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Sample records for aerosol soa generated

  1. Relationship between aerosol oxidation level and hygroscopic properties of laboratory generated secondary organic aerosol (SOA) particles

    NASA Astrophysics Data System (ADS)

    Massoli, P.; Lambe, A.; Ahern, A.; Williams, L. R.; Ehn, M.; Mikkila, J.; Canagaratna, M.; Brune, W. H.; Onasch, T. B.; Jayne, J.; Petdjd, T. T.; Kulmala, M. T.; Laaksonen, A.; Kolb, C. E.; Davidovits, P.; Worsnop, D. R.

    2010-12-01

    Laboratory experiments investigated the relationship between degree of oxidation and hygroscopic properties of secondary organic aerosol (SOA) particles. The hygroscopic growth factor (HGF), the CCN activity (κCCN) and the degree of aerosol oxidation (represented by the atomic O:C ratio) were measured for α-pinene, 1,3,5-trimethylbenzene (TMB), m-xylene and α pinene/m-xylene mixture SOA generated via OH radical oxidation in an aerosol flow reactor. Our results show that both HGF and κCCN increase with O:C. The TMB and m-xylene SOA were, respectively, the least and most hygroscopic of the system studied. An average HGF of 1.25 and a κCCN of 0.2 were measured at O:C of 0.65, in agreement with results reported for ambient data. The HGF based κ(κHGF) under predicted the κCCN values of 20 to 50% for all but the TMB SOA. Within the limitations of instrumental capabilities, we define the extent to which the hygroscopic properties of SOA particles can be predicted from their oxidation level and provide parameterizations suitable for interpreting ambient data.

  2. Relationship between aerosol oxidation level and hygroscopic properties of laboratory generated secondary organic aerosol (SOA) particles

    NASA Astrophysics Data System (ADS)

    Massoli, P.; Lambe, A. T.; Ahern, A. T.; Williams, L. R.; Ehn, M.; Mikkilä, J.; Canagaratna, M. R.; Brune, W. H.; Onasch, T. B.; Jayne, J. T.; Petäjä, T.; Kulmala, M.; Laaksonen, A.; Kolb, C. E.; Davidovits, P.; Worsnop, D. R.

    2010-12-01

    Laboratory experiments investigated the relationship between oxidation level and hygroscopic properties of secondary organic aerosol (SOA) particles generated via OH radical oxidation in an aerosol flow reactor. The hygroscopic growth factor at 90% RH (HGF90%), the CCN activity ($\\kappa$ORG,CCN) and the level of oxidation (atomic O:C ratio) of the SOA particles were measured. Both HGF90% and $\\kappa$ORG,CCN increased with O:C; the HGF90% varied linearly with O:C, while $\\kappa$ORG,CCN mostly followed a nonlinear trend. An average HGF90% of 1.25 and $\\kappa$ORG,CCN of 0.19 were measured for O:C of 0.65, in agreement with results reported for ambient data. The $\\kappa$ORG values estimated from the HGF90% ($\\kappa$ORG,HGF) were 20 to 50% lower than paired $\\kappa$ORG,CCN values for all SOA particles except 1,3,5-trimethylbenzene (TMB), the least hygroscopic of the SOA systems. Within the limitations of instrumental capabilities, we show that differences in hygroscopic behavior among the investigated SOA systems may correspond to differences in elemental composition.

  3. Chemical oxidative potential of secondary organic aerosol (SOA) generated from the photooxidation of biogenic and anthropogenic volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Tuet, Wing Y.; Chen, Yunle; Xu, Lu; Fok, Shierly; Gao, Dong; Weber, Rodney J.; Ng, Nga L.

    2017-01-01

    Particulate matter (PM), of which a significant fraction is comprised of secondary organic aerosols (SOA), has received considerable attention due to its health implications. In this study, the water-soluble oxidative potential (OPWS) of SOA generated from the photooxidation of biogenic and anthropogenic hydrocarbon precursors (isoprene, α-pinene, β-caryophyllene, pentadecane, m-xylene, and naphthalene) under different reaction conditions (RO2+ HO2 vs. RO2+ NO dominant, dry vs. humid) was characterized using dithiothreitol (DTT) consumption. The measured intrinsic OPWS-DTT values ranged from 9 to 205 pmol min-1 µg-1 and were highly dependent on the specific hydrocarbon precursor, with naphthalene and isoprene SOA generating the highest and lowest OPWS-DTT values, respectively. Humidity and RO2 fate affected OPWS-DTT in a hydrocarbon-specific manner, with naphthalene SOA exhibiting the most pronounced effects, likely due to the formation of nitroaromatics. Together, these results suggest that precursor identity may be more influential than reaction condition in determining SOA oxidative potential, demonstrating the importance of sources, such as incomplete combustion, to aerosol toxicity. In the context of other PM sources, all SOA systems, with the exception of naphthalene SOA, were less DTT active than ambient sources related to incomplete combustion, including diesel and gasoline combustion as well as biomass burning. Finally, naphthalene SOA was as DTT active as biomass burning aerosol, which was found to be the most DTT-active OA source in a previous ambient study. These results highlight a need to consider SOA contributions (particularly from anthropogenic hydrocarbons) to health effects in the context of hydrocarbon emissions, SOA yields, and other PM sources.

  4. Transitions from functionalization to fragmentation reactions of laboratory secondary organic aerosol (SOA) generated from the OH oxidation of alkane precursors.

    PubMed

    Lambe, Andrew T; Onasch, Timothy B; Croasdale, David R; Wright, Justin P; Martin, Alexander T; Franklin, Jonathan P; Massoli, Paola; Kroll, Jesse H; Canagaratna, Manjula R; Brune, William H; Worsnop, Douglas R; Davidovits, Paul

    2012-05-15

    Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NO(x). SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0(2,6)]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C(x)H(y)+, C(x)H(y)O+, and C(x)H(y)O(2)+ ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the C(x)H(y)O+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.

  5. Aqueous aerosol SOA formation: impact on aerosol physical properties.

    PubMed

    Woo, Joseph L; Kim, Derek D; Schwier, Allison N; Li, Ruizhi; McNeill, V Faye

    2013-01-01

    Organic chemistry in aerosol water has recently been recognized as a potentially important source of secondary organic aerosol (SOA) material. This SOA material may be surface-active, therefore potentially affecting aerosol heterogeneous activity, ice nucleation, and CCN activity. Aqueous aerosol chemistry has also been shown to be a potential source of light-absorbing products ("brown carbon"). We present results on the formation of secondary organic aerosol material in aerosol water and the associated changes in aerosol physical properties from GAMMA (Gas-Aerosol Model for Mechanism Analysis), a photochemical box model with coupled gas and detailed aqueous aerosol chemistry. The detailed aerosol composition output from GAMMA was coupled with two recently developed modules for predicting a) aerosol surface tension and b) the UV-Vis absorption spectrum of the aerosol, based on our previous laboratory observations. The simulation results suggest that the formation of oligomers and organic acids in bulk aerosol water is unlikely to perturb aerosol surface tension significantly. Isoprene-derived organosulfates are formed in high concentrations in acidic aerosols under low-NO(x) conditions, but more experimental data are needed before the potential impact of these species on aerosol surface tension may be evaluated. Adsorption of surfactants from the gas phase may further suppress aerosol surface tension. Light absorption by aqueous aerosol SOA material is driven by dark glyoxal chemistry and is highest under high-NO(x) conditions, at high relative humidity, in the early morning hours. The wavelength dependence of the predicted absorption spectra is comparable to field observations and the predicted mass absorption efficiencies suggest that aqueous aerosol chemistry can be a significant source of aerosol brown carbon under urban conditions.

  6. 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.

  7. CMAQ Application to the Southern Oxidant and Aerosol Study (SOAS)

    EPA Pesticide Factsheets

    CMAQ was used to simulate conditions during the the Southern Oxidant and Aerosol Study (SOAS) in the summer of 2013. Data collected as part of this study have been used to perform diagnostic model evaluation.

  8. An SOA model for toluene oxidation in the presence of inorganic aerosols.

    PubMed

    Cao, Gang; Jang, Myoseon

    2010-01-15

    A predictive model for secondary organic aerosol (SOA) formation including both partitioning and heterogeneous reactions is explored for the SOA produced from the oxidation of toluene in the presence of inorganic seed aerosols. The predictive SOA model comprises the explicit gas-phase chemistry of toluene, gas-particle partitioning, and heterogeneous chemistry. The resulting products from the explicit gas phase chemistry are lumped into several classes of chemical species based on their vapor pressure and reactivity for heterogeneous reactions. Both the gas-particle partitioning coefficient and the heterogeneous reaction rate constant of each lumped gas-phase product are theoretically determined using group contribution and molecular structure-reactivity. In the SOA model, the predictive SOA mass is decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). OM(P) is estimated from the SOA partitioning model developed by Schell et al. (J. Geophys. Res. 2001, 106, 28275-28293 ) that has been used in a regional air quality model (CMAQ 4.7). OM(H) is predicted from the heterogeneous SOA model developed by Jang et al. (Environ. Sci. Technol. 2006, 40, 3013-3022 ). The SOA model is evaluated using a number of the experimental SOA data that are generated in a 2 m(3) indoor Teflon film chamber under various experimental conditions (e.g., humidity, inorganic seed compositions, NO(x) concentrations). The SOA model reasonably predicts not only the gas-phase chemistry, such as the ozone formation, the conversion of NO to NO(2), and the toluene decay, but also the SOA production. The model predicted that the OM(H) fraction of the total toluene SOA mass increases as NO(x) concentrations decrease: 0.73-0.83 at low NO(x) levels and 0.17-0.47 at middle and high NO(x) levels for SOA experiments with high initial toluene concentrations. Our study also finds a significant increase in the OM(H) mass fraction in the SOA generated with low initial toluene

  9. 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.

