Using emissions data collected during the smog chamber experiments and data available in literature, we build a gross inventory for unspeciated emissions in the United States. We discover that unspeciated organics might be included in the current generation of SOA models but misallocated in terms of its SOA potential. The top six combustion sources (on- and off-road gasoline, on- and off-road diesel, open biomass and wood burning) emit 2.61 Tg yr-1 of unspeciated emissions (20% of US anthropogenic VOC emissions from combustion sources) and are estimated to form a minimum of 0.68 Tg yr-1 of SOA; the estimate is a third of the biogenic SOA produced in the US. We predict that accounting for

  16. Assessment of biogenic secondary organic aerosol in the Himalayas

    NASA Astrophysics Data System (ADS)

    Stone, B. A.; Nguyen, T.; Pradhan, B.; Dangol, P.

    2012-12-01

    Biogenic contributions to secondary organic aerosol (SOA) in the Southeast Asian regional haze were assessed by measurement of particle-phase isoprene, monoterpene, and sesquiterpene photooxidation products in fine particles (PM2.5) at Godavari, Nepal, located in the Himalayas at an elevation of 1600 meters. Organic species were measured in solvent-extracts of filter samples using gas chromatography mass spectrometry (GCMS) and chemical derivatization. Molecular markers for primary aerosol sources—including motor vehicles, biomass burning, and detritus—and SOA tracers were measured. High concentrations of isoprene derivatives, particularly in the late summer months, point to biogenic SOA as a significant source of organic carbon in the Himalayan region. First-generation SOA products from alpha-pinene were detected in all samples, whereas multi-generation products were not, suggesting that monoterpenes were at an early stage of oxidation at Godavari. Biogenic SOA contributions to PM2.5 organic carbon in the 2005 monsoon and post-monsoon season ranged from 2-19% for isoprene, 1-5% for monoterpenes, and 1-4% for sesquiterpenes. Primary and secondary biogenic sources combined accounted for approximately half of observed organic aerosol, suggesting additional aerosol sources and/or precursors are significant in this region.

  17. Can Sesquiterpene SOA be good CCN?

    NASA Astrophysics Data System (ADS)

    Asa-Awuku, A. A.; Tang, X.

    2011-12-01

    Secondary organic aerosol (SOA) particles are formed via gaseous reactions in the atmosphere and have the potential to impact climate and the hydrological cycle through their ability to act as cloud condensation nuclei (CCN). Beta-caryophyllene is a biogenic sesquiterpene emission and is known to react quickly and form low volatility products in the particulate phase. Previous work shows that the hygroscopic material in Beta-caryophyllene SOA may be semivolatile, and the less volatile component less hygroscopic. The less volatile component has been shown to impact the droplet growth kinetics. In this study, we revisit experiments at the University of California, Riverside Bourns College of Engineering- Center for Environmental Research and Technology (CE-CERT) dual 90 m3 indoor smog chamber, in which much lower concentration can be achieved. A suite of gas phase and particle phase instrumentation characterizes the thermodynamic aerosol properties and CCN activity. Hygroscopicity, volatility, particle size, number, mass, and composition and gas phase concentration are measured with, Gas chromatography-mass spectrometry (GC-MS), Scanning Mobility Particle Sizer (SMPS), tandem differential mobility analyzer (TDMA), and High Resolution Aerosol Mass Spectrometry (HR-AMS). In addition to chemical measurements aerosol physical properties are also reported. Experiments are conducted at different conditions to characterize the effect of hydroxyl radical, light, addition of another hydrocarbon precursor (isoprene) on SOA formation and characteristics.

  18. CCN activity and volatility of β-caryophyllene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Frosch, M.; Bilde, M.; Nenes, A.; Praplan, A. P.; Jurányi, Z.; Dommen, J.; Gysel, M.; Weingartner, E.; Baltensperger, U.

    2012-08-01

    In a series of smog chamber experiments, the Cloud Condensation Nuclei (CCN) activity of Secondary Organic Aerosol (SOA) generated from ozonolysis of β-caryophyllene was characterized by determining the CCN derived hygroscopicity parameter, κCCN, from experimental data. Two types of CCN counters, operating at different temperatures, were used. The effect of semi-volatile organic compounds on the CCN activity of SOA was studied using a thermodenuder. Overall, SOA was only slightly CCN active (with κCCN in the range 0.001-0.16), and in dark experiments with no OH scavenger present, κCCN decreased when particles were sent through the thermodenuder (with a temperature up to 50 °C). SOA was generated under different experimental conditions: in some experiments, an OH scavenger (2-butanol) was added. SOA from these experiments was less CCN active than SOA produced in experiments without an OH scavenger (i.e. where OH was produced during ozonolysis). In other experiments, lights were turned on, either without or with the addition of HONO (OH source). This led to the formation of more CCN active SOA. SOA was aged up to 30 h through exposure to ozone and (in experiments with no OH scavenger present) to OH. In all experiments, the derived κCCN consistently increased with time after initial injection of β-caryophyllene, showing that chemical ageing increases the CCN activity of β-caryophyllene SOA. κCCN was also observed to depend on supersaturation, which was explained either as an evaporation artifact from semi-volatile SOA (only observed in experiments lacking light exposure) or, alternatively, by effects related to chemical composition depending on dry particle size. Using the method of Threshold Droplet Growth Analysis it was also concluded that the activation kinetics of the SOA do not differ significantly from calibration ammonium sulphate aerosol.

  19. CCN activity and volatility of β-caryophyllene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Frosch, M.; Bilde, M.; Nenes, A.; Praplan, A. P.; Jurányi, Z.; Dommen, J.; Gysel, M.; Weingartner, E.; Baltensperger, U.

    2013-02-01

    In a series of smog chamber experiments, the cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) generated from ozonolysis of β-caryophyllene was characterized by determining the CCN derived hygroscopicity parameter, κCCN, from experimental data. Two types of CCN counters, operating at different temperatures, were used. The effect of semi-volatile organic compounds on the CCN activity of SOA was studied using a thermodenuder. Overall, SOA was only slightly CCN active (with κCCN in the range 0.001-0.16), and in dark experiments with no OH scavenger present, κCCN decreased when particles were sent through the thermodenuder (with a temperature up to 50 °C). SOA was generated under different experimental conditions: In some experiments, an OH scavenger (2-butanol) was added. SOA from these experiments was less CCN active than SOA produced in experiments without an OH scavenger (i.e. where OH was produced during ozonolysis). In other experiments, lights were turned on, either without or with the addition of HONO (OH source). This led to the formation of more CCN active SOA. SOA was aged up to 30 h through exposure to ozone and (in experiments with no OH scavenger present) to OH. In all experiments, the derived κCCN consistently increased with time after initial injection of β-caryophyllene, showing that chemical ageing increases the CCN activity of β-caryophyllene SOA. κCCN was also observed to depend on supersaturation, which was explained either as an evaporation artifact from semi-volatile SOA (only observed in experiments lacking light exposure) or, alternatively, by effects related to chemical composition depending on dry particle size. Using the method of Threshold Droplet Growth Analysis it was also concluded that the activation kinetics of the SOA do not differ significantly from calibration ammonium sulphate aerosol for particles aged for several hours.

  20. Formation of Organic Tracers for Isoprene SOA under Acidic Conditions

    EPA Science Inventory

    The chemical compositions of a series of secondary organic aerosol (SOA) samples, formed by irradiating mixtures of isoprene and NO in a smog chamber in the absence or presence of acidic aerosols, were analyzed using derivatization-based GC-MS methods. In addition to the known is...

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  2. Exploration of the seasonal variation of organic aerosol composition using an explicit modeling approach

    NASA Astrophysics Data System (ADS)

    Ouzebidour, Farida; Camredon, Marie; Stéphanie La, Yuyi; Madronich, Sasha; Taylor, Julia Lee; Hodzic, Alma; Beekmann, Matthias; Siour, Guillaume; Aumont, Bernard

    2014-05-01

    Organic compounds account for a major fraction of fine aerosols in the atmosphere. This organic fraction is dominated by secondary organic aerosol (SOA). Processes leading to SOA formation are however still uncertain and SOA composition is far from being fully characterized. The goals of this study are to evaluate our current understanding of SOA formation and explore its composition. For this purpose, a box-model that describes explicitly processes involved in SOA formation has been developed. This model includes the emission of 183 gaseous and particulate organic compounds. The oxidation of these emitted organic compounds is described using the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A). Gas/particle partitioning has been implemented considering an ideal homogeneous condensed phase. The generated chemical scheme contains 500,000 species and the gas/particle partitioning is performed for 90,000 of them. Simulations have been performed for summer and winter scenarios representative of continental and urban conditions. NOx and ozone simulated concentrations reproduce the expected winter and summer diurnal evolutions. The predicted organic aerosol composition is a mixture of primary and secondary organic aerosols during the winter and is largely dominated by SOA during the summer.

  3. EVIDENCE FOR ORGANOSULFATES IN SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    Recent work has shown that particle-phase reactions contribute to the formation of secondary organic aerosol (SOA), with enhancements of SOA yields in the presence of acidic seed aerosol. In this study, the chemical composition of SOA from the photooxidations of α-pinene and isop...

  4. Illuminating the Atmospheric Oxidation Mechanisms, SOA Formation Pathways and Radical Yields of the Monoterpene Myrcene

    NASA Astrophysics Data System (ADS)

    Wyche, Kevin; Carr, Timo; Monks, Paul; Ellis, Andrew; Alfarra, Rami; McFiggans, Gordon; Hamilton, Jacqueline; Ward, Martyn; Boss, William; Camredon, Marie

    2010-05-01

    Biogenic Volatile Organic Compounds (BVOCs) are ubiquitous in the global troposphere, being emitted primarily from terrestrial plant life in significant quantities. Indeed, it is estimated that the total annual emission rate of all (non-methane) BVOCs is roughly ten times that of all anthropogenic volatile organic compounds (Guenther et al., 1995). With the exception of methane, the most dominant species of BVOC, in terms of emission strength, reactivity and their impact upon the atmosphere, are terpenes. Terpenes are a subdivision of BVOCs, composed primarily of hemiterpenes (C5), monoterpenes (C10), sesquiterpenes (C15) and diterpenes (C20). Under troposheric conditions terpenes react via complex and extensive gas phase oxidation pathways, have strong photochemical ozone creation potentials, constitute a significant radical source and are known to generate secondary organic aerosol (SOA) in high yields. At present there exists a certain lack of understanding regarding the oxidation mechanisms of certain terpenes and their role in SOA and radical formation. Consequently, as part of the NERC funded Aerosol Coupling in the Earth's System (ACES) and Total RAdical Production from the OZonolysis of alkenes (TRAPOZ) projects, a comprehensive series of simulation chamber experiments were conducted at the University of Manchester aerosol chamber facility, and at the EUropean PHOto REactor (EUPHORE) in order to investigate the gas phase degradation mechanisms, and SOA and radical formation potentials of a number of atmospherically significant terpenes. Both simulation chambers were highly instrumented during all experiments such that detailed and concomitant gas and aerosol phase measurements were made across a range of conditions. The work presented here describes the findings obtained from both photooxidation and ozonolysis experiments involving the common, but less well studied, aliphatic monoterpene, myrcene. The data presented include NOx and ozone measurements and

  5. Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: linking laboratory and field studies

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Fuller, Stephen; Aalto, Juho; Healy, Robert; Alfara, Rami; Ruuskanen, Taina; Wenger, John; McFiggans, Gordon; Kulmala, Markku; Kalberer, Markus

    2013-04-01

    Biogenic volatile organic compounds (BVOCs) play an important role in atmospheric chemistry and give rise to secondary organic aerosols (SOA), which have effects on climate and human health. Laboratory chamber experiments have been performed during several decades in an attempt to mimic atmospheric SOA formation. However, it is still unclear how close the aerosol particles generated in laboratory experiments resemble atmospheric SOA with respect to their detailed chemical composition. To date, most laboratory experiments have been performed using a single organic precursor (e.g., alpha- or beta-pinene, isoprene) while in the atmosphere a wide range of precursors contribute to SOA, which results most likely in a more complex SOA composition compared to the one-precursor laboratory systems. The objective of this work is to compare laboratory generated SOA from oxidation of BVOCs mixtures and remote ambient samples using ultrahigh-resolution mass spectrometry (UHR-MS) that allows detection of hundreds of individual SOA constituents. We examined aerosol samples from a boreal forest site, Hyytiälä, Finland and determined that a dominant fraction of the detected compounds are reaction products of a multi-component mixture of BVOCs. In the subsequent smog chamber experiments, SOA was generated from the ozonolysis and OH initiated reactions with BVOC mixtures containing species (alpha- and beta-pinene, delta-3-carene, and isoprene) that are most abundant in Hyytiälä's environment. The laboratory experiments were performed at conditions (e.g., RH, aerosol seed, and VOC ratios) that would resemble those at the boreal sampling site during the summer period. The elemental composition of the complex mixtures from laboratory generated SOA samples were compared with field samples using statistical data analysis methods.

  6. Influence of Aerosol Acidity on the Chemical Composition of Secondary Organic Aerosol from β-caryophyllene

    NASA Astrophysics Data System (ADS)

    Chan, M.; Surratt, J. D.; Chan, A. W.; Schlling, K.; Offenberg, J. H.; Lewandowski, M.; Edney, E.; Kleindienst, T. E.; Jaoui, M.; Edgerton, E. S.; Tanner, R. L.; Shaw, S. L.; Zheng, M.; Knipping, E. M.; Seinfeld, J.

    2011-12-01

    The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI- TOFMS). A number of first- , second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

  7. Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene

    NASA Astrophysics Data System (ADS)

    Chan, M. N.; Surratt, J. D.; Chan, A. W. H.; Schilling, K.; Offenberg, J. H.; Lewandowski, M.; Edney, E. O.; Kleindienst, T. E.; Jaoui, M.; Edgerton, E. S.; Tanner, R. L.; Shaw, S. L.; Zheng, M.; Knipping, E. M.; Seinfeld, J. H.

    2011-02-01

    The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

  8. Influence of aerosol acidity on the chemical composition of Secondary Organic Aerosol from β-caryophyllene

    NASA Astrophysics Data System (ADS)

    Chan, M. N.; Surratt, J. D.; Chan, A. W. H.; Schilling, K.; Offenberg, J. H.; Lewandowski, M.; Edney, E. O.; Kleindienst, T. E.; Jaoui, M.; Edgerton, E. S.; Tanner, R. L.; Shaw, S. L.; Zheng, M.; Knipping, E. M.; Seinfeld, J. H.

    2010-11-01

    The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increase of acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are identified as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

  9. Secondary organic aerosol formation from m-xylene photooxidation: The role of the phenolic product

    NASA Astrophysics Data System (ADS)

    Nakao, S.; Qi, L.; Clark, C.; Sato, K.; Tang, P.; Cocker, D.

    2009-12-01

    Aromatic hydrocarbons comprise a significant fraction of volatile organic compounds in the urban atmosphere and their importance as precursors to secondary organic aerosols (SOA) has been widely recognized. However, SOA formation from aromatics is one of the least understood processes among all the classes of volatile organic compounds (VOCs) due to its complex multi-generation reactions. Phenolic compounds have been identified as one of the significant products from OH-initiated reaction of aromatic hydrocarbons and are suggested to have a very high potential of SOA formation (e.g., cresol isomers having SOA yield 9~42%, Henry et al., Atmos. Environ., 2008). We examined the effect of extent of oxidation of m-xylene on chemical composition and physical properties using m-xylene and xylenol as reactants in environmental chamber experiments. Chemical composition of SOA was investigated by Liquid Chromatography / Time of Flight Mass Spectrometer (LC/ToF-MS), and Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). Physical properties of SOA such as density, volatility, and hygroscopicity were investigated by Aerosol Particle Mass Analyzer - Scanning Mobility Particle Sizer (APM-SMPS), Hygroscopicity/Volatility - Tandem Differential Mobility Analyzer (H/V-TDMA), respectively. Also SOA yields were obtained to evaluate the importance of xylenol as an intermediate product.

  10. Externally pressurized porous cylinder for multiple surface aerosol generation and method of generation

    DOEpatents

    Apel, Charles T.; Layman, Lawrence R.; Gallimore, David L.

    1988-01-01

    A nebulizer for generating aerosol having small droplet sizes and high efficiency at low sample introduction rates. The nebulizer has a cylindrical gas permeable active surface. A sleeve is disposed around the cylinder and gas is provided from the sleeve to the interior of the cylinder formed by the active surface. In operation, a liquid is provided to the inside of the gas permeable surface. The gas contacts the wetted surface and forms small bubbles which burst to form an aerosol. Those bubbles which are large are carried by momentum to another part of the cylinder where they are renebulized. This process continues until the entire sample is nebulized into aerosol sized droplets.

  11. Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

    NASA Astrophysics Data System (ADS)

    Badali, K. M.; Zhou, S.; Aljawhary, D.; Antiñolo, M.; Chen, W. J.; Lok, A.; Mungall, E.; Wong, J. P. S.; Zhao, R.; Abbatt, J. P. D.

    2015-02-01

    This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA aerosol is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are five times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over three times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloudwater and aerosol chemistry.

  12. Global transformation and fate of SOA: Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions

    SciTech Connect

    Shrivastava, ManishKumar B.; Easter, Richard C.; Liu, Xiaohong; Zelenyuk, Alla; Singh, Balwinder; Zhang, Kai; Ma, Po-Lun; Chand, Duli; Ghan, Steven J.; Jiminez, J. L.; Zhang, Qibin; Fast, Jerome D.; Rasch, Philip J.; Tiitta, P.

    2015-05-16

    Secondary organic aerosols (SOA) are large contributors to fine particle loadings and radiative forcing, but are often represented crudely in global models. We have implemented three new detailed SOA treatments within the Community Atmosphere Model version 5 (CAM5) that allow us to compare the semi-volatile versus non-volatile SOA treatments (based on some of the latest experimental findings) and also investigate the effects of gas-phase fragmentation reactions. For semi-volatile SOA treatments, fragmentation reactions decrease simulated SOA burden from 7.5 Tg to 1.8 Tg. For the non-volatile SOA treatment with fragmentation, the burden is 3.1 Tg. Larger differences between non-volatile and semi-volatile SOA (upto a factor of 5) correspond to continental outflow over the oceans. Compared to a global dataset of surface Aerosol Mass Spectrometer measurements and the US IMPROVE network measurements, the non-volatile SOA with fragmentation treatment (FragNVSOA) agrees best at rural locations. Urban SOA is under-predicted but this may be due to the coarse model resolution. All our three revised treatments show much better agreement with aircraft measurements of organic aerosols (OA) over the N. American Arctic and sub-Arctic in spring and summer, compared to the standard CAM5 formulation. This is due to treating SOA precursor gases from biomass burning, and long-range transport of biomass burning OA at elevated levels. The revised model configuration that include fragmentation (both semi-volatile and non-volatile SOA) show much better agreement with MODIS AOD data over regions dominated by biomass burning during the summer, and predict biomass burning as the largest global source of OA followed by biogenic and anthropogenic sources. The non-volatile and semi-volatile configuration predict the direct radiative forcing of SOA as -0.5 W m-2 and -0.26 W m-2 respectively, at top of the atmosphere, which are higher than previously estimated by most models, but in reasonable

  13. High molecular weight SOA formation during limonene ozonolysis: insights from ultrahigh-resolution FT-ICR mass spectrometry characterization

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

    The detailed molecular composition of laboratory generated limonene ozonolysis secondary organic aerosol (SOA) was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Approximately 1200 molecular formulas were identified in the SOA over the mass range of 140 to 850 Da. Four characteristic groups of high relative abundance species were observed; they indicate an array of accretion products that retain a large fraction of the limonene skeleton. The identified molecular formulas of each of the groups are related to one another by CH2, O and CH2O homologous series. The CH2 and O homologous series of the low molecular weight (MW) SOA (m/z < 300) are explained with a combination of functionalization and fragmentation of radical intermediates and reactive uptake of gas-phase carbonyls. They include isomerization and elimination reactions of Criegee radicals, reactions between alkyl peroxy radicals, and scission of alkoxy radicals resulting from the Criegee radicals. The presence of compounds with 10-15 carbon atoms in the first group (e.g. C11H18O6) provides evidence for SOA formation by the reactive uptake of gas-phase carbonyls during limonene ozonolysis. The high MW compounds (m/z > 300) were found to constitute a significant number fraction of the identified SOA components. The formation of high MW compounds was evaluated by molecular formula trends, fragmentation analysis of select high MW compounds and a comprehensive reaction matrix including the identified low MW SOA, hydroperoxides and Criegee radicals as building blocks. Although the formation of high MW SOA may occur via a variety of radical and non-radical reaction channels, the combined approach indicates a greater importance of the non-condensation reactions over aldol and ester condensation reaction channels. Among these hemi-acetal reactions appear to be most dominant followed by hydroperoxide and Criegee reaction channels.

  14. SOA Measurements vs. Models: A Status Report

    NASA Astrophysics Data System (ADS)

    Jimenez, Jose-Luis; de Gouw, Joost; Hodzic, Alma

    2010-05-01

    The advent of fast and chemically-resolved organic aerosol (OA) and VOC measurements in the last decade has allowed more detailed model-measurement comparisons for OA and secondary OA (SOA). Large model underpredictions have been reported for SOA at many locations, but this is not always the case. Here we summarize the patterns emerging from studies to date, focusing on studies that use highly time and/or chemically resolved OA measurements. The model-measurement comparisons exhibit clear patterns depending on the region of the atmosphere. • At least 8 studies have reported a large (x5-10) underestimation of SOA for polluted regions when using traditional models (those developed until ~2006) (Heald GRL05, Volkamer GRL06, Johnson ACP06, Kleinman ACP08, Matsui JGR09, Dzepina ACP09, Hodzic ACP09, Tsimpidi ACP09). This is especially obvious when models are evaluated with the ΔOA/ΔCO ratio. • Close to pollution sources, discrepancies of an order-of-magnitude in SOA lead to smaller discrepancies (often x2-3) for total OA due to the presence of primary OA (de Gouw EST09). Such OA discrepancies have been repeatedly observed (e.g. Vutukuru JGR06, McKeen JGR07&09, Heald JGR07, Fast ACP09, Hodzic ACP09). • The discrepancy is reduced when recently-updated yields for aromatics (Ng ACP07) and SOA from glyoxal (Volkamer GRL07) are used, and is eliminated when using SOA formation from S/IVOC (Robinson Sci07) although with an overprediction of SOA at long aging times (Dzepina ACP09; Hodzic ACP10), especially with the Grieshop (ACP09) update of the Robison mechanism (Hodzic10). It is not clear whether the urban discrepancy is removed for the right reasons. • 4 evaluations of biogenic SOA formed in unpolluted regions find reasonable agreement between SOA from traditional models and field measurements (Tunved Sci06; Hodzic ACP09; Chen GRL09; Slowik ACPD09). One evaluation reports a significant underprediction (Capes ACP09), although the amount of precursor reacted was

  15. Modeling the influence of alkane molecular structure on secondary organic aerosol formation.

    PubMed

    Aumont, Bernard; Camredon, Marie; Mouchel-Vallon, Camille; La, Stéphanie; Ouzebidour, Farida; Valorso, Richard; Lee-Taylor, Julia; Madronich, Sasha

    2013-01-01

    Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapor pressure. Intermediate Volatility Organic Compounds (IVOC) emitted to the atmosphere are expected to be a substantial source of SOA. These emitted IVOC constitute a complex mixture including linear, branched and cyclic alkanes. The explicit gas-phase oxidation mechanisms are here generated for various linear and branched C10-C22 alkanes using the GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) and SOA formation is investigated for various homologous series. Simulation results show that both the size and the branching of the carbon skeleton are dominant factors driving the SOA yield. However, branching appears to be of secondary importance for the particle oxidation state and composition. The effect of alkane molecular structure on SOA yields appears to be consistent with recent laboratory observations. The simulated SOA composition shows, however, an unexpected major contribution from multifunctional organic nitrates. Most SOA contributors simulated for the oxidation of the various homologous series are far too reduced to be categorized as highly oxygenated organic aerosols (OOA). On a carbon basis, the OOA yields never exceeded 10% regardless of carbon chain length, molecular structure or ageing time. This version of the model appears clearly unable to explain a large production of OOA from alkane precursors. PMID:24600999

  16. Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States.

    PubMed

    Jathar, Shantanu H; Gordon, Timothy D; Hennigan, Christopher J; Pye, Havala O T; Pouliot, George; Adams, Peter J; Donahue, Neil M; Robinson, Allen L

    2014-07-22

    Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles, and biomass burning. About 10-20% of NMOG emissions from these major combustion sources are not routinely speciated and therefore are currently misclassified in emission inventories and chemical transport models. The smog chamber data demonstrate that this misclassification biases model predictions of SOA production low because the unspeciated NMOG produce more SOA per unit mass than the speciated NMOG. We present new source-specific SOA yield parameterizations for these unspeciated emissions. These parameterizations and associated source profiles are designed for implementation in chemical transport models. Box model calculations using these new parameterizations predict that NMOG emissions from the top six combustion sources form 0.7 Tg y(-1) of first-generation SOA in the United States, almost 90% of which is from biomass burning and gasoline vehicles. About 85% of this SOA comes from unspeciated NMOG, demonstrating that chemical transport models need improved treatment of combustion emissions to accurately predict ambient SOA concentrations. PMID:25002466

  17. Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States

    PubMed Central

    Jathar, Shantanu H.; Gordon, Timothy D.; Hennigan, Christopher J.; Pye, Havala O. T.; Pouliot, George; Adams, Peter J.; Donahue, Neil M.; Robinson, Allen L.

    2014-01-01

    Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles, and biomass burning. About 10–20% of NMOG emissions from these major combustion sources are not routinely speciated and therefore are currently misclassified in emission inventories and chemical transport models. The smog chamber data demonstrate that this misclassification biases model predictions of SOA production low because the unspeciated NMOG produce more SOA per unit mass than the speciated NMOG. We present new source-specific SOA yield parameterizations for these unspeciated emissions. These parameterizations and associated source profiles are designed for implementation in chemical transport models. Box model calculations using these new parameterizations predict that NMOG emissions from the top six combustion sources form 0.7 Tg y−1 of first-generation SOA in the United States, almost 90% of which is from biomass burning and gasoline vehicles. About 85% of this SOA comes from unspeciated NMOG, demonstrating that chemical transport models need improved treatment of combustion emissions to accurately predict ambient SOA concentrations. PMID:25002466

  18. Aerosol phase generation of In-Se nanoparticles.

    PubMed

    Geretovszky, Zs; Deppert, K; Karlsson, L S; Karlsson, M N A; Malm, l J O; Mühlberg, M

    2006-03-01

    Results on the generation and heat treatment of In-Se nanoparticles, made by heterogeneous condensation of selenium on indium nanoparticles synthesised via the evaporation/condensation route are reported. In-situ aerosol measurements are complemented with ex-situ analysis, to provide structural, morphological, and compositional information on the In-Se nanoparticles. Our results indicate that prior to heat treatment In-Se nanoparticles have a shape in the aerosol phase, similar to an asymmetric dumbbell. The bigger particle of the dumbbell structure is made up of amorphous Se, while the overall composition of the polycrystalline smaller particle is around InSe. The smaller particle has an intrinsic structure, and consists of different InSe-compounds, with a decreasing In content towards the shell. The shape of the In-Se nanoparticles is different in the aerosol phase and on the surface of the samples. The observed variety of particle sizes and shapes on the sample surface is shown to be partly due to the agglomeration of the aerosol phase binaries (i.e., dumbbells) via coalescence on the surface of the sample and wetting of the sample surface by the Se nanoparticles. These processes make the bigger particle of the dumbbell structure appear almost perfectly hemispherical on the sample surfaces. During heat treatment at lower temperatures mainly the evaporative removal of the big Se particle of the dumbbell structure will take place. Annealing of the smaller particles starts to dominate at temperatures above 240 degrees C and makes the composition of the small particles closer to that of the thermodynamically most favoured In2Se3. PMID:16573110

  19. A New Method to Generate Micron-Sized AerosolS With Narrow Size Distribution

    NASA Astrophysics Data System (ADS)

    Gañón-Calvo, Alfonso; Barrero, Antonio

    1996-11-01

    Aerosols in the micron-size range with a remarkable monodisperse size distribution can be generated from the breaking up process of a capillary microjet. The size of the main droplets and satellites depend on the jet diameter, d_j, as well as the flow rate, Q, and liquid properties which eventually determine the jet`s breaking up. Therefore, the generation and control of capillary microjets is essential to produce sprays of small droplets with narrow size histograms. Electrosprays has been up to now one of the most successful techniques to produce monodisperse micron-size aerosols. As an alternative, we report here a new method, aerospray, to generate capillary micro jets which can compete against the electrospray for the production of aerosols of small droplets with very narrow size distribution. The method is outlined in the following. Liquid coming out from the exit of a capillary needle is sucked by means of a high speed gas stream (usually air) which flows throughout a hole separating two chambers at different pressures. Under certain parametric conditions of liquid properties, liquid and air flow rates, and geometric characteristics (needle and hole diameters, distance from the needle to the hole, etc), the liquid forms a steady capillary microjet of very small diameter which is speeded up an stabilized by the action of the viscous stresses at the gas liquid interface. The jet passes through the hole and goes out the outside chamber where eventually breaks up into microdroplets by varicose instabilities. Measurements from Laser-Doppler PDA Analizer of these aerosprays show that both the droplet size and its standard deviation are comparable to those obtained by electrospray techniques. On the other hand, using the aerospray, the standard deviation of the resulting droplet size distribution is of the order of those that can be obtained by ultrasonic atomization but the mean diameters can be more than one order of magnitude smaller.

  20. The Tao of SOA

    NASA Astrophysics Data System (ADS)

    Shan, Tony C.

    This paper describes a comprehensive framework aiming to facilitate the effective adoption and operationalization of SOA in large enterprise computing environments, which consists of the Strategy, Automation, Methodology, Patterns, Lifecycle, and Engineering (SAMPLE) aspects. The major pain points in SOA are analyzed, such as the increasing dynamics, growing integration, proliferation of techniques, more heterogeneous platforms, disparate visual notations, intricate processes, disjointed operating models, and fragmented activities of WS-* specifications. The overarching SAMPLE model is designed to provide a sophisticated integration of appropriate capabilities and knowledge to filter the inessential from the essential. In the Strategy aspect, a metamodel, technology architecture planning, and strategy roadmapping are presented. The Automation aspect deals with tools, service lifecycle, and COTS mapping. The Methodology aspect covers a hybrid method, SOA principles, and a methodical process. The prominent elements of the Patterns aspect include data caching patterns, a reference model, and open source reference implementation. The Lifecycle aspect contains a methodical means to mature IT systems: review, refactoring, reengineering, and rearchitecting (R4). Finally, the Engineering aspect evolves the traditional software engineering and systems engineering practices to the service engineering discipline. Moreover, a 10-point list of SOA guidance is introduced from a practitioner’s standpoint, which gives best-practice guidelines to adopt and execute SOA practically in big organizations.

  1. Hydroxyl radicals from secondary organic aerosol decomposition in water

    NASA Astrophysics Data System (ADS)

    Tong, Haijie; Arangio, Andrea M.; Lakey, Pascale S. J.; Berkemeier, Thomas; Liu, Fobang; Kampf, Christopher J.; Brune, William H.; Pöschl, Ulrich; Shiraiwa, Manabu

    2016-02-01

    We found that ambient and laboratory-generated secondary organic aerosols (SOA) form substantial amounts of OH radicals upon interaction with liquid water, which can be explained by the decomposition of organic hydroperoxides. The molar OH yield from SOA formed by ozonolysis of terpenes (α-pinene, β-pinene, limonene) is ˜ 0.1 % upon extraction with pure water and increases to ˜ 1.5 % in the presence of Fe2+ ions due to Fenton-like reactions. Upon extraction of SOA samples from OH photooxidation of isoprene, we also detected OH yields of around ˜ 0.1 %, which increases upon addition of Fe2+. Our findings imply that the chemical reactivity and aging of SOA particles is strongly enhanced upon interaction with water and iron. In cloud droplets under dark conditions, SOA decomposition can compete with the classical H2O2 Fenton reaction as the source of OH radicals. Also in the human respiratory tract, the inhalation and deposition of SOA particles may lead to a substantial release of OH radicals, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols.

  2. Modeling the Role of Alkanes, Polycyclic Aromatic Hydrocarbons, and Their Oligomers in Secondary Organic Aerosol Formation

    EPA Science Inventory

    A computationally efficient method to treat secondary organic aerosol (SOA) from various length and structure alkanes as well as SOA from polycyclic aromatic hydrocarbons (PAHs) is implemented in the Community Multiscale Air Quality (CMAQ) model to predict aerosol concentrations ...

  3. 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.

  4. 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.

  5. Characterizing the Amount and Chemistry of Biogenic SOA Formation from Pine Forest Air Using a Flow Reactor

    NASA Astrophysics Data System (ADS)

    Palm, B. B.; Ortega, A. M.; Campuzano Jost, P.; Day, D. A.; Fry, J.; Zarzana, K. J.; Draper, D. C.; Brown, S. S.; Kaser, L.; Karl, T.; Jud, W.; Hansel, A.; Hodzic, A.; Dube, W. P.; Wagner, N. L.; Brune, W. H.; Jimenez, J. L.

    2013-12-01

    The amount and chemistry of biogenic secondary organic aerosol (SOA) formation was characterized as a function of oxidant exposure using a Potential Aerosol Mass (PAM) oxidative flow reactor, sampling air in a terpene- and MBO-dominated pine forest during the 2011 BEACHON-RoMBAS field campaign at the U.S. Forest Service Manitou Forest Experimental Observatory in the Colorado Rocky Mountains. In the reactor, a chosen oxidant (OH, O3, or NO3) was generated and stepped over a range of values up to 10,000 times ambient levels, accelerating the gas-phase and heterogeneous oxidative aging of volatile organic compounds (VOCs), inorganic gases, and preexisting aerosol. The resulting SOA formation was measured using an Aerodyne HR-ToF-AMS, a TSI SMPS and a PTR-TOF-MS. Oxidative processing in the flow reactor was equivalent to a few hours up to ~20 days of atmospheric aging during the ~4-min reactor residence time. During BEACHON-RoMBAS, OH oxidation led to a net production of up to several μg/m3 of SOA at intermediate exposures (1-10 equivalent days) but resulted in net loss of OA mass (up to ~30%) at higher OH exposures (10-20 equivalent days), demonstrating the competing effects of functionalization/condensation vs. fragmentation/evaporation reactions as OH exposure increased. O3 and NO3 oxidation led to smaller (up to 0.5 μg/m3) SOA production, and loss of SOA mass due to fragmentation reactions was not observed. OH oxidation resulted in f44 vs. f43 and Van Krevelen diagram (H:C vs. O:C) slopes similar to ambient oxidation, suggesting the flow reactor oxidation pathways are similar to those in ambient air. Organic nitrate SOA production was observed from NO3 radical oxidation only. New particle formation was observed from OH oxidation, but not O3 or NO3 oxidation under our experimental conditions. An enhancement of SOA production under the influence of anthropogenic pollution (Denver) was also observed. High-resolution AMS measurements showed that the O:C and H

  6. Modeling the formation and aging of secondary organic aerosols in Los Angeles during CalNex 2010

    NASA Astrophysics Data System (ADS)

    Hayes, P. L.; Carlton, A. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S.; Rappenglück, B.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; Zotter, P.; Prévôt, A. S. H.; Szidat, S.; Kleindienst, T. E.; Offenberg, J. H.; Jimenez, J. L.

    2014-12-01

    Four different parameterizations for the formation and evolution of secondary organic aerosol (SOA) are evaluated using a 0-D box model representing the Los Angeles Metropolitan Region during the CalNex 2010 field campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model-measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model/measurement agreement for mass concentration. When comparing the three parameterizations, the Grieshop et al. (2009) parameterization more accurately reproduces both the SOA mass concentration and oxygen-to-carbon ratio inside the urban area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the parameterizations over-predict urban SOA formation at long

  7. High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

    SciTech Connect

    Romonosky, Dian E.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2015-03-19

    A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA constituents

  8. Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

    NASA Astrophysics Data System (ADS)

    Badali, K. M.; Zhou, S.; Aljawhary, D.; Antiñolo, M.; Chen, W. J.; Lok, A.; Mungall, E.; Wong, J. P. S.; Zhao, R.; Abbatt, J. P. D.

    2015-07-01

    This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are 5 times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions, assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloud water and aerosol chemistry.

  9. SOA formation from the photooxidation of α-pinene: systematic exploration of the simulation of chamber data

    NASA Astrophysics Data System (ADS)

    McVay, Renee C.; Zhang, Xuan; Aumont, Bernard; Valorso, Richard; Camredon, Marie; La, Yuyi S.; Wennberg, Paul O.; Seinfeld, John H.

    2016-03-01

    Chemical mechanisms play an important role in simulating the atmospheric chemistry of volatile organic compound oxidation. Comparison of mechanism simulations with laboratory chamber data tests our level of understanding of the prevailing chemistry as well as the dynamic processes occurring in the chamber itself. α-Pinene photooxidation is a well-studied system experimentally, for which detailed chemical mechanisms have been formulated. Here, we present the results of simulating low-NO α-pinene photooxidation experiments conducted in the Caltech chamber with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) under varying concentrations of seed particles and OH levels. Unexpectedly, experiments conducted at low and high OH levels yield the same secondary organic aerosol (SOA) growth, whereas GECKO-A predicts greater SOA growth under high OH levels. SOA formation in the chamber is a result of a competition among the rates of gas-phase oxidation to low-volatility products, wall deposition of these products, and condensation into the aerosol phase. Various processes - such as photolysis of condensed-phase products, particle-phase dimerization, and peroxy radical autoxidation - are explored to rationalize the observations. In order to explain the observed similar SOA growth at different OH levels, we conclude that vapor wall loss in the Caltech chamber is likely of order 10-5 s-1, consistent with previous experimental measurements in that chamber. We find that GECKO-A tends to overpredict the contribution to SOA of later-generation oxidation products under high-OH conditions. Moreover, we propose that autoxidation may alternatively resolve some or all of the measurement-model discrepancy, but this hypothesis cannot be confirmed until more explicit mechanisms are established for α-pinene autoxidation. The key role of the interplay among oxidation rate, product volatility, and vapor-wall deposition in chamber experiments is

  10. SOA VOLATILITY EVOLUTION: FORMATION AND OXIDATION OVER THE LIFECYCLE OF PM2.5

    EPA Science Inventory

    Secondary Organic Aerosols are a major, possibly dominant, source of organic PM2.5 that remain enigmatic. Enormous progress has been made in the past 15 years regarding SOA formation, starting with recognition that most SOA products are semivolatile, continuing to a...

  11. Externally pressurized porous cylinder for multiple surface aerosol generation and method of generation

    DOEpatents

    Apel, C.T.; Layman, L.R.; Gallimore, D.L.

    1988-05-10

    A nebulizer is described for generating aerosol having small droplet sizes and high efficiency at low sample introduction rates. The nebulizer has a cylindrical gas permeable active surface. A sleeve is disposed around the cylinder and gas is provided from the sleeve to the interior of the cylinder formed by the active surface. In operation, a liquid is provided to the inside of the gas permeable surface. The gas contacts the wetted surface and forms small bubbles which burst to form an aerosol. Those bubbles which are large are carried by momentum to another part of the cylinder where they are renebulized. This process continues until the entire sample is nebulized into aerosol sized droplets. 2 figs.

  12. A New Electrospray Aerosol Generator with High Particle Transmission Efficiency

    PubMed Central

    Fu, Huijing; Patel, Anand C.; Holtzman, Michael J.; Chen, Da-Ren

    2012-01-01

    A new single-capillary electrospray (ES) aerosol generator has been developed for monodisperse particle production with maximal transmission efficiency. The new generator consists of both a spray chamber in a point-to-orifice-plate configuration and a charge reduction chamber that can hold up to 4 Nuclespot ionizers (Model P-2042, NRD Inc.). The 2 chambers are partitioned by an orifice plate. To optimize the particle transmission efficiency of the prototype, a systematic study was performed on the generator by varying the system setup and operation. Two key dimensions of the generator setup, the orifice diameter and the distance from the capillary tip to the orifice plate, were varied. Fluorescence analysis was applied to characterize the loss of ES-generated particles at different locations of the prototype. It was found that particle loss in the generator could be reduced by either increasing the orifice diameter or decreasing the distance between the capillary tip and the orifice plate. Increasing either the total radioactivity of the ionizers or the flowrate of the particle carrier gas also further decreased the particle loss in the system. The maximum particle transmission efficiency of 88.0% was obtained with the spray chamber fully opened to the charge reduction chamber, the capillary tip at the same level as the orifice plate, and 4 bipolar ionizers installed. PMID:22829715

  13. A New Electrospray Aerosol Generator with High Particle Transmission Efficiency.

    PubMed

    Fu, Huijing; Patel, Anand C; Holtzman, Michael J; Chen, Da-Ren

    2011-01-01

    A new single-capillary electrospray (ES) aerosol generator has been developed for monodisperse particle production with maximal transmission efficiency. The new generator consists of both a spray chamber in a point-to-orifice-plate configuration and a charge reduction chamber that can hold up to 4 Nuclespot ionizers (Model P-2042, NRD Inc.). The 2 chambers are partitioned by an orifice plate. To optimize the particle transmission efficiency of the prototype, a systematic study was performed on the generator by varying the system setup and operation. Two key dimensions of the generator setup, the orifice diameter and the distance from the capillary tip to the orifice plate, were varied. Fluorescence analysis was applied to characterize the loss of ES-generated particles at different locations of the prototype. It was found that particle loss in the generator could be reduced by either increasing the orifice diameter or decreasing the distance between the capillary tip and the orifice plate. Increasing either the total radioactivity of the ionizers or the flowrate of the particle carrier gas also further decreased the particle loss in the system. The maximum particle transmission efficiency of 88.0% was obtained with the spray chamber fully opened to the charge reduction chamber, the capillary tip at the same level as the orifice plate, and 4 bipolar ionizers installed. PMID:22829715

  14. Limited influence of dry deposition of semivolatile organic vapors on secondary organic aerosol formation in the urban plume

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Aumont, B.; Lee-Taylor, J.; Karl, T.; Camredon, M.; Mouchel-Vallon, C.

    2013-06-01

    The dry deposition of volatile organic compounds (VOCs) and its impact on secondary organic aerosols (SOA) are investigated in the Mexico City plume. Gas-phase chemistry and gas-particle partitioning of oxygenated VOCs are modeled with the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) from C3 to C25 alkanes, alkenes, and light aromatics. Results show that dry deposition of oxidized gases is not an efficient sink for SOA, as it removes <5% of SOA within the city's boundary layer and ~15% downwind. Dry deposition competes with the gas-particle uptake, and only gases with fewer than ~12 carbons dry deposit while longer species partition to SOA. Because dry deposition of submicron aerosols is slow, condensation onto particles protects organic gases from deposition, thus increasing their atmospheric burden and lifetime. In the absence of this condensation, ~50% of the regionally produced mass would have been dry deposited.

  15. Primary and Secondary Contributions to the Organic Aerosol Over the Amazon Determined by STXM-NEXAFS

    NASA Astrophysics Data System (ADS)

    Andreae, M. O.; Pöhlker, C.; Wiedemann, K. T.; Sinha, B.; Artaxo, P.; Kilcoyne, D.; Smith, M. L.; Martin, S. T.; Poeschl, U.

    2011-12-01

    We investigated the morphology and chemical composition of aerosol samples from a pristine tropical environment, the Amazon Basin, using Scanning Transmission X-ray Microscopy - Near Edge X-ray Absorption Fine Structure (STXMNEXAFS) analysis. The NEXAFS spectra were used to estimate the elemental ratios of C, N and O, as well as the chemical bonding state of these elements. The aim of this study was to investigate the microphysical and chemical properties of a tropical background aerosol and its internal mixing state. The samples were collected in the Amazonian rainforest during the rainy season and can be regarded as a nearly pristine background aerosol. Lab-generated SOA-samples (produced by the (photo)oxidation of isoprene, alpha-pinene and beta-caryophyllene), microtome slices of fungal spores, and aerosolized authentic organic compounds were measured as reference samples. The STXM-NEXAFS results of the lab-generated SOA have been analyzed and compared to SOA from the Amazonian region. In the lab samples, SOA occurred as droplets of different sizes, sometimes exhibiting internal structures ('raisin-like' structure). The spectral characteristics of the lab samples depend on the precursors applied for their generation. The Amazonian aerosol was found to be dominated by drop-like organic particles in the fine mode (often in internal mixture with solid particles), and Primary Biological Aerosol Particles (PBAP) in the coarse mode. Liquid organic aerosol coatings were also frequently observed on the PBAPs. Unexpectedly, many ambient SOA samples show a high content of N (around 20% or even more) as well as the frequent occurrence of potassium. Furthermore, the spectra exhibit characteristic signal patterns for different functional groups. In most cases, the spectrum near the C-edge is dominated by either the hydroxyl or the carboxylate signal, but prominent peaks for ketone carbonyls, alkanes and alkenes have also been observed. Based on these results, a new

  16. Secondary organic aerosol formation from the photo-oxidation of benzene

    NASA Astrophysics Data System (ADS)

    Borrás, Esther; Tortajada-Genaro, Luis Antonio

    2012-02-01

    The production of condensate compounds from the degradation of benzene by OH radical chemistry was studied. Secondary organic aerosol (SOA) formation was investigated in the EUPHORE ( European Photoreactor) simulation chambers. Experiments were performed under different OH-production conditions - addition of H 2O 2, NO or HONO -, in a high-volume reactor, with natural light and in the absence of seed aerosols. The consumption of precursor/reagents, the formation of gas-phase and particulate-phase products and the temporal evolution of aerosol were monitored. Several aerosol physical properties - mass concentration, overall aerosol yield, particle size distribution and density - were determined and found to be clearly dependent on OH radical production and NO x concentrations. Furthermore, the use of one and/or two products gas-particle partitioning absorption models allowed us to determine the aerosol yield curves. The SOA yield ranged from 1.6 to 9.7 %, with higher SOA formation under low-NO x conditions. Chemical characterization of the SOA was carried out, determining multi-oxygenated condensed organic compounds by a method based on the gas chromatography-mass spectrometry technique. Several ring-retaining and ring-cleavage products were identified and quantified. The compounds with the highest percentage contribution to the total aerosol mass were 4-nitrobenzene-1,2-diol, butenedioic acid, succinic acid and trans-trans-muconic. In addition, a multigenerational study was performed comparing with the photo-oxidations of phenol and catechol. The results showed that although the mass concentration of SOA produced was different, the physical and chemical properties were quite similar. Finally, we suggest a general mechanism to describe how changes in benzene degradation pathways - rate of OH generation and concentration of NO x - could justify the variation in SOA production and properties.

  17. FTIR Analysis of Functional Groups in Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Shokri, S. M.; McKenzie, G.; Dransfield, T. J.

    2012-12-01

    Secondary organic aerosols (SOA) are suspensions of particulate matter composed of compounds formed from chemical reactions of organic species in the atmosphere. Atmospheric particulate matter can have impacts on climate, the environment and human health. Standardized techniques to analyze the characteristics and composition of complex secondary organic aerosols are necessary to further investigate the formation of SOA and provide a better understanding of the reaction pathways of organic species in the atmosphere. While Aerosol Mass Spectrometry (AMS) can provide detailed information about the elemental composition of a sample, it reveals little about the chemical moieties which make up the particles. This work probes aerosol particles deposited on Teflon filters using FTIR, based on the protocols of Russell, et al. (Journal of Geophysical Research - Atmospheres, 114, 2009) and the spectral fitting algorithm of Takahama, et al (submitted, 2012). To validate the necessary calibration curves for the analysis of complex samples, primary aerosols of key compounds (e.g., citric acid, ammonium sulfate, sodium benzoate) were generated, and the accumulated masses of the aerosol samples were related to their IR absorption intensity. These validated calibration curves were then used to classify and quantify functional groups in SOA samples generated in chamber studies by MIT's Kroll group. The fitting algorithm currently quantifies the following functionalities: alcohols, alkanes, alkenes, amines, aromatics, carbonyls and carboxylic acids.

  18. Light absorption by secondary organic aerosol from α-pinene: Effects of oxidants, seed aerosol acidity, and relative humidity

    SciTech Connect

    Song, Chen; Gyawali, Madhu; Zaveri, Rahul A.; Shilling, John E.; Arnott, W. Patrick

    2013-10-25

    It is well known that light absorption from dust and black carbon aerosols has a warming effect on climate while light scattering from sulfate, nitrate, and sea salt aerosols has a cooling effect. However, there are large uncertainties associated with light absorption and scattering by different types of organic aerosols, especially in the near-UV and UV spectral regions. In this paper, we present the results from a systematic laboratory study focused on measuring light absorption by secondary organic aerosols (SOAs) generated from dark α-pinene + O3 and α-pinene + NOx + O3 systems in the presence of neutral and acidic sulfate seed aerosols. Light absorption was monitored using photoacoustic spectrometers at four different wavelengths: 355, 405, 532, and 870 nm. Significant light absorption at 355 and 405 nm was observed for the SOA formed from α-pinene + O3 + NO3 system only in the presence of highly acidic sulfate seed aerosols under dry conditions. In contrast, no absorption was observed when the relative humidity was elevated to greater than 27% or in the presence of neutral sulfate seed aerosols. Organic nitrates in the SOA formed in the presence of neutral sulfate seed aerosols were found to be nonabsorbing, while the light-absorbing compounds are speculated to be aldol condensation oligomers with nitroxy organosulfate groups that are formed in highly acidic sulfate aerosols. Finally and overall, these results suggest that dark α-pinene + O3 and α-pinene + NOx + O3 systems do not form light-absorbing SOA under typical atmospheric conditions.

  19. Light absorption by secondary organic aerosol from α-pinene: Effects of oxidants, seed aerosol acidity, and relative humidity

    NASA Astrophysics Data System (ADS)

    Song, Chen; Gyawali, Madhu; Zaveri, Rahul A.; Shilling, John E.; Arnott, W. Patrick

    2013-10-01

    is well known that light absorption from dust and black carbon aerosols has a warming effect on climate while light scattering from sulfate, nitrate, and sea salt aerosols has a cooling effect. However, there are large uncertainties associated with light absorption and scattering by different types of organic aerosols, especially in the near-UV and UV spectral regions. In this paper, we present the results from a systematic laboratory study focused on measuring light absorption by secondary organic aerosols (SOAs) generated from dark α-pinene + O3 and α-pinene + NOx + O3 systems in the presence of neutral and acidic sulfate seed aerosols. Light absorption was monitored using photoacoustic spectrometers at four different wavelengths: 355, 405, 532, and 870 nm. Significant light absorption at 355 and 405 nm was observed for the SOA formed from α-pinene + O3 + NO3 system only in the presence of highly acidic sulfate seed aerosols under dry conditions. In contrast, no absorption was observed when the relative humidity was elevated to greater than 27% or in the presence of neutral sulfate seed aerosols. Organic nitrates in the SOA formed in the presence of neutral sulfate seed aerosols were found to be nonabsorbing, while the light-absorbing compounds are speculated to be aldol condensation oligomers with nitroxy organosulfate groups that are formed in highly acidic sulfate aerosols. Overall, these results suggest that dark α-pinene + O3 and α-pinene + NOx + O3 systems do not form light-absorbing SOA under typical atmospheric conditions.

  20. Science Opportunity Analyzer (SOA) Version 8

    NASA Technical Reports Server (NTRS)

    Witoff, Robert J.; Polanskey, Carol A.; Aguinaldo, Anna Marie A.; Liu, Ning; Hofstadter, Mark D.

    2013-01-01

    SOA allows scientists to plan spacecraft observations. It facilitates the identification of geometrically interesting times in a spacecraft s orbit that a user can use to plan observations or instrument-driven spacecraft maneuvers. These observations can then be visualized multiple ways in both two- and three-dimensional views. When observations have been optimized within a spacecraft's flight rules, the resulting plans can be output for use by other JPL uplink tools. Now in its eighth major version, SOA improves on these capabilities in a modern and integrated fashion. SOA consists of five major functions: Opportunity Search, Visualization, Observation Design, Constraint Checking, and Data Output. Opportunity Search is a GUI-driven interface to existing search engines that can be used to identify times when a spacecraft is in a specific geometrical relationship with other bodies in the solar system. This function can be used for advanced mission planning as well as for making last-minute adjustments to mission sequences in response to trajectory modifications. Visualization is a key aspect of SOA. The user can view observation opportunities in either a 3D representation or as a 2D map projection. Observation Design allows the user to orient the spacecraft and visualize the projection of the instrument field of view for that orientation using the same views as Opportunity Search. Constraint Checking is provided to validate various geometrical and physical aspects of an observation design. The user has the ability to easily create custom rules or to use official project-generated flight rules. This capability may also allow scientists to easily assess the cost to science if flight rule changes occur. Data Output allows the user to compute ancillary data related to an observation or to a given position of the spacecraft along its trajectory. The data can be saved as a tab-delimited text file or viewed as a graph. SOA combines science planning functionality unique to

  1. Aerosol formation by ozonolysis of α- and β-pinene with initial concentrations below 1 ppb

    NASA Astrophysics Data System (ADS)

    Saathoff, Harald; Naumann, Karl-Heinz; Möhler, Ottmar

    2014-05-01

    Secondary organic aerosols (SOA) from the oxidation of biogenic volatile organic compounds (BVOC) are a large fraction of the tropospheric aerosol especially over tropical continental regions. The dominant SOA forming compounds are monoterpenes of which pinene is the most abundant. The reactions of monoterpenes with OH radicals, NO3 radicals, and ozone yield secondary organic aerosol mass in highly variable yields. Despite the various studies on SOA formation the influence of temperature and precursor concentrations on SOA yields are still major uncertainties in tropospheric aerosol models. In previous studies we observed a negative temperature dependence of SOA yields for SOA from ozonolysis α-pinene and limonene (Saathoff et al., 2009). However, this study as well as most of the literature data for measured SOA yields is limited to terpene concentrations of several ppb and higher (e.g. Bernard et al., 2012), hence about an order of magnitude higher than terpene concentrations even near their sources. Monoterpene concentrations in and above tropical or boral forests reach values up to a few tenth of a ppb during daytime decreasing rapidly with altitude in the boundary layer (Kesselmeier et al. 2000; Boy et al., 2004). Therefore we investigated the yield of SOA material from the ozonolysis of α- and β-pinene under simulated tropospheric conditions in the large aerosol chamber AIDA on time scales of several hours and for terpene concentrations between 0.1 and 1 ppb. The temperatures investigated were 243, 274, and 296 K with relative humidities ranging from 25% to 41%. The organic aerosol was generated by controlled oxidation with an excess of ozone (220-930 ppb) and the aerosol yield is calculated from size distributions measured with differential mobility analysers (SMPS, TSI, 3071 & 3080N) in the size range between 2 and 820 nm. On the basis of the measured initial particle size distribution, particle number concentration (CPC, TSI, 3775, 3776, 3022), and

  2. Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Kinetics and SOA yields

    NASA Astrophysics Data System (ADS)

    Richards-Henderson, Nicole K.; Hansel, Amie K.; Valsaraj, Kalliat T.; Anastasio, Cort

    2014-10-01

    Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) × 109 M-1 s-1 at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol-1 Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 ± 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions.

  3. SOA Formation from Photooxidation of Individual PAHs and Mixtures

    NASA Astrophysics Data System (ADS)

    Chen, C. L.; Kacarab, M.; Tang, P.; Cocker, D. R., III

    2014-12-01

    Individual SOA experiments on PAHs such as naphthalene and methylnaphthalenes were conducted at the UCR CE-CERT environmental chamber. Measurements were made with a suite of instrumentation that includes HR-ToF-AMS, VTDMA, and APM-SMPS to comprehensively understand the chemical composition characteristics, volatility and density of particles. Our results indicated that the SOA yield from PAHs is large and the elemental and chemical composition analysis of HR-ToF-AMS revealed that oxygen-to-carbon ratio (O/C) increases with oxidation time and also suggested that the SOA from these three PAHs are mostly low volatility OOA. The density of aerosol formed from 1-methylnaphthalene photooxidation under high NOx condition was observed to decrease from 1.5 g/cm3 to 0.7 g/cm3 during the course of experiment. Transmission electron microscopy (TEM) of 1-methylnaphthalene SOA showed that the SOA coagulated after 5~6 hours photooxidation to form fractal-like particles. The sensitivity of SOA formation to varying HC mixtures is further explored. Serial mixtures of PAHs photooxidation experiments were conducted, including naphthalene, 1-methylnapthalene, 2-methylnaphtalene with m-xylene, and/or the surrogate mixture used to develop the Carter O3 reactivity scales. Preliminary results show that the SOA formation from m-xylene and naphthalene mixture photooxidation was found to be suppressed by m-xylene, and the volatility measured as volume remaining fraction (VRF) of the m-xylene and naphthalene mixture increases from 0.2 to 0.4, which indicates the volatility of mixture SOA is dominated by m-xylene SOA.

  4. SOA governance in healthcare organisations.

    PubMed

    Koumaditis, Konstantinos; Themistocleous, Marinos; Vassilakopoulos, Georgios

    2013-01-01

    Service Oriented Architecture (SOA) is increasingly adopted by many sectors, including healthcare. Due to the nature of healthcare systems there is a need to increase SOA adoption success rates as the non integrated nature of healthcare systems is responsible for medical errors that cause the loss of tens of thousands patients per year. Following our previous research [1] we propose that SOA governance is a critical success factor for SOA success in healthcare. Literature reports multiple SOA governance models that have limitations and they are confusing. In addition to this, there is a lack of healthcare specific SOA governance models. This highlights a literature void and thus the purpose of this paper is to proposed a healthcare specific SOA governance framework. PMID:23823423

  5. EPA STAR Grants Contribution to the SOAS Campaign

    EPA Science Inventory

    This poster explains how EPA Science to Achieve Results (STAR) grantees contributed to the summer 2013 inter-agency Southeast Atmosphere Study (SAS), specifically the Southern Oxidant and Aerosol Study (SOAS). There is also a brief explanation of EPA scientist involvement in this...

  6. The STAR Grants Contribution to the SOAS Campaign

    EPA Science Inventory

    The Southern Oxidant and Aerosol Study (SOAS) is a community-led field campaign that was part of the Southeast Atmosphere Study (SAS). As one of the largest field studies in decades to characterize air quality in the Southeastern United States, SAS is a collaborative project invo...

  7. Photochemical processing of organic aerosol at nearby continental sites: contrast between urban plumes and regional aerosol

    NASA Astrophysics Data System (ADS)

    Slowik, J. G.; Brook, J.; Chang, R. Y.-W.; Evans, G. J.; Hayden, K.; Jeong, C.-H.; Li, S.-M.; Liggio, J.; Liu, P. S. K.; McGuire, M.; Mihele, C.; Sjostedt, S.; Vlasenko, A.; Abbatt, J. P. D.

    2011-03-01

    As part of the BAQS-Met 2007 field campaign, Aerodyne time-of-flight aerosol mass spectrometers (ToF-AMS) were deployed at two sites in southwestern Ontario from 17 June to 11 July 2007. One instrument was located at Harrow, ON, a rural, agriculture-dominated area approximately 40 km southeast of the Detroit/Windsor/Windsor urban area and 5 km north of Lake Erie. The second instrument was located at Bear Creek, ON, a rural site approximately 70 km northeast of the Harrow site and 50 km east of Detroit/Windsor. Positive matrix factorization analysis of the combined organic mass spectral dataset yields factors related to secondary organic aerosol (SOA), direct emissions, and a factor tentatively attributed to the reactive uptake of isoprene and/or condensation of its early generation reaction products. This is the first application of PMF to simultaneous AMS measurements at different sites, an approach which allows for self-consistent, direct comparison of the datasets. Case studies are utilized to investigate processing of SOA from (1) fresh emissions from Detroit/Windsor and (2) regional aerosol during periods of inter-site flow. A strong correlation is observed between SOA/excess CO and photochemical age as represented by the NOx/NOy ratio for Detroit/Windsor outflow. Although this correlation is not evident for more aged air, measurements at the two sites during inter-site transport nevertheless show evidence of continued atmospheric processing by SOA production. However, the rate of SOA production decreases with airmass age from an initial value of ~10.1 μg m-3 ppmvCO-1 h-1 for the first ~10 h of plume processing to near-zero in an aged airmass (i.e. after several days). The initial SOA production rate is comparable to the observed rate in Mexico City over similar timescales.

  8. Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States

    EPA Science Inventory

    Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles,...

  9. Elemental Composition Analysis to Investigate NOx Effects on Secondary Organic Aerosol from α-Pinene Using Ultrahigh Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Lim, H. J.; Park, J. H.; Babar, Z.

    2015-12-01

    Secondary organic aerosol (SOA) accounts for 20-70% of atmospheric fine aerosol. NOx plays crucial roles in SOA formation and consequently affects the composition and yield of SOA. SOA component speciation is incomplete due to its complex composition of polar oxygenated and multifunctional species. In this study, ultrahigh resolution mass spectrometry (UHR MS) was applied to improve the understanding of NOx effects on biogenic SOA formation by identifying the elemental composition of SOA. Additional research aim was to investigate oligomer components that are considered as a driving force for SOA formation and growth. In this study α-pinene SOA from photochemical reaction was examined. SOA formation was performed in the absence and presence of NOx at dry condition (<5% RH) of room temperature (~25oC) in ~8 m3 KNU smog chamber. SOA was collected on Teflon-coated glass fiber filter, which was extracted using acetonitrile and analyzed by ultrahigh resolution 15T FT-ICR MS. UHR MS data were interpreted in various ways including molecular formula, Kendrick diagram, van Krevelen diagram, and double bond equivalent values. Substantially large fractions of them are nitrogen containing species. Thousands of individual species of SOA were identified. For SOA in the absence of NOx. intensity normalized mean O/C, H/C, N/C, OM/OC ratios were 0.43, 1.52, 0.02, and 1.68, respectively. For SOA in the presence of NOx, those ratios were 0.52, 0.95, 0.08, and 1.48, respectively. 4 different oligomer formation mechanisms (addition, H abstraction, hydrolysis and de-hydrolysis reaction) were examined on the basis of SOA compositions. Detailed discussion will be presented on the molecular structure and building block of oligomers in SOA as well as the evolution of individual elemental composition by multi-generation reactions. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2011-01350000).

  10. Composition and formation of organic aerosol particles in the Amazon

    NASA Astrophysics Data System (ADS)

    Pöhlker, C.; Wiedemann, K.; Sinha, B.; Shiraiwa, M.; Gunthe, S. S.; Artaxo, P.; Gilles, M. K.; Kilcoyne, A. L. D.; Moffet, R. C.; Smith, M.; Weigand, M.; Martin, S. T.; Pöschl, U.; Andreae, M. O.

    2012-04-01

    We applied scanning transmission X-ray microscopy with near edge X-ray absorption fine structure (STXM-NEXAFS) analysis to investigate the morphology and chemical composition of aerosol samples from a pristine tropical environment, the Amazon Basin. The samples were collected in the Amazonian rainforest during the rainy season and can be regarded as a natural background aerosol. The samples were found to be dominated by secondary organic aerosol (SOA) particles in the fine and primary biological aerosol particles (PBAP) in the coarse mode. Lab-generated SOA-samples from isoprene and terpene oxidation as well as pure organic compounds from spray-drying of aqueous solution were measured as reference samples. The aim of this study was to investigate the microphysical and chemical properties of a tropical background aerosol in the submicron size range and its internal mixing state. The lab-generated SOA and pure organic compounds occurred as spherical and mostly homogenous droplet-like particles, whereas the Amazonian SOA particles comprised a mixture of homogeneous droplets and droplets having internal structures due to atmospheric aging. In spite of the similar morphological appearance, the Amazon samples showed considerable differences in elemental and functional group composition. According to their NEXAFS spectra, three chemically distinct types of organic material were found and could be assigned to the following three categories: (1) particles with a pronounced carboxylic acid (COOH) peak similar to those of laboratory-generated SOA particles from terpene oxidation; (2) particles with a strong hydroxy (COH) signal similar to pure carbohydrate particles; and (3) particles with spectra resembling a mixture of the first two classes. In addition to the dominant organic component, the NEXAFS spectra revealed clearly resolved potassium (K) signals for all analyzed particles. During the rainy season and in the absence of anthropogenic influence, active biota is

  11. Secondary aerosol formation from the oxidation of biogenic hydrocarbons by chlorine atoms

    NASA Astrophysics Data System (ADS)

    Cai, Xuyi; Griffin, Robert J.

    2006-07-01

    The chlorine atom (Cl) is a potential oxidant of volatile organic compounds (VOCs) in the atmosphere and is hypothesized to lead to secondary organic aerosol (SOA) formation in coastal and industrialized areas. The purpose of this paper is to test this hypothesis and to quantify the SOA formation potentials of the common monoterpenes α-pinene, β-pinene, and d-limonene when oxidized by Cl in laboratory chamber experiments. Results indicate that the oxidation of these monoterpenes generates significant amounts of aerosol. The SOA yields of α-pinene, β-pinene, and d-limonene in this study are comparable to those when they are oxidized by ozone, by nitrate radical, and in photooxidation scenarios. For aerosol mass up to 30.0 μg m-3, their yields reach approximately 0.20, 0.20, and 0.30, respectively. For d-limonene, data indicate two yield curves that depend on the initial concentration ratio of Cl precursor to d-limonene. It is argued theoretically that multiple SOA yield curves may be common for VOCs, depending on the initial concentration ratio of oxidant to VOC. SOA formation from the three typical monoterpenes when oxidized by Cl in the marine boundary layer, coastal areas, and inland industrialized areas could be a source of organic aerosol in the early morning.

  12. Fourier Transform Infrared Spectroscopy for Identification and Quantification of Organic Functional Groups in Aqueous Phase Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    George, K.; Ruthenburg, T. C.; Smith, J.; Anastasio, C.; Dillner, A. M.

    2011-12-01

    Particles in the atmosphere influence visibility, climate, and human health. Secondary organic aerosols (SOA) formed from chemical reactions in the atmosphere constitute a portion of total organic particle mass. Most research on SOA has focused on gas phase reactions; however, reactions taking place in cloud and fog drops may be significant. One group of water-soluble compounds that participate in these reactions is phenols. Phenols, emitted from biomass burning, react in the aqueous phase to form low-volatility SOA products. The products formed from these reactions are currently poorly characterized. In order to characterize laboratory-generated samples, we are developing an attenuated total reflectance-Fourier transform infrared spectroscopic (ATR-FTIR) technique to identify and quantify organic functional groups in SOA. Aqueous SOA is made in the laboratory by illuminating solutions of phenolic compounds with an oxidant. The illuminated solution is then blown to dryness in order to determine the mass of SOA produced. The dry SOA is reconstituted in water and drops of this solution are placed onto a single-reflection ATR accessory. In order to identify and quantify functional groups in the complex SOA samples, it is necessary to calibrate with compounds and mixtures of compounds containing bond types similar to those found in the laboratory-generated SOA. Initially, focus has been placed on multiple peaks located in the region between 1800 cm-1 and 800 cm-1, including peaks for C=O and C-O. We distinguish between characteristic absorbances to begin determining the organic functional group composition of the SOA samples. This ATR-FTIR technique complements information from mass spectrometry measurements and allows us to quantify organic mass for non-volatile SOA products.