    2012-08-01

    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. Several experiments with exclusively anthropogenic 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 (0.5-9%) 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 anthropogenic SOA enabled application of a simplified model to calculate the chemical turnover of the anthropogenic 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 at 343 K: 0.86-0.94). The anthropogenic 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 anthropogenic SOA the reaction mixtures needed a higher OH dose that also increased O/C and provided a less volatile aerosol. A strong positive correlation was found between changes in volatility and O/C with the exception during dark

  10. The SOA formation model combined with semiempirical quantum chemistry for predicting UV-Vis absorption of secondary organic aerosols.

    PubMed

    Zhong, Min; Jang, Myoseon; Oliferenko, Alexander; Pillai, Girinath G; Katritzky, Alan R

    2012-07-07

    A new model for predicting the UV-visible absorption spectra of secondary organic aerosols (SOA) has been developed. The model consists of two primary parts: a SOA formation model and a semiempirical quantum chemistry method. The mass of SOA is predicted using the PHRCSOA (Partitioning Heterogeneous Reaction Consortium Secondary Organic Aerosol) model developed by Cao and Jang [Environ. Sci. Technol., 2010, 44, 727]. The chemical composition is estimated using a combination of the kinetic model (MCM) and the PHRCSOA model. The absorption spectrum is obtained by taking the sum of the spectrum of each SOA product calculated using a semiempirical NDDO (Neglect of Diatomic Differential Overlap)-based method. SOA was generated from the photochemical reaction of toluene or α-pinene at different NO(x) levels (low NO(x): 24-26 ppm, middle NO(x): 49 ppb, high NO(x): 104-105 ppb) using a 2 m(3) indoor Teflon film chamber. The model simulation reasonably agrees with the measured absorption spectra of α-pinene SOA but underestimates toluene SOA under high and middle NO(x) conditions. The absorption spectrum of toluene SOA is moderately enhanced with increasing NO(x) concentrations, while that of α-pinene SOA is not affected. Both measured and calculated UV-visible spectra show that the light absorption of toluene SOA is much stronger than that of α-pinene SOA.

  11. 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

  12. Organosulfates as tracers for secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) in the atmosphere.

    PubMed

    Zhang, Haofei; Worton, David R; Lewandowski, Michael; Ortega, John; Rubitschun, Caitlin L; Park, Jeong-Hoo; Kristensen, Kasper; Campuzano-Jost, Pedro; Day, Douglas A; Jimenez, Jose L; Jaoui, Mohammed; Offenberg, John H; Kleindienst, Tadeusz E; Gilman, Jessica; Kuster, William C; de Gouw, Joost; Park, Changhyoun; Schade, Gunnar W; Frossard, Amanda A; Russell, Lynn; Kaser, Lisa; Jud, Werner; Hansel, Armin; Cappellin, Luca; Karl, Thomas; Glasius, Marianne; Guenther, Alex; Goldstein, Allen H; Seinfeld, John H; Gold, Avram; Kamens, Richard M; Surratt, Jason D

    2012-09-04

    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 (C(5)H(12)O(6)S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM(2.5)) 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 PM(2.5) 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.

  13. 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

  14. 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

  15. 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

  16. 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

  17. 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

  18. 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

  19. 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.

  20. 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

  1. Formation of Epoxide Derived SOA and Gas-Phase Acids through Aqueous Aerosol Processing in the Southeastern United States during SOAS

    NASA Astrophysics Data System (ADS)

    Skog, K.; Teng, A.; Nguyen, T. B.; Nguyen, K.; Suda, S. R.; Xu, L.; Isaacman-VanWertz, G. A.; Feiner, P. A.; Zhang, L.; Olson, K. F.; Koss, A.; Wild, R. J.; St Clair, J.; Crounse, J.; Baumann, K.; Wennberg, P. O.; Petters, M.; Carlton, A. M. G.; Ng, N. L.; Brune, W. H.; De Gouw, J. A.; Goldstein, A. H.; Brown, S. S.; Edgerton, E. S.; McNeill, V. F.; Keutsch, F. N.

    2015-12-01

    Secondary organic aerosol (SOA) contributes to climate and adversely affects human health, but the formation of SOA is poorly understood. Recent studies have proposed that aqueous processing of water-soluble compounds like glyoxal and IEPOX can help explain the abundance of organosulfates, higher oxygen to carbon ratios, and SOA abundance. A comprehensive set of ambient gas- and aerosol-phase data was collected during June and July of 2013 as part of the Southern Oxidant and Aerosol Study (SOAS) at the Centreville, AL ground site. Both gas-phase photochemistry and aqueous-phase aerosol chemistry were modeled using a zero-dimensional box model. While it has been suggested that glyoxal can contribute to aqueous aerosol through the formation of acids and higher-molecular-weight compounds, it did not produce enhanced aqSOA concentrations. Instead, processing of aqueous glyoxal resulted in the production of gas-phase acids. AqSOA consisted almost entirely of epoxide processing products, mainly from the processing of IEPOX to methyl tetrol, and the organosulfate. In addition, the pinene oxides contributed to the formation of aqSOA, through the formation of organosulfates, diols, and organonitrates. These data are consistent with the abundance of IEPOX and pinene oxide organonitrate derived SOA seen at this site.

  2. simpleGAMMA - a reduced model of secondary organic aerosol formation in the aqueous aerosol phase (aaSOA)

    NASA Astrophysics Data System (ADS)

    Woo, J. L.; McNeill, V. F.

    2015-01-01

    There is increasing evidence that the uptake and aqueous processing of water-soluble volatile organic compounds (VOCs) by wet aerosols or cloud droplets is an important source of secondary organic aerosol (SOA). We recently developed GAMMA (Gas-Aerosol Model for Mechanism Analysis), a zero-dimensional kinetic model that couples gas-phase and detailed aqueous-phase atmospheric chemistry for speciated prediction of SOA and organosulfate formation in cloudwater or aqueous aerosols. Results from GAMMA simulations of SOA formation in aerosol water (McNeill et al., 2012) indicate that it is dominated by two pathways: isoprene epoxydiol (IEPOX) uptake followed by ring-opening chemistry (under low-NOx conditions) and glyoxal uptake. This suggested that it is possible to model the majority of aqueous aerosol phase SOA mass using a highly simplified reaction scheme. We have therefore developed a reduced version of GAMMA, simpleGAMMA. Close agreement in predicted aaSOA mass is observed between simpleGAMMA and GAMMA under all conditions tested (between pH 1-4 and RH 40-80%) after 12 h of simulation. simpleGAMMA is computationally efficient and suitable for coupling with larger-scale atmospheric chemistry models.

  3. Identification and Characterization of Biogenic SOA Component in Ambient Aerosols Based on Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Jimenez, J.; Allan, J. D.; Kiendler-Scharr, A.; Tian, J.; Canagaratna, M. R.; Williams, B.; Worsnop, D. R.; Coe, H.; Goldstein, A.; Mentel, T. F.

    2008-12-01

    Recently studies have shown that multivariate factor analysis of the highly time-resolved mass spectral data obtained with an Aerodyne Aerosol Mass Spectrometer (AMS) may allow the classification and simplification of complex organic aerosol (OA) mixtures into components that are chemically meaningful and can be related to different sources and transformation processes. Two factor analysis techniques, including the Multiple Component Analysis (MCA) method (Zhang et al., 2007) and the Positive Matrix Factorization (PMF) method (Paatero and Tapper, 1994), were applied to a Quadrupole-AMS dataset acquired from Chebogue Pt., Nova Scotia in summer 2004. Multiple OA components were determined, including a hydrocarbon-like OA (HOA) component similar in mass spectra to the hydrocarbon substances observed at urban locations and two oxygenated OA (OA) components that show different fragmentation patterns and oxygen-to-carbon ratios in their mass spectra. The HOA component correlates with inert primary emission tracers (e.g., EC and CO) and likely represents diluted POA transported from urban locations. The highly oxygenated component (OOA-I) correlates well with sulfate and shows a mass spectrum resembling that of fulvic acid - a model compound representative for highly processed/oxidized organics in the environment. The less oxygenated OA component (OOA-II) reveals a mass spectral pattern that compares well with those of the biogenic SOA produced from the mixture of VOCs emitted by spruce, pine and birch trees during exposure to ozone and UV-photolysis in the Jülich plant chamber. In addition, the time series of OOA-II correlates with biogenic SOA tracer compounds determined by the thermal desorption aerosol GC/MS-FID (TAG) instrument. Furthermore, the time-resolved size distributions of OOA components, their correlations with parallel gas and aerosol measurements, and backtrajectory analysis of air masses all support the association of OOA-II to biogenic sources. Finally

  4. 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

  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. 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.

  8. Primary particulate emissions and secondary organic aerosol (SOA) formation from idling diesel vehicle exhaust in China.

    PubMed

    Deng, Wei; Hu, Qihou; Liu, Tengyu; Wang, Xinming; Zhang, Yanli; Song, Wei; Sun, Yele; Bi, Xinhui; Yu, Jianzhen; Yang, Weiqiang; Huang, Xinyu; Zhang, Zhou; Huang, Zhonghui; He, Quanfu; Mellouki, Abdelwahid; George, Christian

    2017-03-26

    In China diesel vehicles dominate the primary emission of particulate matters from on-road vehicles, and they might also contribute substantially to the formation of secondary organic aerosols (SOA). In this study tailpipe exhaust of three typical in-use diesel vehicles under warm idling conditions was introduced directly into an indoor smog chamber with a 30m(3) Teflon reactor to characterize primary emissions and SOA formation during photo-oxidation. The emission factors of primary organic aerosol (POA) and black carbon (BC) for the three types of Chinese diesel vehicles ranged 0.18-0.91 and 0.15-0.51gkg-fuel(-1), respectively; and the SOA production factors ranged 0.50-1.8gkg-fuel(-1) and SOA/POA ratios ranged 0.7-3.7 with an average of 2.2. The fuel-based POA emission factors and SOA production factors from this study for idling diesel vehicle exhaust were 1-3 orders of magnitude higher than those reported in previous studies for idling gasoline vehicle exhaust. The emission factors for total particle numbers were 0.65-4.0×10(15)particleskg-fuel(-1), and particles with diameters less than 50nm dominated in total particle numbers. Traditional C2-C12 precursor non-methane hydrocarbons (NMHCs) could only explain less than 3% of the SOA formed during aging and contribution from other precursors including intermediate volatile organic compounds (IVOC) needs further investigation.

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. Oxidant supply and aqueous photochemical SOA formation in cloud droplets and aqueous aerosol

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    Many recent laboratory, field and model studies point to significant contributions to the total secondary organic aerosol (SOA) budget from aqueous phase reactions in cloud droplets and aqueous aerosol particles. Laboratory studies of the photochemical oxidation of glyoxal and methylglyoxal in the aqueous phase show a strong dependence on the initial concentration of dissolved organics, with preferential formation of large molecules (dimers, oligomers) at the high concentrations found in ambient deliquesced aerosol particles. In such experimental studies OH radicals are produced in the aqueous phase (via hydrogen peroxide photolysis) and OH radical is assumed to be the major oxidant. An explicit aqueous photooxidation mechanism has been validated, in part, based on the observed temporal evolution of organic intermediates and products in these experiments. In this work, this mechanism was incorporated into multiphase process models (box, cloud parcel) in order to further explore aqueous SOA formation in dilute cloud droplets and concentrated aerosol particles. We found that the predicted SOA mass in both aqueous phases can be comparable despite the much lower liquid water content in aerosols, where oligomer formation is favored. Direct uptake from the gas phase was the largest source of OH radicals in the aqueous phase. In-situ production through the Fenton reaction (Fe), hydrogen peroxide and nitrate photolysis were minor sources. Since phase transfer is slower than the OH(aq) consumption by organics, modeled OH(aq) concentrations were smaller by 1-2 orders of magnitude than predicted based on thermodynamic equilibrium. Our model studies suggest that, unless there are substantial additional sources of OH radical in the aqueous phase, aqueous SOA formation will be oxidant limited. Since the phase transfer rate is a function of the drop (or particle) surface area, aqueous SOA formation may occur preferentially at or near the drop/particle surface (e.g., be surface

  14. Molecular Composition and Volatility of Organic Aerosol in the Southeastern U.S.: Implications for IEPOX Derived SOA.

    PubMed

    Lopez-Hilfiker, F D; Mohr, C; D'Ambro, E L; Lutz, A; Riedel, T P; Gaston, C J; Iyer, S; Zhang, Z; Gold, A; Surratt, J D; Lee, B H; Kurten, T; Hu, W W; Jimenez, J; Hallquist, M; Thornton, J A

    2016-03-01

    We present measurements as part of the Southern Oxidant and Aerosol Study (SOAS) during which atmospheric aerosol particles were comprehensively characterized. We present results utilizing a Filter Inlet for Gases and AEROsol coupled to a chemical ionization mass spectrometer (CIMS). We focus on the volatility and composition of isoprene derived organic aerosol tracers and of the bulk organic aerosol. By utilizing the online volatility and molecular composition information provided by the FIGAERO-CIMS, we show that the vast majority of commonly reported molecular tracers of isoprene epoxydiol (IEPOX) derived secondary organic aerosol (SOA) is derived from thermal decomposition of accretion products or other low volatility organics having effective saturation vapor concentrations <10(-3) μg m(-3). In addition, while accounting for up to 30% of total submicrometer organic aerosol mass, the IEPOX-derived SOA has a higher volatility than the remaining bulk. That IEPOX-SOA, and more generally bulk organic aerosol in the Southeastern U.S. is comprised of effectively nonvolatile material has important implications for modeling SOA derived from isoprene, and for mechanistic interpretations of molecular tracer measurements. Our results show that partitioning theory performs well for 2-methyltetrols, once accretion product decomposition is taken into account. No significant partitioning delays due to aerosol phase or viscosity are observed, and no partitioning to particle-phase water or other unexplained mechanisms are needed to explain our results.

  15. Fundamental Heterogeneous Reaction Chemistry Related to Secondary Organic Aerosols (SOA) in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Akimoto, H.

    2016-11-01

    Typical reaction pathways of formation of dicarboxylic acids, larger multifunctional compounds, oligomers, and organosulfur and organonitrogen compounds in secondary organic aerosols (SOA), revealed by laboratory experimental studies are reviewed with a short introduction to field observations. In most of the reactions forming these compounds, glyoxal, methyl glyoxal and related difunctional carbonyl compounds play an important role as precursors, and so their formation pathways in the gas phase are discussed first. A substantial discussion is then presented for the OH-initiated aqueous phase radical oxidation reactions of glyoxal and other carbonyls which form dicarboxylic acids, larger multifunctional compounds and oligomers, and aqueous-phase non-radical reactions which form oligomers, organosulfates and organonitrogen compounds. Finally, the heterogeneous oxidation reaction of gaseous O3, OH and NO3 with liquid and solid organic aerosols at the air-particle interface is discussed relating to the aging of SOA in the atmosphere.

  16. 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.

  17. 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.

  18. 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

  19. Aerosol mass spectrometric features of biogenic SOA: observations from a plant chamber and in rural atmospheric environments.

    PubMed

    Kiendler-Scharr, Astrid; Zhang, Qi; Hohaus, Thorsten; Kleist, Einhard; Mensah, Amewu; Mentel, Thomas F; Spindler, Christian; Uerlings, Ricarda; Tillmann, Ralf; Wildt, Jürgen

    2009-11-01

    Secondary organic aerosol (SOA) is known to form from a variety of anthropogenic and biogenic precursors. Current estimates of global SOA production vary over 2 orders of magnitude. Since no direct measurement technique for SOA exists, quantifying SOA remains a challenge for atmospheric studies. The identification of biogenic SOA (BSOA) based on mass spectral signatures offers the possibility to derive source information of organic aerosol (OA) with high time resolution. Here we present data from simulation experiments. The BSOA from tree emissions was characterized with an Aerodyne quadrupole aerosol mass spectrometer (Q-AMS). Collection efficiencies were close to 1, and effective densities of the BSOA were found to be 1.3 +/- 0.1 g/cm(3). The mass spectra of SOA from different trees were found to be highly similar. The average BSOA mass spectrum from tree emissions is compared to a BSOA component spectrum extracted from field data. It is shown that overall the spectra agree well and that the mass spectral features of BSOA are distinctively different from those of OA components related to fresh fossil fuel and biomass combustions. The simulation chamber mass spectrum may potentially be useful for the identification and interpretation of biogenic SOA components in ambient data sets.

  20. 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.

  1. Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

    NASA Astrophysics Data System (ADS)

    Sareen, Neha; Carlton, Annmarie G.; Surratt, Jason D.; Gold, Avram; Lee, Ben; Lopez-Hilfiker, Felipe D.; Mohr, Claudia; Thornton, Joel A.; Zhang, Zhenfa; Lim, Yong B.; Turpin, Barbara J.

    2016-11-01

    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, and health. 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 additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus

  2. 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

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

    DOE PAGES

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; ...

    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

  4. simpleGAMMA v1.0 - a reduced model of secondary organic aerosol formation in the aqueous aerosol phase (aaSOA)

    NASA Astrophysics Data System (ADS)

    Woo, J. L.; McNeill, V. F.

    2015-06-01

    There is increasing evidence that the uptake and aqueous processing of water-soluble volatile organic compounds (VOCs) by wet aerosols or cloud droplets is an important source of secondary organic aerosol (SOA). We recently developed GAMMA (Gas-Aerosol Model for Mechanism Analysis), a zero-dimensional kinetic model that couples gas-phase and detailed aqueous-phase atmospheric chemistry for speciated prediction of SOA and organosulfate formation in cloud water or aqueous aerosols. Results from GAMMA simulations of SOA formation in aerosol water (aaSOA) (McNeill et al., 2012) indicate that it is dominated by two pathways: isoprene epoxydiol (IEPOX) uptake followed by ring-opening chemistry (under low-NOx conditions) and glyoxal uptake. This suggested that it is possible to model the majority of aaSOA mass using a highly simplified reaction scheme. We have therefore developed a reduced version of GAMMA, simpleGAMMA. Close agreement in predicted aaSOA mass is observed between simpleGAMMA and GAMMA under all conditions tested (between pH 1-4 and RH 40-80 %) after 12 h of simulation. simpleGAMMA is computationally efficient and suitable for coupling with larger-scale atmospheric chemistry models or analyzing ambient measurement data.

  5. Generation of aerosolized drugs.

    PubMed

    Wolff, R K; Niven, R W

    1994-01-01

    The expanding use of inhalation therapy has placed demands on current aerosol generation systems that are difficult to meet with current inhalers. The desire to deliver novel drug entities such as proteins and peptides, as well as complex formulations including liposomes and microspheres, requires delivery systems of improved efficiency that will target the lung in a reproducible manner. These efforts have also been spurred by the phase out of chlorofluorocarbons (CFCs) and this has included a directed search for alternative propellants. Consequently, a variety of new aerosol devices and methods of generating aerosols are being studied. This includes the use of freon replacement propellants, dry powder generation systems, aqueous unit spray systems and microprocessor controlled technologies. Each approach has advantages and disadvantages depending upon each principle of action and set of design variables. In addition, specific drugs may be better suited for one type of inhaler device vs. another. The extent to which aerosol generation systems achieve their goals is discussed together with a summary of selected papers presented at the recent International Congress of Aerosols in Medicine.

  6. 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

  7. Photonic generation of ultra-wideband signals by direct current modulation on SOA section of an SOA-integrated SGDBR laser.

    PubMed

    Lv, Hui; Yu, Yonglin; Shu, Tan; Huang, Dexiu; Jiang, Shan; Barry, Liam P

    2010-03-29

    Photonic ultra-wideband (UWB) pulses are generated by direct current modulation of a semiconductor optical amplifier (SOA) section of an SOA-integrated sampled grating distributed Bragg reflector (SGDBR) laser. Modulation responses of the SOA section of the laser are first simulated with a microwave equivalent circuit model. Simulated results show a resonance behavior indicating the possibility to generate UWB signals with complex shapes in the time domain. The UWB pulse generation is then experimentally demonstrated for different selected wavelength channels with an SOA-integrated SGDBR laser.