  13. Complex refractive indices in the near-ultraviolet spectral region of biogenic secondary organic aerosol aged with ammonia

    SciTech Connect

    Flores, J. M.; Washenfelder, Rebecca; Adler, Gabriela; Lee, H-J; Segev, Lior; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey; Brown, Steven; Rudich, Yinon

    2014-05-14

    Atmospheric absorption by brown carbon aerosol may play an important role in global radiative forcing. Brown carbon arises from both primary and secondary sources, but the mechanisms and reactions for the latter are highly uncertain. One proposed mechanism is the reaction of ammonia or amino acids with carbonyl products in secondary organic aerosol (SOA). We generated SOA in situ by reacting biogenic alkenes (α-pinene, limonene, and α-humulene) with excess ozone, humidifying the resulting aerosol, and reacting the humidified aerosol with gaseous ammonia. We determined the complex refractive indices (RI) in the 360 – 420 nm range for these aerosols using broadband cavity enhanced spectroscopy (BBCES). The average real part (n) of the measured spectral range of the NH3-aged α-pinene SOA increased from n = 1.50 (±0.01) for the unreacted SOA to n = 1.57 (± 0.01) after a 1.5h exposure to 1.9 ppm NH3; whereas,the imaginary component (k) remained below k < 0.001 (± 0.002). For the limonene and α-humulene SOA the real part did not change significantly, and we observed a small change in the imaginary component of the RI. The imaginary component increased from k = 0.0 to an average k= 0.029 (± 0.021) for α-humulene SOA, and from k < 0.001 (± 0.002) to an average k = 0.032 (±0.019) for limonene SOA after a 1.5 h exposure to 1.3 and 1.9 ppm of NH3, respectively. Collected filter samples of the aged and unreacted α-pinene SOA and limonene SOA were analyzed off-line with nanospray desorption electrospray ionization high resolution mass spectrometry (nano-DESI/HR-MS), and in-situ with a Time-of-Fligh Aerosol Mass Spectrometer, confirming that the SOA reacted and that various nitrogen-containing reaction products formed. If we assume that NH3 aging reactions scale linearly with time and concentration, then a 1.5 h reaction with 1 ppm NH3 in the laboratory is equivalent to 24 h reaction with 63 ppbv NH3, indicating that the observed aerosol absorption will be limited

  14. Aerosols generated by spills of viscous solutions and slurries

    SciTech Connect

    Ballinger, M Y; Hodgson, W H

    1986-12-01

    Safety assessments and environmental impact statements for nuclear fuel cycle facilities require an estimate of potential airborne releases caused by accidents. Aerosols generated by accidents are being investigated by Pacific Northwest Laboratory to develop methods for estimating source terms from these accidents. Experiments were run by spilling viscous solutions and slurries to determine the mass and particle-size distribution of the material made airborne. In all cases, 1 L of solution was spilled from a height of 3 m. Aqueous solutions of sucrose (0 to 56%) gave a range of viscosities from 1.3 to 46 cp. The percent of spill mass made airborne from the spills of these solutions ranged from 0.001 to 0.0001. The mass of particles made airborne decreased as solution viscosity increased. Slurry loading ranged from 25 to 51% total solids. The maximum source airborne (0.0046 wt %) occurred with the slurry that had the lightest loading of soluble solids. The viscosity of the carrying solution also had an impact on the source term from spilling slurries. The effect of surface tension on the source term was examined in two experiments. Surface tension was halved in these spills by adding a surfactant. The maximum weight percent airborne from these spills was 0.0045, compared to 0.003 for spills with twice the surface tension. The aerodynamic mass medium diameters for the aerosols produced by spills of the viscous solutions, slurries, and low surface tension liquids ranged from 0.6 to 8.4 ..mu..m, and the geometric standard deviation ranged from 3.8 to 28.0.

  15. A Comparison of Parameterizations of Secondary Organic Aerosol Production: Global Budget and Spatiotemporal Variability

    NASA Astrophysics Data System (ADS)

    Liu, J.; Chen, Z.; Horowitz, L. W.; Carlton, A. M. G.; Fan, S.; Cheng, Y.; Ervens, B.; Fu, T. M.; He, C.; Tao, S.

    2014-12-01

    Secondary organic aerosols (SOA) have a profound influence on air quality and climate, but large uncertainties exist in modeling SOA on the global scale. In this study, five SOA parameterization schemes, including a two-product model (TPM), volatility basis-set (VBS) and three cloud SOA schemes (Ervens et al. (2008, 2014), Fu et al. (2008) , and He et al. (2013)), are implemented into the global chemical transport model (MOZART-4). For each scheme, model simulations are conducted with identical boundary and initial conditions. The VBS scheme produces the highest global annual SOA production (close to 35 Tg·y-1), followed by three cloud schemes (26-30 Tg·y-1) and TPM (23 Tg·y-1). Though sharing a similar partitioning theory to the TPM scheme, the VBS approach simulates the chemical aging of multiple generations of VOCs oxidation products, resulting in a much larger SOA source, particularly from aromatic species, over Europe, the Middle East and Eastern America. The formation of SOA in VBS, which represents the net partitioning of semi-volatile organic compounds from vapor to condensed phase, is highly sensitivity to the aging and wet removal processes of vapor-phase organic compounds. The production of SOA from cloud processes (SOAcld) is constrained by the coincidence of liquid cloud water and water-soluble organic compounds. Therefore, all cloud schemes resolve a fairly similar spatial pattern over the tropical and the mid-latitude continents. The spatiotemporal diversity among SOA parameterizations is largely driven by differences in precursor inputs. Therefore, a deeper understanding of the evolution, wet removal, and phase partitioning of semi-volatile organic compounds, particularly above remote land and oceanic areas, is critical to better constrain the global-scale distribution and related climate forcing of secondary organic aerosols.

  16. Reactive uptake of HOCl to laboratory generated sea salt particles and nascent sea-spray aerosol

    NASA Astrophysics Data System (ADS)

    Campbell, N. R.; Ryder, O. S.; Bertram, T. H.

    2013-12-01

    Field observations suggest that the reactive uptake of HOCl on marine aerosol particles is an important source of chlorine radicals, particularly under low NOx conditions. However to date, laboratory measurements disagree on the magnitude of the reactive uptake coefficient for HOCl by a factor of 5 (γ(HOCl) ranges between 0.0004 and 0.0018), and there are no measurements of γ(HOCl) on nascent sea-spray aerosol. Here, we present measurements of the reactive uptake of HOCl to laboratory generated sodium chloride and sea-spray aerosol particles generated in a novel Marine Aerosol Reference Tank (MART), coupled to an entrained aerosol flow reactor and Chemical Ionization Mass Spectrometer (CIMS). Measurements of γ(HOCl) retrieved here are compared against those in the literature, and the role of organic coatings on nascent sea-spray aerosol is explored.

  17. Aerosol from Organic Nitrogen in the Southeast United States

    EPA Science Inventory

    Biogenic volatile organic compounds (BVOCs) contribute significantly to organic aerosol in the southeastern United States. During the Southern Oxidant and Aerosol Study (SOAS), a portion of ambient organic aerosol was attributed to isoprene oxidation and organic nitrogen from BVO...

  18. High-resolution mass spectrometry and molecular characterization of aqueous photochemistry products of common types of secondary organic aerosols.

    PubMed

    Romonosky, Dian E; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A

    2015-03-19

    This work presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d-limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow-tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx-generated SOA had more unique visual appearance and indicated a lower extent of product overlap. Furthermore, the fraction of nitrogen-containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone-driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NOx photooxidation of 1,3,5-trimethylbenzene and guaiacol were more resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of

  19. Volatility of methylglyoxal cloud SOA formed through OH radical oxidation and droplet evaporation

    NASA Astrophysics Data System (ADS)

    Ortiz-Montalvo, Diana L.; Schwier, Allison N.; Lim, Yong B.; McNeill, V. Faye; Turpin, Barbara J.

    2016-04-01

    The volatility of secondary organic aerosol (SOA) formed through cloud processing (aqueous hydroxyl radical (radOH) oxidation and droplet evaporation) of methylglyoxal (MGly) was studied. Effective vapor pressure and effective enthalpy of vaporization (ΔHvap,eff) were determined using 1) droplets containing MGly and its oxidation products, 2) a Vibrating Orifice Aerosol Generator (VOAG) system, and 3) Temperature Programmed Desorption Aerosol-Chemical Ionization Mass Spectrometry (TPD Aerosol-CIMS). Simulated in-cloud MGly oxidation (for 10-30 min) produces an organic mixture of higher and lower volatility components with an overall effective vapor pressure of (4 ± 7) × 10-7 atm at pH 3. The effective vapor pressure decreases by a factor of 2 with addition of ammonium hydroxide (pH 7). The fraction of organic material remaining in the particle-phase after drying was smaller than for similar experiments with glycolaldehyde and glyoxal SOA. The ΔHvap,eff of pyruvic acid and oxalic acid + methylglyoxal in the mixture (from TPD Aerosol-CIMS) were smaller than the theoretical enthalpies of the pure compounds and smaller than that estimated for the entire precursor/product mix after droplet evaporation. After 10-30 min of aqueous oxidation (one cloud cycle) the majority of the MGly + radOH precursor/product mix (even neutralized) will volatilize during droplet evaporation; neutralization and at least 80 min of oxidation at 10-12 M radOH (or >12 h at 10-14 M) is needed before low volatility ammonium oxalate exceeds pyruvate.

  20. Hydroxyl radicals from secondary organic aerosol decomposition in water

    NASA Astrophysics Data System (ADS)

    Tong, H.; Arangio, A. M.; Lakey, P. S. J.; Berkemeier, T.; Liu, F.; Kampf, C. J.; Pöschl, U.; Shiraiwa, M.

    2015-11-01

    We found that ambient and laboratory-generated secondary organic aerosols (SOA) form substantial amounts of OH radicals upon interaction with liquid water, which can be explained by the decomposition of organic hydroperoxides. The molar OH yield from SOA formed by ozonolysis of terpenes (α-pinene, β-pinene, limonene) is ~ 0.1 % upon extraction with pure water and increases to ~ 1.5 % in the presence of Fe2+ ions due to Fenton-like reactions. Our findings imply that the chemical reactivity and aging of SOA particles is strongly enhanced upon interaction with water and iron. In cloud droplets under dark conditions, SOA decomposition can compete with the classical H2O2 Fenton reaction as the source of OH radicals. Also in the human respiratory tract, the inhalation and deposition of SOA particles may lead to a substantial release of OH radicals, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols.

  1. Hydroxyl radicals from secondary organic aerosol decomposition in water

    NASA Astrophysics Data System (ADS)

    Tong, Haijie; Arangio, Andrea M.; Lakey, Pascale S. J.; Berkemeier, Thomas; Liu, Fobang; Kampf, Christopher. J.; Pöschl, Ulrich; Shiraiwa, Manabu

    2016-04-01

    We found that ambient and laboratory-generated secondary organic aerosols (SOA) form substantial amounts of OH radicals upon interaction with liquid water, which can be explained by the decomposition of organic hydroperoxides. The molar OH yield from SOA formed by ozonolysis of terpenes (α-pinene, β-pinene, and limonene) is ~ 0.1% upon extraction with pure water, and which increases to ~ 1.5% in the presence of iron ions due to Fenton-like reactions. Our findings imply that the chemical reactivity and aging of SOA particles is strongly enhanced upon interaction with water and iron. In cloud droplets under dark conditions, SOA decomposition can compete with the classical hydrogen peroxide Fenton reaction as the source of OH radicals. Also in the human respiratory tract, the inhalation and deposition of SOA particles may lead to a substantial release of OH radicals, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols.

  2. SOA formation from the photooxidation of α-pinene: systematic exploration of the simulation of chamber data

    NASA Astrophysics Data System (ADS)

    McVay, R. C.; Zhang, X.; Aumont, B.; Valorso, R.; Camredon, M.; La, Y. S.; Wennberg, P. O.; Seinfeld, J. H.

    2015-11-01

    Chemical mechanisms play an important role in simulating the atmospheric chemistry of volatile organic compound oxidation. Comparison of mechanism simulations with laboratory chamber data tests our level of understanding of the prevailing chemistry as well as the dynamic processes occurring in the chamber itself. α-pinene photooxidation is a well-studied system experimentally, for which detailed chemical mechanisms have been formulated. Here, we present the results of simulating low-NO α-pinene photooxidation experiments conducted in the Caltech chamber with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) under varying concentrations of seed particles and OH levels. Unexpectedly, experiments conducted at low and high OH levels yield the same SOA growth, whereas GECKO-A predicts greater SOA growth under high OH levels. SOA formation in the chamber is a result of a competition among the rates of gas-phase oxidation to low volatility products, wall deposition of these products, and condensation into the aerosol phase. Various processes, such as photolysis of condensed-phase products, particle-phase dimerization, and peroxy radical autoxidation, are explored to rationalize the observations. In order to explain the observed similar SOA growth under different OH levels, we conclude that vapor wall loss in the Caltech chamber is likely of order 10-5 s-1, consistent with previous experimental measurements in that chamber. We find that GECKO-A tends to overpredict the contribution to SOA of later-generation oxidation products under high OH conditions. The key role of the interplay among oxidation rate, product volatility, and vapor-wall deposition in chamber experiments is illustrated.

  3. Integrating phase and composition of secondary organic aerosol from the ozonolysis of α-pinene

    PubMed Central

    Kidd, Carla; Perraud, Véronique; Wingen, Lisa M.; Finlayson-Pitts, Barbara J.

    2014-01-01

    Airborne particles are important for public health, visibility, and climate. Predicting their concentrations, effects, and responses to control strategies requires accurate models of their formation and growth in air. This is challenging, as a large fraction is formed by complex reactions of volatile organic compounds, generating secondary organic aerosol (SOA), which grows to sizes important for visibility, climate, and deposition in the lung. Growth of SOA is particularly sensitive to the phase/viscosity of the particles and remains poorly understood. We report studies using a custom-designed impactor with a germanium crystal as the impaction surface to study SOA formed from the ozonolysis of α-pinene at relative humidities (RHs) up to 87% at 297 ± 2 K (which corresponds to a maximum RH of 70–86% inside the impactor). The impaction patterns provide insight into changes in phase/viscosity as a function of RH. Attenuated total reflectance-Fourier transform infrared spectroscopy and aerosol mass spectrometry provide simultaneous information on composition changes with RH. The results show that as the RH at which the SOA is formed increases, there is a decrease in viscosity, accompanied by an increasing contribution from carboxylic acids and a decreasing contribution from higher molecular mass products. In contrast, SOA that is formed dry and subsequently humidified remains solid to high RH. The results of these studies have significant implications for modeling the growth, aging, and ultimately, lifetime of SOA in the atmosphere. PMID:24821796

  4. Influence of realistic airflow rate on aerosol generation by nebulizers.

    PubMed

    Vecellio, Laurent; Kippax, Paul; Rouquette, Stephane; Diot, Patrice

    2009-04-17

    Mathematical models are available which predict aerosol deposition in the respiratory system assuming that the aerosol concentration and size are constant during inhalation. In this study, we constructed a sinusoidal breathing model to calculate the aerosol concentration produced by a nebulizer as a function of inhalation time. The laser diffraction technique (Spraytec, Malvern Instruments Ltd., Malvern, UK) was used to validate this model as it allows the aerosol concentration and particle size to be measured in real time. Each nebulizer was attached to a special glass measurement cell and a sine-wave pump. Two standard jet nebulizers (Mistyneb and Microneb), two breath-enhanced jet nebulizers (Pari LC+ and Atomisor NL9M) and three mesh nebulizers (Eflow, Aeroneb Go and Aeroneb Pro with Idehaler) were characterized. Results obtained were consistent in terms of curve profile between the proposed model and the laser diffraction measurements. The standard jet and mesh nebulizers produced significant variations in aerosol concentration during inhalation, whereas the breath-enhanced jet nebulizers produced a constant aerosol concentration. All of the nebulizers produced a relatively constant particle size distribution. Our findings confirm that the concentration observed during inhalation is often not constant over time. The laser diffraction method allows the concentration and size of particles for each unit volume of air inhaled to be measured and could therefore be used to predict the aerosol deposition pattern more precisely. PMID:19150494

  5. Investigation of formation and ageing of biogenic secondary aerosols by soft ionization aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Müller, Lars; Reinnig, Marc-Christopher; Vogel, Alexander; Mentel, Thomas; Tillmann, Ralf; Schlosser, E.; Wahner, Andreas; Donahue, Neil; Saathoff, Harald; Hoffmann, Thorsten

    2010-05-01

    The knowledge of the chemical composition of secondary organic aerosol is one essential key to understand the significance and fate of SOA in the atmosphere. However, the chemical evolution of SOA, from the very first condensing/nucleating molecules to the final oxidation products is still insufficiently understood and object of current research [1-3]. Consequently, the formation and photochemical ageing of secondary organic aerosol (SOA) was investigated in a series of reaction chamber experiments by applying on-line aerosol mass spectrometry (atmospheric pressure chemical ionization mass spectrometry (APCI/MS)) as well as off-line high performance liquid chromatography mass spectrometry (HPLC-MS). In a set of experiments, performed in the large outdoor reaction chamber SAPHIR (Jülich, Germany), SOA was generated from a boreal mixture of biogenic VOCs. During a two-day experiment the generated biogenic SOA was exposed to OH-radicals and the temporal evolution of the chemical composition was characterized. The applied on-line MS method not only provides highly time resolved chemical information (such as an AMS) but also allows molecular identification/quantification of specific marker compounds. Several first and higher generation BSOA products were identified. Among the higher generation products, especially a tricarboxylic acid (3-methyl-1,2,3-butanetricarboxylic acid) [2] was observed as an eye-catching oxidative processing marker. A more detailed investigation of hydroxyl radical induced SOA aging at the AIDA chamber facility in Karlsruhe, again using terpenes as SOA precursors, clearly showed that the formation of the tricarboxylic acid takes place in the gas phase by the reaction of semivolatile first generation products and hydroxyl radicals. Actually, there were no indications for OH induced oxidation of compounds in the condensed phase. The consequences of these results will be discussed in the contribution. 1. Rudich, Y., N.M. Donahue, and T.F. Mentel

  6. Enhancement effect of relative humidity on the formation and regional respiratory deposition of secondary organic aerosol.

    PubMed

    Yu, Kuo-Pin; Lin, Chi-Chi; Yang, Shang-Chun; Zhao, Ping

    2011-07-15

    In this study, we investigated the effect of relative humidity (RH) on the formation of secondary organic aerosol (SOA) generated from the ozonolysis of d-limonene in an environmental chamber. The mass yield and the number concentration of SOA increased seven and eight times, respectively, when the RH increased from 18% to 82%. The measured total loss rates (apparent loss rates) of the number and mass concentration of SOA in the chamber ranged from 1.70 to 1.77 h(-1) and from 2.51 to 2.61 h(-1), respectively, at a controlled ventilation rate of 0.72±0.04 h(-1). The wall-deposition-loss-rate coefficient observed (1.00±0.02 h(-1)) was approximate to the estimated value based on Zhao and Wu's model which includes the factors of turbulence, Brownian diffusion, turbophoresis and surface roughness. According to the ICRP (International Commission on Radiological Protection) model, the inhaled SOA particles are deposited primarily in the alveoli of the lung. The integrated alveolar deposited dose of the mass (surface area) of SOA over 3h accounted for 74.0-74.8% (74.3-74.9%) of the total deposited dose at the investigated RH. Raising the RH resulted in the growth of SOA particle sizes and increment of the deposition dose but did not cause significant changes in the ratio of regional to the total respiratory deposition of SOA. PMID:21570180

  7. Sources, properties, aging, and anthropogenic influences on OA and SOA over the Southeast US and the Amazon during SOAS, DC3, SEAC4RS, and GoAmazon

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.; Campuzano Jost, P.; Hu, W.; Palm, B. B.; Thompson, S.; Krechmer, J.; Day, D. A.; Stark, H.; Peng, Z.; Ortega, A. M.; Isaacman, G. A.; Goldstein, A. H.; Holzinger, R.; de Sá, S. S.; Martin, S. T.; Alexander, M. L.; Guenther, A. B.; Canagaratna, M. R.; Massoli, P.; Kimmel, J.; Jayne, J. T.; Worsnop, D. R.; Brune, W. H.; Lee-Taylor, J. M.; Hodzic, A.; Madronich, S.; Offenberg, J. H.; Ferreira De Brito, J.; Artaxo, P.; Manzi, A. O.

    2014-12-01

    The SE US and the Amazon have large sources of biogenic VOCs and varying anthropogenic pollution impact, and often poor aerosol model performance. Recent results on the sources, properties, aging, and impact of anthropogenic pollution on OA and secondary OA (SOA) over these regions will be presented. SOA from IEPOX accounts for 14-17% of the OA on average over the SE US and extending up to 6 km. Higher IEPOX-SOA correlates with airmasses of high isoprene, IEPOX, sulfate, acidity, and lower NO. The IEPOX organosulfate accounts for ~10% of IEPOX-SOA over the SE US. The AMS ion C5H6O+ is shown to be a good marker of IEPOX-SOA, while total m/z 82 (as in ACSM) suffers larger interferences. The sinks of IEPOX-SOA via both OH oxidation and evaporation are slow. The low-volatility of IEPOX-SOA contrasts with the small semivolatile molecules that have so far been identified as its components, suggesting the importance of oligomerization. Urban SOA is estimated to account for 25% of the OA in the SE US using either the GEOS-Chem model or the measured 14C (using recent results that urban SOA (POA) is 30% (50%) non-fossil, mainly due to cooking emissions). An oxidation flow reactor (OFR) is used to investigate SOA formation by OH, O3, and NO3 in-situ. Largest SOA formation is always observed at night when monoterpenes (MT) are largest, and is underpredicted by SOA models that use MT as precursors but ignore partially-oxidized products. Closure results from models (VBS and GECKO-A) that account for the whole oxidation chain will be presented. The partitioning of organic acids is found to proceed rapidly in response to temperature changes, in contrast with recent reports of very slow equilibration. The agreement with absorptive partitioning theory is reasonable for most species, except small acids that may be formed by thermal decomposition during analysis. Partitioning data from four instruments is compared, with reasonable agreement in many cases including the rapid response

  8. Water uptake is independent of the inferred composition of secondary aerosols derived from multiple biogenic VOCs

    NASA Astrophysics Data System (ADS)

    Alfarra, M. R.; Good, N.; Wyche, K. P.; Hamilton, J. F.; Monks, P. S.; Lewis, A. C.; McFiggans, G. B.

    2013-04-01

    We demonstrate that the water uptake properties derived from sub- and super-saturated measurements of chamber-generated biogenic secondary organic aerosol (SOA) particles are independent of their degree of oxidation determined using both online and offline methods. SOA particles are formed from the photooxidation of five structurally different biogenic VOCs representing a broad range of emitted species and their corresponding range of chemical reactivity: α-pinene, β-caryophyllene, limonene, myrcene and linalool. The fractional contribution of mass fragment 44 to the total organic signal (f44) is used to characterise the extent of oxidation of the formed SOA as measured online by an aerosol mass spectrometer. Results illustrate that the values of f44 are dependent on the precursor, the extent of photochemical ageing as well as on the initial experimental conditions. SOA generated from a single biogenic precursor should therefore not be used as a general proxy for biogenic SOA. Similarly, the generated SOA particles exhibit a range of hygroscopic properties depending on the precursor, its initial mixing ratio and photochemical ageing. The activation behaviour of the formed SOA particles show no temporal trends with photochemical ageing. The average κ values derived from the HTDMA and CCNc are generally found to cover the same range for each precursor under two different initial mixing ratio conditions. A positive correlation is observed between the hygroscopicity of particles of a single size and f44 for α-pinene, β-caryophyllene, linalool and myrcene, but not for limonene SOA. The investigation of the generality of this relationship reveal that α-pinene, limonene, linalool and myrcene are all able to generate particles with similar hygroscopicity (κHTDMA ~0.1) despite f44 exhibiting a relatively wide range of values (~4 to 11%). Similarly, κCCN is found to be independent of f44. The same findings are also true when sub- and super-saturated water uptake

  9. Water uptake is independent of the inferred composition of secondary aerosols derived from multiple biogenic VOCs

    NASA Astrophysics Data System (ADS)

    Alfarra, M. R.; Good, N.; Wyche, K. P.; Hamilton, J. F.; Monks, P. S.; Lewis, A. C.; McFiggans, G.

    2013-12-01

    We demonstrate that the water uptake properties derived from sub- and super-saturated measurements of chamber-generated biogenic secondary organic aerosol (SOA) particles are independent of their degree of oxidation, determined using both online and offline methods. SOA particles are formed from the photooxidation of five structurally different biogenic VOCs, representing a broad range of emitted species and their corresponding range of chemical reactivity: α-pinene, β-caryophyllene, limonene, myrcene and linalool. The fractional contribution of mass fragment 44 to the total organic signal (f44) is used to characterise the extent of oxidation of the formed SOA as measured online by an aerosol mass spectrometer. Results illustrate that the values of f44 are dependent on the precursor, the extent of photochemical ageing as well as on the initial experimental conditions. SOA generated from a single biogenic precursor should therefore not be used as a general proxy for biogenic SOA. Similarly, the generated SOA particles exhibit a range of hygroscopic properties, depending on the precursor, its initial mixing ratio and photochemical ageing. The activation behaviour of the formed SOA particles show no temporal trends with photochemical ageing. The average κ values derived from the HTDMA and CCNc are generally found to cover the same range for each precursor under two different initial mixing ratio conditions. A positive correlation is observed between the hygroscopicity of particles of a single size and f44 for α-pinene, β-caryophyllene, linalool and myrcene, but not for limonene SOA. The investigation of the generality of this relationship reveals that α-pinene, limonene, linalool and myrcene are all able to generate particles with similar hygroscopicity (κHTDMA ~0.1) despite f44 exhibiting a relatively wide range of values (~4 to 11%). Similarly, κCCN is found to be independent of f44. The same findings are also true when sub- and super-saturated water uptake

  10. Bedding disposal cabinet for containment of aerosols generated by animal cage cleaning procedures.

    PubMed Central

    Baldwin, C L; Sabel, F L; Henke, C B

    1976-01-01

    Laboratory tests with aerosolized spores and animal room tests with uranine dye indicate the effectiveness of a prototype bedding disposal cabinet in reducing airborne contamination generated by cage cleaning procedures. Images PMID:826219

  11. Bedding disposal cabinet for containment of aerosols generated by animal cage cleaning procedures.

    PubMed

    Baldwin, C L; Sabel, F L; Henke, C B

    1976-02-01

    Laboratory tests with aerosolized spores and animal room tests with uranine dye indicate the effectiveness of a prototype bedding disposal cabinet in reducing airborne contamination generated by cage cleaning procedures. PMID:826219

  12. Secondary Organic Aerosol Formation in Aerosol Water by Photochemical Reactions of Gaseous Mixture of Monoterpene and Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Lim, H.; Yi, S.; Park, J.; Cho, H.; Jung, K.

    2011-12-01

    There exist large uncertainties in model predictions for climate change and regional air quality. It could be caused by incomplete integration of secondary organic aerosol (SOA) formation in atmospheric chemical models. Recent laboratory studies have found SOA formation through chemical reactions on aerosol surface and in aerosol water. Water soluble organics formed by photochemical degradation of biogenic organics including isoprene and anthropogenic aromatics are predicted to form substantial amount of SOA through the newly found pathways. Although SOA formation in bulk aqueous solution was reported for laboratory experiments of various precursors (e.g., water soluble carbonyls and phenols), little is known for SOA formation in real aerosol water. In this study, photochemical reactions of the gaseous mixture of monoterpene and hydrogen peroxide were examined to investigate SOA formation through reactions in real aerosol phase water. SOA formation was conducted using a flow tube reactor (ID 30 cm x L 150 cm, FEP) and a smog chamber using FEP film in the presence of dry and wet seed particles. Acidity and chemical composition of seed aerosol were also controlled as important parameters influencing SOA formation. Particle size distribution and aerosol composition were analyzed to account for differences in SOA formation mechanisms and yields for dry and wet particles. The differences might be mainly associated with SOA formation in aerosol phase water. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2011-0000221).

  13. Terpenylic acid and nine-carbon multifunctional compounds formed during the aging of β-pinene ozonolysis secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Sato, Kei; Jia, Tianyu; Tanabe, Kiyoshi; Morino, Yu; Kajii, Yoshizumi; Imamura, Takashi

    2016-04-01

    Recent field and laboratory studies suggest that forest aerosol particles contain more highly functionalized organic molecules than pinonic acid, a traditional molecular maker of secondary organic aerosol (SOA) particles. To investigate the reaction mechanisms during the aging of biogenic SOAs, the gases and particles formed from the ozonolysis of β- and α-pinene were exposed to OH radicals in a laboratory chamber. The particle samples were collected before and after OH exposure for analysis by liquid chromatography-negative electrospray ionization time-of-flight mass spectrometry. Pinic acid and terpenylic acid were abundant products in both β- and α-pinene ozonolysis SOA particles. Terpenylic acid and products with m/z 201.08 present in β-pinene SOA particles increased upon exposing SOA to OH radicals, whereas 3-methyl-1,2,3-butanetricarboxylic acid present in α-pinene SOA particles increased upon exposing SOA to OH radicals. The products with m/z 201.08 were suggested to be C9H14O5 compounds. Similar C9H14O5 compounds and terpenylic acid were also detected in SOA particles formed from the photooxidation of nopinone, a major first-generation product of β-pinene ozonolysis. The OH-initiated oxidation of nopinone will contribute to the formation of terpenylic acid and C9H14O5 compounds during the aging of β-pinene SOA. A formation mechanism for terpenylic acid via gas-phase diaterpenylic acid formation followed by self-dehydration in the condensed phase was suggested.

  14. Effect of Hydrophobic Primary Organic Aerosols on Secondary Organic Aerosol Formation from Ozonolysis of α-Pinene

    SciTech Connect

    Song, Chen; Zaveri, Rahul A.; Alexander, M. Lizabeth; Thornton, Joel A.; Madronich, Sasha; Ortega, John V.; Zelenyuk, Alla; Yu, Xiao-Ying; Laskin, Alexander; Maughan, A. D.

    2007-10-16

    Semi-empirical secondary organic aerosol (SOA) models typically assume a well-mixed organic aerosol phase even in the presence of hydrophobic primary organic aerosols (POA). This assumption significantly enhances the modeled SOA yields as additional organic mass is made available to absorb greater amounts of oxidized secondary organic gases than otherwise. We investigate the applicability of this critical assumption by measuring SOA yields from ozonolysis of α-pinene (a major biogenic SOA precursor) in a smog chamber in the absence and in the presence of dioctyl phthalate (DOP) and lubricating oil seed aerosol. These particles serve as surrogates for urban hydrophobic POA. The results show that these POA did not enhance the SOA yields. If these results are found to apply to other biogenic SOA precursors, then the semi-empirical models used in many global models would predict significantly less biogenic SOA mass and display reduced sensitivity to anthropogenic POA emissions than previously thought.

  15. CONTRIBUTIONS OF TOLUENE AND Α -PINENE TO SOA FORMED IN AN IRRADIATED TOLUENE/Α-PINENE/NOX/AIR MIXTURE: COMPARISON OF RESULTS USING 14C CONTENT AND SOA ORGANIC TRACER METHODS

    EPA Science Inventory

    An organic tracer method, recently proposed for estimating individual contributions of toluene and α-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydro...

  16. Heterogeneous SOA yield from ozonolysis of monoterpenes in the presence of inorganic acid

    NASA Astrophysics Data System (ADS)

    Northcross, Amanda L.; Jang, Myoseon

    The secondary organic aerosol (SOA) yield of a series of montoerpenes was investigated to determine the relative amounts of organic mass, which can be attributed to mass produced by heterogeneous acid-catalyzed reactions. Five monoterpenes ( α-pinene, terpinolene, d-limonene, Δ2-carene, β-pinene) were studied using a 2 m 3 indoor Teflon chamber and SOA was created in the presence of both acidic and neutral inorganic seed aerosol. The relative humidity was varied to create differing acidic seed environments. The heterogeneous aerosol production was influenced by the seed mass concentration, the acidity of the inorganic seed aerosol, and also molecular structure of the monoterpene ozonolysis products. This study also can be incorporated with our previously presented model of the kinetic expression for SOA mass production from heterogeneous acid-catalyzed reactions.

  17. Role of methyl group number on SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions

    NASA Astrophysics Data System (ADS)

    Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker, D. R., III

    2016-02-01

    Substitution of methyl groups onto the aromatic ring determines the secondary organic aerosol (SOA) formation from the monocyclic aromatic hydrocarbon precursor (SOA yield and chemical composition). This study links the number of methyl groups on the aromatic ring to SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions (HC/NO > 10 ppbC : ppb). Monocyclic aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from monocyclic aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low-NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from monocyclic aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests that, as more methyl groups are attached on the aromatic ring, SOA products from these monocyclic aromatic hydrocarbons become less oxidized per mass/carbon on the basis of SOA yield or chemical composition.

  18. Biogenic amines in submicron marine aerosol (Invited)

    NASA Astrophysics Data System (ADS)

    Facchini, M.