  8. Global Transformation and Fate of Secondary Organic Aerosols: Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions

    NASA Astrophysics Data System (ADS)

    Shrivastava, M. B.; Easter, R. C.; Liu, X.; Zelenyuk, A.; Singh, B.; Zhang, K.; Ma, P. L.; Chand, D.; Ghan, S. J.; Jimenez, J. L.; Zhang, Q.; Fast, J. D.; Rasch, P. J.; Tiitta, P.

    2014-12-01

    Secondary organic aerosols (SOA) 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. Our 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 (also supported by satellite data), which undergoes less wet removal compared to the surface OA sources in the standard CAM5. Although the total simulated OA from biomass burning agrees better with aircraft measurements, recent field observations typically report lower SOA formation, suggesting that constraining the POA-SOA split from biomass burning should be the focus of future studies. The non-volatile and semi-volatile configurations 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 agreement with

  9. 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.

  10. Highly stable aerosol generator

    SciTech Connect

    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.

  11. 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.

  12. 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

  13. Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

    DOE PAGES

    Hu, Weiwei; Palm, Brett B.; Day, Douglas A.; ...

    2016-09-19

    Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated withmore » an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding  ∼  100 µg m−3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0 ± 2.0  ×  10−13 cm3 molec−1 s−1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (>  1  ×  1012 molec cm−3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH =  0.59 ± 0.33 in SE US and γOH =  0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical

  14. Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

    SciTech Connect

    Hu, Weiwei; Palm, Brett B.; Day, Douglas A.; Campuzano-Jost, Pedro; Krechmer, Jordan E.; Peng, Zhe; de Sá, Suzane S.; Martin, Scot T.; Alexander, M. Lizabeth; Baumann, Karsten; Hacker, Lina; Kiendler-Scharr, Astrid; Koss, Abigail R.; de Gouw, Joost A.; Goldstein, Allen H.; Seco, Roger; Sjostedt, Steven J.; Park, Jeong-Hoo; Guenther, Alex B.; Kim, Saewung; Canonaco, Francesco; Prévôt, André S. H.; Brune, William H.; Jimenez, Jose L.

    2016-01-01

    Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ~100 µg m-3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0 ± 2.0 ×10-13 cm3 molec-1 s-1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 1012 molec cm-3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH = 0.59±0.33 in SE US and γOH = 0.68±0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake

  15. Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

    NASA Astrophysics Data System (ADS)

    Hu, Weiwei; Palm, Brett B.; Day, Douglas A.; Campuzano-Jost, Pedro; Krechmer, Jordan E.; Peng, Zhe; de Sá, Suzane S.; Martin, Scot T.; Lizabeth Alexander, M.; Baumann, Karsten; Hacker, Lina; Kiendler-Scharr, Astrid; Koss, Abigail R.; de Gouw, Joost A.; Goldstein, Allen H.; Seco, Roger; Sjostedt, Steven J.; Park, Jeong-Hoo; Guenther, Alex B.; Kim, Saewung; Canonaco, Francesco; Prévôt, André S. H.; Brune, William H.; Jimenez, Jose L.

    2016-09-01

    Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16-36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ˜ 100 µg m-3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0 ± 2.0 × 10-13 cm3 molec-1 s-1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 1012 molec cm-3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH = 0.59 ± 0.33 in SE US and γOH = 0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.

  16. 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.

  17. Evaluation of a quantitative structure-property relationship (QSPR) for predicting mid-visible refractive index of secondary organic aerosol (SOA).

    PubMed

    Redmond, Haley; Thompson, Jonathan E

    2011-04-21

    In this work we describe and evaluate a simple scheme by which the refractive index (λ = 589 nm) of non-absorbing components common to secondary organic aerosols (SOA) may be predicted from molecular formula and density (g cm(-3)). The QSPR approach described is based on three parameters linked to refractive index-molecular polarizability, the ratio of mass density to molecular weight, and degree of unsaturation. After computing these quantities for a training set of 111 compounds common to atmospheric aerosols, multi-linear regression analysis was conducted to establish a quantitative relationship between the parameters and accepted value of refractive index. The resulting quantitative relationship can often estimate refractive index to ±0.01 when averaged across a variety of compound classes. A notable exception is for alcohols for which the model consistently underestimates refractive index. Homogenous internal mixtures can conceivably be addressed through use of either the volume or mole fraction mixing rules commonly used in the aerosol community. Predicted refractive indices reconstructed from chemical composition data presented in the literature generally agree with previous reports of SOA refractive index. Additionally, the predicted refractive indices lie near measured values we report for λ = 532 nm for SOA generated from vapors of α-pinene (R.I. 1.49-1.51) and toluene (R.I. 1.49-1.50). We envision the QSPR method may find use in reconstructing optical scattering of organic aerosols if mass composition data is known. Alternatively, the method described could be incorporated into in models of organic aerosol formation/phase partitioning to better constrain organic aerosol optical properties.

  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

    SciTech Connect

    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 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. 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.

  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

    DOE PAGES

    La, Y. S.; Camredon, M.; Ziemann, P. J.; ...

    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

  20. Acid-catalyzed Reactions in Model Secondary Organic Aerosol (SOA): Insights using Desorption-electrospray Ionization (DESI) Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Fiddler, M. N.; Cooks, R. G.; Shepson, P.

    2008-12-01

    Atmospheric aerosols are presently little understood in terms of their sources, formation, and effect on climate forcing, despite their significant impacts on climate change and respiratory health. Secondary organic aerosols (SOA), which were thought to arise entirely from simple gas-particle partitioning, have recently been found to contain oligomeric species which result from the condensed-phase reactions of volatile organic compounds (VOCs). The non-methane VOC with the greatest emission flux, isoprene, is known to produce aerosols through chemistry involving its oxidation products. We selected one of its major oxidation product, methacrolein, to assess its role in oligomeric SOA formation in response to the acidic conditions found in cloud water. Since it has been found that acidified aerosol produces oligomeric species with greater molecular weight and yield, acid-catalyzed oligomerization is likely a significant process in the formation of SOA. Aqueous solutions of methacrolein were acidified with sulfuric acid, and studied using linear ion trap mass spectrometry (LIT-MS) with a home-built desorption-electrospray ionization (DESI) source. An extremely heterogeneous mixture of products was produced in this system, resulting from hydrolysis, acid- catalyzed oxidation, reduction, and organosulfate formation. Evidence for disproportionation and heterocycle formation are proposed as reaction mechanisms hitherto unrecognized in the production of SOA. The proposed structure and formation mechanism for several species, based upon their MS/MS spectra, will also be presented.

  1. 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...

  2. 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

  3. 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

  4. 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

  5. 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.

  6. 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...

  7. [Numerical modeling analysis of secondary organic aerosol (SOA) combined with the ground-based measurements in the Pearl River Delta region].

    PubMed

    Guo, Xiao-Shuang; Situ, Shu-Ping; Wang, Xue-Mei; Ding, Xiang; Wang, Xin-Ming; Yan, Cai-Qing; Li, Xiao-Ying; Zheng, Mei

    2014-05-01

    Two simulations were conducted with different secondary organic aerosol (SOA) methods-VBS (volatile basis set) approach and SORGAM (secondary organic aerosol model) , which have been coupled in the WRF/Chem (weather research and forecasting model with chemistry) model. Ground-based observation data from 18th to 25th November 2008 were used to examine the model performance of SOA in the Pearl River Delta(PRD)region. The results showed that VBS approach could better reproduce the temporal variation and magnitude of SOA compared with SORGAM, and the mean absolute deviation and correlation coefficient between the observed and the simulated data using VBS approach were -4.88 microg m-3 and 0.91, respectively, while they were -5.32 microg.m-3 and 0. 18 with SORGAM. This is mainly because the VBS approach considers SOA precursors with a wider volatility range and the process of chemical aging in SOA formation. Spatiotemporal distribution of SOA in the PRD from the VBS simulation was also analyzed. The results indicated that the SOA has a significant diurnal variation, and the maximal SOA concentration occurred at noon and in the early afternoon. Because of the transport and the considerable spatial distribution of O3 , the SOA concentrations were different in different PRD cities, and the highest concentration of SOA was observed in the downwind area, including Zhongshan, Zhuhai and Jiangmen.

  8. Stable passive optical clock generation in SOA-based fiber lasers.

    PubMed

    Wang, Jing-Yun; Lin, Kuei-Huei; Chen, Hou-Ren

    2015-02-15

    Stable optical pulse trains are obtained from 1.3-μm and 1.5-μm semiconductor optical amplifier (SOA)-based fiber lasers using passive optical technology. The waveforms depend on SOA currents, and the repetition rates can be tuned by varying the relative length of sub-cavities. The output pulse trains of these SOA-based fiber lasers are stable against intracavity polarization adjustment and environmental perturbation. The optical clock generation is explained in terms of mode competition, self-synchronization, and SOA saturation. Without resorting to any active modulation circuits or devices, the technology used here is simple and may find various applications in the future.

  9. 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.

  10. 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.

  11. Laboratory studies on optical properties of secondary organic aerosols generated during the photooxidation of toluene and the ozonolysis of α-pinene

    NASA Astrophysics Data System (ADS)

    Nakayama, Tomoki; Matsumi, Yutaka; Sato, Kei; Imamura, Takashi; Yamazaki, Akihiro; Uchiyama, Akihiro

    2010-12-01

    It has recently been suggested that some organic aerosols can absorb solar radiation, especially at the shorter visible and UV wavelengths. Although quantitative characterization of the optical properties of secondary organic aerosols (SOAs) is required in order to confirm the effect of SOAs on the atmospheric radiation balance, the light absorption of SOAs has not yet been thoroughly investigated. In this study, we conducted laboratory experiments to measure the optical properties of SOAs generated during the photooxidation of toluene in the presence of NOx and the ozonolysis of α-pinene. Extinction and scattering coefficients of the SOAs were measured by a cavity ring-down aerosol extinction spectrometer and an integrating nephelometer, respectively. Refractive indices of the SOAs were determined so that the measured particle size dependence of the extinction and scattering efficiencies could be reproduced by calculations using Mie scattering theory. As a result, significant light absorption was found at 355 nm for the toluene SOAs. In contrast, no significant absorption was found either at 355 or 532 nm for the α-pinene SOAs. Using the obtained refractive index, mass absorption cross-section values of the toluene SOAs were calculated to be 0.3-3 m2 g-1 at 355 nm. The results indicate that light absorption by the SOAs formed from the photooxidation of aromatic hydrocarbons have a potential to influence the total aerosol light absorption, especially at UV wavelengths.

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. Cloud Condensation Nuclei Activity, Droplet Growth Kinetics and Hygroscopicity of Biogenic and Anthropogenic Secondary Organic Aerosol (SOA)

    NASA Astrophysics Data System (ADS)

    Zhao, Defeng; Buchholz, Angela; Kortner, Birthe; Schlag, Patrick; Rubach, Florian; Hendrik, Fucks; Kiendler-Scharr, Astrid; Tillmann, Ralf; Wahner, Andreas; Hallquist, Mattias; Flores, Michel; Rudich, Yinon; Glasius, Marianne; Kourtchev, Ivan; Kalberer, Markus; Mentel, Thomas

    2015-04-01

    Recent field data and model analysis show that secondary organic aerosol (SOA) formation is enhanced under anthropogenic influences (de Gouw et al. 2005, Spracklen et al. 2011). The interaction of biogenic VOCs (BVOCs) with anthropogenic emissions such as anthropogenic VOCs (AVOCs) could change the particle formation yields and the aerosol properties, as was recently demonstrated (Emanuelsson et al., 2013; Flores et al., 2014). However, the effect of the interaction of BVOCs with AVOCs on cloud condensation nuclei (CCN) activity and hygroscopicity of SOA remains elusive. Characterizing such changes is necessary in order to assess the indirect radiative forcing of biogenic aerosols that form under anthropogenic influence. In this study, we investigated the influence of AVOCs on CCN activation and hygroscopic growth of BSOA. SOA was formed from photooxidation of monoterpenes and aromatics as representatives of BVOCs and AVOCs, respectively. The hygroscopicity and CCN activation of BSOA were studied and compared with that of anthropogenic SOA (ASOA) and the mixture of ASOA and BSOA (ABSOA). We found that ASOA had a significantly higher hygroscopicity than BSOA at similar OH dose, which is attributed to a higher oxidation level of ASOA. While the ASOA fraction had an enhancing effect on the hygroscopicity of ABSOA compared to BSOA, the hygroscopicity of ABSOA cannot be explained by a linear combination of the pure ASOA and BSOA systems, indicating potentially additional non-linear effects such as oligomerization. However, in contrast to hygroscopicity, ASOA showed similar CCN activity as BSOA, in spite of its higher oxidation level. The ASOA fraction did not enhance the CCN activity of ABSOA. The discrepancy between hygroscopicity and CCN activity is discussed. In addition, BSOA, ABSOA and ASOA formed similar droplet size with ammonium sulfate in CCN at a given supersaturation, indicating none of these aerosols had a delay in the water uptake in the supersaturated

  17. 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.

  18. Simulation of aromatic SOA formation using the lumping model integrated with explicit gas-phase kinetic mechanisms and aerosol-phase reactions

    NASA Astrophysics Data System (ADS)

    Im, Y.; Jang, M.; Beardsley, R. L.

    2013-03-01

    The Unified Partitioning-Aerosol phase Reaction (UNIPAR) model has been developed to predict the secondary organic aerosol (SOA) formation through multiphase reactions. An explicit gas-kinetic model was employed to express gas-phase oxidation of aromatic hydrocarbons. Gas-phase products are grouped based on volatility (6 levels) and reactivity (5 levels) and used to construct the stoichiometric coefficients (αi,j) matrix, the set of parameters used to describe the concentrations of organic compounds in multiphase. Weighting of the αi,j matrix as a function of NOx improved the evaluation of NOx effects on SOA. The total amount of organic matter (OMT) is predicted by two modules in the UNIPAR model: OMP by a partitioning process and OMAR by aerosol-phase reactions. OMP is estimated using the SOA partitioning model that has been used in a regional air quality model (CMAQ 5.0.1). OMAR predicts multiphase reactions of organic compounds, such as oligomerization, acid-catalyzed reactions, and organosulfate (OS) formation. The model was evaluated with the SOA data produced from the photooxidation of toluene and 1,3,5-trimethylbenzene using an outdoor reactor (UF-APHOR chamber). The model reasonably simulates SOA formation under various aerosol acidities, NOx concentrations, humidities and temperatures. Furthermore, the OS fraction in the SOA predicted by the model was in good agreement with the experimentally measured OS fraction.

  19. A novel ultrasonic aerosol generator.

    PubMed

    Davies, A; Hudson, N; Pirie, L

    1995-07-01

    An ultrasonic aerosol generator constructed from a domestic humidifier is described which has been used to produce liquid aerosols for physiological investigations. The instrument was constructed from a Pifco domestic humidifier modified to include an energy guide to direct the oscillations of the transducer through the coupling water, which would normally be aerosolized, onto a small membrane based sample chamber containing the liquid to be aerosolized. The size distribution of the aerosol produced was found to be between 2 and 6 mm, optimum for diffuse intrapulmonary deposition. Up to 4 ml/min of aqueous liquid was used; however the sample chamber could be made small enough to contain economic amounts of expensive material to administer by inhalation. The instrument has proved to be reliable over a period of three years.

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

    PubMed

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

    2014-05-12

    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.

  1. 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

  2. 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.

  3. 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

  4. Simulation of aromatic SOA formation using the lumping model integrated with explicit gas-phase kinetic mechanisms and aerosol-phase reactions

    NASA Astrophysics Data System (ADS)

    Im, Y.; Jang, M.; Beardsley, R. L.

    2014-04-01

    The Unified Partitioning-Aerosol phase Reaction (UNIPAR) model has been developed to predict the secondary organic aerosol (SOA) formation through multiphase reactions. The model was evaluated with aromatic SOA data produced from the photooxidation of toluene and 1,3,5-trimethylbenzene (135-TMB) under various concentrations of NOx and SO2 using an outdoor reactor (University of Florida Atmospheric PHotochemical Outdoor Reactor (UF-APHOR) chamber). When inorganic species (sulfate, ammonium and water) are present in aerosol, the prediction of both toluene SOA and 135-TMB SOA, in which the oxygen-to-carbon (O : C) ratio is lower than 0.62, are approached under the assumption of a complete organic/electrolyte-phase separation below a certain relative humidity. An explicit gas-kinetic model was employed to express gas-phase oxidation of aromatic hydrocarbons. Gas-phase products are grouped based on their volatility (6 levels) and reactivity (5 levels) and exploited to construct the stoichiometric coefficient (αi,j) matrix, the set of parameters used to describe the concentrations of organic compounds in multiphase. Weighting of the αi,j matrix as a function of NOx improved the evaluation of NOx effects on aromatic SOA. The total amount of organic matter (OMT) is predicted by two modules in the UNIPAR model: OMP by a partitioning process and OMAR by aerosol-phase reactions. The OMAR module predicts multiphase reactions of organic compounds, such as oligomerization, acid-catalyzed reactions, and organosulfate (OS) formation. The model reasonably simulates SOA formation under various aerosol acidities, NOx concentrations, humidities and temperatures. Furthermore, the OS fractions in the SOA predicted by the model were in good agreement with the experimentally measured OS fractions.

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

    PubMed

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

    2015-01-06

    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 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.

  6. Tracking Changes in Absorptivity, Stiffness, and Organic Chemical Composition in Laboratory Generated HULIS SOA using Atomic Force Microscopy and X-ray Microscopy

    NASA Astrophysics Data System (ADS)

    Hawkins, L. N.; Lemire, A.; Kong, W.

    2014-12-01

    Light absorbing organic compounds are among the many products of aqueous phase secondary organic aerosol formation. Once formed, these compounds can alter the optical and material properties of SOA in ways that impact their ability to scatter and absorb solar radiation, deliquesce and evaporate quickly during cloud cycling, and react with gas phase species such as oxidants. To quantify these effects, we have characterized the changes in UV-visible absorption, stiffness, and particle shape that occur when aqueous SOA is exposed to repeated wet-dry cycles and photooxidation. Material properties were measured with Atomic Force Microscopy of atomized laboratory generated SOA; this material was created by combining glyoxal, methylglyoxal, or glycolaldehyde with ammonium sulfate, glycine, or methylamine in solution and either spray drying or evaporating the bulk solution. In addition to optical and material properties, changes in organic functional groups were tracked using scanning transmission x-ray microscopy (STXM) of the near carbon edge x-ray absorption fine structure (NEXAFS). Photooxidation experiments of the same aqueous SOA revealed concomitant changes in the organic functional groups and light absorption spectra, along with measurable changes in particle stiffness.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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

  12. Time delay generation at high frequency using SOA based slow and fast light.

    PubMed

    Berger, Perrine; Bourderionnet, Jérôme; Bretenaker, Fabien; Dolfi, Daniel; Alouini, Mehdi

    2011-10-24

    We show how Up-converted Coherent Population Oscillations (UpCPO) enable to get rid of the intrinsic limitation of the carrier lifetime, leading to the generation of time delays at any high frequencies in a single SOA device. The linear dependence of the RF phase shift with respect to the RF frequency is theoretically predicted and experimentally evidenced at 16 and 35 GHz.

  13. 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.

  14. 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.

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

    PubMed

    Nakahara, Tatsushi; Takahashi, Ryo

    2013-05-06

    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.

  16. Modeling the formation of secondary organic aerosol (SOA). 2. The predicted effects of relative humidity on aerosol formation in the alpha-pinene-, beta-pinene-, sabinene-, delta 3-carene-, and cyclohexene-ozone systems.