    2010-12-01

    Ammonium salts of dimethyl and diethyl amine (DMA+ and DEA+) have been detected in size segregated marine samples collected in the North Atlantic over open ocean and at a coastal site. DMA+ and DEA+ peak in the accumulation mode range while very low concentration, close to detection limit, are observed in the coarse size fractions, as well as in sea spray aerosol artificially generated in the laboratory using sea water. These results indicate a secondary formation pathway. DMA+ and DEA+ represent up to 20% of secondary organic aerosol (SOA) in our samples , and to our knowledge they are the most abundant organic species besides MSA ever detected in clean marine aerosol . Maximum concentrations have been observed during spring and summer when the biological activity is high and in clean marine air masses, thus indicating biogenic sources. Total organic nitrogen (ON) concentration also peaks in the accumulation mode range and represents in our samples a fraction from 32 to 54 % of the total SOA. Ammonium salt formation from biogenic amines might be an important source of marine SOA and atmospheric nitrogen at the global scale with a seasonal variation connected to the oceanic biological productivity and an atmospheric cycle parallel to that of the organosulfur species.

  19. In Vitro Evaluation of a Device for Intra-Pulmonary Aerosol Generation and Delivery

    PubMed Central

    Syedain, Zeeshan H.; Naqwi, Amir A.; Dolovich, Myrna; Somani, Arif

    2015-01-01

    For infants born with respiratory distress syndrome (RDS), liquid bolus delivery of surfactant administered through an endotracheal tube is common practice. While this method is generally effective, complications such as transient hypoxia, hypercapnia, and altered cerebral blood flow may occur. Aerosolized surfactant therapy has been explored as an alternative. Unfortunately, past efforts have led to disappointing results as aerosols were generated outside the lungs with significant pharyngeal deposition and minimal intrapulmonary instillation. A novel aerosol generator (Microjet™) is evaluated herein for intrapulmonary aerosol generation within an endotracheal tube and tested with Curosurf and Infasurf surfactants. Compared with other aerosol delivery devices, this process utilizes low air flow (range 0.01-0.2 L/min) that is ideal for limiting potential barotrauma to the premature newborn lung. The mass mean diameter (MMD) of the particles for both tested surfactants was less than 4 μm, which is ideal for both uniform and distal lung delivery. As an indicator of phospholipid function, surfactant surface tension was measured before and after aerosol formation; with no significant difference. Moreover, this device has an outside diameter of <1mm, which permits insertion into an endotracheal tube (of even 2.0 mm). In the premature infant where intravenous access is either technically challenging or difficult, aerosol drug delivery may provide an alternative route in patient resuscitation, stabilization and care. Other potential applications of this type of device include the delivery of nutrients, antibiotics, and analgesics via the pulmonary route. PMID:26884641

  20. 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.

  1. First Estimates of the Radiative Forcing of Aerosols Generated from Biomass Burning Using Satellite Data

    NASA Technical Reports Server (NTRS)

    Christopher, Sundar A.; Kliche, Donna A.; Chou, Joyce; Welch, Ronald M.

    1996-01-01

    Collocated measurements from the Advanced Very High Resolution Radiometer (AVHRR) and the Earth Radiation Budget Experiment (ERBE) scanner are used to examine the radiative forcing of atmospheric aerosols generated from biomass burning for 13 images in South America. Using the AVHRR, Local Area Coverage (LAC) data, a new technique based on a combination of spectral and textural measures is developed for detecting these aerosols. Then, the instantaneous shortwave, longwave, and net radiative forcing values are computed from the ERBE instantaneous scanner data. Results for the selected samples from 13 images show that the mean instantaneous net radiative forcing for areas with heavy aerosol loading is about -36 W/sq m and that for the optically thin aerosols are about -16 W/sq m. These results, although preliminary, provide the first estimates of radiative forcing of atmospheric aerosols from biomass burning using satellite data.

  2. First Estimates of the Radiative Forcing of Aerosols Generated from Biomass Burning using Satellite Data

    NASA Technical Reports Server (NTRS)

    Chistopher, Sundar A.; Kliche, Donna V.; Chou, Joyce; Welch, Ronald M.

    1996-01-01

    Collocated measurements from the Advanced Very High Resolution Radiometer (AVHRR) and the Earth Radiation Budget Experiment (ERBE) scanner are used to examine the radiative forcing of atmospheric aerosols generated from biomass burning for 13 images in South America. Using the AVHRR, Local Area Coverage (LAC) data, a new technique based on a combination of spectral and textural measures is developed for detecting these aerosols. Then, the instantaneous shortwave, longwave, and net radiative forcing values are computed from the ERBE instantaneous scanner data. Results for the selected samples from 13 images show that the mean instantaneous net radiative forcing for areas with heavy aerosol loading is about -36 W/sq m and that for the optically thin aerosols are about -16 W/sq m. These results, although preliminary, provide the first estimates of radiative forcing of atmospheric aerosols from biomass burning using satellite data.

  3. Global mechanistic model of SOA formation: effects of different chemical mechanisms

    NASA Astrophysics Data System (ADS)

    Lin, G.; Penner, J. E.; Sillman, S.; Taraborrelli, D.; Lelieveld, J.

    2011-09-01

    Recent experimental findings indicate that Secondary Organic Aerosol (SOA) represents an important and, under many circumstances, the major fraction of the organic aerosol burden. Here, we use a global 3-d model (IMPACT) to test the results of different mechanisms for the production of SOA. The basic mechanism includes SOA formation from organic nitrates and peroxides produced from an explicit chemical formulation, using partition coefficients based on thermodynamic principles. We also include the formation of non-evaporative SOA from the reaction of glyoxal and methylglyoxal on aqueous aerosols and cloud droplets as well as from the reaction of epoxides on aqueous aerosols. A model simulation including these SOA formation mechanisms gives an annual global SOA production of 113.5 Tg. The global production of SOA is substantially decreased to 85.0 Tg yr-1 if the HOx regeneration mechanism proposed by Peeters et al. (2009) is used. Model predictions with and without this HOx regeneration scheme are compared with multiple surface observation datasets, namely: the Interagency Monitoring of Protected Visual Environments (IMPROVE) for the United States, the European Monitoring and Evaluation Programme (EMEP) as well as Aerosol Mass Spectrometry (AMS) data measured in both Northern Hemisphere and tropical forest regions. All model simulations realistically predict the organic carbon mass observed in the Northern Hemisphere, although they tend to overestimate the concentrations in tropical forest regions. This overestimate may result from an unrealistically high uptake rate of glyoxal and methylglyoxal on aqueous aerosols and in cloud drops. The modeled OC in the free troposphere is in agreement with measurements in the ITCT-2K4 aircraft campaign over the North America and in pollution layers in Asia during the INTEX-B campaign, although the model underestimates OC in the free troposphere during the ACE-Asia campaign off the coast of Japan.

  4. Science Opportunity Analyzer (SOA): Not Just Another Pretty Face

    NASA Technical Reports Server (NTRS)

    Polanskey, Carol A.; Streiiffert, Barbara; O'Reilly, Taifun

    2004-01-01

    This viewgraph presentation reviews the Science Opportunity Analyzer (SOA). For the first time at JPL, the Cassini mission to Saturn is using distributed science operations for sequence generation. This means that scientist at other institutions has more responsibility to build the spacecraft sequence. Tools are required to support the sequence development. JPL tools required a complete configuration behind a firewall, and the tools that the user community had developed did not interface with the JPL tools. Therefore the SOA was created to bridge the gap between the remote scientists and the JPL operations teams. The presentation reviews the development of the SOA, and what was required of the system. The presentation reviews the functions that the SOA performed.

  5. Influence of Aerosol Acidity on the Formation of Secondary Organic Aerosol from Biogenic Precursor Hydrocarbons

    EPA Science Inventory

    Secondary organic aerosol (SOA) formation and dynamics may be important factors for the role of aerosols in adverse health effects, visibility and climate change. Formation of SOA occurs when a parent volatile organic compound is oxidized to create products that form in a conden...

  6. Simulation of SOA formation and composition from oxidation of toluene and m-xylene in chamber experiments

    NASA Astrophysics Data System (ADS)

    Xu, J.; Liu, Y.; Nakao, S.; Cocker, D.; Griffin, R. J.

    2013-12-01

    Aromatic hydrocarbons contribute an important fraction of anthropogenic reactive volatile organic compounds (VOCs) in the urban atmosphere. Photo-oxidation of aromatic hydrocarbons leads to secondary organic products that have decreased volatilities or increased solubilities and can form secondary organic aerosol (SOA). Despite the crucial role of aromatic-derived SOA in deteriorating air quality and harming human health, its formation mechanism is not well understood and model simulation of SOA formation still remains difficult. The dependence of aromatic SOA formation on nitrogen oxides (NOx) is not captured fully by most SOA formation models. Most models predict SOA formation under high NOx levels well but underestimate SOA formation under low NOx levels more representative of the ambient atmosphere. Thus, it is crucial to investigate the NOx-dependent chemistry in aromatic photo-oxidation systems and correspondingly update SOA formation models. In this study, NOx-dependent mechanisms of toluene and m-xylene SOA formation are updated using the gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) coupled to a gas/aerosol partitioning model. The updated models were optimized by comparing to eighteen University of California, Riverside United States Environmental Protection Agency (EPA) chamber experiment runs under both high and low NOx conditions. Correction factors for vapor pressures imply uncharacterized aerosol-phase association chemistry. Simulated SOA speciation implies the importance of ring-opening products in governing SOA formation (up to 40%~60% for both aromatics). The newly developed model can predict strong decreases of m-xylene SOA yield with increasing NOx. Speciation distributions under varied NOx levels implies that the well-known competition between RO2 + HO2 and RO2 + NO (RO2 = peroxide bicyclic radical) may not be the only factor influencing SOA formation. The reaction of aromatic peroxy radicals with NO competing with its self

  7. Spectra Aerosol Light Scattering and Absorption for Laboratory and Urban Aerosol

    NASA Astrophysics Data System (ADS)

    Gyawali, Madhu S.

    Atmospheric aerosols considerably influence the climate, reduce visibility, and cause problems in human health. Aerosol light absorption and scattering are the important factors in the radiation transfer models. However, these properties are associated with large uncertainties in climate modeling. In addition, atmospheric aerosols widely vary in composition and size; their optical properties are highly wavelength dependent. This work presents the spectral dependence of aerosol light absorption and scattering throughout the ultraviolet to near-infrared regions. Data were collected in Reno, NV from 2008 to 2010. Also presented in this study are the aerosol optical and physical properties during carbonaceous aerosols and radiative effects study (CARES) conducted in Sacramento area during 2010. Measurements were made using photoacoustic instruments (PA), including a novel UV 355 nm PA of our design and manufacture. Comparative analyses are presented for three main categories: (1) aerosols produced by wildfires and traffic emissions, (2) laboratory-generated and wintertime ambient urban aerosols, and (3) urban plume and biogenic emissions. In these categories, key questions regarding the light absorption by secondary organic aerosols (SOA), so-called brown carbon (BrC), and black carbon (BC) will be discussed. An effort is made to model the emission and aging of urban and biomass burning aerosol by applying shell-core calculations. Multispectral PA measurements of aerosols light absorption and scattering coefficients were used to calculate the Angstrom exponent of absorption (AEA) and single scattering albedo (SSA). The AEA and SSA values were analyzed to differentiate the aerosol sources. The California wildfire aerosols exhibited strong wavelength dependence of aerosol light absorption with AEA as lambda -1 for 405 and 870 nm, in contrast to the relatively weak wavelength dependence of traffic emissions aerosols for which AEA varied approximately as lambda-1. By using

  8. AEROSOLS GENERATED BY LIQUID SLUDGE APPLICATION TO LAND

    EPA Science Inventory

    A preliminary screen was conducted at six sites to characterize sludge with regard to bacterial and viral microorganisms, trace metals, organoechlorine pesticides, and PCB's, and to evaluate each site for its suitability for aerosol monitoring. Four sites were selected for aeroso...

  9. High-efficiency particulate air filter test stand and aerosol generator for particle loading studies.

    PubMed

    Arunkumar, R; Hogancamp, Kristina U; Parsons, Michael S; Rogers, Donna M; Norton, Olin P; Nagel, Brian A; Alderman, Steven L; Waggoner, Charles A

    2007-08-01

    This manuscript describes the design, characterization, and operational range of a test stand and high-output aerosol generator developed to evaluate the performance of 30 x 30 x 29 cm(3) nuclear grade high-efficiency particulate air (HEPA) filters under variable, highly controlled conditions. The test stand system is operable at volumetric flow rates ranging from 1.5 to 12 standard m(3)/min. Relative humidity levels are controllable from 5%-90% and the temperature of the aerosol stream is variable from ambient to 150 degrees C. Test aerosols are produced through spray drying source material solutions that are introduced into a heated stainless steel evaporation chamber through an air-atomizing nozzle. Regulation of the particle size distribution of the aerosol challenge is achieved by varying source solution concentrations and through the use of a postgeneration cyclone. The aerosol generation system is unique in that it facilitates the testing of standard HEPA filters at and beyond rated media velocities by consistently providing, into a nominal flow of 7 standard m(3)/min, high mass concentrations (approximately 25 mg/m(3)) of dry aerosol streams having count mean diameters centered near the most penetrating particle size for HEPA filters (120-160 nm). Aerosol streams that have been generated and characterized include those derived from various concentrations of KCl, NaCl, and sucrose solutions. Additionally, a water insoluble aerosol stream in which the solid component is predominantly iron (III) has been produced. Multiple ports are available on the test stand for making simultaneous aerosol measurements upstream and downstream of the test filter. Types of filter performance related studies that can be performed using this test stand system include filter lifetime studies, filtering efficiency testing, media velocity testing, evaluations under high mass loading and high humidity conditions, and determination of the downstream particle size distributions. PMID

  10. High-efficiency particulate air filter test stand and aerosol generator for particle loading studies

    NASA Astrophysics Data System (ADS)

    Arunkumar, R.; Hogancamp, Kristina U.; Parsons, Michael S.; Rogers, Donna M.; Norton, Olin P.; Nagel, Brian A.; Alderman, Steven L.; Waggoner, Charles A.

    2007-08-01

    This manuscript describes the design, characterization, and operational range of a test stand and high-output aerosol generator developed to evaluate the performance of 30×30×29cm3 nuclear grade high-efficiency particulate air (HEPA) filters under variable, highly controlled conditions. The test stand system is operable at volumetric flow rates ranging from 1.5to12standardm3/min. Relative humidity levels are controllable from 5%-90% and the temperature of the aerosol stream is variable from ambient to 150°C. Test aerosols are produced through spray drying source material solutions that are introduced into a heated stainless steel evaporation chamber through an air-atomizing nozzle. Regulation of the particle size distribution of the aerosol challenge is achieved by varying source solution concentrations and through the use of a postgeneration cyclone. The aerosol generation system is unique in that it facilitates the testing of standard HEPA filters at and beyond rated media velocities by consistently providing, into a nominal flow of 7standardm3/min, high mass concentrations (˜25mg/m3) of dry aerosol streams having count mean diameters centered near the most penetrating particle size for HEPA filters (120-160nm). Aerosol streams that have been generated and characterized include those derived from various concentrations of KCl, NaCl, and sucrose solutions. Additionally, a water insoluble aerosol stream in which the solid component is predominantly iron (III) has been produced. Multiple ports are available on the test stand for making simultaneous aerosol measurements upstream and downstream of the test filter. Types of filter performance related studies that can be performed using this test stand system include filter lifetime studies, filtering efficiency testing, media velocity testing, evaluations under high mass loading and high humidity conditions, and determination of the downstream particle size distributions.

  11. Acid-catalyzed Heterogeneous Reactions in SOA Formation

    NASA Astrophysics Data System (ADS)

    Ng, N.; Keywood, M.; Varutbangkul, V.; Gao, S.; Loewer, E.; Surratt, J.; Richard, F. C.; John, S. H.

    2003-12-01

    The importance of heterogeneous reactions in secondary organic aerosol (SOA) formation has recently excited a great deal of interest in the aerosol community. Jang and Kamens (2001) showed enhanced aerosol yield from aldehydes, which can be produced by atmospheric photochemical reactions, in the presence of acidic seed. They suggest that the carbonyl functional groups of the aldehydes further react in the aerosol phase via hydration, polymerization, and hemiacetal/acetal formation with alcohols at an accelerated rate in the presence of acid. Jang et al. (2003) demonstrated similar results using a flow reactor and Czoschke et al. (in press) qualitatively showed increased yields for isoprene and alpha-pinene ozonolysis in the presence of acidic seed. While these findings are intriguing and important, the conditions under which the experiments were carried out were atmospherically unrealistic. A series of SOA formation experiments have been carried out in the Caltech Indoor Chamber Facility, which is comprised of dual 28 m3 FEP Teflon chambers, with the flexibility to carry out both dark ozonolysis and photochemical OH oxidation reactions. Cycloheptene and alpha-pinene were oxidized in the presence of neutral seed under dry (<10% RH) and humid (50% RH) conditions and in the presence of acidic seed under humid (50% RH) conditions. The SOA yields for these experiments will be presented, and the extent of the influence of acid-catalyzed reactions on SOA yield will be discussed. Reference List 1. Cocker, D. R. III. and R. C. Flagan and J. H. Seinfeld, State-of-the-art chamber facility for studying atmospheric aerosol chemistry, Environmental Science and Technology, 35, 2594-2601, 2001. 2. Czoschke, N. M., M. Jang, and R. M. Kamens, Effect of acid seed on biogenic sceondary organic aerosol growth, Atmospheric Environment, In press. 3. Jang, M., S. Lee, and R. M. Kamens, Organic aerosol growth by acid-catalyzed heterogeneous reactions of octanal in a flow reactor

  12. Effective Henry's Law constant measurements for glyoxal in model aerosols containing sulfate

    NASA Astrophysics Data System (ADS)

    Kampf, C.; Waxman, E.; Slowik, J.; Dommen, J.; Prevot, A.; Baltensperger, U.; Noziere, B.; Hoffmann, T.; Volkamer, R.

    2012-04-01

    Traditional models represent secondary organic aerosol (SOA) formation based on the gas-phase oxidation of a limited set of precursor molecules. However, these models tend to under-estimate the amounts and degree of oxygenation of actual SOA, indicating missing processes. One such source that has become increasingly important in recent years is glyoxal (CHOCHO, the smallest alpha-dicarbonyl). Unlike traditional SOA precursors, glyoxal forms SOA by partitioning to the aqueous phase according to Henry's Law. This work presents an analysis of Henry's Law constants for glyoxal uptake to laboratory-generated aerosols in a dynamically coupled gas-aerosol system. We combine CU LED-CE-DOAS measurements of gas-phase glyoxal with online HR-Tof-AMS and time-resolved HPLC ESI MS/MS particle-phase measurements to characterize the time resolved evolution of glyoxal partitioning, and relate molecular-specific measurements to AMS mass spectra. The experiments were performed in the simulation chamber facility at PSI, Switzerland, and investigate ammonium sulfate (AS), and mixed AS / fulvic acid seed aerosols under relative humidity conditions ranging from 50 to 85% RH. The Henry's Law and effective Henry's Law constants are compared with other values reported in the literature.

  13. Effective Henry's Law constant measurements for glyoxal in model aerosols containing sulfate

    NASA Astrophysics Data System (ADS)

    Kampf, C. J.; Waxman, E.; Slowik, J. G.; Dommen, J.; Prevot, A. S.; Noziere, B.; Hoffmann, T.; Volkamer, R.

    2011-12-01

    Traditional models represent secondary organic aerosol (SOA) formation based on the gas-phase oxidation of a limited set of precursor molecules. However, these models tend to under-estimate the amounts and degree of oxygenation of actual SOA, indicating missing processes. One such source that has become increasingly important in recent years is glyoxal (CHOCHO, the smallest alpha-dicarbonyl). Unlike traditional SOA precursors, glyoxal forms SOA by partitioning to the aqueous phase according to Henry's Law. This work presents an analysis of Henry's Law constants for glyoxal uptake to laboratory-generated aerosols in a dynamically coupled gas-aerosol system. We combine CU LED-CE-DOAS measurements of gas-phase glyoxal with online HR-Tof-AMS and time-resolved HPLC ESI MS/MS particle-phase measurements to characterize the time resolved evolution of glyoxal partitioning, and relate molecular-specific measurements to AMS mass spectra. The experiments were performed in the simulation chamber facility at PSI, Switzerland, and investigate ammonium sulfate (AS), and mixed AS / fulvic acid seed aerosols under relative humidity conditions ranging from 50 to 85% RH. The Henry's Law and effective Henry's Law constants are compared with other values reported in the literature.

  14. Development and characterization of a resistance spot welding aerosol generator and inhalation exposure system.

    PubMed

    Afshari, Aliakbar; Zeidler-Erdely, Patti C; McKinney, Walter; Chen, Bean T; Jackson, Mark; Schwegler-Berry, Diane; Friend, Sherri; Cumpston, Amy; Cumpston, Jared L; Leonard, H Donny; Meighan, Terence G; Frazer, David G; Antonini, James M

    2014-10-01

    Limited information exists regarding the health risks associated with inhaling aerosols that are generated during resistance spot welding of metals treated with adhesives. Toxicology studies evaluating spot welding aerosols are non-existent. A resistance spot welding aerosol generator and inhalation exposure system was developed. The system was designed by directing strips of sheet metal that were treated with an adhesive to two electrodes of a spot welder. Spot welds were made at a specified distance from each other by a computer-controlled welding gun in a fume collection chamber. Different target aerosol concentrations were maintained within the exposure chamber during a 4-h exposure period. In addition, the exposure system was run in two modes, spark and no spark, which resulted in different chemical profiles and particle size distributions. Complex aerosols were produced that contained both metal particulates and volatile organic compounds (VOCs). Size distribution of the particles was multi-modal. The majority of particles were chain-like agglomerates of ultrafine primary particles. The submicron mode of agglomerated particles accounted for the largest portion of particles in terms of particle number. Metal expulsion during spot welding caused the formation of larger, more spherical particles (spatter). These spatter particles appeared in the micron size mode and accounted for the greatest amount of particles in terms of mass. With this system, it is possible to examine potential mechanisms by which spot welding aerosols can affect health, as well as assess which component of the aerosol may be responsible for adverse health outcomes. PMID:25140455

  15. Effect of Slow Aging Reactions on Optical Properties of Secondary Organic Aerosol Prepared by Oxidation of Selected Monoterpenes

    NASA Astrophysics Data System (ADS)

    Nizkorodov, S. A.; Bones, D. L.; Henricksen, D. K.; Mang, S. A.; Bateman, A. P.; Pan, X.; Nguyen, T. B.; Gonsior, M.; Cooper, W.; Laskin, J.; Laskin, A.

    2009-05-01

    Organic particulate matter (PM) has a major impact on atmospheric chemistry, climate, and human health. Secondary organic aerosol (SOA) accounts for a rather significant fraction of organic PM; this includes SOA produced by oxidation of biogenically emitted monoterpenes. Once such SOA is formed, it is believed to undergo slow aging processes, which may have large effects on the physical and chemical properties of the particles. This presentation focuses on the effect of slow chemical aging on optical properties of SOA formed from the ozone-induced oxidation of limonene, myrcene, and other selected monoterpenes. Several complementary techniques including high resolution electrospray ionization mass spectrometry, FTIR spectroscopy, UV/vis spectroscopy, NMR spectroscopy, 3D-fluorescence spectroscopy, and photodissociation spectroscopy are used to probe the aging-induced changes in physical properties and chemical composition of laboratory generated SOA. Limonene SOA appears to undergo a dramatic change in its absorption spectrum on a time scale of hours; it develops strong visible bands in the 400-500 nm region, and becomes fluorescent. This transformation is catalyzed by ammonium sulfate and certain amino acids. This rather unusual aging process can potentially contribute to the formation of brown carbon in biogenic SOA.

  16. Model Representation of Secondary Organic Aerosol in CMAQ v4.7

    EPA Science Inventory

    Numerous scientific upgrades to the representation of secondary organic aerosol (SOA) are incorporated into the Community Multiscale Air Quality (CMAQ) modeling system. Additions include several recently identified SOA precursors: benzene, isoprene, and sesquiterpenes; and pathwa...

  17. Investigation of the Correlation between Odd Oxygen and Secondary Organic Aerosol in Mexico City and Houston

    EPA Science Inventory

    Many recent models underpredict secondary organic aerosol (SOA) particulate matter(PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much b...

  18. Electrospray neutralization process and apparatus for generation of nano-aerosol and nano-structured materials

    DOEpatents

    Bailey, Charles L.; Morozov, Victor; Vsevolodov, Nikolai N.

    2010-08-17

    The claimed invention describes methods and apparatuses for manufacturing nano-aerosols and nano-structured materials based on the neutralization of charged electrosprayed products with oppositely charged electrosprayed products. Electrosprayed products include molecular ions, nano-clusters and nano-fibers. Nano-aerosols can be generated when neutralization occurs in the gas phase. Neutralization of electrospan nano-fibers with molecular ions and charged nano-clusters may result in the formation of fibrous aerosols or free nano-mats. Nano-mats can also be produced on a suitable substrate, forming efficient nano-filters.

  19. 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

  20. Neurotoxicity following acute inhalation of aerosols generated during resistance spot weld-bonding of carbon steel.

    PubMed

    Sriram, Krishnan; Jefferson, Amy M; Lin, Gary X; Afshari, Aliakbar; Zeidler-Erdely, Patti C; Meighan, Terence G; McKinney, Walter; Jackson, Mark; Cumpston, Amy; Cumpston, Jared L; Leonard, Howard D; Frazer, David G; Antonini, James M

    2014-10-01

    Welding generates complex metal aerosols, inhalation of which is linked to adverse health effects among welders. An important health concern of welding fume (WF) exposure is neurological dysfunction akin to Parkinson's disease (PD). Some applications in manufacturing industry employ a variant welding technology known as "weld-bonding" that utilizes resistance spot welding, in combination with adhesives, for metal-to-metal welding. The presence of adhesives raises additional concerns about worker exposure to potentially toxic components like Methyl Methacrylate, Bisphenol A and volatile organic compounds (VOCs). Here, we investigated the potential neurotoxicological effects of exposure to welding aerosols generated during weld-bonding. Male Sprague-Dawley rats were exposed (25 mg/m³ targeted concentration; 4 h/day × 13 days) by whole-body inhalation to filtered air or aerosols generated by either weld-bonding with sparking (high metal, low VOCs; HM) or without sparking (low metal; high VOCs; LM). Fumes generated under these conditions exhibited complex aerosols that contained both metal oxide particulates and VOCs. LM aerosols contained a greater fraction of VOCs than HM, which comprised largely metal particulates of ultrafine morphology. Short-term exposure to LM aerosols caused distinct changes in the levels of the neurotransmitters, dopamine (DA) and serotonin (5-HT), in various brain areas examined. LM aerosols also specifically decreased the mRNA expression of the olfactory marker protein (Omp) and tyrosine hydroxylase (Th) in the olfactory bulb. Consistent with the decrease in Th, LM also reduced the expression of dopamine transporter (Slc6a3; Dat), as well as, dopamine D2 receptor (Drd2) in the olfactory bulb. In contrast, HM aerosols induced the expression of Th and dopamine D5 receptor (Drd5) mRNAs, elicited neuroinflammation and blood-brain barrier-related changes in the olfactory bulb, but did not alter the expression of Omp. Our findings

  1. Neurotoxicity following acute inhalation of aerosols generated during resistance spot weld-bonding of carbon steel

    PubMed Central

    Sriram, Krishnan; Jefferson, Amy M.; Lin, Gary X.; Afshari, Aliakbar; Zeidler-Erdely, Patti C.; Meighan, Terence G.; McKinney, Walter; Jackson, Mark; Cumpston, Amy; Cumpston, Jared L.; Leonard, Howard D.; Frazer, David G.; Antonini, James M.

    2015-01-01

    Welding generates complex metal aerosols, inhalation of which is linked to adverse health effects among welders. An important health concern of welding fume (WF) exposure is neurological dysfunction akin to Parkinson’s disease (PD). Some applications in manufacturing industry employ a variant welding technology known as “weld-bonding” that utilizes resistance spot welding, in combination with adhesives, for metal-to-metal welding. The presence of adhesives raises additional concerns about worker exposure to potentially toxic components like Methyl Methacrylate, Bisphenol A and volatile organic compounds (VOCs). Here, we investigated the potential neurotoxicological effects of exposure to welding aerosols generated during weld-bonding. Male Sprague–Dawley rats were exposed (25 mg/m3 targeted concentration; 4 h/day × 13 days) by whole-body inhalation to filtered air or aerosols generated by either weld-bonding with sparking (high metal, low VOCs; HM) or without sparking (low metal; high VOCs; LM). Fumes generated under these conditions exhibited complex aerosols that contained both metal oxide particulates and VOCs. LM aerosols contained a greater fraction of VOCs than HM, which comprised largely metal particulates of ultrafine morphology. Short-term exposure to LM aerosols caused distinct changes in the levels of the neurotransmitters, dopamine (DA) and serotonin (5-HT), in various brain areas examined. LM aerosols also specifically decreased the mRNA expression of the olfactory marker protein (Omp) and tyrosine hydroxylase (Th) in the olfactory bulb. Consistent with the decrease in Th, LM also reduced the expression of dopamine transporter (Slc6a3; Dat), as well as, dopamine D2 receptor (Drd2) in the olfactory bulb. In contrast, HM aerosols induced the expression of Th and dopamine D5 receptor (Drd5) mRNAs, elicited neuroinflammation and blood–brain barrier-related changes in the olfactory bulb, but did not alter the expression of Omp. Our findings

  2. High-Efficiency Generation and Delivery of Aerosols Through Nasal Cannula During Noninvasive Ventilation

    PubMed Central

    Walenga, Ross L.; Son, Yoen-Ju; Hindle, Michael

    2013-01-01

    Abstract Background Previous studies have demonstrated the delivery of pharmaceutical aerosols through nasal cannula and the feasibility of enhanced condensational growth (ECG) with a nasal interface. The objectives of this study were to develop a device for generating submicrometer aerosols with minimal depositional loss in the formation process and to improve aerosol delivery efficiencies through nasal cannulas. Methods A combination of in vitro experiments and computational fluid dynamics (CFD) simulations that used the strengths of each method was applied. Aerosols were formed using a conventional mesh nebulizer, mixed with ventilation gas, and heated to produce submicrometer sizes. An improved version of the mixer and heater unit was developed based on CFD simulations, and performance was verified with experiments. Aerosol delivery was considered through a commercial large-bore adult cannula, a divided (D) design for use with ECG, and a divided and streamlined (DS) design. Results The improved mixer design reduced the total deposition fraction (DF) of drug within the mixer by a factor of 3 compared with an initial version, had a total DF of approximately 10%, and produced submicrometer aerosols at flow rates of 10 and 15 L/min. Compared with the commercial and D designs for submicrometer aerosols, the DS cannula reduced depositional losses by a factor of 2–3 and retained only approximately 5% or less of the nebulized dose at all flow rates considered. For conventional-sized aerosols (3.9 and 4.7 μm), the DS device provided delivery efficiencies of approximately 80% and above at flow rates of 2–15 L/min. Conclusions Submicrometer aerosols can be formed using a conventional mesh nebulizer and delivered through a nasal cannula with total delivery efficiencies of 80–90%. Streamlining the nasal cannula significantly improved the delivery efficiency of both submicrometer and micrometer aerosols; however, use of submicrometer particles with ECG delivery

  3. Formation of Secondary Organic Aerosol from Irradiated a-Pinene/Tolueme/NOx Mixtures and the Effect of Isoprene and Sulfur Dioxide

    EPA Science Inventory

    Secondary organic aerosol (SOA) was generated by irradiating a series of a-pinene/toluene/NOx mixtures in the absence and presence of isoprene or sulfur dioxide. The purpose of the experiment was to evaluate the extent to which chemical perturbations to this base-case (a-pinene/...

  4. Atmospheric Oxidation of 1,3-Butadiene: Characterization of gas and aerosol reaction products and implication for PM2.5

    EPA Science Inventory

    Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H2O2 or NOx. Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gas and pa...

  5. Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield

    DOE PAGESBeta

    Lambe, A. T.; Chhabra, P. S.; Onasch, T. B.; Brune, W. H.; Hunter, J. F.; Kroll, J. H.; Cummings, M. J.; Brogan, J. F.; Parmar, Y.; Worsnop, D. R.; et al

    2015-03-18

    We performed a systematic intercomparison study of the chemistry and yields of secondary organic aerosol (SOA) generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0 × 108 to 2.2 × 1010 molec cm-3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2 × 106 to 2 × 107 molec cm-3 over exposure times of several hours. The OH concentration in themore » chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. In most cases, for a specific SOA type the most-oxidized chamber SOA and the least-oxidized flow reactor SOA have similar mass spectra, oxygen-to-carbon and hydrogen-to-carbon ratios, and carbon oxidation states at integrated OH exposures between approximately 1 × 1011 and 2 × 1011 molec cm-3 s, or about 1–2 days of equivalent atmospheric oxidation. This observation suggests that in the range of available OH exposure overlap for the flow reactor and chambers, SOA elemental composition as measured by an aerosol mass spectrometer is similar whether the precursor is exposed to low OH concentrations over long exposure times or high OH concentrations over short exposure times. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of

  6. Naphthalene SOA: redox activity and naphthoquinone gas-particle partitioning

    NASA Astrophysics Data System (ADS)

    McWhinney, R. D.; Zhou, S.; Abbatt, J. P. D.