    PubMed

    Seinfeld, J H; Erdakos, G B; Asher, W E; Pankow, J F

    2001-05-01

    Atmospheric oxidation of volatile organic compounds can lead to the formation of secondary organic aerosol (SOA) through the gas/particle (G/P) partitioning of the oxidation products. Since water is ubiquitous in the atmosphere, the extent of the partitioning for any individual organic product depends not only on the amounts and properties of the partitioning organic compounds, but also on the amount of water present. Predicting the effects of water on the atmospheric G/P distributions of organic compounds is, therefore, central to understanding SOA formation. The goals of the current work are to gain understanding of how increases in RH affect (1) overall SOA yields, (2) water uptake by SOA, (3) the behaviors of individual oxidation products, and (4) the fundamental physical properties of the SOA phase that govern the G/P distribution of each of the oxidation products. Part 1 of this series considered SOA formation from five parent hydrocarbons in the absence of water. This paper predicts how adding RH to those systems uniformly increases both the amount of condensed organic mass and the amount of liquid water in the SOA phase. The presence of inorganic components is not considered. The effect of increasing RH is predicted to be stronger for SOA produced from cyclohexene as compared to SOA produced from four monoterpenes. This is likely a result of the greater general degree of oxidation (and hydrophilicity) of the cyclohexene products. Good agreement was obtained between predicted SOA yields and laboratory SOA yield data actually obtained in the presence of water. As RH increases, the compounds that play the largest roles in changing both the organic and water masses in the SOA phase are those with vapor pressures that are intermediate between those of essentially nonvolatile and highly volatile species. RH-driven changes in the compound-dependent G/P partitioning coefficient Kp result from changes in both the average molecular weight MWom of the absorbing

  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. 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.

  19. 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.

  20. 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.

  1. Molecular size evolution of oligomers in organic aerosols collected in urban atmospheres and generated in a smog chamber.

    PubMed

    Kalberer, Markus; Sax, Mirjam; Samburova, Vera

    2006-10-01

    Only a minor fraction of the total organic aerosol mass can be resolved on a molecular level. High molecular weight compounds in organic aerosols have recently gained much attention because this class of compound potentially explains a major fraction of the unexplained organic aerosol mass. These compounds have been identified with different mass spectrometric methods, and compounds with molecular masses up to 1000 Da are found in secondary organic aerosols (SOA) generated from aromatic and terpene precursors in smog chamber experiments. Here, we apply matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) to SOA particles from two biogenic precursors, alpha-pinene and isoprene. Similar oligomer patterns are found in these two SOA systems, but also in SOA from trimethylbenzene, an anthropogenic SOA precursor. However, different maxima molecular sizes were measured for these three SOA systems. While oligomers in alpha-pinene and isoprene have sizes mostly below 600-700 Da, they grow up to about 1000 Da in trimethylbenzene-SOA. The final molecular size of the oligomers is reached early during the particle aging process, whereas other particle properties related to aging, such as the overall acid concentration or the oligomer concentration, increase continuously over a much longer time scale. This kinetic behavior of the oligomer molecular size growth can be explained by a chain growth kinetic regime. Similar oligomer mass patterns were measured in aqueous extracts of ambient aerosol samples (measured with the same technique). Distinct differences between summer and winter were observed. In summer a few single mass peaks were measured with much higher intensity than in winter, pointing to a possible difference in the formation processes of these compounds in winter and summer.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  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. Effects of seed aerosols on the growth of secondary organic aerosols from the photooxidation of toluene.

    PubMed

    Hao, Li-qing; Wang, Zhen-ya; Huang, Ming-qiang; Fang, Li; Zhang, Wei-jun

    2007-01-01

    Hydroxyl radical (.OH)-initiated photooxidation reaction of toluene was carried out in a self-made smog chamber. Four individual seed aerosols such as ammonium sulfate, ammonium nitrate, sodium silicate and calcium chloride, were introduced into the chamber to assess their influence on the growth of secondary organic aerosols (SOA). It was found that the low concentration of seed aerosols might lead to high concentration of SOA particles. Seed aerosols would promote rates of SOA formation at the start of the reaction and inhibit its formation rate with prolonging the reaction time. In the case of ca. 9000 pt/cm3 seed aerosol load, the addition of sodium silicate induced a same effect on the SOA formation as ammonium nitrate. The influence of the four individual seed aerosols on the generation of SOA decreased in the order of calcium chloride>sodium silicate and ammonium nitrate>ammonium sulfate.

  11. Proposal for all-optical switchable and tunable ultrawideband monocycle generation utilizing SOA wavelength conversion and time delay

    NASA Astrophysics Data System (ADS)

    Hu, Zhefeng; Xu, Jianhui; Hou, Min

    2017-03-01

    An all-optical ultrawideband monocycle generator based on wavelength conversion in a semiconductor optical amplifier (SOA) and optical tunable delay in an optical delay line (ODL) is proposed and simulated. The system achieves optically switchable in pulse polarity and tunable in both the pulsewidth and radio frequency (RF) spectrum.

  12. 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

    2016-06-07

    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.

  13. A photonic-assisted periodic triangular-shaped pulses generator based on FWM effect in an SOA

    NASA Astrophysics Data System (ADS)

    Yuan, Jin; Ning, Tigang; Li, Jing; Chen, Hongyao; Li, Yueqin; Zhang, Chan

    2016-12-01

    We propose a photonic-assisted triangular-shaped pulse train generator based on four-wave mixing effect (FWM) in a semiconductor optical amplifier (SOA). A dual-parallel Mach-Zehnder operated at quadrupling RF modulation is employed to generate two primary sidebands (±2nd) in spectrum of the triangular-shaped pulse. Then the FWM effect leads to generation of two new frequency components. By setting the modulation index and bias current of the SOA properly, the generated harmonics of optical intensity can be corresponding to the Fourier components of typical periodic triangular pulses. Finally, a triangular pulse train with tunable repetition rate can be obtained. Numerical simulations have been taken to evaluate the impact of several key parameters to make the scheme more practical.

  14. 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.

  15. High Concentration Standard Aerosol Generator.

    DTIC Science & Technology

    1985-07-31

    materials. In addition to material problems, many liquids are extremely flammable or explosive when aerosolized. This can be checked by putting a small...Hochriner. D. (1975) Stub 3A 440-445. St6ber, W. Flachsbart, H. and Hochramn, D. (1970) Staub 3^, 277. Yoshida. H. Fujii, K. Yomimoto, Y. Masuda. H. and

  16. [Numerical simulation study of SOA in Pearl River Delta region].

    PubMed

    Cheng, Yan-li; Li, Tian-tian; Bai, Yu-hua; Li, Jin-long; Liu, Zhao-rong; Wang, Xue-song

    2009-12-01

    Secondary organic aerosols (SOA) is an important component of the atmospheric particle pollution, thus, determining the status and sources of SOA pollution is the premise of deeply understanding the occurrence, development law and the influence factors of the atmospheric particle pollution. Based on the pollution sources and meteorological data of Pearl River Delta region, the study used the two-dimensional model coupled with SOA module to stimulate the status and source of SOA pollution in regional scale. The results show: the generation of SOA presents obvious characteristics of photochemical reaction, and the high concentration appears at about 14:00; SOA concentration is high in some areas of Guangshou and Dongguan with large pollution source-emission, and it is also high in some areas of Zhongshan, Zhuhai and Jiangmen which are at downwind position of Guangzhou and Dongguan. Contribution ratios of several main pollution sources to SOA are: biogenic sources 72.6%, mobile sources 30.7%, point sources 12%, solvent and oil paint sources 12%, surface sources less than 5% respectively.

  17. High-bandwidth generation of duobinary and alternate-mark-inversion modulation formats using SOA-based signal processing.

    PubMed

    Dailey, James M; Power, Mark J; Webb, Roderick P; Manning, Robert J

    2011-12-19

    We report on the novel all-optical generation of duobinary (DB) and alternate-mark-inversion (AMI) modulation formats at 42.6 Gb/s from an input on-off keyed signal. The modulation converter consists of two semiconductor optical amplifier (SOA)-based Mach-Zehnder interferometer gates. A detailed SOA model numerically confirms the operational principles and experimental data shows successful AMI and DB conversion at 42.6 Gb/s. We also predict that the operational bandwidth can be extended beyond 40 Gb/s by utilizing a new pattern-effect suppression scheme, and demonstrate dramatic reductions in patterning up to 160 Gb/s. We show an increasing trade-off between pattern-effect reduction and mean output power with increasing bitrate.

  18. 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

  19. Critical factors determining the variation in SOA yields from terpene ozonolysis: a combined experimental and computational study.

    PubMed

    Donahue, Neil M; Hartz, Kara E Huff; Chuong, Bao; Presto, Albert A; Stanier, Charles O; Rosenhørn, Thomas; Robinson, Allen L; Pandis, Spyros N

    2005-01-01

    A substantial fraction of the total ultrafine particulate mass is comprised of organic compounds. Of this fraction, a significant subfraction is secondary organic aerosol (SOA), meaning that the compounds are a by-product of chemistry in the atmosphere. However, our understanding of the kinetics and mechanisms leading to and following SOA formation is in its infancy. We lack a clear description of critical phenomena; we often don't know the key, rate limiting steps in SOA formation mechanisms. We know almost nothing about aerosol yields past the first generation of oxidation products. Most importantly, we know very little about the derivatives in these mechanisms; we do not understand how changing conditions, be they precursor levels, oxidant concentrations, co-reagent concentrations (i.e., the VOC/NOx ratio) or temperature will influence the yields of SOA. In this paper we explore the connections between fundamental details of physical chemistry and the multitude of steps associated with SOA formation, including the initial gas-phase reaction mechanisms leading to condensible products, the phase partitioning itself, and the continued oxidation of the condensed-phase organic products. We show that SOA yields in the alpha-pinene + ozone are highly sensitive to NOx, and that SOA yields from beta-caryophylene + ozone appear to increase with continued ozone exposure, even as aerosol hygroscopicity increases as well. We suggest that SOA yields are likely to increase substantially through several generations of oxidative processing of the semi-volatile products.

  20. 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...

  1. 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.

  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 PAGES

    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. SOA Formation from Aqueous Processing of BVOCs in the Southeastern United States during SOAS

    NASA Astrophysics Data System (ADS)

    Skog, K.; Keutsch, F. N.