    2013-10-01

    Chamber secondary organic aerosol (SOA) from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox-active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. These results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10-4 m3 μg-1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. Also, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

  7. Secondary organic aerosol formation of relevance to the marine boundary layer

    NASA Astrophysics Data System (ADS)

    Cai, Xuyi

    The chlorine atom (Cl) is a potential oxidant of volatile organic compounds (VOCs) in the atmosphere and is hypothesized to lead to secondary organic aerosol (SOA) formation in coastal areas. The purpose of this dissertation is to test this hypothesis and quantify the SOA formation potentials of some representative biogenic and anthropogenic hydrocarbons when oxidized by Cl in laboratory chamber experiments. The chosen model compounds for biogenic and anthropogenic hydrocarbons in this study are three monoterpenes (alpha-pinene, beta-pinene, and d-limonene) and two aromatics (m-xylene and toluene), respectively. Results indicate that the oxidation of these monoterpenes and aromatics generates significant amounts of aerosol. The SOA yields of alpha-pinene, beta-pinene, and d-limonene obtained in this study are comparable to those when they are oxidized by ozone, by nitrate radical, and in photooxidation scenarios. For aerosol mass up to 30.0 mug m-3, their yields reach approximately 0.20, 0.20, and 0.30, respectively. The SOA yields for m-xylene and toluene are found to be in the range of 0.035 to 0.12 for aerosol concentrations up to 19 mug m-3. For d-limonene and toluene, data indicate two yield curves that depend on the initial concentration ratios of Cl precursor to hydrocarbon hydrocarbon. Zero-dimensional calculations based on these yields show that SOA formation from the five model compounds when oxidized by Cl in the marine boundary layer could be a significant source of SOA in the early morning. In addition, the mechanistic reaction pathways for Cl oxidation of alpha-pinene, beta-pinene, d-limonene, and toluene with Cl have been developed within the framework of the Caltech Atmospheric Chemistry Mechanisms (CACM). Output from the developed mechanisms is combined with an absorptive partitioning model to predict precursor decay curves and time-dependent SOA concentrations in experiments. Model calculations are able to match (in general within general +/- 50

  8. Measurements of the volatility of aerosols from alpha-pinene ozonolysis.

    PubMed

    Stanier, Charles O; Pathak, Ravi K; Pandis, Spyros N

    2007-04-15

    The temperature-dependence of secondary organic aerosol (SOA) concentrations is measured using a temperature-controlled smog chamber. Aerosols are generated from reaction of alpha-pinene (14-150 ppb) and ozone at a constant temperature of 22 +/- 2 degrees C in the presence of the OH-scavenger 2-butanol. After the reactions are completed the chamber is heated or cooled in a range from 20 to 40 degrees C. SOA volume concentrations increase at temperatures below the initial formation temperature and decrease at elevated temperatures. The response to the temperature change as measured by percent mass change per degree ranged from -0.4 to -3.6% K(-1), for a total mass reduction of 5-60% upon heating from 22 to 35 degrees C. The reported range is due to two factors: (1) experimental uncertainty, arising mainly from uncertainty in evaporation and condensation behavior of particles lost to the chamber wall; (2) differences in the temperature response from experiment to experiment. Aerosol temperature sensitivity was also measured by tandem differential mobility analysis (TDMA) where similarly generated SOA were heated from 20 to 25 degrees C to 30-40 degrees C with residence times of 0.5-1.5 min, resulting in particle volume reductions of up to 20%. The TDMA experiments indicate that evaporation of the SOA particles in this system occurs with a potentially significant mass transfer limitation (e.g., accommodation coefficient <0.1). PMID:17533835

  9. Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Madronich, S.; Aumont, B.; Baker, A.; Camredon, M.; Hodzic, A.; Tyndall, G. S.; Apel, E.; Zaveri, R. A.

    2011-12-01

    The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations made in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 μg m-3, and SOA peaking at 10-15 μg m-3 during mid-day. The majority (≥75%) of the model SOA stems from reaction products of the large n-alkanes, used here as surrogates for all emitted hydrocarbons of similar volatility, with the remaining SOA originating mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by δ-hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.

  10. Aerosol Data Assimilation with the Next Generation Meteorological Satellite (Himawari-8)

    NASA Astrophysics Data System (ADS)

    Yumimoto, K.; Sekiyama, T. T.; Murakami, H.; Kikuchi, M.; Nagao, T. M.; Tanaka, T. Y.; Ogi, A.; Maki, T.

    2015-12-01

    The Japan Meteorological Agency (JMA) launched a new generation geostationary meteorological satellite, Himawari-8, on 7 October 2014. The Advanced Himawari Imager (AHI) aboard Himawari-8 is a 16 channel multispectral imager including three observational bands (i.e. RGB) in visible lights with 1km horizontal and 10-minite temporal resolutions covering the East Asia and Western Pacific regions. The visible imaging sensor allows us to obtain aerosol optical observations with unprecedented spatial and temporal resolutions and horizontal coverage. Meteorological Research Institute (MRI)/JMA have been developing an aerosol data assimilation system with a global aerosol transport model (MASINGAR mk-2) and the Local Ensemble Transform Kalman Filter (LETKF) for the operational aerosol (Asian dust) forecasting system (Yumimoto et al., under review). In this study, we have the first attempt to assimilate aerosol retrievals derived from the next generation meteorological satellite in the assimilation system. Our preliminary experiment results show that assimilation of full disk aerosol optical thickness (AOT) from Himawari-8 successfully reduces overestimates of anthropogenic pollution outflow from the Asian Continent, and compensates underestimates of dust outflow from the Australian continent.

  11. Aerosol data assimilation using data from Himawari-8, a next-generation geostationary meteorological satellite

    NASA Astrophysics Data System (ADS)

    Yumimoto, K.; Nagao, T. M.; Kikuchi, M.; Sekiyama, T. T.; Murakami, H.; Tanaka, T. Y.; Ogi, A.; Irie, H.; Khatri, P.; Okumura, H.; Arai, K.; Morino, I.; Uchino, O.; Maki, T.

    2016-06-01

    Himawari-8, a next-generation geostationary meteorological satellite, was launched on 7 October 2014 and became operational on 7 July 2015. The advanced imager on board Himawari-8 is equipped with 16 observational bands (including three visible and three near-infrared bands) that enable retrieval of full-disk aerosol optical properties at 10 min intervals from geostationary (GEO) orbit. Here we show the first application of aerosol optical properties (AOPs) derived from Himawari-8 data to aerosol data assimilation. Validation of the assimilation experiment by comparison with independent observations demonstrated successful modeling of continental pollution that was not predicted by simulation without assimilation and reduced overestimates of dust front concentrations. These promising results suggest that AOPs derived from Himawari-8/9 and other planned GEO satellites will considerably improve forecasts of air quality, inverse modeling of emissions, and aerosol reanalysis through assimilation techniques.

  12. Multiday production of condensing organic aerosol mass in urban and forest outflow

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.; Camredon, M.; Valorso, R.

    2015-01-01

    Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for multiple days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (~50%) and of shorter duration (1-2 days). The multiday production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction products of both aromatics and alkanes, especially those with relatively low carbon numbers (C4-15). In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions and different vapor pressure schemes, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.

  13. Multiday production of condensing organic aerosol mass in urban and forest outflow

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.; Camredon, M.; Valorso, R.

    2014-07-01

    Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for several days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (∼50%) and of shorter duration (1-2 days). The production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction products of both aromatics and alkanes. In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.

  14. Multiday production of condensing organic aerosol mass in urban and forest outflow

    DOE PAGESBeta

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.; Camredon, M.; Valorso, R.

    2015-01-16

    Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for multiple days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (~50%) and of shorter duration (1–2 days). The multiday production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction productsmore » of both aromatics and alkanes, especially those with relatively low carbon numbers (C4–15). In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions and different vapor pressure schemes, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

  15. Multiday production of condensing organic aerosol mass in urban and forest outflow

    DOE PAGESBeta

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.; Camredon, M.; Valorso, R.

    2014-07-03

    Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for several days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (∼50%) and of shorter duration (1–2 days). The production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction products ofmore » both aromatics and alkanes. In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

  16. Soot aggregate restructuring due to coatings of secondary organic aerosol derived from aromatic precursors.

    PubMed

    Schnitzler, Elijah G; Dutt, Ashneil; Charbonneau, André M; Olfert, Jason S; Jäger, Wolfgang

    2014-12-16

    Restructuring of monodisperse soot aggregates due to coatings of secondary organic aerosol (SOA) derived from hydroxyl radical-initiated oxidation of toluene, p-xylene, ethylbenzene, and benzene was investigated in a series of photo-oxidation (smog) chamber experiments. Soot aggregates were generated by combustion of ethylene using a McKenna burner, treated by denuding, size-selected by a differential mobility analyzer, and injected into a smog chamber, where they were exposed to low vapor pressure products of aromatic hydrocarbon oxidation, which formed SOA coatings. Aggregate restructuring began once a threshold coating mass was reached, and the degree of the subsequent restructuring increased with mass growth factor. Although significantly compacted, fully processed aggregates were not spherical, with a mass-mobility exponent of 2.78, so additional SOA was required to fill indentations between collapsed branches of the restructured aggregates before the dynamic shape factor of coated particles approached 1. Trends in diameter growth factor, effective density, and dynamic shape factor with increasing mass growth factor indicate distinct stages in soot aggregate processing by SOA coatings. The final degree and coating mass dependence of soot restructuring were found to be the same for SOA coatings from all four aromatic precursors, indicating that the surface tensions of the SOA coatings are similar. PMID:25390075

  17. How important are glassy SOA ice nuclei for the formation of cirrus clouds?

    NASA Astrophysics Data System (ADS)

    Zhou, C.; Penner, J. E.; Lin, G.; Liu, X.; Wang, M.

    2014-12-01

    Extremely low ice numbers (i.e. 5 - 100 / L) have been observed in the tropical troposphere layer (TTL) in a variety of field campaigns. Various mechanisms have been proposed to explain these low numbers, including the effect of glassy secondary organic aerosol acting as heterogeneous ice nuclei (IN). In this study, we explored these effects using the CAM5.3 model. SOA fields were provided by an offline version of the University of Michigan-IMPACT model, which has a detailed process-based mechanism that describes aerosol microphysics and SOA formation through both gas phase and multiphase reactions. The transition criterion of SOA to glassy heterogeneous IN follows the parameterization developed by Wang et al. 2012. With this parameterization, glassy SOA IN form mainly when the temperature (T) is lower than 210K. In the default CAM5.3 set-up in which only the fraction of Aitken mode sulfate aerosols with diameter larger than 100nm participate in the ice nucleation (Liu and Penner 2005 parameterization), glassy SOA IN are shown to decrease the ice number (Ni) by suppressing some of the homogeneous freezing at low temperatures thereby leading to an improved representation of the relationship between Ni and T compared to the observations summarized by Kramer et al. 2009. However, when we allow the total number of the Aitken mode sulfate particles to participate in homogeneous freezing, glassy SOA IN have only a small impact on the relationship between Ni and T. If the subgrid updraft velocity is decreased to 0.1 m/s (compared to 0.2 m/s in the default set-up), there is a large decrease of Ni, since homogeneous freezing is more easily suppressed by glassy SOA IN at these updrafts. We also present the effects of glassy SOA IN using an alternative ice nucleation scheme (Barahona and Nenes, 2009).

  18. 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.

  19. A novel micropump droplet generator for aerosol drug delivery: Design simulations

    PubMed Central

    Su, Guoguang; Longest, P. Worth; Pidaparti, Ramana M.

    2010-01-01

    One challenge of generating a liquid aerosol is finding an efficient way to break up bulk amounts of the compound into micron-sized droplets. Traditional methods of aerosol generation focus on the principle of creating the liquid droplets by blowing air at high speed over or through a liquid. In this study, a novel micropump droplet generator (MDG) is proposed based on a microfluidics device to produce monodisperse droplets on demand (DoD). The micropump design was employed to both pump the fluid into the air and to encourage droplet breakup and aerosol formation. Computational simulation modeling of the new MDG was developed and validated with comparisons to experimental data for current generators. The device was found to produce an aerosol similar to a vibrating orifice DoD device. Most importantly, the input power required by the newly proposed device (MDG) was several orders of magnitude below existing DoD generators for a similar droplet output. Based on the simulation results obtained in comparison with current DoD generators, the MDG device performed effectively at higher frequencies, smaller nozzle diameters, and regardless of the liquid viscosity of the solution. PMID:21151580

  20. Global modeling of SOA formation from dicarbonyls, epoxides, organic nitrates and peroxides

    NASA Astrophysics Data System (ADS)

    Lin, G.; Penner, J. E.; Sillman, S.; Taraborrelli, D.; Lelieveld, J.

    2012-05-01

    Recent experimental findings indicate that secondary organic aerosol (SOA) represents an important and, under many circumstances, the major fraction of the organic aerosol burden. Here, we use a global 3-D model (IMPACT) to test the results of different mechanisms for the production of SOA. The basic mechanism includes SOA formation from organic nitrates and peroxides produced from an explicit chemical formulation, using partition coefficients based on thermodynamic principles together with assumptions for the rate of formation of low-volatility oligomers. We also include the formation of low-volatility SOA from the reaction of glyoxal and methylglyoxal on aqueous aerosols and cloud droplets as well as from the reaction of epoxides on aqueous aerosols. A model simulation including these SOA formation mechanisms gives an annual global SOA production of 120.5 Tg. The global production of SOA is decreased substantially to 90.8 Tg yr-1 if the HOx regeneration mechanism proposed by Peeters et al. (2009) is used. Model predictions with and without this HOx (OH and HO2 regeneration scheme are compared with multiple surface observation datasets, namely: the Interagency Monitoring of Protected Visual Environments (IMPROVE) for the United States, the European Monitoring and Evaluation Programme (EMEP), and aerosol mass spectrometry (AMS) data measured in both the Northern Hemisphere and tropical forest regions. All model simulations show reasonable agreement with the organic carbon mass observed in the IMPROVE network and the AMS dataset, however observations in Europe are significantly underestimated, which may be caused by an underestimation of primary organic aerosol emissions (POA) in winter and of emissions and/or SOA production in the summer. The modeled organic aerosol concentrations tend to be higher by roughly a factor of three when compared with measurements at three tropical forest sites. This overestimate suggests that more measurements and model studies are

  1. Influence of atmospheric parameters on vertical profiles and horizontal transport of aerosols generated in the surf zone

    NASA Astrophysics Data System (ADS)

    Kusmierczyk-Michulec, J.; Tedeschi, G.; Van Eijk, A. M. J.; Piazzola, J.

    2013-10-01

    The vertical and horizontal transport of aerosols generated over the surf zone is discussed. Experimental data were collected during the second campaign of the Surf Zone Aerosol Experiment that took place in Duck NC (USA) in November 2007. The Empirical Orthogonal Function (EOF) method was used to analyze the vertical concentration gradients, and allowed separating the surf aerosols from aerosols advected from elsewhere. The numerical Marine Aerosol Concentration Model (MACMod) supported the analysis by confirming that the concentration gradients are more pronounced under stable conditions and that aerosol plumes are then more confined to the surface. The model also confirmed the experimental observations made during two boat runs along the offshore wind vector that surf-generated aerosols are efficiently advected out to sea over several tens of kilometers.

  2. Sources, Properties, Aging, and Anthropogenic Influences on OA and SOA over the Southeast US and the Amazon duing SOAS, DC3, SEAC4RS, and GoAmazon

    EPA Science Inventory

    The SE US and the Amazon have large sources of biogenic VOCs, varying anthropogenic pollution impacts, and often poor organic aerosol (OA) model performance. Recent results on the sources, properties, aging, and impact of anthropogenic pollution on OA and secondary OA (SOA) over ...

  3. Aerosol Production in a Mixed Deciduous/Coniferous Forest

    NASA Astrophysics Data System (ADS)

    Slade, N.; Mielke, L.; Alaghmand, M.; Galloway, M.; Kammrath, A.; Keutsch, F.; Hansen, R.; Griffith, S.; Dusanter, S.; Stevens, P.; Carroll, M.; Bertman, S.; Shepson, P.

    2008-12-01

    Aerosols are of fundamental concern because of their impacts on air quality, human health and radiative forcing. Recent studies have focused on secondary organic aerosol (SOA) production due to oxidation of volatile organic compounds (VOCs), and more importantly biogenic-VOCs (BVOCs), in particular, isoprene. However, the SOA precursors are not well understood because the mechanisms have shown that isoprene oxidation can contribute to aerosol production through multiple generation oxidation products. For terpenes, it is more likely that primary or secondary oxidation products lead to particle formation. In the present study, we measured the aerosol size distribution, along with O3, HOx, NOx, NOy and BVOCs, in a mixed deciduous forest that is undergoing successional transition to a conifer-dominated species mix. This study was conducted in a rural forest environment in northern Michigan as a part of the summer 2008 PROPHET campaign at the University of Michigan Biological Station (UMBS). We examine here the potential BVOC contribution to aerosol formation. A TSI, inc. Scanning Mobility Particle Sizer (SMPS) was used to measure aerosol number density in the size range, 15 nm < x < 711 nm and a Proton Transfer Reaction - Linear Ion Trap (PTR-LIT) mass spectrometer for quantifying isoprene and other BVOCs, including methyl vinyl ketone and methacrolein, and total monoterpenes. Preliminary results show periods of new particle production. Here we use a unique set of BVOC, HOx, NOx, NOy, O3 and meteorological data to examine conditions leading to new particle production.

  4. Measuring aerosols generated inside armoured vehicles perforated by depleted uranium ammunition.

    PubMed

    Parkhurst, M A

    2003-01-01

    In response to questions raised after the Gulf War about the health significance of exposure to depleted uranium (DU), the US Department of Defense initiated a study designed to provide an improved scientific basis for assessment of possible health effects on soldiers in vehicles struck by these munitions. As part of this study, a series of DU penetrators were fired at an Abrams tank and a Bradley fighting vehicle, and the aerosols generated by vehicle perforation were collected and characterised. A robust sampling system was designed to collect aerosols in this difficult environment and monitor continuously the sampler flow rates. The aerosol samplers selected for these tests included filter cassettes, cascade impactors, a five-stage cyclone and a moving filter. Sampler redundancy was an integral part of the sampling system to offset losses from fragment damage. Wipe surveys and deposition trays collected removable deposited particulate matter. Interior aerosols were analysed for uranium concentration and particle size distribution as a function of time. They were also analysed for uranium oxide phases, particle morphology and dissolution in vitro. These data, currently under independent peer review, will provide input for future prospective and retrospective dose and health risk assessments of inhaled or ingested DU aerosols. This paper briefly discusses the target vehicles, firing trajectories, aerosol samplers and instrumentation control systems, and the types of analyses conducted on the samples. PMID:14526950

  5. Dioxinlike properties of a trichloroethylene combustion-generated aerosol

    SciTech Connect

    Villalobos, S.A.; Anderson, M.J.; Hinton, D.E.

    1996-07-01

    Conventional chemical analyses of incineration by-products identify compounds of known toxicity but often fail to indicate the presence of other chemicals that may pose health risks. In a previous report, extracts from soot aerosols formed during incomplete combustion of trichloroethylene (TCE) and pyrolysis of plastics exhibited a dioxinlike response when subjected to a keratinocyte assay. To verify this dioxinlike effect, the complete extract, its polar and nonpolar fractions, some containing primarily halogenated aromatic hydrocarbons, were evaluated for toxicity using an embryo assay, for antiestrogenicity using primary liver cell cultures, and for the ability to transform the aryl hydrocarbon receptor into its DNA binding form using liver cytosol in a gel retardation assay. Each of these assays detect dioxinlike effects. Medaka (Oryzias latipes) embryos and primary liver cell cultures of rainbow trout (Oncorhynchus mykiss) were exposed to concentrations of extract ranging from 0.05 to 45 {mu}g/l. 67 refs., 7 figs., 3 tabs.

  6. A closed-loop control "playback" smoking machine for generating mainstream smoke aerosols.

    PubMed

    Shihadeh, Alan; Azar, Sima

    2006-01-01

    A first generation smoking machine capable of reading and replicating detailed puffing behavior from recorded smoking topography data is presented. Unlike standard smoking machines, which model human puffing behavior as a steady periodic waveform with a fixed puff frequency, volume, and duration, this novel machine generates a mainstream smoke aerosol by automatically "playing-back" puff topography recordings. Because combustion chemistry is highly non-linear, representing real smoking behavior with a smoothed periodic waveform may result in a tobacco smoke aerosol with a significantly different chemical composition and physical properties than that generated by a smoker. The machine presented here utilizes a rapid closed-loop control algorithm coded in Labview to generate smoke aerosols for toxicological assessment and inhalation studies. To illustrate its use, dry particulate matter and carbon monoxide yields generated using the playback and equivalent periodic puffing regimens are compared for a single smoking session by a 26-year-old male narghile water-pipe smoker. It was found that the periodic puffing regimen yielded 20% less carbon monoxide (CO) than the played-back smoking session, indicating that steady periodic smoking regimens, which are widely used in tobacco smoke research, may not produce realistic smoke aerosols. PMID:16796538

  7. Photooxidation of 2-methyl-3-Buten-2-ol (MBO) as a potential source of secondary organic aerosol.

    PubMed

    Chan, Arthur W H; Galloway, Melissa M; Kwan, Alan J; Chhabra, Puneet S; Keutsch, Frank N; Wennberg, Paul O; Flagan, Richard C; Seinfeld, John H

    2009-07-01

    2-Methyl-3-buten-2-ol (MBO) is an important biogenic hydrocarbon emitted in large quantities by pine forests. Atmospheric photooxidation of MBO is known to lead to oxygenated compounds, such as glycolaldehyde, which is the precursor to glyoxal. Recent studies have shown that the reactive uptake of glyoxal onto aqueous particles can lead to formation of secondary organic aerosol (SOA). In this work, MBO photooxidation under high- and low-NO(x) conditions was performed in dual laboratory chambers to quantify the yield of glyoxal and investigate the potential for SOA formation. The yields of glycolaldehyde and 2-hydroxy-2-methylpropanal (HMPR), fragmentation products of MBO photooxidation, were observed to be lower at lower NO(x) concentrations. Overall, the glyoxal yield from MBO photooxidation was 25% under high-NO(x) and 4% under low-NO(x) conditions. In the presence of wet ammonium sulfate seed and under high-NO(x) conditions, glyoxal uptake and SOA formation were not observed conclusively, due to relatively low (< 30 ppb) glyoxal concentrations. Slight aerosol formation was observed under low-NO(x) and dry conditions, with aerosol mass yields on the order of 0.1%. The small amount of SOA was not related to glyoxal uptake, but is likely a result of reactions similar to those that generate isoprene SOA under low-NO(x) conditions. The difference in aerosol yields between MBO and isoprene photooxidation under low-NO(x) conditions is consistent with the difference in vapor pressures between triols (from MBO) and tetrols (from isoprene). Despite its structural similarity to isoprene, photooxidation of MBO is not expected to make a significant contribution to SOA formation. PMID:19673246

  8. EFFECT OF ACIDITY ON SECONDARY ORGANIC AEROSOL FORMATION FROM ISOPRENE

    EPA Science Inventory

    The effect of particle-phase acidity on secondary organic aerosol (SOA) formation from isoprene is investigated in a laboratory chamber study, in which the acidity of the inorganic seed aerosol was controlled systematically. The observed enhancement in SOA mass concentration is c...

  9. Secondary organic aerosol formation of primary, secondary and tertiary Amines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Amines have been widely identified in ambient aerosol in both urban and rural environments and they are potential precursors for formation of nitrogen-containing secondary organic aerosols (SOA). However, the role of amines in SOA formation has not been well studied. In this wrok, we use UC-Riversid...

  10. Time-of-flight aerosol mass spectrometry: Measuring gaseous iodine species after selective uptake in lab-generated aerosols

    NASA Astrophysics Data System (ADS)

    Kundel, Michael; Ries, Marco; Schott, Mathias; Hoffmann, Thorsten

    2010-05-01

    Reactive iodine species play an important role in the marine atmospheric chemistry. Recent studies show that iodine containing compounds (e.g. I2 and ICl) are involved in the tropospheric ozone depletion, the enrichment of iodine in marine aerosols and the formation of new particles in the marine boundary layer (MBL). Various laboratory and field measurements report that molecular iodine (I2) and organoiodine compounds (e.g. CH3I, CH2I2) are the most important precursors for reactive iodine in the MBL[1],[2]. However, the identification and quantification of reactive iodine containing compounds are still analytical challenges. Here, we present a new application of the time-of-flight aerosol mass spectrometer (ToF-AMS) for the quantification of gaseous I2 and ICl in real-time. Time-of-flight aerosol mass spectrometry enables the real-time analysis of the particle size, the particle mass and the chemical composition of non-refractory aerosols[3]. The aerosol enters the ToF-AMS through a critical orifice of 100 μm inner diameter. An aerodynamic lens system focuses the particles in a size range of 50-600 nm as a narrow beam into the vacuum system. While most of the air is removed by a skimmer, the particle beam is transmitted into the particle-sizing chamber. After passing the particle-sizing chamber, the non-refractory particles are flash-vaporized on a heated tungsten surface (500-600 °C) and then ionized by electron impact. The generated ions are extracted by an orthogonal extractor into the time-of-flight mass spectrometer, where the time resolved particle mass detection is performed. Since gaseous compounds are removed inside the ToF-AMS, a direct measurement of gaseous iodine species is not possible. Therefore gaseous iodine species have to be transferred from the gas phase to the particle phase before entering the ToF-AMS. For this purpose α-cyclodextrin (α-CD) particles were used as selective sampling probes for I2 and 1,3,5-trimethoxybenzene (1,3,5-TMB

  11. Composition of Secondary Organic Aerosols Produced by Photo-Oxidation of Biomass Burning Emissions in a Smog Chamber

    NASA Astrophysics Data System (ADS)

    Desyaterik, Y.; Sullivan, A.; Hennigan, C. J.; Robinson, A. L.; Collett, J. L.

    2009-12-01

    Knowledge of the chemical composition of atmospheric organic aerosols (OA) is essential for accurate representation of OA in air quality and climate models. Both the sources of OA and their properties and effects remain poorly understood. In particular, we still know relatively little about the atmospheric formation of secondary organic aerosols (SOA). There is growing interest in the impact of biomass burning emissions on air quality, human health, and radiative forcing. Through a series of experiments, we are working to quantify changes in the chemical composition of wood smoke particles as a result of photochemical aging under well-controlled laboratory conditions. One specific objective of this study is to identify markers for biomass burning SOA and test whether these markers can be used in atmospheric samples to quantify SOA formation from aging of biomass burning emissions. We analyzed SOA generated in a smog chamber by photooxidation of smoke produced by burning oak wood. In order to initiate photochemistry, the chamber was irradiated with UV light. Aqueous extracts of collected aerosol samples were analyzed with Electrospray Ionization Time-of-Flight Mass Spectrometry. The high mass accuracy of these measurements reduces ambiguity in the assignment of elemental compositions for observed ions. Analysis has shown that primary oak smoke aerosol includes products of the thermal decomposition of cellulose (levoglucosan, cyclotene etc.) and lignin (guaiacol and syringol derivatives, mostly aldehydes and alcohols). After 2 hours of aging at typical summertime hydroxyl radical concentrations, the aerosol mass increased 2.5 fold due to the production of secondary organic aerosol. Mass spectra of the secondary organic aerosol formed are dominated by organic nitrates (nitrophenol, nitrocresol, nitrocatechol, and nitroguaiacol) and aromatic acids (benzoic acid, mono and di-hydroxybenzoic acid). Both nitrates and acids most likely are formed due to oxidation of the

  12. Chemical Characterization of Secondary Organic Aerosol Formed from Atmospheric Aqueous-phase Reactions of Phenolic Compounds

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Anastasio, C.; Zhang, Q.

    2012-12-01

    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phenol, guaiacol and syringol) with two oxidants - excited triplet states (3C*) of non-phenolic aromatic carbonyls and hydroxyl radical (OH). By employing four analytical methods including high-resolution aerosol mass spectrometry, total organic carbon analysis, ion chromatography, and liquid chromatography-mass spectrometry, we thoroughly characterize the chemical compositions of the low volatility reaction products of phenols and propose formation mechanisms based on this information. Our results indicate that phenolic SOA is highly oxygenated, with O/C ratios in the range of 0.83-1.03, and that the SOA of phenol is usually more oxidized than those of guaiacol and syringol. Among the three precursors, syringol generates the largest fraction of higher molecular weight (MW) products. For the same precursor, the SOA formed via reaction with 3C* is less oxidized than that formed via reaction with OH. In addition, oxidation by 3C* enhances the formation of higher MW species, including phenolic dimers, higher oligomers and hydroxylated products, compared to reactions initiated by OH, which appear to favor the formation of organic acids. However, our results indicate that the yields of small organic acids (e.g., formate, acetate, oxalate, and malate) are low for both reaction pathways, together accounting for less than 5% of total SOA mass.

  13. Computer-automated silica aerosol generator and animal inhalation exposure system

    PubMed Central

    McKinney, Walter; Chen, Bean; Schwegler-Berry, Diane; Frazer, Dave G.

    2015-01-01

    Inhalation exposure systems are necessary tools for determining the dose response relationship of inhaled toxicants under a variety of exposure conditions. The objective of this study was to develop an automated computer controlled system to expose small laboratory animals to precise concentrations of uniformly dispersed airborne silica particles. An acoustical aerosol generator was developed which was capable of re-suspending particles from bulk powder. The aerosolized silica output from the generator was introduced into the throat of a venturi tube. The turbulent high-velocity air stream within the venturi tube increased the dispersion of the re-suspended powder. That aerosol was then used to expose small laboratory animals to constant aerosol concentrations, up to 20mg/m3, for durations lasting up to 8h. Particle distribution and morphology of the silica aerosol delivered to the exposure chamber were characterized to verify that a fully dispersed and respirable aerosol was being produced. The inhalation exposure system utilized a combination of airflow controllers, particle monitors, data acquisition devices and custom software with automatic feedback control to achieve constant and repeatable exposure environments. The automatic control algorithm was capable of maintaining median aerosol concentrations to within ±0.2 mg/m3 of a user selected target concentration during exposures lasting from 2 to 8 h. The system was able to reach 95% of the desired target value in <10min during the beginning phase of an exposure. This exposure system provided a highly automated tool for conducting inhalation toxicology studies involving silica particles. PMID:23796015

  14. Effect of hydrophilic organic seed aerosols on secondary organic aerosol formation from ozonolysis of α-pinene.

    PubMed

    Song, Chen; Zaveri, Rahul A; Shilling, John E; Alexander, M Lizabeth; Newburn, Matt

    2011-09-01

    Gas-particle partitioning theory is widely used in atmospheric models to predict organic aerosol loadings. This theory predicts that secondary organic aerosol (SOA) yield of an oxidized volatile organic compound product will increase as the mass loading of preexisting organic aerosol increases. In a previous work, we showed that the presence of model hydrophobic primary organic aerosol (POA) had no detectable effect on the SOA yields from ozonolysis of α-pinene, suggesting that the condensing SOA compounds form a separate phase from the preexisting POA. However, a substantial faction of atmospheric aerosol is composed of polar, hydrophilic organic compounds. In this work, we investigate the effects of model hydrophilic organic aerosol (OA) species such as fulvic acid, adipic acid, and citric acid on the gas-particle partitioning of SOA from α-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of α-pinene SOA into the particle-phase. The other two seed particles have a negligible effect on the α-pinene SOA yields, suggesting that α-pinene SOA forms a well-mixed organic aerosol phase with citric acid and a separate phase with adipic acid and fulvic acid. This finding highlights the need to improve the thermodynamics treatment of organics in current aerosol models that simply lump all hydrophilic organic species into a single phase, thereby potentially introducing an erroneous sensitivity of SOA mass to emitted OA species. PMID:21790137

  15. Soft ionization chemical analysis of secondary organic aerosol from green leaf volatiles emitted by turf grass.

    PubMed

    Jain, Shashank; Zahardis, James; Petrucci, Giuseppe A

    2014-05-01

    Globally, biogenic volatile organic compound (BVOC) emissions contribute 90% of the overall VOC emissions. Green leaf volatiles (GLVs) are an important component of plant-derived BVOCs, including cis-3-hexenylacetate (CHA) and cis-3-hexen-1-ol (HXL), which are emitted by cut grass. In this study we describe secondary organic aerosol (SOA) formation from the ozonolysis of dominant GLVs, their mixtures and grass clippings. Near-infrared laser desorption/ionization aerosol mass spectrometry (NIR-LDI-AMS) was used for chemical analysis of the aerosol. The chemical profile of SOA generated from grass clippings was correlated with that from chemical standards of CHA and HXL. We found that SOA derived from HXL most closely approximated SOA from turf grass, in spite of the approximately 5× lower emission rate of HXL as compared to CHA. Ozonolysis of HXL results in formation of low volatility, higher molecular weight compounds, such as oligomers, and formation of ester-type linkages. This is in contrast to CHA, where the hydroperoxide channel is the dominant oxidation pathway, as oligomer formation is inhibited by the acetate functionality. PMID:24666343

  16. Study for radionuclide transfer ratio of aerosols generated during heat cutting

    SciTech Connect

    Iguchi, Yukihiro; Baba, Tsutomu; Kawakami, Hiroto; Kitahara, Takashi; Watanabe, Atsushi; Kodama, Mitsuhiro

    2007-07-01

    The metallic elements with a low melting point and high vapor pressure seemed to transfer in aerosols selectively at dismantling reactor internals using heat cutting. Therefore, the arc melting tests of neutron irradiated zirconium alloy were conducted to investigate the radionuclide transfer behavior of aerosols generated during the heat cutting of activated metals. The arc melting test was conducted using a tungsten inert gas welding machine in an inert gas or air atmosphere. The radioactive aerosols were collected by filter and charcoal filter. The test sample was obtained from Zry-2 fuel cladding irradiated in a Japanese boiling water reactor for five fuel cycles. The activity analysis, chemical composition measurement and scanning electron microscope observation of aerosols were carried out. Some radionuclides were enriched in the aerosols generated in an inert gas atmosphere and the radionuclide transfer ratio did not change remarkably by the presence of air. The transfer ratio of Sb-125 was almost the same as that of Co-60. It was expected that Sb-125 was enriched from other elements since Sb is an element with a low melting point and high vapor pressure compared with the base metal (Zr). In the viewpoint of the environmental impact assessment, it became clear that the influence if Sb-125 is comparable to Co-60. The transfer ratio of Mn-54 was one order higher compared with other radionuclides. The results were discussed on the basis of thermal properties and oxide formation energy of the metallic elements. (authors)

  17. Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3-D model

    NASA Astrophysics Data System (ADS)

    Knote, C.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J.; Fast, J.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R.; Tyndall, G.; Washenfelder, R.; Waxman, E.; Zhang, Q.