    2013-12-01

    Secondary organic aerosol (SOA) contributes to climate change and adversely affects human health, but the formation of SOA is poorly understood. Recent studies have shown that aqueous processing of water soluble compounds like glyoxal and glycolaldehyde can help close the gap in our understanding of SOA formation. During June and July of 2013, a comprehensive suite of instruments were deployed at the Southern Oxidant and Aerosol Study (SOAS) Centreville, AL ground site measuring oxidants, glyoxal and glycolaldehyde as well as their precursors, anthropogenic influence, aerosol properties and meteorology. Results from a zero-dimensional gas phase photochemical model and a zero-dimensional aqueous SOA model will be compared to the observations. Analysis will focus on the modeled contribution of glyoxal and glycolaldehyde in the context of closing the aqueous SOA budget.

  5. Secondary Organic Aerosol Formation from 2-Methyl-3-Buten-2-ol (MBO) Photooxidation: Evidence for Acid-Catalyzed Reactive Uptake of Epoxide

    NASA Astrophysics Data System (ADS)

    Surratt, J. D.; Zhang, H.; Worton, D. R.; Lewandowski, M.; Ortega, J.; Zhang, Z.; Lin, Y.; Park, J.; Kristensen, K.; Bhathela, N.; Campuzano-Jost, P.; Day, D. A.; Jimenez, J. L.; Jaoui, M.; Offenberg, J. H.; Kleindienst, T. E.; Gilman, J. B.; De Gouw, J. A.; Park, C.; Schade, G. W.; Frossard, A. A.; Russell, L. M.; Kaser, L.; Jud, W.; Hansel, A.; Karl, T.; Glasius, M.; Gold, A.; Seinfeld, J.; Guenther, A. B.

    2012-12-01

    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 aerosol acidity levels. Results indicate SOA was enhanced with increasing aerosol acidity especially under low-NO conditions. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C5H12O6S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. This organosulfate species was also observed and correlated with aerosol acidity from ambient fine aerosol (PM2.5) samples that were collected from different field campaigns where MBO emissions are important, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Importantly, this compound can account for as high as 1% of the total organic aerosol mass in the atmosphere. It is hypothesized that MBO epoxide generated under low-NO conditions is the precursor to MBO SOA based upon the above results. Thus, the MBO epoxide was synthesized in high purity to investigate its potential to form SOA via reactive uptake in a series of controlled dark chamber studies. Our results suggest the MBO epoxide substantially forms SOA only in the presence of acidic seed aerosols. The chemical characterization results of the SOA constituents are consistent with field measurements in terms of the major SOA tracers.

  6. How will SOA change in the future?: SOA IN THE FUTURE

    SciTech Connect

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

    2016-02-17

    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.

  7. 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.

    2015-09-01

    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 UCD/CIT air quality model and applied to air quality episodes in California and the eastern US. The mass, composition and properties of SOA predicted using SOM are 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 tested. Consequently, the use of low and high NOx yields perturbs SOA

  8. 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

  9. Explicit modelling of SOA formation from α-pinene photooxidation: sensitivity to vapour pressure estimation

    NASA Astrophysics Data System (ADS)

    Valorso, R.; Aumont, B.; Camredon, M.; Raventos-Duran, T.; Mouchel-Vallon, C.; Ng, N. L.; Seinfeld, J. H.; Lee-Taylor, J.; Madronich, S.

    2011-07-01

    The sensitivity of the formation of secondary organic aerosol (SOA) to the estimated vapour pressures of the condensable oxidation products is explored. A highly detailed reaction scheme was generated for α-pinene photooxidation using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A). Vapour pressures (Pvap) were estimated with three commonly used structure activity relationships. The values of Pvap were compared for the set of secondary species generated by GECKO-A to describe α-pinene oxidation. Discrepancies in the predicted vapour pressures were found to increase with the number of functional groups borne by the species. For semi-volatile organic compounds (i.e. organic species of interest for SOA formation), differences in the predicted Pvap range between a factor of 5 to 200 on average. The simulated SOA concentrations were compared to SOA observations in the Caltech chamber during three experiments performed under a range of NOx conditions. While the model captures the qualitative features of SOA formation for the chamber experiments, SOA concentrations are systematically overestimated. For the conditions simulated, the modelled SOA speciation appears to be rather insensitive to the Pvap estimation method.

  10. Explicit modelling of SOA formation from α-pinene photooxidation: sensitivity to vapour pressure estimation

    NASA Astrophysics Data System (ADS)

    Valorso, R.; Aumont, B.; Camredon, M.; Raventos-Duran, T.; Mouchel-Vallon, C.; Ng, N. L.; Seinfeld, J. H.; Lee-Taylor, J.; Madronich, S.

    2011-03-01

    The sensitivity of the formation of secondary organic aerosol (SOA) to the estimated vapour pressures of the condensable oxidation products is explored. A highly detailed reaction scheme was generated for α-pinene photooxidation using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A). Vapour pressures (Pvap) were estimated with three commonly used structure activity relationships. The values of Pvap were compared for the set of secondary species generated by GECKO-A to describe α-pinene oxidation. Discrepancies in the predicted vapour pressures were found to increase with the number of functional groups borne by the species. For semi-volatile organic compounds (i.e. organic species of interest for SOA formation), differences in the predicted Pvap range between a factor of 5 to 200 in average. The simulated SOA concentrations were compared to SOA observations in the Caltech chamber during three experiments performed under a range of NOx conditions. While the model captures the qualitative features of SOA formation for the chamber experiments, SOA concentrations are systematically overestimated. For the conditions simulated, the modelled SOA speciation appears to be rather insensitive to the Pvap estimation method.

  11. 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.

  12. 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

  13. 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 ...

  14. 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.

  15. All-optical UWB generation and modulation using SOA-XPM effect and DWDM-based multi-channel frequency discrimination.

    PubMed

    Wang, Fei; Dong, Jianji; Xu, Enming; Zhang, Xinliang

    2010-11-22

    An all-optical UWB pulses generation and modulation scheme using cross phase modulation (XPM) effect of semiconductor optical amplifier (SOA) and DWDM-based multi-channel frequency discrimination is proposed and demonstrated, which has potential application in multiuser UWB-Over-Fiber communication systems. When a Gaussian pulse light and a wavelength-tunable CW probe light are together injected into the SOA, the probe light out from the SOA will have a temporal chirp due to SOA-XPM effect. When the chirped probe light is tuned to the slopes of single DWDM channel transmittance curve, the optical phase modulation to intensity modulation conversion is achieved at DWDM that serves as a multi-channel frequency discriminator, the inverted polarity Gaussian monocycle and doublet pulse is detected by a photodetector, respectively. If the probe lights are simultaneously aimed to different slopes of several DWDM channels, multi-channel or binary-phase-coded UWB signal generation can be acquired. Using proposed scheme, pulse amplitude modulation (PAM), pulse polarity modulation (PPM) and pulse shape modulation (PSM) to UWB pulses also can be conveniently realized.

  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. 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.

  18. Secondary organic aerosol formation by limonene ozonolysis: Parameterizing multi-generational chemistry in ozone- and residence time-limited indoor environments

    NASA Astrophysics Data System (ADS)

    Waring, Michael S.

    2016-11-01

    Terpene ozonolysis reactions can be a strong source of secondary organic aerosol (SOA) indoors. SOA formation can be parameterized and predicted using the aerosol mass fraction (AMF), also known as the SOA yield, which quantifies the mass ratio of generated SOA to oxidized terpene. Limonene is a monoterpene that is at sufficient concentrations such that it reacts meaningfully with ozone indoors. It has two unsaturated bonds, and the magnitude of the limonene ozonolysis AMF varies by a factor of ∼4 depending on whether one or both of its unsaturated bonds are ozonated, which depends on whether ozone is in excess compared to limonene as well as the available time for reactions indoors. Hence, this study developed a framework to predict the limonene AMF as a function of the ozone [O3] and limonene [lim] concentrations and the air exchange rate (AER, h-1), which is the inverse of the residence time. Empirical AMF data were used to calculate a mixing coefficient, β, that would yield a 'resultant AMF' as the combination of the AMFs due to ozonolysis of one or both of limonene's unsaturated bonds, within the volatility basis set (VBS) organic aerosol framework. Then, β was regressed against predictors of log10([O3]/[lim]) and AER (R2 = 0.74). The β increased as the log10([O3]/[lim]) increased and as AER decreased, having the physical meaning of driving the resultant AMF to the upper AMF condition when both unsaturated bonds of limonene are ozonated. Modeling demonstrates that using the correct resultant AMF to simulate SOA formation owing to limonene ozonolysis is crucial for accurate indoor prediction.

  19. Aerosol generation and measurement of multi-wall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Myojo, Toshihiko; Oyabu, Takako; Nishi, Kenichiro; Kadoya, Chikara; Tanaka, Isamu; Ono-Ogasawara, Mariko; Sakae, Hirokazu; Shirai, Tadashi

    2009-01-01

    Mass production of some kinds of carbon nanotubes (CNT) is now imminent, but little is known about the risk associated with their exposure. It is important to assess the propensity of the CNT to release particles into air for its risk assessment. In this study, we conducted aerosolization of a multi-walled CNT (MWCNT) to assess several aerosol measuring instruments. A Palas RBG-1000 aerosol generator applied mechanical stress to the MWCNT by a rotating brush at feed rates ranging from 2 to 20 mm/h, which the MWCNT was fed to a two-component fluidized bed. The fluidized bed aerosol generator was used to disperse the MWCNT aerosol once more. We monitored the generated MWCNT aerosol concentrations based on number, area, and mass using a condensation particle counter and nanoparticle surface area monitor. Also we quantified carbon mass in MWCNT aerosol samples by a carbon monitor. The shape of aerosolized MWCNT fibers was observed by a scanning electron microscope (SEM). The MWCNT was well dispersed by our system. We found isolated MWCNT fibers in the aerosols by SEM and the count median lengths of MWCNT fibers were 4-6 μm. The MWCNT was quantified by the carbon monitor with a modified condition based on the NIOSH analytical manual. The MWCNT aerosol concentration (EC mass base) was 4 mg/m3 at 2 mm/h in this study.

  20. 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.

  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.

  2. 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

  3. 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.