    2013-10-01

    New pathways to form secondary organic aerosols (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous-phase of cloud droplets and deliquesced aerosols where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include a detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aqueous-phase of aerosols. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. In all simulations the LA basin was found to be the hotspot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a simple uptake coefficient, as frequently employed in global modeling studies, leads to higher SOA contributions from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to be the main contributor to SOA mass compared to a volume process and reversible formation. We find that contribution of the latter is limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A kinetic limitation in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute >20% of glyoxal SOA mass, and the total mass formed (5.8% of total SOA in the LA

  18. Organic aerosol mixing observed by single-particle mass spectrometry.

    PubMed

    Robinson, Ellis Shipley; Saleh, Rawad; Donahue, Neil M

    2013-12-27

    We present direct measurements of mixing between separately prepared organic aerosol populations in a smog chamber using single-particle mass spectra from the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Docosane and docosane-d46 (22 carbon linear solid alkane) did not show any signs of mixing, but squalane and squalane-d62 (30 carbon branched liquid alkane) mixed on the time scale expected from a condensational-mixing model. Docosane and docosane-d46 were driven to mix when the chamber temperature was elevated above the melting point for docosane. Docosane vapors were shown to mix into squalane-d62, but not the other way around. These results are consistent with low diffusivity in the solid phase of docosane particles. We performed mixing experiments on secondary organic aerosol (SOA) surrogate systems finding that SOA derived from toluene-d8 (a surrogate for anthropogenic SOA (aSOA)) does not mix into squalane (a surrogate for hydrophobic primary organic aerosol (POA)) but does mix into SOA derived from α-pinene (biogenic SOA (bSOA) surrogate). For the aSOA/POA, the volatility of either aerosol does not limit gas-phase diffusion, indicating that the two particle populations do not mix simply because they are immiscible. In the aSOA/bSOA system, the presence of toluene-d8-derived SOA molecules in the α-pinene-derived SOA provides evidence that the diffusion coefficient in α-pinene-derived SOA is high enough for mixing on the time scale of 1 min. The observations from all of these mixing experiments are generally invisible to bulk aerosol composition measurements but are made possible with single-particle composition data. PMID:24131283

  19. NEW VERSATILE AEROSOL GENERATION SYSTEM DEVELOPED FOR USE IN A LARGE WIND TUNNEL

    EPA Science Inventory

    A new aerosol generation system was developed to accommodate a variety of research activities performed within a large wind tunnel. Because many of the velocity measurements are taken in the wind tunnel with a laser Doppler anemometer (LDA), it is necessary to maintain an aero...

  20. [Use of an aerosol generator (Guard) to control injurious insects in forestry, agriculture, and medical disinsection].

    PubMed

    Abdraziakov, O N; Ermishev, Iu V; Levkov, P A

    2012-01-01

    The Guard aerosol generator is a universal multioperational device without a field-of-use restriction in the application of permitted chemical and biological substances, by combining the function of a controlled dispersion aerosol generator and a remote small- and large-drop sprayer in one mechanism and can use aerosol pesticides. The drop fractionation range is as follows: 3-50, 50-100, 100-300, and 200-400 microm for aerosol, dead water, small-drop, and large-drop spraying, respectively, with smooth and step control of working liquid drops. Treatment using the Guard generator has been shown to be highly effective against agricultural and forestry pests. This paper describes the advantages of the Guard sprayer over those of the conventional air and ground ones. The long-term use of the Guard generator to control mosquitoes and ticks in the Tyumen region could substantially improve the epidemiological situation of tick-borne infections and protect children's recreation centers from attacks of bloodsuckers. PMID:22774514

  1. Application of Ion Mobility Mass Spectrometry for Detection and Identification of Oxidized Organic Species during SOAS 2013

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    We present results obtained with a chemical ionization ion mobility time-of-flight mass spectrometer (CI-IMS-TOF) that was deployed during the Southern Oxidant and Aerosol Study (SOAS) at the Supersite in Centreville, AL. This two dimensional technique, which separates ions on the basis of their interactions with buffer gases before analysis by high-resolution time-of-flight mass spectrometry, allows for detailed separation and identification of isomeric and isobaric species. During SOAS the IMS-TOF was coupled to a chemical ionization source that utilized NO3- as the reagent ion. The NO3- reagent ion clusters with highly oxidized species and allows for a unique means of directly detecting particle phase precursors in the gas phase. Gas phase molecules corresponding to oxidized products of isoprene and terpenes were detected throughout the campaign with a time resolution of 5 minutes. Ion mobility separation and trends observed for several of these key species are discussed. In addition to ambient sampling, the CI-IMS-TOF was also operated behind a potential aerosol mass (PAM) flow reactor which exposed ambient air to high levels of OH radical. Ambient CI-IMS-TOF spectra obtained with and without the flow reactor are presented and compared with laboratory flow reactor spectra generated from isoprene and terpene precursors.

  2. Effects of acute single intranasal instillation of secondary organic aerosol on neurological and immunological biomarkers in the brain and lung of BALB/c mice.

    PubMed

    Win-Shwe, Tin-Tin; Fujitani, Yuji; Sone, Hideko; Furuyama, Akiko; Nitta, Hiroshi; Hirano, Seishiro

    2013-02-01

    Recently, we have reported that primary particles from diesel exhaust affect nervous system, immune system, and learning ability in mice. Currently, in vivo and in vitro studies have shown that secondary organic aerosol (SOA) generated from the coal-fired power plant induced adverse effects in lung and heart. However, the effect of SOA on central nervous system is still unknown. In the present study, using potential biomarkers recognized in previous studies of primary particles, we investigated the effect of acute single administration of SOA on the expression levels of various biomarkers in the brain and lung of mice. We generated the SOA by addition of ozone (O(3)) to the diesel exhaust particle (DEP). Eight-week-old male BALB/c mice were administered DEP or DEP+O(3) (SOA) (50 µg/50 µl/mouse) intranasally. Twenty-four hour after acute single exposure to SOA, olfactory bulb, hippocampus and lung from all mice were collected and mRNA expressions of neurological and immunological biomarkers were examined using real-time RT-PCR analysis and histological examination. Proinflammatory cytokines, their transcription factor and neurotrophin mRNA were remarkably increased in lung of mice exposed to SOA but not in the brain. Microarray data showed that changes of the inflammatory reaction and metabolizing enzyme gene cluster were observed in the brain and lung. Our findings suggested that an acute single exposure of SOA does not affect biomarkers in the brain of normal healthy individuals. Our present results also clearly indicate that SOA induces inflammatory responses in the lung by modulating proinflammatory cytokines, transcription factor and inflammatory responsive neurotrophins. PMID:23358141

  3. 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

  4. Impacts of aqueous phase radical mechanism of oligomerization of methyl vinyl ketone (MVK) on SOA formation: on the prevailing role of dissolved oxygen

    NASA Astrophysics Data System (ADS)

    Renard, P.; Ervens, B.; Siekmann, F.; Vassalo, L.; Ravier, S.; Clement, J.; Monod, A.

    2012-12-01

    It is now recognized that the aqueous phase photochemistry of organic compounds in cloud droplets and deliquescent aerosol particles lead to the formation of oligomers and thus it might produce a substantial amount of atmospheric Secondary Organic Aerosol (SOA) with unique properties. However, the chemical mechanisms leading to these oligomers are still poorly understood, and consequently, their atmospheric impacts are difficult to assess. The goal of this study was to investigate the atmospheric impact of an aqueous phase radical mechanism of oligomerization of methyl vinyl ketone (MVK: one of the main reaction products of isoprene) on SOA formation. Aqueous phase photooxidation of MVK was investigated in a photoreactor using photolysis of H2O2 as OH radical generator. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature and highest MVK initial concentrations. A radical mechanism of polymerization is proposed to explain this oligomer formation. Furthermore, we quantified the total amount of carbon present in oligomers, and the initial radical branching ratios. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the multiphase system as compared to other aqueous phase as well as traditional SOA sources.

  5. Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3D model

    NASA Astrophysics Data System (ADS)

    Knote, C. J.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J. F.; Fast, J. D.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R. M.; Tyndall, G. S.; Washenfelder, R. A.; Waxman, E.; Zhang, Q.

    2013-12-01

    Formation of secondary organic aerosols (SOA) through multi-phase processing of glyoxal has been proposed recently as a relevant contributor to SOA mass. Glyoxal has both anthropogenic and biogenic sources, and readily partitions into the aqueous-phase of cloud droplets and aerosols. Both reversible and irreversible chemistry in the liquid-phase has been observed. A recent laboratory study indicates that the presence of salts in the liquid-phase strongly enhances the Henry';s law constant of glyoxal, allowing for much more effective multi-phase processing. In our work we investigate the contribution of glyoxal to SOA formation on the regional scale. We employ the regional chemistry transport model WRF-chem with MOZART gas-phase chemistry and MOSAIC aerosols, which we both extended to improve the description of glyoxal formation in the gas-phase, and its interactions with aerosols. The detailed description of aerosols in our setup allows us to compare very simple (uptake coefficient) parameterizations of SOA formation from glyoxal, as has been used in previous modeling studies, with much more detailed descriptions of the various pathways postulated based on laboratory studies. Measurements taken during the CARES and CalNex campaigns in California in summer 2010 allowed us to constrain the model, including the major direct precursors of glyoxal. Simulations at convection-permitting resolution over a 2 week period in June 2010 have been conducted to assess the effect of the different ways to parameterize SOA formation from glyoxal and investigate its regional variability. We find that depending on the parameterization used the contribution of glyoxal to SOA is between 1 and 15% in the LA basin during this period, and that simple parameterizations based on uptake coefficients derived from box model studies lead to higher contributions (15%) than parameterizations based on lab experiments (1%). A kinetic limitation found in experiments hinders substantial contribution

  6. Biotic stress: a significant contributor to organic aerosol in Europe?

    NASA Astrophysics Data System (ADS)

    Bergström, R.; Hallquist, M.; Simpson, D.; Wildt, J.; Mentel, T. F.

    2014-12-01

    We have investigated the potential impact on organic aerosol formation from biotic stress-induced emissions (SIE) of organic molecules from forests in Europe (north of lat. 45° N). Emission estimates for sesquiterpenes (SQT), methyl salicylate (MeSA) and unsaturated C17 compounds, due to different stressors, are based on experiments in the Jülich Plant Atmosphere Chamber (JPAC), combined with estimates of the fraction of stressed trees in Europe based on reported observed tree damage. SIE were introduced in the EMEP MSC-W chemical transport model and secondary organic aerosol (SOA) yields from the SIE were taken from the JPAC experiments. Based on estimates of current levels of infestation and the JPAC aerosol yields, the model results suggest that the contribution to SOA in large parts of Europe may be substantial. It is possible that SIE contributes as much, or more, to organic aerosol than the constitutive biogenic VOC emissions, at least during some periods. Based on the assumptions in this study, SIE-SOA are estimated to constitute between 50 and 70 % of the total biogenic SOA (BSOA) in a current-situation scenario where the biotic stress in northern and central European forests causes large SIE of MeSA and SQT. An alternative current-situation scenario with lower SIE, consisting solely of SQT, leads to lower SIE-SOA, between 20 and 40 % of the total BSOA. Hypothetical future scenarios with increased SIE, due to higher degrees of biotic stress, show that SOA formation due to SIE can become even larger. Unsaturated C17 BVOC (biogenic volatile organic compounds) emitted by spruce infested by the forest-honey generating bark louse, Cinara pilicornis, have a high SOA-forming potential. A model scenario investigating the effect of a regional, episodic infestation of Cinara pilicornis in Baden-Württemberg, corresponding to a year with high production of forest honey, shows that these types of events could lead to very large organic aerosol formation in the

  7. Radiative Effects of Aerosols Generated from Biomass Burning, Dust Storms, and Forest Fires

    NASA Technical Reports Server (NTRS)

    Christopher Sundar A.; Vulcan, Donna V.; Welch, Ronald M.

    1996-01-01

    Atmospheric aerosol particles, both natural and anthropogenic, are important to the earth's radiative balance. They scatter the incoming solar radiation and modify the shortwave reflective properties of clouds by acting as Cloud Condensation Nuclei (CCN). Although it has been recognized that aerosols exert a net cooling influence on climate (Twomey et al. 1984), this effect has received much less attention than the radiative forcings due to clouds and greenhouse gases. The radiative forcing due to aerosols is comparable in magnitude to current anthropogenic greenhouse gas forcing but opposite in sign (Houghton et al. 1990). Atmospheric aerosol particles generated from biomass burning, dust storms and forest fires are important regional climatic variables. A recent study by Penner et al. (1992) proposed that smoke particles from biomass burning may have a significant impact on the global radiation balance. They estimate that about 114 Tg of smoke is produced per year in the tropics through biomass burning. The direct and indirect effects of smoke aerosol due to biomass burning could add up globally to a cooling effect as large as 2 W/sq m. Ackerman and Chung (1992) used model calculations and the Earth Radiation Budget Experiment (ERBE) data to show that in comparison to clear days, the heavy dust loading over the Saudi Arabian peninsula can change the Top of the Atmosphere (TOA) clear sky shortwave and longwave radiant exitance by 40-90 W/sq m and 5-20 W/sq m, respectively. Large particle concentrations produced from these types of events often are found with optical thicknesses greater than one. These aerosol particles are transported across considerable distances from the source (Fraser et al. 1984). and they could perturb the radiative balance significantly. In this study, the regional radiative effects of aerosols produced from biomass burning, dust storms and forest fires are examined using the Advanced Very High Resolution Radiometer (AVHRR) Local Area

  8. Formation of secondary organic aerosol from isoprene oxidation over Europe

    NASA Astrophysics Data System (ADS)

    Karl, M.; Tsigaridis, K.; Vignati, E.; Dentener, F.

    2009-01-01

    The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr-1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of particulate organic matter (POM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates POM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr-1). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Tropospheric isoprene SOA production over Europe in summer more than doubles when, in addition to pre-existing carbonaceous aerosols, condensation of semi volatile vapours on ammonium and sulphate aerosols is considered. Consequently, smog chamber experiments on SOA formation should be

  9. Physicochemical Characterization of Lake Spray Aerosol Generated from Great Lakes Water Samples

    NASA Astrophysics Data System (ADS)

    Ault, A. P.; Axson, J. L.; May, N.; Pratt, K.

    2014-12-01

    Wave breaking across bodies of water releases particles into the air which can impact climate and human health. Similar to sea spray aerosols formed through marine wave breaking, freshwater lakes generate lake spray aerosol (LSA). LSA can impact climate directly through scattering/absorption and indirectly through cloud nucleation. In addition, these LSA are suggested to impact human health through inhalation of these particles during algal bloom periods characterized by toxic cyanobacteria. Few studies have been conducted to assess the physical and chemical properties of freshwater LSA. Herein, we discuss constructing a LSA generation system and preliminary physical and chemical characterization of aerosol generated from water samples collected at various sites across Lake Erie, Lake Huron, Lake Superior, and Lake Michigan. Information on aerosol size distributions, number concentrations, and chemical composition will be discussed as a function of lake water blue-green algae concentration, dissolved organic carbon concentration, temperature, conductivity, and dissolved oxygen concentration. These studies represent a first step towards evaluating the potential for LSA to impact climate and health in the Great Lakes region.

  10. OH-Radical initiated ageing of biogenic secondary organic aerosols - A detailed chemical analysis

    NASA Astrophysics Data System (ADS)

    Müller, L.; Reinnig, M.-C.; Mentel, Th. F.; Tillmann, R.; Schlosser, E.; Wahner, A.; Saathoff, H.; Donahue, N. M.; Hoffmann, T.

    2009-04-01

    The chemical ageing[1] of secondary organic aerosol (SOA) was investigated in two series of experiments using on-line mass spectrometry and off-line high performance liquid chromatography mass spectrometry (HPLC-MS). In a set of photochemical experiments, performed in the large outdoor reaction chamber SAPHIR (Jülich, Germany), SOA was generated from a boreal mixture including mono- and sesquiterpenes (α-pinene, β-pinene, Δ3-carene, limonene, caryophyllene). During a long time experiment (30h) the generated SOA was exposed to OH-radicals and the chemical composition was analyzed on-line using atmospheric pressure ionization mass spectrometry (API-MS). The on-line method provides highly time resolved chemical information and therefore a direct insight into the temporal changes of SOA-composition. In parallel, filter samples analysed by HPLC-MS allow the enrichment of trace compounds and finally an unambiguous identification of individual substances. In addition, filter samples allow a direct comparison to samples from field studies. The ageing experiments showed a clear change in SOA composition. The compounds observed can be divided into two groups: A group of first generation SOA-compounds, generated by the OH oxidation of the terpenes and a group of second generation compounds, generated by the reaction of OH with SOA compounds. Among the second generation products, especially a tricarboxylic acid (3-methyl-1,2,3-butanetricarboxylic acid, m/z 203)[2] was observed to be a good marker compound for BSOA ageing. A further set of experiments was carried out in another large aerosol chamber facility, the AIDA chamber of the Research Centre Karlsruhe. In this dark chamber, the experiments focused on the OH-induced ageing of α-pinene SOA and the influence of temperature. The results clearly show that the tricarboxylic acid is a distinctive marker for OH radical induced BSOA ageing and identify cis-pinonic acid as its precursor. To connect the results of the

  11. [Pollution characteristics of microbial aerosols generated from a municipal sewage treatment plant].

    PubMed

    Qiu, Xiong-Hui; Li, Yan-Peng; Niu, Tie-Jun; Li, Mei-Ling; Ma, Zhi-Hui; Miao, Ying; Wang, Xiang-Jun

    2012-07-01

    To characterize the pollution characteristics of microbial aerosols emitted from municipal sewage treatment plants, microbial aerosols were sampled with an Andersen 6-stage impactor at different treatment units of a Xi'an sewage treatment plant between June 2011 and July 2011. The plate-culture and colony-counting methods were employed to determine the concentrations, particle size distributions and median diameters of the airborne bacteria, fungi and actinomycetes. The results showed that the highest concentrations of bacteria (7 866 CFU x m(-3) +/- 960 CFU x m(-3)) and actinomycetes (2 139 CFU x m(-3) +/- 227 CFU x m(-3)) were found in the sludge-dewatering house while the highest fungi concentration (2156 CFU x m(-3) +/- 119 CFU x m(-3)) in the oxidation ditch. The airborne bacteria, fungi and actinomycetes all showed a skewed distribution in particle size. The peaks of bacteria and fungi were in the size range of 2.1-3.3 microm, whereas the peak of airborne actinomycetes was between 1. 1-2.1 microm in size. In general, the order of the median diameters of different microbial aerosols generated from the sewage treatment plant was airborne bacteria > airborne fungi > airborne actinomycetes. In addition, the spatial variation characteristics of microbial aerosols showed that the larger the particle size of the microorganism, the faster the reducing rate of the aerosol concentration. The variations in the reducing rate of concentration with particle sizes can be ordered as airborne bacteria > airborne fungi > airborne actinomycetes. PMID:23002590

  12. A qualitative comparison of secondary organic aerosol yields and composition from ozonolysis of monoterpenes at varying concentrations of NO2

    NASA Astrophysics Data System (ADS)

    Draper, D. C.; Farmer, D. K.; Desyaterik, Y.; Fry, J. L.

    2015-11-01

    The effect of NO2 on secondary organic aerosol (SOA) formation from ozonolysis of α-pinene, β-pinene, Δ3-carene, and limonene was investigated using a dark flow-through reaction chamber. SOA mass yields were calculated for each monoterpene from ozonolysis with varying NO2 concentrations. Kinetics modeling of the first-generation gas-phase chemistry suggests that differences in observed aerosol yields for different NO2 concentrations are consistent with NO3 formation and subsequent competition between O3 and NO3 to oxidize each monoterpene. α-Pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. β-Pinene and Δ3-carene produced fewer particles at higher [NO2], but both retained moderate mass yields. Limonene exhibited both higher number concentrations and greater mass concentrations at higher [NO2]. SOA from each experiment was collected and analyzed by HPLC-ESI-MS, enabling comparisons between product distributions for each system. In general, the systems influenced by NO3 oxidation contained more high molecular weight products (MW > 400 amu), suggesting the importance of oligomerization mechanisms in NO3-initiated SOA formation. α-Pinene, which showed anomalously low aerosol mass yields in the presence of NO2, showed no increase in these oligomer peaks, suggesting that lack of oligomer formation is a likely cause of α-pinene's near 0 % yields with NO3. Through direct comparisons of mixed-oxidant systems, this work suggests that NO3 is likely to dominate nighttime oxidation pathways in most regions with both biogenic and anthropogenic influences. Therefore, accurately constraining SOA yields from NO3 oxidation, which vary substantially with the volatile organic compound precursor, is essential in predicting nighttime aerosol production.

  13. Effect of Hydrophilic Organic Seed Aerosols on Secondary Organic Aerosol Formation from Ozonolysis of α-Pinene

    SciTech Connect

    Song, Chen; Zaveri, Rahul A.; Shilling, John E.; Alexander, M. L.; Newburn, Matthew K.

    2011-07-26

    Gas-particle partitioning theory is widely used in atmospheric models to predict organic aerosol loadings. This theory predicts that secondary organic aerosol (SOA) yield of an oxidized VOC product will increase as the mass loading of preexisting organic aerosol increases. In a previous study, we showed that the presence of model hydrophobic primary organic aerosol (POA) had no detectable effect on the secondary organic aerosol (SOA) yields from ozonolysis of {alpha}-pinene, suggesting that the condensing SOA compounds form a separate phase from the preexisting POA. However, non-polar, hydrophobic POA may gradually become polar and hydrophilic as it undergoes oxidative aging while POA formed from biomass burning is already somewhat polar and hydrophilic. In this study, we investigate the effects of model hydrophilic POA such as fulvic acid, adipic acid and citric acid on the gas-particle partitioning of SOA from {alpha}-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of {alpha}-pinene SOA into the particle-phase. The other two POA seed particles have negligible effect on the {alpha}-pinene SOA yields, suggesting that {alpha}-pinene SOA forms a well-mixed organic aerosol phase with citric acid while a separate phase with adipic acid and fulvic acid. This finding highlights the need to improve the thermodynamics treatment of organics in current aerosol models that simply lump all hydrophilic organic species into a single phase, thereby potentially introducing an erroneous sensitivity of SOA mass to emitted POA.

  14. Dioxinlike properties of a trichloroethylene combustion-generated aerosol.

    PubMed Central

    Villalobos, S A; Anderson, M J; Denison, M S; Hinton, D E; Tullis, K; Kennedy, I M; Jones, A D; Chang, D P; Yang, G; Kelly, P

    1996-01-01

    Conventional chemical analyses of incineration by-products identify compounds of known toxicity but often fail to indicate the presence of other chemicals that may pose health risks. In a previous report, extracts from soot aerosols formed during incomplete combustion of trichloroethylene (TCE) and pyrolysis of plastics exhibited a dioxinlike response when subjected to a keratinocyte assay. To verify this dioxinlike effect, the complete extract, its polar and nonpolar fractions, some containing primarily halogenated aromatic hydrocarbons, were evaluated for toxicity using an embryo assay, for antiestrogenicity using primary liver cell cultures, and for the ability to transform the aryl hydrocarbon receptor into its DNA binding form using liver cytosol in a gel retardation assay. Each of these assays detect dioxinlike effects. Medaka (Oryzias latipes) embryos and primary liver cell cultures of rainbow trout (Oncorhynchus mykiss) were exposed to concentrations of extract ranging from 0.05 to 45 micrograms/l. Cardiotoxicity with pericardial, yolk sac, and adjacent peritoneal edema occurred after exposure of embryos to concentrations of 7 micrograms/l or greater. These same exposure levels were associated with abnormal embryo development and, at the higher concentrations, death. Some of the fractions were toxic but none was as toxic as the whole extract. In liver cells, total cellular protein and cellular lactate dehydrogenase activity were not altered by in vitro exposure to whole extract (0.05-25 micrograms/l). However, induction of cytochrome P4501A1 protein and ethoxyresorufin O-deethylase activity occurred. In the presence of whole extract, estradiol-dependent vitellogenin synthesis was reduced. Of the fractions, only fraction 1 (nonpolar) showed a similar trend, although vitellogenin synthesis inhibition was not significant. The soot extract and fractions bound to the Ah receptor and showed a significantly positive result in the gel retardation/DNA binding test

  15. Aerosol generation and characterization of multi-walled carbon nanotubes exposed to cells cultured at the air-liquid interface.

    PubMed

    Polk, William W; Sharma, Monita; Sayes, Christie M; Hotchkiss, Jon A; Clippinger, Amy J

    2016-01-01

    Aerosol generation and characterization are critical components in the assessment of the inhalation hazards of engineered nanomaterials (NMs). An extensive review was conducted on aerosol generation and exposure apparatus as part of an international expert workshop convened to discuss the design of an in vitro testing strategy to assess pulmonary toxicity following exposure to aerosolized particles. More specifically, this workshop focused on the design of an in vitro method to predict the development of pulmonary fibrosis in humans following exposure to multi-walled carbon nanotubes (MWCNTs). Aerosol generators, for dry or liquid particle suspension aerosolization, and exposure chambers, including both commercially available systems and those developed by independent researchers, were evaluated. Additionally, characterization methods that can be used and the time points at which characterization can be conducted in order to interpret in vitro exposure results were assessed. Summarized below is the information presented and discussed regarding the relevance of various aerosol generation and characterization techniques specific to aerosolized MWCNTs exposed to cells cultured at the air-liquid interface (ALI). The generation of MWCNT aerosols relevant to human exposures and their characterization throughout exposure in an ALI system is critical for extrapolation of in vitro results to toxicological outcomes in humans. PMID:27108236

  16. Experimental demonstration and devices optimization of NRZ-DPSK amplitude regeneration scheme based on SOAs.

    PubMed

    Cao, Tong; Chen, Liao; Yu, Yu; Zhang, Xinliang

    2014-12-29

    We propose and experimentally demonstrate a novel scheme which can simultaneously realize wavelength-preserving and phase-preserving amplitude noise compression of a 40 Gb/s distorted non-return-to-zero differential-phase-shift keying (NRZ-DPSK) signal. In the scheme, two semiconductor optical amplifiers (SOAs) are exploited. The first one (SOA1) is used to generate the inverted signal based on SOA's transient cross-phase modulation (T-XPM) effect and the second one (SOA2) to regenerate the distorted NRZ-DPSK signal using SOA's cross-gain compression (XGC) effect. In the experiment, the bit error ratio (BER) measurements show that power penalties of constructive and destructive demodulation at BER of 10-9 are -1.75 and -1.01 dB, respectively. As the nonlinear effects and the requirements of the two SOAs are completely different, quantum-well (QW) structures has been separately optimized. A complicated theoretical model by combining QW band structure calculation with SOA's dynamic model is exploited to optimize the SOAs, in which both interband effect (carrier density variation) and intraband effect (carrier temperature variation) are taken into account. Regarding SOA1, we choose the tensile strained QW structure and large optical confinement factor to enhance the T-XPM effect. Regarding SOA2, the compressively strained QW structure is selected to reduce the impact of excess phase noise induced by amplitude fluctuations. Exploiting the optimized QW SOAs, better amplitude regeneration performance is demonstrated successfully through numerical simulation. The proposed scheme is intrinsically stable comparing with the interferometer structure and can be integrated on a chip, making it a practical candidate for all-optical amplitude regeneration of high-speed NRZ-DPSK signal. PMID:25607178

  17. Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

    SciTech Connect

    Lee-Taylor, J.; Madronich, Sasha; Aumont, B.; Baker, A.; Camredon, M.; Hodzic, Alma; Tyndall, G. S.; Apel, Eric; Zaveri, Rahul A.

    2011-12-21

    The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations made in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 ug m-3, and SOA peaking at 10-15 μg m-3 during mid-day. The majority (> 75%) of the model SOA stems from the large n-alkanes, with the remainder mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by *- hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.

  18. Ultrahigh-resolution FT-ICR mass spectrometry characterization of a-pinene ozonolysis SOA

    EPA Science Inventory

    Secondary organic aerosol (SOA) of α-pinene ozonolysis with and without hydroxyl radical scavenging hexane was characterized by ultrahigh-resolution. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Molecular formulas for more than 900 negative ions were i...

  19. Mitigating secondary aerosol generation potentials from biofuel use in the energy sector.

    PubMed

    Tiwary, Abhishek; Colls, Jeremy

    2010-01-01

    This paper demonstrates secondary aerosol generation potential of biofuel use in the energy sector from the photochemical interactions of precursor gases on a life cycle basis. The paper is divided into two parts-first, employing life cycle analysis (LCA) to evaluate the extent of the problem for a typical biofuel based electricity production system using five baseline scenarios; second, proposing adequate mitigation options to minimise the secondary aerosol generation potential on a life cycle basis. The baseline scenarios cover representative technologies for 2010 utilising energy crop (miscanthus), short rotation coppiced chips and residual/waste wood in different proportions. The proposed mitigation options include three approaches-biomass gasification prior to combustion, delaying the harvest of biomass, and increasing the geographical distance between the biomass plant and the harvest site (by importing the biofuels). Preliminary results indicate that the baseline scenarios (assuming all the biomass is sourced locally) bear significant secondary aerosol formation potential on a life cycle basis from photochemical neutralisation of acidic emissions (hydrogen chloride and sulphur dioxide) with ammonia. Our results suggest that gasification of miscanthus biomass would provide the best option by minimising the acidic emissions from the combustion plant whereas the other two options of delaying the harvest or importing biofuels from elsewhere would only lead to marginal reduction in the life cycle aerosol loadings of the systems. PMID:19878969

  20. The occupational exposure limit for fluid aerosol generated in metalworking operations: limitations and recommendations.

    PubMed

    Park, Donguk

    2012-03-01

    The aim of this review was to assess current knowledge related to the occupational exposure limit (OEL) for fluid aerosols including either mineral or chemical oil that are generated in metalworking operations, and to discuss whether their OEL can be appropriately used to prevent several health risks that may vary among metalworking fluid (MWF) types. The OEL (time-weighted average; 5 mg/m(3), short-term exposure limit ; 15 mg/m(3)) has been applied to MWF aerosols without consideration of different fluid aerosol-size fractions. The OEL, is also based on the assumption that there are no significant differences in risk among fluid types, which may be contentious. Particularly, the health risks from exposure to water-soluble fluids may not have been sufficiently considered. Although adoption of The National Institute for Occupational Safety and Health's recommended exposure limit for MWF aerosol (0.5 mg/m(3)) would be an effective step towards minimizing and evaluating the upper respiratory irritation that may be caused by neat or diluted MWF, this would fail to address the hazards (e.g., asthma and hypersensitivity pneumonitis) caused by microbial contaminants generated only by the use of water-soluble fluids. The absence of an OEL for the water-soluble fluids used in approximately 80-90 % of all applicants may result in limitations of the protection from health risks caused by exposure to those fluids. PMID:22953224

  1. Design, demonstration and performance of a versatile electrospray aerosol generator for nanomaterial research and applications

    NASA Astrophysics Data System (ADS)

    Jennerjohn, Nancy; Eiguren-Fernandez, Arantzazu; Prikhodko, Sergey; Fung, David C.; Hirakawa, Karen S.; Zavala-Mendez, Jose D.; Hinds, William; Kennedy, Nola J.

    2010-06-01

    Carbon nanotubes are difficult to aerosolize in a controlled manner. We present a method for generating aerosols not only of carbon nanotubes, but also of many reference and proprietary materials including quantum dots, diesel particulate matter, urban dust, and their mixtures, using electrospraying. This method can be used as a teaching tool, or as the starting point for advanced research, or to deliver nanomaterials in animal exposure studies. This electrospray system generates 180 µg of nanotubes per m3 of carrier gas, and thus aerosolizes an occupationally relevant mass concentration of nanotubes. The efficiency achievable for single-walled carbon nanotubes is 9.4%. This system is simple and quick to construct using ordinary lab techniques and affordable materials. Since it is easy to replace soiled parts with clean ones, experiments on different types of nanomaterial can be performed back to back without contamination from previous experiments. In this paper, the design, fabrication, operation and characterization of our versatile electrospray method are presented. Also, the morphological changes that carbon nanotubes undergo as they make the transition from dry powders to aerosol particles are presented.

  2. Photochemical production of aerosols from real plant emissions

    NASA Astrophysics Data System (ADS)

    Mentel, Th. F.; Wildt, J.; Kiendler-Scharr, A.; Kleist, E.; Tillmann, R.; Dal Maso, M.; Fisseha, R.; Hohaus, Th.; Spahn, H.; Uerlings, R.; Wegener, R.; Griffiths, P. T.; Dinar, E.; Rudich, Y.; Wahner, A.

    2009-07-01

    Emission of biogenic volatile organic compounds (VOC) which on oxidation form secondary organic aerosols (SOA) can couple the vegetation with the atmosphere and climate. Particle formation from tree emissions was investigated in a new setup: a plant chamber coupled to a reaction chamber for oxidizing the plant emissions and for forming SOA. Emissions from the boreal tree species birch, pine, and spruce were studied. In addition, α-pinene was used as reference compound. Under the employed experimental conditions, OH radicals were essential for inducing new particle formation, although O3 (≤80 ppb) was always present and a fraction of the monoterpenes and the sesquiterpenes reacted with ozone before OH was generated. Formation rates of 3 nm particles were linearly related to the VOC carbon mixing ratios, as were the maximum observed volume and the condensational growth rates. For all trees, the threshold of new particle formation was lower than for α-pinene. It was lowest for birch which emitted the largest fraction of oxygenated VOC (OVOC), suggesting that OVOC may play a role in the nucleation process. Incremental mass yields were ≍5% for pine, spruce and α-pinene, and ≍10% for birch. α-Pinene was a good model compound to describe the yield and the growth of SOA particles from coniferous emissions. The mass fractional yields agreed well with observations for boreal forests. Despite the somewhat enhanced VOC and OH concentrations our results may be up-scaled to eco-system level. Using the mass fractional yields observed for the tree emissions and weighting them with the abundance of the respective trees in boreal forests SOA mass concentration calculations agree within 6% with field observations. For a future VOC increase of 50% we predict a particle mass increase due to SOA of 19% assuming today's mass contribution of pre-existing aerosol and oxidant levels.

  3. Photochemical production of aerosols from real plant emissions

    NASA Astrophysics Data System (ADS)

    Mentel, Th. F.; Wildt, J.; Kiendler-Scharr, A.; Kleist, E.; Tillmann, R.; Dal Maso, M.; Fisseha, R.; Hohaus, Th.; Spahn, H.; Uerlings, R.; Wegener, R.; Griffiths, P. T.; Dinar, E.; Rudich, Y.; Wahner, A.

    2009-01-01

    By emission of volatile organic compounds (VOC) which on oxidation form secondary organic aerosols (SOA) the vegetation is coupled to atmosphere and climate. New particle formation from tree emissions was investigated in a new setup: a plant chamber coupled to a reaction chamber for oxidizing the plant emissions and for forming SOA. The boreal tree species birch, pine, and spruce were studied and α-pinene was used as reference compound. Under the experimental conditions OH radicals were essential for inducing new particle formation, although O3 (≤80 ppb) was always present and a part of the monoterpenes and the sesquiterpenes reacted already with ozone before OH was generated. Formation rates of 3 nm particles were linearly related to the carbon mixing ratios of the VOC, as were the maximum observed volume and the condensational growth rates. The threshold of new particle formation was lower for the tree emissions than for α-pinene. It was lowest for birch with the largest fraction of oxygenated VOC (OVOC) suggesting that OVOC may play a pivotal role in new particle formation. Incremental mass yields were ≍5% for pine, spruce and α-pinene, and ≍10% for birch. α-Pinene was a good model compound to describe the yield and the growth of SOA particles from coniferous emissions. The mass fractional yields agreed well with observations for boreal forests. Despite our somewhat enhanced VOC and OH concentrations our results may thus be up-scaled to eco-system level. Using the mass fractional yields observed for the tree emissions and weighting them with the abundance of the respective trees in boreal forests we calculate SOA mass concentrations which agree within 6% with field observations. For a future VOC increase of 50% we predict a particle mass increase due to SOA of 19% assuming today's mass contribution of pre-existing aerosol.

  4. Modeling the organic aerosol fraction within the Mexico City basin during the MILAGRO field experiment

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Jimenez, J. L.; Madronich, S.; Aiken, A. C.; Bessagnet, B.; Fast, J.; Lamarque, J. F.; Onasch, T. B.; Roux, G.; Ulbrich, I. M.

    2009-04-01

    The meso-scale chemistry-transport model CHIMERE is used to asses our understanding of major sources and formation processes leading to a fairly abundant fraction of organic aerosols (OA, including primary OA (POA) and secondary OA (SOA)) observed in Mexico City during the MILAGRO field project (March 2006). Chemical analysis of submicron aerosols from aerosol mass spectrometers (AMS) indicate that carbonaceous particles found in the Mexico City basin have a large fraction of oxygenated organic species (OOA) which show strong correspondence with SOA, and that their production actively continues downwind of the city. The SOA formation is modeled according to the first-generation oxidation of anthropogenic (i.e. aromatics, alkanes) and biogenic (i.e. monoterpenes and isoprene) precursors and their partitioning into both organic and aqueous phases. The near-surface model evaluation shows that predicted OA correlates reasonably well with measurements during the campaign, however it remains a factor of 2-3 lower than the measured TOA. One of the reasons for this large gap is the inability of the model to simulate TOA peaks associated with the biomass burning events suggesting that near-city fires are not correctly represented in the emissions inventory (most likely too small to be detected by satellites). Fairly good agreement is found between observed and predicted POA within the city indicating that primary emissions are reasonable. Consistent with previous studies in Mexico City, large discrepancies are found for SOA species characterized by a factor of 5-10 model underestimate. When only anthropogenic SOA precursors were considered, the model was able to reproduce the sharp increase in SOA concentrations during the late morning at both urban and near-urban locations. However, predicted SOA concentrations were unrealistically low when photochemistry was not active, especially overnight. These discrepancies were not significantly reduced when greatly enhanced

  5. Dependence of Isoprene SOA Yield on the Phase of Ammonium Sulfate Seed Particles

    NASA Astrophysics Data System (ADS)

    Wong, J. P. S.; Lee, A.; Abbatt, J.

    2014-12-01

    Current atmospheric models have difficulty predicting the mass of ambient organic bearing particles, suggesting unidentified formation mechanisms. As well, there is growing evidence that the partitioning of water-soluble organic gases to particle-phase liquid water and their subsequent condensed-phase reactions can form additional SOA to that formed by more traditional mechanisms. While previous studies have investigated the formation of isoprene SOA under a range of relative humidity (RH) conditions, the role of particle-phase liquid water in SOA formation remains unclear. The objective of this work is to investigate the effects of particle-phase liquid water on isoprene SOA yield. SOA was generated from the OH oxidation of isoprene at RH 75% in the presence of either effloresced (i.e. dry) or deliquesced (i.e. wet) ammonium sulfate (AS) particles. Results suggest that SOA yield is enhanced for wet AS seed particles. The effects of particle acidity on SOA formation will be presented as well. These experimental results demonstrate the importance of particle-phase liquid water on the uptake of volatile organic gases and their contributions to SOA formation.

  6. Similarities in STXM-NEXAFS Spectra of Atmospheric Particles and Secondary Organic Aerosol Generated from Glyoxal, α-Pinene, Isoprene, 1,2,4-Trimethylbenzene, and d-Limonene

    SciTech Connect

    Shakya, Kabindra M.; Liu, Shang; Takahama, Satoshi; Russell, Lynn M.; Keutsch, Frank N.; Galloway, Melissa M.; Shilling, John E.; Hiranuma, Naruki; Song, Chen; Kim, Hwajin; Paulson, Suazanne E.; Pfaffenberger, Lisa; Barmet, Peter; Slowik, J. G.; Prevot, A. S. H.; Dommen, J.; Baltensperger, Urs

    2013-02-06

    Functional group composition of particles produced in smog chambers are examined using scanning transmission X-ray microscopy (STXM) with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in order to identify characteristic spectral signatures for secondary organic aerosol (SOA). Glyoxal uptake studies showed absorption for mainly alkyl, carbon-nitrogen (C-N), and carboxylic carbonyl groups. The SOA formed from the photooxidation of α-pinene (with and without isoprene) showed stronger absorptions for alkyl and carbonyl groups than the glyoxal studies. The mass ratio of carbonyl to acid group was larger in α-pinene-only experiments relative to the mixed α-pinene-isoprene experiments. The chamber particle spectra were compared with the ambient particle spectra from multiple field campaigns to understand the potential SOA sources. One hundred nineteen particles from six field campaigns had spectral features that were considered similar to the chamber-SOA particles: MILAGRO-2006 (9 particles), VOCALS-2008 (42 particles), Whistler-2008 (22 particles), Scripps Pier-2009 (9 particles), Bakersfield-2010 (25 particles), and Whistler-2010 (12 particles). These similarities with SOA formed from glyoxal, α-pinene (with and without isoprene), 1,2,4-trimethylbenzene, and limonene provide spectroscopic evidence of SOA products from these precursors in ambient particles.

  7. Effect of aerosol particles generated by ultrasonic humidifiers on the lung in mouse

    PubMed Central

    2013-01-01

    Background Ultrasonic humidifiers silently generate water droplets as a cool fog and produce most of the dissolved minerals in the fog in the form of an aerosolized “white dust.” However, the health effect of these airborne particles is largely unknown. This study aimed to characterize the aerosol particles generated by ultrasonic humidifiers and to investigate their effect on the lung tissue of mice. Methods An ultrasonic humidifier was operated with tap water, high-silica water, ultrapure water, or other water types. In a chamber (0.765 m3, ventilation ratio 11.5 m3/hr), male ICR mice (10-week-old) were exposed by inhalation to an aerosol-containing vapor generated by the humidifier. After exposure for 7 or 14 days, lung tissues and bronchoalveolar lavage fluid (BALF) were collected from each mouse and examined by microarray, quantitative reverse transcription-polymerase chain reaction, and light and electron microscopy. Results Particles generated from the humidifier operated with tap water had a mass concentration of 0.46 ± 0.03 mg/m3, number concentration of (5.0 ± 1.1) × 104/cm3, and peak size distribution of 183 nm. The particles were phagocytosed by alveolar macrophages in the lung of mice. Inhalation of particles caused dysregulation of genes related to mitosis, cell adhesion molecules, MHC molecules and endocytosis, but did not induce any signs of inflammation or tissue injury in the lung. Conclusion These results indicate that aerosol particles released from ultrasonic humidifiers operated with tap water initiated a cellular response but did not cause severe acute inflammation in pulmonary tissue. Additionally, high mineral content tap water is not recommended and de-mineralized water should be recommended in order to exclude any adverse effects. PMID:24359587

  8. Effect of operation conditions of the drop-on-demand aerosol generator on aerosol characteristics: Pseudo-cinematographic and plasma mass spectrometric studies

    NASA Astrophysics Data System (ADS)

    Orlandini v. Niessen, Jan O.; Krone, Karin M.; Bings, Nicolas H.

    2014-02-01

    The recently presented drop-on-demand (DOD) aerosol generator overcomes some of the drawbacks of pneumatic nebulization, as its aerosol is no longer generated by gas-liquid interaction. In the current study, an advanced imaging technique is presented, based on a CCD camera equipped with magnifying telecentric optics to allow for fast, automated and precise aerosol characterization as well as fundamental studies on the droplet generation processes by means of pseudo-cinematography. The DOD aerosol generator is thoroughly characterized regarding its droplet size distribution, which shows few distinct populations rather than a continuous distribution. Other important figures, such as the Sauter diameter (D3,2) of 22 μm and the span of 0.4 were also determined. Additionally, the influence of the electrical operation conditions of the dosing device on the aerosol generation process is described. The number and volume of the generated droplets were found to be very reproducible and user-variable, e.g. from 17 to 27 μm (D3,2), within a span of 0.07-0.89. The performances of different setups of the DOD as liquid sample introduction system in ICP-MS are correlated to the respective achievable aerosol characteristics and are also compared to the performance of a state-of-the-art μ-flow nebulizer (EnyaMist). The DOD system allowed for improved sensitivity, but slightly elevated signal noise and overall comparable limits of detection. The results are critically discussed and future directions are outlined.

  9. Transition metal associations with primary biological particles in sea spray aerosol generated in a wave channel.

    PubMed

    Guasco, Timothy L; Cuadra-Rodriguez, Luis A; Pedler, Byron E; Ault, Andrew P; Collins, Douglas B; Zhao, Defeng; Kim, Michelle J; Ruppel, Matthew J; Wilson, Scott C; Pomeroy, Robert S; Grassian, Vicki H; Azam, Farooq; Bertram, Timothy H; Prather, Kimberly A

    2014-01-21

    In the ocean, breaking waves generate air bubbles which burst at the surface and eject sea spray aerosol (SSA), consisting of sea salt, biogenic organic species, and primary biological aerosol particles (PBAP). Our overall understanding of atmospheric biological particles of marine origin remains poor. Here, we perform a control experiment, using an aerosol time-of-flight mass spectrometer to measure the mass spectral signatures of individual particles generated by bubbling a salt solution before and after addition of heterotrophic marine bacteria. Upon addition of bacteria, an immediate increase occurs in the fraction of individual particle mass spectra containing magnesium, organic nitrogen, and phosphate marker ions. These biological signatures are consistent with 21% of the supermicrometer SSA particles generated in a previous study using breaking waves in an ocean-atmosphere wave channel. Interestingly, the wave flume mass spectral signatures also contain metal ions including silver, iron, and chromium. The nascent SSA bioparticles produced in the wave channel are hypothesized to be as follows: (1) whole or fragmented bacterial cells which bioaccumulated metals and/or (2) bacteria-derived colloids or biofilms which adhered to the metals. This study highlights the potential for transition metals, in combination with specific biomarkers, to serve as unique indicators for the presence of marine PBAP, especially in metal-impacted coastal regions. PMID:24328130

  10. VOC emissions, evolutions and contributions to SOA formation at a receptor site in eastern China

    NASA Astrophysics Data System (ADS)

    Yuan, B.; Hu, W. W.; Shao, M.; Wang, M.; Chen, W. T.; Lu, S. H.; Zeng, L. M.; Hu, M.

    2013-09-01

    Volatile organic compounds (VOCs) were measured by two online instruments (GC-FID/MS and PTR-MS) at a receptor site on Changdao Island (37.99° N, 120.70° E) in eastern China. Reaction with OH radical dominated chemical losses of most VOC species during the Changdao campaign. A photochemical-age-based parameterization method is used to calculate VOC emission ratios and to quantify the evolution of ambient VOCs. The calculated emission ratios of most hydrocarbons agree well with those obtained from emission inventory data, but determined emission ratios of oxygenated VOCs (OVOCs) are significantly higher than those from emission inventory data. The photochemical-age-based parameterization method is also used to investigate primary emissions and secondary formation of organic aerosol. The primary emission ratio of organic aerosol (OA) to CO is determined to be 14.9 μg m-3 ppm-1, and secondary organic aeorosols (SOA) are produced at an enhancement ratio of 18.8 μg m-3 ppm-1 to CO after 50 h of photochemical processing in the atmosphere. SOA formation is significantly higher than the level determined from VOC oxidation under both high-NOx (2.0 μg m-3 ppm-1 CO) and low-NOx conditions (6.5 μg m-3 ppm-1 CO). Polycyclic aromatic hydrocarbons (PAHs) and higher alkanes (> C10) account for as high as 17.4% of SOA formation, which suggests semi-volatile organic compounds (SVOCs) may be a large contributor to SOA formation during the Changdao campaign. The SOA formation potential of primary VOC emissions determined from field campaigns in Beijing and Pearl River Delta (PRD) is lower than the measured SOA levels reported in the two regions, indicating SOA formation is also beyond explainable by VOC oxidation in the two city clusters.

  11. 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.

  12. Secondary organic aerosol: a comparison between foggy and nonfoggy days.

    PubMed

    Kaul, D S; Gupta, Tarun; Tripathi, S N; Tare, V; Collett, J L

    2011-09-01

    Carbonaceous species, meteorological parameters, trace gases, and fogwater chemistry were measured during winter in the Indian city of Kanpur to study secondary organic aerosol (SOA) during foggy and clear (nonfoggy) days. Enhanced SOA production was observed during fog episodes. It is hypothesized that aqueous phase chemistry in fog drops is responsible for increasing SOA production. SOA concentrations on foggy days exceeded those on clear days at all times of day; peak foggy day SOA concentrations were observed in the evening vs peak clear day SOA concentrations which occurred in the afternoon. Changes in biomass burning emissions on foggy days were examined because of their potential to confound estimates of SOA production based on analysis of organic to elemental carbon (OC/EC) ratios. No evidence of biomass burning influence on SOA during foggy days was found. Enhanced oxidation of SO(2) to sulfate during foggy days was observed, possibly causing the regional aerosol to become more acidic. No evidence was found in this study, either, for effects of temperature or relative humidity on SOA production. In addition to SOA production, fogs can also play an important role in cleaning the atmosphere of carbonaceous aerosols. Preferential scavenging of water-soluble organic carbon (WSOC) by fog droplets was observed. OC was found to be enriched in smaller droplets, limiting the rate of OC deposition by droplet sedimentation. Lower EC concentrations were observed on foggy days, despite greater stagnation and lower mixing heights, suggesting fog scavenging and removal of EC was active as well. PMID:21790145

  13. Overview of the Capstone depleted uranium study of aerosols from impact with armored vehicles: test setup and aerosol generation, characterization, and application in assessing dose and risk.

    PubMed

    Parkhurst, Mary Ann; Guilmette, Raymond A

    2009-03-01

    The Capstone Depleted Uranium (DU) Aerosol Characterization and Risk Assessment Study was conducted to generate data about DU aerosols generated during the perforation of armored combat vehicles with large-caliber DU penetrators, and to apply the data in assessments of human health risks to personnel exposed to these aerosols, primarily through inhalation, during the 1991 Gulf War or in future military operations. The Capstone study consisted of two components: 1) generating, sampling, and characterizing DU aerosols by firing at and perforating combat vehicles, and 2) applying the source-term quantities and characteristics of the aerosols to the evaluation of doses and risks. This paper reviews the background of the study including the bases for the study, previous reviews of DU particles and health assessments from DU used by the U.S. military, the objectives of the study components, the participants and oversight teams, and the types of exposures it was intended to evaluate. It then discusses exposure scenarios used in the dose and risk assessment and provides an overview of how the field tests and dose and risk assessments were conducted. PMID:19204481

  14. Modeling the formation and aging of secondary organic aerosols in Los Angeles during CalNex 2010

    DOE PAGESBeta

    Hayes, P. L.; Carlton, A. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S.; Rappenglück, B.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; et al

    2015-05-26

    Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidationmore » of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model–measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model–measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the

  15. Modeling the formation and aging of secondary organic aerosols in Los Angeles during CalNex 2010

    NASA Astrophysics Data System (ADS)

    Hayes, P. L.; Carlton, A. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S.; Rappengluck, B.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; Zotter, P.; Prevot, A. S. H.; Szidat, S.; Kleindienst, T. E.; Offenberg, J. H.; Ma, P. K.; Jimenez, J. L.

    2015-05-01

    Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model-measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model-measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed

  16. Molecular Formula Characterization of Biogenic Secondary Organic Aerosol: Descriptive Statistical Evaluation

    NASA Astrophysics Data System (ADS)

    Dalbec, M.; Zhao, Y.; Fisseha, R.; Putman, A.; Kundu, S.; Rahn, T. A.; Mazzoleni, L. R.

    2013-12-01

    The detailed molecular composition of approximately 20 laboratory generated terpene ozonolysis secondary organic aerosol (SOA) samples was studied using ultrahigh resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Individual experiments were conducted with one of four terpene SOA precursors (α-pinene, β-pinene, limonene or β-caryophyllene), varied relative humidity (RH) conditions (0%, 4%, or 30%) and the presence or absence of cyclohexane (serving as a radical scavenger). In this work, we focus on the molecular composition of the SOA experiments conducted at 4% and 30% RH without cyclohexane. In each of the experimental SOA samples, the oxygen number and the DBE values increase with increasing carbon number and three or four distinct groups (aka oligomer groups) were observed in the mass spectra. The overall bulk properties, such as the elemental ratios and the average number of double bond equivalents (DBE), of the SOA were highly similar. Despite the high number of identified species (N ≥ 1000) in each SOA sample, compounds unique to the SOA formed at either 4% or 30% RH conditions were comparatively low (< 200). An exception to this was observed for the D-limonene ozonolysis SOA formed at 4% RH conditions where over 450 unique molecular formulas were observed. Due to the similarity in the bulk properties and composition of the SOA from the experiments, multivariate statistics were used to distinguish the experiments from each other. Hierarchical cluster analysis and principal component analysis was performed using the molecular formulas and their relative abundances for all of the identified species. Slight compositional differences between the experiments showed that experiments with the same terpene SOA precursor were most closely related regardless of the RH or the presence/absence of cyclohexane. Furthermore, SOA experiments with D-limonene and β-caryophyllene as precursors were clearly distinguished from β-pinene and

  17. High molecular weight SOA formation during limonene ozonolysis: insights from ultrahigh-resolution FT-ICR mass spectrometry characterization

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

    The detailed molecular composition of secondary organic aerosols (SOA) from limonene ozonolysis was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. High molecular weight (MW) compounds (m/z > 300) were found to constitute a significant number fraction of the identified SOA components. Double bond equivalents (DBE = the number of rings plus the number of double bonds) increased with MW. The O:C ratios and relative abundances of compounds decreased with increasing MW. The mass spectra of limonene contain 4 distinct clusters of negative ions: Group I (140 < m/z < 300), Group II (300 < m/z < 500), Group III (500 < m/z < 700) and Group IV (700 < m/z < 850). A number of CH2 and O homologous series of low MW SOA (Group 1) with carbon number 7-15 and oxygen number 3-9 were observed. Their occurrence can be explained with isomerization and elimination reactions of Criegee radicals, reactions between alkyl peroxy radicals, and scission of alkoxy radicals resulting from the Criegee radicals. Additionally, fragmentation analysis and observations of formaldehyde homologous series provide evidence for aerosol growth by the reactive uptake of generated gas-phase carbonyls in limonene ozonolysis. The decreasing O:C ratios between group of compounds indicated the importance of condensation (aldol and esterification) reaction pathways for high MW compound formation. However, the prominent DBE changes of 2 between the groups of compounds and selected fragmentation (MS/MS) analysis of Group II and Group III ions indicated a predominance of non-condensation (hydroperoxide, Criegee and hemi-acetal) reaction pathways. A reaction matrix created with the combination of low MW SOA, hydroperoxides, and Criegee radicals indicated higher frequencies for the hemi-acetal and condensation reaction pathways. Overall, the combined approach confirms the importance of non-condensation reaction pathways over condensation reaction pathways. Among

  18. Hygroscopic properties of smoke-generated organic aerosol particles emitted in the marine atmosphere

    NASA Astrophysics Data System (ADS)

    Wonaschütz, A.; Coggon, M.; Sorooshian, A.; Modini, R.; Frossard, A. A.; Ahlm, L.; Mülmenstädt, J.; Roberts, G. C.; Russell, L. M.; Dey, S.; Brechtel, F. J.; Seinfeld, J. H.

    2013-10-01

    During the Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE), a plume of organic aerosol was produced by a smoke generator and emitted into the marine atmosphere from aboard the R/V Point Sur. In this study, the hygroscopic properties and the chemical composition of the plume were studied at plume ages between 0 and 4 h in different meteorological conditions. In sunny conditions, the plume particles had very low hygroscopic growth factors (GFs): between 1.05 and 1.09 for 30 nm and between 1.02 and 1.1 for 150 nm dry size at a relative humidity (RH) of 92%, contrasted by an average marine background GF of 1.6. New particles were produced in large quantities (several 10 000 cm-3), which lead to substantially increased cloud condensation nuclei (CCN) concentrations at supersaturations between 0.07 and 0.88%. Ratios of oxygen to carbon (O : C) and water-soluble organic mass (WSOM) increased with plume age: from < 0.001 to 0.2, and from 2.42 to 4.96 μg m-3, respectively, while organic mass fractions decreased slightly (~ 0.97 to ~ 0.94). High-resolution aerosol mass spectrometer (AMS) spectra show that the organic fragment m/z 43 was dominated by C2H3O+ in the small, new particle mode and by C3H7+ in the large particle mode. In the marine background aerosol, GFs for 150 nm particles at 40% RH were found to be enhanced at higher organic mass fractions: an average GF of 1.06 was observed for aerosols with an organic mass fraction of 0.53, and a GF of 1.04 for an organic mass fraction of 0.35.

  19. SOA Formation form the NO3 radicals Chemistry of Isoprene, Monoterpenes, Sesquiterpenes, Biogenic Oxygenated Compounds, and Aromatics

    NASA Astrophysics Data System (ADS)

    Kleindienst, T. E.; Jaoui, M.; Docherty, K.; Corse, E.; Offenberg, J. H.; Lewandowski, M.

    2011-12-01

    Volatile organic compounds (VOCs) are oxidized in the atmosphere primarily by hydroxyl radicals (OH) during daylight hours but also by nitrate radicals (NO3) during overnight, photochemically inactive periods. While reactions with OH have received considerable attention with regard to gas-phase reaction products and secondary organic aerosol (SOA) formation, less is known about the mechanisms and products resulting from nighttime NO3 reactions despite their potential for SOA formation. To date, there have been limited studies on the chemical characteristics of aerosol reaction products formed from VOCs oxidation with NO3, and few SOA reaction products have been identified. Nighttime reactions have nevertheless been incorporated into some air quality models despite the limited information available and substantial uncertainties which still exist. The National Exposure Research Laboratory of the U.S. Environmental Protection Agency recently undertook an integrated laboratory research effort to better understand the contribution of NO3 reactions to nighttime SOA formation. Isoprene, methacrolein, a-pinene, b-pinene, d-limonene, b-caryophyllene, farnesene, a-humulene, 2-methyl-3-buten-2-ol, toluene, m-xylene, and naphthalene were reacted with NO3 under a wide range of conditions in a series of separate photochemical reaction chamber experiments. These hydrocarbons are thought to contribute to ambient SOA formation. NO3 was formed through thermal decomposition of N2O5. The yield, physical characteristics, and composition of SOA formed in each experiment was analyzed by a suite of instruments including a scanning mobility particle sizer, a Sunset Labs semi continuous EC-OC monitor, a volatility differential mobility analyzer, a direct insertion probe-mass spectrometer, a high resolution time-of-flight aerosol mass spectrometer, and a gas-chromatography-mass spectrometer. To understand the relative contributions of nighttime versus daytime VOCs reactions, a similar

  20. A Coupled Programme of Aerosol Research Within the OP3 and ACES Projects

    NASA Astrophysics Data System (ADS)

    McFiggans, G.; Aces Aerosol Teams, P A

    2008-12-01

    The oxidation of organic compounds in the troposphere plays a central role in the generation of ozone, and leads to the formation of secondary organic aerosol (SOA) and other secondary pollutants. Approximately 90% of organic material emitted globally is estimated to originate from biogenic sources, with almost half of all reactive biogenic volatile organic compounds (BVOC) being emitted from tropical and sub-tropical forests. It is becoming increasingly clear from observational studies that biogenic SOA (BSOA) is the dominant source of aerosol organic carbon concentrations in remote environments. This provides part of the motivation for the OP3 project. Ground-based aerosol measurements at the Global Atmosphere Watch (GAW) site in Danum Valley Conservation Area in OP3 were provided by a suite of instrumentation for full composition and physical property characterisation (size distribution, hygroscopicity and CCN activation). To further enhance our understanding of aerosol processes in the Borneo rainforest, additional capability was assembled within the UK NERC funded "Aerosol Coupling in the Earth System" (ACES) programme. Field component enhancements to the OP3 aerosol payload by ACES included a deployment of aerosol and precursor flux measurements within the forest canopy to characterise primary bioaerosol sources and in-canopy chemistry leading to formation of secondary aerosol components. In addition, measurements of VOCs and aerosol composition were made above an oil palm plantation to assess the impact of land-use change on aerosol processes. ACES is a coupled programme of field, chamber, mechanism development and modelling investigations aiming to reduce uncertainties in our fundamental understanding of BSOA formation and the subsequent impact on atmospheric composition. In addition to summarising aerosol field measurements within ACES / OP3, we will present an overview of the status of the ACES chamber and modelling results with the overall aim to: i

  1. Global modeling of SOA: the use of different mechanisms for aqueous-phase formation

    NASA Astrophysics Data System (ADS)

    Lin, G.; Sillman, S.; Penner, J. E.; Ito, A.

    2014-06-01

    There is growing interest in the formation of secondary organic aerosol (SOA) through condensed aqueous-phase reactions. In this study, we use a global model (IMPACT) to investigate the potential formation of SOA in the aqueous phase. We compare results from several multiphase process schemes with detailed aqueous-phase reactions to schemes that use a first-order gas-to-particle formation rate based on uptake coefficients. The predicted net global SOA production rate in cloud water ranges from 13.1 Tg yr-1 to 46.8 Tg yr-1 while that in aerosol water ranges from -0.4 Tg yr-1 to 12.6 Tg yr-1. The predicted global burden of SOA formed in the aqueous phase ranges from 0.09 Tg to 0.51 Tg. A sensitivity test to investigate two representations of cloud water content from two global models shows that increasing cloud water by an average factor of 2.7 can increase the net SOA production rate in cloud water by a factor of 4 at low altitudes (below approximately 900 hPa). We also investigated the importance of including dissolved Fe chemistry in cloud water aqueous reactions. Adding these reactions increases the formation rate of aqueous-phase OH by a factor of 2.6 and decreases the amount of global aqueous SOA formed by 31%. None of the mechanisms discussed here is able to provide a best fit for all observations. Rather, the use of an uptake coefficient method for aerosol water and a multi-phase scheme for cloud water provides the best fit in the Northern Hemisphere and the use of multiphase process scheme for aerosol and cloud water provides the best fit in the tropics. The model with Fe chemistry underpredicts oxalate measurements in all regions. Finally, the comparison of oxygen-to-carbon (O / C) ratios estimated in the model with those estimated from measurements shows that the modeled SOA has a slightly higher O / C ratio than the observed SOA for all cases.

  2. Linking biogenic hydrocarbons to biogenic aerosol in the Borneo rainforest

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Alfarra, M. R.; Robinson, N.; Ward, M. W.; Lewis, A. C.; McFiggans, G. B.; Coe, H.; Allan, J. D.

    2013-11-01

    Emissions of biogenic volatile organic compounds are though to contribute significantly to secondary organic aerosol formation in the tropics, but understanding these transformation processes has proved difficult, due to the complexity of the chemistry involved and very low concentrations. Aerosols from above a Southeast Asian tropical rainforest in Borneo were characterised using liquid chromatography-ion trap mass spectrometry, high-resolution aerosol mass spectrometry and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) techniques. Oxygenated compounds were identified in ambient organic aerosol that could be directly traced back to isoprene, monoterpenes and sesquiterpene emissions, by combining field data on chemical structures with mass spectral data generated from synthetically produced products created in a simulation chamber. Eighteen oxygenated species of biogenic origin were identified in the rainforest aerosol from the precursors isoprene, α-pinene, limonene, α-terpinene and β-caryophyllene. The observations provide the unambiguous field detection of monoterpene and sesquiterpene oxidation products in SOA above a pristine tropical rainforest. The presence of 2-methyl tetrol organosulfates and an associated sulfated dimer provides direct evidence that isoprene in the presence of sulfate aerosol can make a contribution to biogenic organic aerosol above tropical forests. High-resolution mass spectrometry indicates that sulfur can also be incorporated into oxidation products arising from monoterpene precursors in tropical aerosol.

  3. Linking biogenic hydrocarbons to biogenic aerosol in the Borneo rainforest

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Alfarra, M. R.; Robinson, N.; Ward, M. W.; Lewis, A. C.; McFiggans, G. B.; Coe, H.; Allan, J. D.

    2013-07-01

    Emissions of biogenic volatile organic compounds are though to contribute significantly to secondary organic aerosol formation in the tropics, but understanding the process of these transformations has proved difficult, due to the complexity of the chemistry involved and very low concentrations. Aerosols from above a South East Asian tropical rainforest in Borneo were characterised using liquid chromatography-ion trap mass spectrometry, high resolution aerosol mass spectrometry and fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) techniques. Oxygenated compounds were identified in ambient organic aerosol that could be directly traced back to isoprene, monoterpenes and sesquiterpene emissions, by combining field data on chemical structures with mass spectral data generated from synthetically produced products created in a simulation chamber. Eighteen oxygenated species of biogenic origin were identified in the rainforest aerosol from the precursors isoprene, α-pinene, limonene, α-terpinene and β-caryophyllene. The observations provide the unambiguous field detection of monoterpene and sesquiterpene oxidation products in SOA above a pristine tropical rainforest. The presence of 2-methyltetrol organosulfates and an associated sulfated dimer provides direct evidence that isoprene in the presence of sulfate aerosol can make a contribution to biogenic organic aerosol above tropical forests. High-resolution mass spectrometry indicates that sulfur can also be incorporated into oxidation products arising from monoterpene precursors in tropical aerosol.

  4. Emissions and Characteristics of Ice Nucleating Particles Associated with Laboratory Generated Nascent Sea Spray Aerosol

    NASA Astrophysics Data System (ADS)

    McCluskey, C. S.; Hill, T. C. J.; Beall, C.; Sultana, C. M.; Moore, K.; Cornwell, G.; Lee, C.; Al-Mashat, H.; Laskina, O.; Trueblood, J.; Grassian, V. H.; Prather, K. A.; Kreidenweis, S. M.; DeMott, P. J.

    2015-12-01

    Accurate emission rates and activity spectra of atmospheric ice nucleating particles (INPs) are required for proper representation of aerosol-cloud interactions in atmospheric modeling studies. However, few investigations have quantified or characterized oceanic INP emissions. In conjunction with the Center for Aerosol Impacts on the Climate and the Environment, we have directly measured changes in INP emissions and properties of INPs from nascent sea spray aerosol (SSA) through the evolution of phytoplankton blooms. Multiple offline and online instruments were used to monitor aerosol chemistry and size, and bulk water characteristics during two phytoplankton bloom experiments. Two methods were utilized to monitor the number concentrations of INPs from 0 to -34 °C: The online CSU continuous flow diffusion chamber (CFDC) and collections processed offline using the CSU ice spectrometer. Single particle analyses were performed on ice crystal residuals downstream of the CFDC, presumed to be INPs, via scanning transmission electron microscopy (STEM) and Raman microspectroscopy. Preliminary results indicate that laboratory-generated nascent SSA corresponds to number concentrations of INPs that are generally consistent with open ocean regions, based on current knowledge. STEM analyses revealed that the sizes of ice crystal residuals that were associated with nascent SSA ranged from 0.3 to 2.5 μm. Raman microspectroscopy analysis of 1 μm sized residuals found a variety of INP identities, including long chain organics, diatom fragments and polysaccharides. Our data suggest that biological processes play a significant role in ocean INP emissions by generating the species and compounds that were identified during these studies.

  5. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

    2015-08-01

    This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low and high NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NOx) to ~45 % (high NOx) for α-pinene, ~15 % for toluene, ~25 % for C12 n-alkane, and ~10 % for C16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of JSOA

  6. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

    2015-03-01

    This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOA). Typically only photolysis of smaller organic molecules (e.g. formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low- and high-NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after four days of chemical aging under those conditions (equivalent to eight days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields i.e ~15% (low-NOx) to ~45% (high-NOx) for α-pinene, ~15% for toluene, ~25% for C12-alkane, and ~10% for C16-alkane. The small effect on low volatility n-alkanes such as C16-alkane is due to the rapid partitioning of early-generation products to the particle phase where they are assumed to be protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass seems increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas-phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an estimated SOA photolysis rate of JSOA=4 x 10-4JNO2. Modeling

  7. Photoacoustic optical properties at UV, VIS, and near IR wavelengths for laboratory generated and winter time ambient urban aerosols

    NASA Astrophysics Data System (ADS)

    Gyawali, M.; Arnott, W. P.; Zaveri, R. A.; Song, C.; Moosmüller, H.; Liu, L.; Mishchenko, M. I.; Chen, L.-W. A.; Green, M. C.; Watson, J. G.; Chow, J. C.

    2012-03-01

    We present the laboratory and ambient photoacoustic (PA) measurement of aerosol light absorption coefficients at ultraviolet wavelength (i.e., 355 nm) and compare with measurements at 405, 532, 870, and 1047 nm. Simultaneous measurements of aerosol light scattering coefficients were achieved by the integrating reciprocal nephelometer within the PA's acoustic resonator. Absorption and scattering measurements were carried out for various laboratory-generated aerosols, including salt, incense, and kerosene soot to evaluate the instrument calibration and gain insight on the spectral dependence of aerosol light absorption and scattering. Ambient measurements were obtained in Reno, Nevada, between 18 December 2009 and 18 January 2010. The measurement period included days with and without strong ground level temperature inversions, corresponding to highly polluted (freshly emitted aerosols) and relatively clean (aged aerosols) conditions. Particulate matter (PM) concentrations were measured and analyzed with other tracers of traffic emissions. The temperature inversion episodes caused very high concentration of PM2.5 and PM10 (particulate matter with aerodynamic diameters less than 2.5 μm and 10 μm, respectively) and gaseous pollutants: carbon monoxide (CO), nitric oxide (NO), and nitrogen dioxide (NO2). The diurnal change of absorption and scattering coefficients during the polluted (inversion) days increased approximately by a factor of two for all wavelengths compared to the clean days. The spectral variation in aerosol absorption coefficients indicated a significant amount of absorbing aerosol from traffic emissions and residential wood burning. The analysis of single scattering albedo (SSA), Ångström exponent of absorption (AEA), and Ångström exponent of scattering (AES) for clean and polluted days provides evidences that the aerosol aging and coating process is suppressed by strong temperature inversion under cloudy conditions. In general, measured UV

  8. Photoacoustic optical properties at UV, VIS, and near IR wavelengths for laboratory generated and winter time ambient urban aerosols

    SciTech Connect

    Gyawali, Madhu S.; Arnott, W. Patrick; Zaveri, Rahul A.; Song, Chen; Moosmuller, H.; Liu, Li; Mishchenko, M.; Chen, L-W A.; Green, M.; Watson, J. G.; Chow, J. C.

    2012-03-08

    We present the laboratory and ambient photoacoustic (PA) measurement of aerosol light absorption coefficients at ultraviolet wavelength (i.e., 355 nm) and compare with measurements at 405, 532, 870, and 1047 nm. Simultaneous measurements of aerosol light scattering coefficients were achieved by the integrating reciprocal nephelometer within the PA's acoustic resonator. Absorption and scattering measurements were carried out for various laboratory generated aerosols, including salt, incense, and kerosene soot to evaluate the instrument calibration and gain insight on the spectral dependence of aerosol light absorption and scattering. Ambient measurements were obtained in Reno, Nevada, between 18 December 2009 and 18 January 2010. The measurement period included days with and without strong ground level temperature inversions, corresponding to highly polluted (freshly emitted aerosols) and relatively clean (aged aerosols) conditions. Particulate matter (PM) concentrations were measured and analyzed with other tracers of traffic emissions. The temperature inversion episodes caused very high concentration of PM{sub 2.5} and PM{sub 10} (particulate matter with aerodynamic diameters less than 2.5 {mu}m and 10 {mu}m, respectively) and gaseous pollutants: carbon monoxide (CO), nitric oxide (NO), and nitrogen dioxide (NO{sub 2}). The diurnal change of absorption and scattering coefficients during the polluted (inversion) days increased approximately by a factor of two for all wavelengths compared to the clean days. The spectral variation in aerosol absorption coefficients indicated a significant amount of absorbing aerosol from traffic emissions and residential wood burning. The analysis of single scattering albedo (SSA), Angstrom exponent of absorption (AEA), and Angstrom exponent of scattering (AES) for clean and polluted days provides evidences that the aerosol aging and coating process is suppressed by strong temperature inversion under cloudy conditions. In general

  9. Photoacoustic Optical Properties at UV, VIS, and near IR Wavelengths for Laboratory Generated and Winter Time Ambient Urban Aerosols

    NASA Technical Reports Server (NTRS)

    Gyawali, M.; Arnott, W. P.; Zaveri, R. A.; Song, C.; Moosmuller, H.; Liu, L.; Mishchenko, M. I.; Chen, L.-W.A.; Green, M. C.; Watson, J. G.; Chow, J. C.

    2012-01-01

    We present the laboratory and ambient photoacoustic (PA) measurement of aerosol light absorption coefficients at ultraviolet wavelength (i.e., 355 nm) and compare with measurements at 405, 532, 870, and 1047 nm. Simultaneous measurements of aerosol light scattering coefficients were achieved by the integrating reciprocal nephelometer within the PA's acoustic resonator. Absorption and scattering measurements were carried out for various laboratory generated aerosols, including salt, incense, and kerosene soot to evaluate the instrument calibration and gain insight on the spectral dependence of aerosol light absorption and scattering. Ambient measurements were obtained in Reno, Nevada, between 18 December 2009 and 18 January 2010. The measurement period included days with and without strong ground level temperature inversions, corresponding to highly polluted (freshly emitted aerosols) and relatively clean (aged aerosols) conditions. Particulate matter (PM) concentrations were measured and analyzed with other tracers of traffic emissions. The temperature inversion episodes caused very high concentration of PM (sub 2.5) and PM( sub 10) (particulate matter with aerodynamic diameters less than 2.5 micrometers and 10 micrometers, respectively) and gaseous pollutants: carbon monoxide (CO), nitric oxide (NO), and nitrogen dioxide (NO2). The diurnal change of absorption and scattering coefficients during the polluted (inversion) days increased approximately by a factor of two for all wavelengths compared to the clean days. The spectral variation in aerosol absorption coefficients indicated a significant amount of absorbing aerosol from traffic emissions and residential wood burning. The analysis of single scattering albedo (SSA), Angstrom exponent of absorption (AEA), and Angstrom exponent of scattering (AES) for clean and polluted days provides evidences that the aerosol aging and coating process is suppressed by strong temperature inversion under cloudy conditions. In

  10. Secondary organic aerosol formation and primary organic aerosol oxidation from biomass burning smoke in a flow reactor during FLAME-3

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Day, D. A.; Cubison, M. J.; Brune, W. H.; Bon, D.; de Gouw, J. A.; Jimenez, J. L.

    2013-05-01

    We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A potential aerosol mass "PAM" flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~ 1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days aging in the atmosphere. VOC observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in an total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net SOA to POA ratio of biomass burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OHexp), typically peaking around three days of equivalent atmospheric photochemical age (OHexp ~ 3.9 × 1011 molecules cm-3 s-1), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors. The mass of SOA formed often exceeds the mass of the known VOC precursors, indicating the likely importance of primary semivolatile/intermediate volatility

  11. Characterisation of Secondary Organic Aerosol Formed from the Photooxidation of Isoprene during Cloud Condensation-Evaporation Cycles (CUMULUS Project)

    NASA Astrophysics Data System (ADS)

    Doussin, J. F.; Giorio, C.; Bregonzio-Rozier, L.; Siekmann, F.; Temime-Roussel, B.; Gratien, A.; Ravier, S.; Pangui, E.; Tapparo, A.; Kalberer, M.; Vermeylen, R.; Claeys, M.; Monod, A.

    2014-12-01

    Biogenic volatile organic compounds (BVOCs) undergo many oxidation processes in the atmosphere accompanied by formation of water-soluble compounds. These compounds could partition into atmospheric water droplets, and react within the aqueous phase producing higher molecular weight and less volatile compounds which could form new aerosol (Ervens et al., 2011). This work investigates the formation and composition of secondary organic aerosol (SOA) from the photooxidation of isoprene and methacrolein (its main first-generation oxidation product) and the effect of cloud water on SOA formation and composition. The experiments were performed within the CUMULUS project (CloUd MULtiphase chemistry of organic compoUndS in the troposphere) at the 4.2 m3 stainless steel CESAM chamber (Wang et al., 2011). In each experiment, isoprene or methacrolein was injected in the chamber together with HONO under dry conditions before irradiation. The experimental protocol was optimised to generate cloud events in the chamber, lasting for ca. 10 minutes in the presence of light. Gas phase compounds were analyzed on-line by a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-ToF-MS), a Fourier Transform Infrared Spectrometer (FTIR), NOx and O3 analyzers. SOA formation and composition were analysed on-line with a Scanning Mobility Particle Sizer (SMPS) and an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and off-line through sampling on filters and analysis in GC-MS and LC-MS. We observed that during cloud formation water soluble gas-phase oxidation products readily partitioned into cloud droplets and new SOA was promptly produced. Chemical composition, elemental ratios and density of SOA were compared before, during cloud formation and after cloud evaporation. Ervens, B. et al. (2011) Atmos. Chem. Phys. 11, 11069-11102. Wang, J. et al. (2011) Atmos. Measur. Tech. 4, 2465-2494.

  12. Aerosol Generation and Circulation in the Shore Zone of a Large Alpine Lake - Lake Tahoe, CA.

    NASA Astrophysics Data System (ADS)

    Vancuren, R. A.; Pederson, J. R.; Lashgari, A.; Dolislager, L.; McCauley, E.

    2007-12-01

    The temporal, spatial, and size-distribution patterns of particles in ambient air over shore areas and the surface of Lake Tahoe (Nevada and California) were studied as part of the 2003-2004 Lake Tahoe Atmospheric Deposition Study (LTADS). The concentration of population along the shoreline of Lake Tahoe makes accurate characterization of local aerosol generation and transport especially important in estimation of annual particle flux onto the surface of the lake. Road dust and smoke are major components of aerosols around the lake, and strong gradients in concentrations and size distributions occur as functions of location, land use, traffic activity, and time of day. Measurements taken while cruising on the lake show that aerosol concentrations in near-shore areas are primarily controlled by a combination of diurnal cycling of land- and lake- breezes coupled with varying particle emissions driven by cycles of human activity. Source-associated particle size distributions were shown to be conserved over wide ranges of particle concentrations. Particle concentrations over water were shown to be highly localized, with highest concentrations just offshore from urbanized areas, lowest concentrations along undeveloped shoreline, and low-to-intermediate concentrations over the middle areas of the lake. Based in part on these observations, particle deposition to the lake is seen to be dominated by mesoscale processes, with only minor contributions from regional or large scale atmospheric circulation.

  13. Advanced nebulizer designs employing vibrating mesh/aperture plate technologies for aerosol generation.

    PubMed

    Waldrep, J C; Dhand, R

    2008-04-01

    Recent technological advances and improved nebulizer designs have overcome many limitations of jet nebulizers. Newer devices employ a vibrating mesh or aperture plate (VM/AP) for the generation of therapeutic aerosols with consistent, increased efficiency, predominant aerosol fine particle fractions, low residuals, and the ability to nebulize even microliter volumes. These enhancements are achieved through several different design features and include improvements that promote patient compliance, such as compact design, portability, shorter treatment durations, and quiet operation. Current VM/AP devices in clinical use are the Omron MicroAir, the Nektar Aeroneb, and the Pari eFlow. However, some devices are only approved for use with specific medications. Development of "smart nebulizers" such as the Respironics I-neb couple VM technologies with coordinated delivery and optimized inhalation patterns to enhance inhaled drug delivery of specialized, expensive formulations. Ongoing development of advanced aerosol technologies should improve clinical outcomes and continue to expand therapeutic options as newer inhaled drugs become available. PMID:18393813

  14. Enhancing Trust in SOA Based Collaborative Environments

    NASA Astrophysics Data System (ADS)

    Boursas, Latifa; Bourimi, Mohamed; Hommel, Wolfgang; Kesdogan, Dogan

    Considering trust and privacy requirements for online and collaborative distance learning environments, this paper discusses potential extensions of SOA based applications to simultaneously support authentication and authorization services, and offering mutual trust to both learners and service providers. This study shows that the security mechanisms integrated in the SOA platform can be effectively extended and correlated with a trust model.

  15. Formation of secondary organic aerosol from isoprene oxidation over Europe

    NASA Astrophysics Data System (ADS)

    Karl, M.; Tsigaridis, K.; Vignati, E.; Dentener, F.

    2009-09-01

    The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr-1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of organic matter (OM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates OM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr-1). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights in isoprene SOA formation mechanisms

  16. Concentrations and sources of organic carbon aerosols in the free troposphere over North America

    NASA Astrophysics Data System (ADS)

    Heald, Colette L.; Jacob, Daniel J.; Turquety, SolèNe; Hudman, Rynda C.; Weber, Rodney J.; Sullivan, Amy P.; Peltier, Richard E.; Atlas, Eliot L.; de Gouw, Joost A.; Warneke, Carsten; Holloway, John S.; Neuman, J. Andrew; Flocke, Frank M.; Seinfeld, John H.

    2006-12-01

    Aircraft measurements of water-soluble organic carbon (WSOC) aerosol over NE North America during summer 2004 (ITCT-2K4) are simulated with a global chemical transport model (GEOS-Chem) to test our understanding of the sources of organic carbon (OC) aerosol in the free troposphere (FT). Elevated concentrations were observed in plumes from boreal fires in Alaska and Canada. WSOC aerosol concentrations outside of these plumes average 0.9 ± 0.9 μg C m-3 in the FT (2-6 km). The corresponding model value is 0.7 ± 0.6 μg C m-3, including 42% from biomass burning, 36% from biogenic secondary organic aerosol (SOA), and 22% from anthropogenic emissions. Previous OC aerosol observations over the NW Pacific in spring 2001 (ACE-Asia) averaged 3.3 ± 2.8 μg C m-3 in the FT, compared to a model value of 0.3 ± 0.3 μg C m-3. WSOC aerosol concentrations in the boundary layer (BL) during ITCT-2K4 are consistent with OC aerosol observed at the IMPROVE surface network. The model is low in the boundary layer by 30%, which we attribute to secondary formation at a rate comparable to primary anthropogenic emission. Observed WSOC aerosol concentrations decrease by a factor of 2 from the BL to the FT, as compared to a factor of 10 decrease for sulfate, indicating that most of the WSOC aerosol in the FT originates in situ. Despite reproducing mean observed WSOC concentrations in the FT to within 25%, the model cannot account for the variance in the observations (R = 0.21). Covariance analysis of FT WSOC aerosol with other measured chemical variables suggests an aqueous-phase mechanism for SOA generation involving biogenic precursors.

  17. Investigations of BVOC-SOA-cloud-climate feedbacks via interactive biogenic emissions using NorESM

    NASA Astrophysics Data System (ADS)

    Alterskjær, Kari; Egill Kristjansson, Jon; Grini, Alf; Iversen, Trond; Kirkevåg, Alf; Olivié, Dirk; Schulz, Michael; Seland, Øyvind

    2016-04-01

    Climate feedbacks represent a large source of uncertainty in future climate projections. One such feedback involves a change in emissions of biogenic volatile organic compounds (BVOCs) under global warming and a subsequent change in cloud radiative effects. Parts of the atmospheric BVOCs will oxidize in the atmosphere, which may reduce their volatility enough to form secondary organic aerosols (SOA). A changed SOA load will affect cloud radiative properties through aerosol-cloud interactions (ACI) and therefore act to reduce or enhance the temperature change resulting from greenhouse gases alone. In order to study this effect, a development version of the Norwegian Earth System Model (NorESM) has been extended to include explicit atmospheric particle nucleation and a treatment of SOA based on work by Risto Makkonen and collaborators. Biogenic sources of monoterpene and isoprene are interactively calculated by the Model of Emissions of Gases and Aerosols from Nature (MEGAN), version 2.1, incorporated into the Community Land Model, version 4.5. Monoterpene and isoprene are oxidized by O3, OH and NO3 to form SOA with a yield of 15 % and 5 % respectively. It is assumed that 50 % of the product from monoterpene ozonolysis is of low enough volatility to nucleate new particles. The remaining oxidized BVOCs condensate onto preexisting particles. The model improvements include three new tracers to account for both SOA and the BVOCs. This allows for transport of both SOA and precursor gases, making it possible for SOA to form above the surface layer of the model. The new SOA treatment also changes the size distribution of most model aerosols due to condensation. Preliminary results from 6-year simulations with prescribed sea surface temperatures show that the present day emissions of both isoprene (435.9 Tg/yr) and monoterpenes (121.4 Tg/yr) are within the range found in other studies. The resulting SOA production is on the order of 77 Tg/yr, also within the range found by

  18. A Novel PTR-ToF-MS Inlet System for On-line Chemical Analysis of SOA

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    Secondary organic aerosol (SOA) is formed from biogenic and anthropogenic precursors in the atmosphere. Because of its impact on human health and the environment there is a strong interest in understanding the chemistry of SOA formation and transformation. Its volatility, chemical complexity and reactivity and low ambient concentrations challenge the chemical analysis of SOA. Here we present a novel analytical setup for on-line measurements of SOA under ambient conditions by chemical ionization mass spectrometry. The method overcomes current limitations in the chemical analysis of SOA by combining on-line enrichment of the particle concentration and on-line mass spectrometric detection using soft chemical ionization. On-line sampling allows for highly time-resolved analysis of organic aerosol compounds and avoids potential sampling artifacts from sample pre-collection and pretreatment. The deployment of a soft ionization method minimizes the fragmentation of fragile organic aerosol compounds in the mass spectrometer. A proton-transfer-reaction time-of-flight mass-spectrometer (PTR-ToF-MS) is combined with a three-stage aerosol inlet system consisting of an activated carbon monolith denuder, an aerodynamic lens (ADL) and a thermodesorption unit. The denuder strips off gas-phase organic compounds and the ADL enriches the particle concentration in the sample flow. Ultimately, organic aerosol compounds are volatilized at 120 °C in the thermodesorption unit before being introduced into the PTR-ToF-MS system for chemical analysis. The ADL is designed to increase the particle concentration in the sample flow by a factor of up to 50 for particles in the size range between 50 and 1000 nm. This novel enrichment step enables the real-time in situ analysis of SOA at sub µg/m³-levels by PTR-ToF-MS. This work is funded through the PIMMS ITN, which is supported by the European Commission's 7th Framework Programme under grant agreement number 287382.

  19. Novel Measurements of Aerosol Particle Interfaces Using Biphasic Microfluidics

    NASA Astrophysics Data System (ADS)

    Metcalf, A. R.; Dutcher, C. S.

    2014-12-01

    Secondary organic aerosol (SOA) particles are nearly ubiquitous in the atmosphere and yet there remains large uncertainties in their formation processes and ambient properties. These particles are complex microenvironments, which can contain multiple interfaces due to internal aqueous-organic phase partitioning and to the external liquid-vapor surface. These aerosol interfaces can profoundly affect the fate of condensable organic compounds emitted into the atmosphere by altering the way in which organic vapors interact with the ambient aerosol. Aerosol interfaces affect particle internal structure, species uptake, equilibrium partitioning, activation to cloud condensation or ice nuclei, and optical properties. For example, organic thin films can shield the core of the aerosol from the ambient environment, which may disrupt equilibrium partitioning and mass transfer. To improve our ability to accurately predict the fate of SOA in the atmosphere, we must improve our knowledge of aerosol interfaces and their interactions with the ambient environment. Few technologies exist to accurately probe aerosol interfaces at atmospherically-relevant conditions. In this talk, a novel method using biphasic microscale flows will be introduced for generating, trapping, and perturbing complex interfaces at atmospherically relevant conditions. These microfluidic experiments utilize high-speed imaging to monitor interfacial phenomena at the microscale and are performed with phase contrast and fluorescence microscopy on a temperature-controlled inverted microscope stage. From these experiments, interfacial thermodynamic properties such as surface tension, rheological properties such as interfacial moduli, and kinetic properties such as mass transfer coefficients can be measured or inferred. Chemical compositions of the liquid phases studied here span a range of viscosities and include electrolyte and water soluble organic acid species often observed in the atmosphere, such as mixtures

  20. Aerosol generation and charging phenomena in plasma- enhanced chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Forsyth, Bruce Riley

    This thesis is concerned with advancing the theoretical study of the origin and acquisition of particle charge from aerosol generation. A newly designed integral mobility charge analyzer was constructed and calibrated to measure the electrical charge distribution on aerosol particles between 10 nanometer (nm) and 10 micrometer ( m m). The charge analyzer can be used in a wide variety of laboratory and industrial applications due to its broad operating range. Initially, the analyzer performance was tested by generating a variety of aerosol particles with and without neutralization by two different radioactive sources. As a result, experimental charge distributions can be compared with analytical and numerical models of spray and contact electrification related to the interface's double layer. The liquid surface can be simply modeled as a flat plate electrical capacitor with a stored dipole charge layer near the interface. Experimental research will investigate the charge state of a surface double layer using the interaction of dissolved particles. Ion interactions with a particle- liquid interface in the electrical double layer can be analyzed by measuring the aerosol charge distribution from different concentrations of salts, colloids and organic solutions. However, the main thesis research goal is to monitor charged contaminants in process exhaust using the developed integral mobility charge analyzer. Experimental measurements can then be correlated with the dynamic behavior of different nucleated species in the reactor. Hypothetically, particles formed in the plasma volume will have a different charge and size distribution than exhaust line particles originating from unreacted gas species in the pump line. A thorough understanding of the charge level of particles within the plasma volume is necessary to understand the charging, trapping and behavior of contaminant species in the CVD film processes. Charge neutralization by free ion attachment in the exhaust lines

  1. The Effect of Aerosol Hygroscopicity and Volatility on Aerosol Optical Properties During Southern Oxidant and Aerosol Study

    NASA Astrophysics Data System (ADS)

    Khlystov, A.; Grieshop, A. P.; Saha, P.; Subramanian, R.

    2014-12-01

    Secondary organic aerosol (SOA) from biogenic sources can influence optical properties of ambient aerosol by altering its hygroscopicity and contributing to light absorption directly via formation of brown carbon and indirectly by enhancing light absorption by black carbon ("lensing effect"). The magnitude of these effects remains highly uncertain. A set of state-of-the-art instruments was deployed at the SEARCH site near Centerville, AL during the Southern Oxidant and Aerosol Study (SOAS) campaign in summer 2013 to measure the effect of relative humidity and temperature on aerosol size distribution, composition and optical properties. Light scattering and absorption by temperature- and humidity-conditioned aerosols was measured using three photo-acoustic extinctiometers (PAX) at three wavelengths (405 nm, 532 nm, and 870 nm). The sample-conditioning system provided measurements at ambient RH, 10%RH ("dry"), 85%RH ("wet"), and 200 C ("TD"). In parallel to these measurements, a long residence time temperature-stepping thermodenuder (TD) and a variable residence time constant temperature TD in combination with three SMPS systems and an Aerosol Chemical Speciation Monitor (ACSM) were used to assess aerosol volatility and kinetics of aerosol evaporation. We will present results of the on-going analysis of the collected data set. We will show that both temperature and relative humidity have a strong effect on aerosol optical properties. SOA appears to increase aerosol light absorption by about 10%. TD measurements suggest that aerosol equilibrated fairly quickly, within 2 s. Evaporation varied substantially with ambient aerosol loading and composition and meteorology.

  2. Development of the aerosol generation system for simulating the dry deposition behavior of radioaerosol emitted by the accident of FDNPP

    NASA Astrophysics Data System (ADS)

    Zhang, Z.

    2015-12-01

    A large amount of radioactivity was discharged by the accident of FDNPP. The long half-life radionuclide, 137Cs was transported through the atmosphere mainly as the aerosol form and deposited to the forests in Fukushima prefecture. After the dry deposition of the 137Cs, the foliar uptake process would occur. To evaluate environmental transfer of radionuclides, the dry deposition and following foliar uptake is very important. There are some pioneering studies for radionuclide foliar uptake with attaching the solution containing stable target element on the leaf, however, cesium oxide aerosols were used for these deposition study [1]. In the FDNPP case, 137Cs was transported in sulfate aerosol form [2], so the oxide aerosol behaviors could not represent the actual deposition behavior in this accident. For evaluation of whole behavior of 137Cs in vegetation system, fundamental data for deposition and uptake process of sulfate aerosol was desired. In this study, we developed aerosol generation system for simulating the dry deposition and the foliar uptake behaviors of aerosol in the different chemical constitutions. In this system, the method of aerosol generation based on the spray drying. Solution contained 137Cs was send to a nozzle by a syringe pump and spraying with a high speed air flow. The sprayed mist was generated in a chamber in the relatively high temperature. The solution in the mist was dried quickly, and micro size solid aerosols consisting 137Cs were generated. The aerosols were suctioned by an ejector and transported inside a tube by the dry air flow, then were directly blown onto the leaves. The experimental condition, such as the size of chamber, chamber temperature, solution flow rate, air flow rate and so on, were optimized. In the deposition experiment, the aerosols on leaves were observed by a SEM/EDX system and the deposition amount was evaluated by measuring the stable Cs remaining on leaf. In the presentation, we will discuss the detail

  3. Near-Range Receiver Unit of Next Generation PollyXT Used with Koldeway Aerosol Raman Lidar in Arctic

    NASA Astrophysics Data System (ADS)

    Stachlewska, Iwona S.; Markowicz, Krzysztof M.; Ritter, Christoph; Neuber, Roland; Heese, Birgit; Engelmann, Ronny; Linne, Holger

    2016-06-01

    The Near-range Aerosol Raman lidar (NARLa) receiver unit, that was designed to enhance the detection range of the NeXT generation PollyXT Aerosol-Depolarization-Raman (ADR) lidar of the University of Warsaw, was employed next the Koldeway Aerosol Raman Lidar (KARL) at the AWI-IPEV German-French station in Arctic during Spring 2015. Here we introduce shortly design of both lidars, the scheme of their installation next to each other, and preliminary results of observations aiming at arctic haze investigation by the lidars and the iCAP a set of particle counter and aethalometer installed under a tethered balloon.

  4. Mechanisms of Formation of Secondary Organic Aerosols and Implications for Global Radiative Forcing

    SciTech Connect

    John H. Seinfeld

    2011-12-08

    Organic material constitutes about 50% of global atmospheric aerosol mass, and the dominant source of organic aerosol is the oxidation of volatile hydrocarbons, to produce secondary organic aerosol (SOA). Understanding the formation of SOA is crucial to predicting present and future climate effects of atmospheric aerosols. The goal of this program is to significantly increase our understanding of secondary organic aerosol (SOA) formation in the atmosphere. Ambient measurements indicate that the amount of SOA in the atmosphere exceeds that predicted in current models based on existing laboratory chamber data. This would suggest that either the SOA yields measured in laboratory chambers are understated or that all major organic precursors have not been identified. In this research program we are systematically exploring these possibilities.

  5. Multiple Stokes wavelength generation in H2, D2, and CH4 for lidar aerosol measurements

    NASA Technical Reports Server (NTRS)

    Chu, Zhiping; Wilkerson, Thomas D.; Singh, Upendra N.

    1991-01-01

    Experimental results are reported of multiple Stokes generation of a frequency-doubled Nd:YAG laser in H2, D2, and CH4 in a focusing geometry. The energies at four Stokes orders were measured as functions of pump energy and gas pressure. The characteristics of the Stokes radiation generated in these gases are compared for optical production of multiple wavelengths. The competition between Raman components is analyzed in terms of cascade Raman scattering and four-wave mixing. The results indicate the possibility of using these generation processes for atmospheric aerosol measurements by means of multiwavelength lidar systems. Also, this study distinguishes between the gases, as regards the tendency to produce several wavelengths (H2,D2) versus the preference to produce mainly first Stokes radiation (CH4).

  6. Comparison of secondary organic aerosol formed with an aerosol flow reactor and environmental reaction chambers: effect of oxidant concentration, exposure time and seed particles on chemical composition and yield

    DOE PAGESBeta

    Lambe, A. T.; Chhabra, P. S.; Onasch, T. B.; Brune, W. H.; Hunter, J. F.; Kroll, J. H.; Cummings, M. J.; Brogan, J. F.; Parmar, Y.; Worsnop, D. R.; et al

    2014-12-02

    We performed a systematic intercomparison study of the chemistry and yields of SOA generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0×108 to 2.2×1010 molec cm-3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2×106 to 2×107 molec cm-3 over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, butmore » the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. A linear correlation analysis of the mass spectra (m=0.91–0.92, r2=0.93–0.94) and carbon oxidation state (m=1.1, r2=0.58) of SOA produced in the flow reactor and environmental chambers for OH exposures of approximately 1011 molec cm-3 s suggests that the composition of SOA produced in the flow reactor and chambers is the same within experimental accuracy as measured with an aerosol mass spectrometer. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors, rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are

  7. Secondary Organic Aerosol Formation and Organic Nitrate Yield from NO3 Oxidation of Biogenic Hydrocarbons

    PubMed Central

    2014-01-01

    The secondary organic aerosol (SOA) mass yields from NO3 oxidation of a series of biogenic volatile organic compounds (BVOCs), consisting of five monoterpenes and one sesquiterpene (α-pinene, β-pinene, Δ-3-carene, limonene, sabinene, and β-caryophyllene), were investigated in a series of continuous flow experiments in a 10 m3 indoor Teflon chamber. By making in situ measurements of the nitrate radical and employing a kinetics box model, we generate time-dependent yield curves as a function of reacted BVOC. SOA yields varied dramatically among the different BVOCs, from zero for α-pinene to 38–65% for Δ-3-carene and 86% for β-caryophyllene at mass loading of 10 μg m–3, suggesting that model mechanisms that treat all NO3 + monoterpene reactions equally will lead to errors in predicted SOA depending on each location’s mix of BVOC emissions. In most cases, organonitrate is a dominant component of the aerosol produced, but in the case of α-pinene, little organonitrate and no aerosol is formed. PMID:25229208

  8. Interpretation of Secondary Organic Aerosol Formation from Diesel Exhaust Photooxidation in an Environmental Chamber

    SciTech Connect

    Nakao, Shunsuke; Shrivastava, ManishKumar B.; Nguyen, Anh; Jung, Hee-Jung; Cocker, David R.

    2011-04-14

    Secondary organic aerosol (SOA) formation from diesel exhaust in a smog chamber was investigated. Particle volume measurement based on mobility diameter is shown to underestimate SOA formation from diesel exhaust due to the external void space of agglomerate particles, in which case mass-based measurement technique is necessary. Rapid determination of particle effective density as a function of particle mass was performed by an Aerosol Particle Mass analyzer – Scanning Mobility Particle Sizer (APM-SMPS) to obtain particle mass concentration and fractal dimension. Continuous aging of aerosol was observed in terms of atomic ratio (O/C), from 0.05 to 0.25 in 12 hours, underscoring the importance of multi-generational oxidation of low-volatile organic vapors emitted from diesel engine as the significant source of oxygenated SOA. Experimental conditions possibly have strong impacts on physical evolution of diesel particulates in a smog chamber. Higher particle effective densities were observed when raw exhaust was injected into a full bag as opposed to filling a bag with diluted exhaust using an ejector diluter. When longer transfer line was used for injecting diesel exhaust into the smog chamber, rapid particle coagulation was observed, leading to increasing particle volume concentration in dark while its mass concentration is decreasing.

  9. EVALUATION OF SECONDARY ORGANIC AEROSOL FORMATION IN WINTER. (R823514)

    EPA Science Inventory

    Three different methods are used to predict secondary organic aerosol (SOA)
    concentrations in the San Joaquin Valley of California during the winter of 1995-1996 [Integrated
    Monitoring Study, (IMS95)]. The first of these methods estimates SOA by using elemental carbon as

  10. Estimating the direct and indirect effects of secondary organic aerosols using ECHAM5-HAM

    NASA Astrophysics Data System (ADS)

    O'Donnell, D.; Tsigaridis, K.; Feichter, J.

    2011-08-01

    Secondary organic aerosol (SOA) has been introduced into the global climate-aerosol model ECHAM5/HAM. The SOA module handles aerosols originating from both biogenic and anthropogenic sources. The model simulates the emission of precursor gases, their chemical conversion into condensable gases, the partitioning of semi-volatile condenable species into the gas and aerosol phases. As ECHAM5/HAM is a size-resolved model, a new method that permits the calculation of partitioning of semi-volatile species between different size classes is introduced. We compare results of modelled organic aerosol concentrations against measurements from extensive measurement networks in Europe and the United States, running the model with and without SOA. We also compare modelled aerosol optical depth against measurements from the AERONET network of grond stations. We find that SOA improves agreement between model and measurements in both organic aerosol mass and aerosol optical depth, but does not fully correct the low bias that is present in the model for both of these quantities. Although many models now include SOA, any overall estimate of the direct and indirect effects of these aerosols is still lackin