  4. Early stage composition of SOA produced by α-pinene/ozone reaction: α-Acyloxyhydroperoxy aldehydes and acidic dimers

    NASA Astrophysics Data System (ADS)

    Witkowski, Bartłomiej; Gierczak, Tomasz

    2014-10-01

    Composition of the freshly formed secondary organic aerosol (SOA) generated by ozonolysis of cyclohexene, cyclohexene-d10 (model precursors) and α-pinene was studied using liquid chromatography coupled to electrospray ionization tandem mass spectrometry (LC-ESI/MS2). SOA was generated in the flow-tube reactor under the following conditions: 22 ± 2 °C, 1 atm and reaction time was approx. 30 s. In an attempt to resolve the current ambiguities, regarding the structure of α-pinene SOA nucleating agents, analytical methods for analysis of α-acyloxyhydroperoxy aldehydes and oligomers containing carboxylic group were developed to study the potential nucleating agents. Negatively charged m/z 351, 341, 337, 357 and 367 ions corresponding to the acidic oligomers were detected in freshly formed α-pinene SOA. For the first time, structures and formation mechanism for compounds detected as m/z 337 and 351 ions were proposed. Based on the model precursor analysis (cyclohexene and cyclohexene-d10) it was concluded that these compounds were most likely formed via aldol reaction of the lower molecular weight aerosol components. α-Acyloxyhydroperoxy aldehydes were studied in the SOA samples using previously developed, novel method, based on the prediction of fragmentation spectrum for the compounds of interest. It was concluded that α-acyloxyhydroperoxy aldehydes were not formed in significant quantities. Based on the obtained results, possible SOA formation and growth mechanism is discussed.

  5. 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.

  6. Evaporation kinetics and phase of laboratory and ambient secondary organic aerosol.

    PubMed

    Vaden, Timothy D; Imre, Dan; Beránek, Josef; Shrivastava, Manish; Zelenyuk, Alla

    2011-02-08

    Field measurements of secondary organic aerosol (SOA) find significantly higher mass loads than predicted by models, sparking intense effort focused on finding additional SOA sources but leaving the fundamental assumptions used by models unchallenged. Current air-quality models use absorptive partitioning theory assuming SOA particles are liquid droplets, forming instantaneous reversible equilibrium with gas phase. Further, they ignore the effects of adsorption of spectator organic species during SOA formation on SOA properties and fate. Using accurate and highly sensitive experimental approach for studying evaporation kinetics of size-selected single SOA particles, we characterized room-temperature evaporation kinetics of laboratory-generated α-pinene SOA and ambient atmospheric SOA. We found that even when gas phase organics are removed, it takes ∼24 h for pure α-pinene SOA particles to evaporate 75% of their mass, which is in sharp contrast to the ∼10 min time scale predicted by current kinetic models. Adsorption of "spectator" organic vapors during SOA formation, and aging of these coated SOA particles, dramatically reduced the evaporation rate, and in some cases nearly stopped it. Ambient SOA was found to exhibit evaporation behavior very similar to that of laboratory-generated coated and aged SOA. For all cases studied in this work, SOA evaporation behavior is nearly size-independent and does not follow the evaporation kinetics of liquid droplets, in sharp contrast with model assumptions. The findings about SOA phase, evaporation rates, and the importance of spectator gases and aging all indicate that there is need to reformulate the way SOA formation and evaporation are treated by models.

  7. Evaporation kinetics and phase of laboratory and ambient secondary organic aerosol

    PubMed Central

    Vaden, Timothy D.; Imre, Dan; Beránek, Josef; Shrivastava, Manish; Zelenyuk, Alla

    2011-01-01

    Field measurements of secondary organic aerosol (SOA) find significantly higher mass loads than predicted by models, sparking intense effort focused on finding additional SOA sources but leaving the fundamental assumptions used by models unchallenged. Current air-quality models use absorptive partitioning theory assuming SOA particles are liquid droplets, forming instantaneous reversible equilibrium with gas phase. Further, they ignore the effects of adsorption of spectator organic species during SOA formation on SOA properties and fate. Using accurate and highly sensitive experimental approach for studying evaporation kinetics of size-selected single SOA particles, we characterized room-temperature evaporation kinetics of laboratory-generated α-pinene SOA and ambient atmospheric SOA. We found that even when gas phase organics are removed, it takes ∼24 h for pure α-pinene SOA particles to evaporate 75% of their mass, which is in sharp contrast to the ∼10 min time scale predicted by current kinetic models. Adsorption of “spectator” organic vapors during SOA formation, and aging of these coated SOA particles, dramatically reduced the evaporation rate, and in some cases nearly stopped it. Ambient SOA was found to exhibit evaporation behavior very similar to that of laboratory-generated coated and aged SOA. For all cases studied in this work, SOA evaporation behavior is nearly size-independent and does not follow the evaporation kinetics of liquid droplets, in sharp contrast with model assumptions. The findings about SOA phase, evaporation rates, and the importance of spectator gases and aging all indicate that there is need to reformulate the way SOA formation and evaporation are treated by models. PMID:21262848

  8. Generation of 21.3 Gbaud 8PSK signal using an SOA-based all-optical phase modulator.

    PubMed

    Dailey, J M; Webb, R P; Manning, R J

    2011-12-12

    We describe a novel SOA-based all-optical pure-phase modulator, and show how deleterious cross-gain modulation from the SOAs can be suppressed by utilizing an integrated interferometer structure. We experimentally demonstrate the use of the optical gate as a π/4 phase modulator producing 21.3 Gbaud 8PSK from 21.3 Gbit/s OOK and 21.3 Gbaud QPSK inputs. The modulator produces 3 dB of gain and coherent detection-based bit error rate measurements indicate a 2.4 dB excess penalty.

  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.

    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.

  10. 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).

  11. 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.

  12. 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

  13. Steady generation of aerosols with an improved constant output atomizer

    NASA Technical Reports Server (NTRS)

    Dea, J. Y.; Katz, U.

    1981-01-01

    It is common practice to generate laboratory aerosols of soluble materials with pneumatic atomizers. In a typical device, a solution of the substance to be aerosolized is injected into a jet of air and the liquid is broken up into very small droplets. After forced evaporation, a dry aerosol of the solute is produced. A number of commercially available devices were tested, and despite differences in design, all the atomizers tested suffered from short- and/or long-term fluctuations of their output particle number concentrations. The mechanisms responsible for atomizer instabilities are discussed and methods for alleviating these problems are considered.

  14. 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

  15. 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...

  16. Analysis of the hygroscopic and volatile properties of ammonium sulphate seeded and unseeded SOA particles

    NASA Astrophysics Data System (ADS)

    Meyer, N. K.; Duplissy, J.; Gysel, M.; Metzger, A.; Dommen, J.; Weingartner, E.; Alfarra, M. R.; Prevot, A. S. H.; Fletcher, C.; Good, N.; McFiggans, G.; Jonsson, Â. M.; Hallquist, M.; Baltensperger, U.; Ristovski, Z. D.

    2009-01-01

    The volatile and hygroscopic properties of ammonium sulphate seeded and unseeded secondary organic aerosol (SOA) derived from the photo-oxidation of atmospherically relevant concentrations of α-pinene were studied. The seed particles were electrospray generated ammonium sulphate ((NH4)2SO4) having diameters of approximately 33 nm with a quasi-mono-disperse size distribution (geometric standard deviation σg=1.3). The volatile and hygroscopic properties of both seeded and unseeded SOA were simultaneously measured with a VH-TDMA (volatility - hygroscopicity tandem differential mobility analyzer). VH-TDMA measurements of unseeded SOA show a decrease in the hygroscopic growth (HGF) factor for increased volatilisation temperatures such that the more volatile compounds appear to be more hygroscopic. This is opposite to the expected preferential evaporation of more volatile but less hygroscopic material, but could also be due to enhanced oligomerisation occurring at the higher temperature in the thermodenuder. In addition, HGF measurements of seeded SOA were measured as a function of time at two relative humidities, below (RH 75%) and above (RH 85%) the deliquescence relative humidity (DRH) of the pure ammonium sulphate seeds. As these measurements were conducted during the onset phase of photo-oxidation, during particle growth, they enabled us to find the dependence of the HGF as a function of the volume fraction of the SOA coating. HGF's measured at RH of 85% showed a continuous decrease as the SOA coating thickness increased. The measured growth factors show good agreements with ZSR predictions indicating that, at these RH values, there are only minor solute-solute interactions. At 75% RH, as the SOA fraction increased, a rapid increase in the HGF was observed indicating that an increasing fraction of the (NH4)2SO4 is subject to a phase transition, going into solution, with an increasing volume fraction of SOA. To our knowledge this is the first time that SOA derived

  17. Aerosol Generation by Modern Flush Toilets.

    PubMed

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

    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- μ m fluorescent microspheres served as microbe surrogates in separate trials in a mockup 5 m(3) water closet (WC). Bowl water seeding was approximately 10(12) particles/mL. Droplet nuclei were sampled onto 0.2- μ m 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 <2μm diameter and>99%<5μ m. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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...

  2. 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

  3. Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions.

    PubMed

    Donahue, Neil M; Henry, Kaytlin M; Mentel, Thomas F; Kiendler-Scharr, Astrid; Spindler, Christian; Bohn, Birger; Brauers, Theo; Dorn, Hans P; Fuchs, Hendrik; Tillmann, Ralf; Wahner, Andreas; Saathoff, Harald; Naumann, Karl-Heinz; Möhler, Ottmar; Leisner, Thomas; Müller, Lars; Reinnig, Marc-Christopher; Hoffmann, Thorsten; Salo, Kent; Hallquist, Mattias; Frosch, Mia; Bilde, Merete; Tritscher, Torsten; Barmet, Peter; Praplan, Arnaud P; DeCarlo, Peter F; Dommen, Josef; Prévôt, Andre S H; Baltensperger, Urs

    2012-08-21

    The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models.

  4. Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions

    PubMed Central

    Donahue, Neil M.; Henry, Kaytlin M.; Mentel, Thomas F.; Kiendler-Scharr, Astrid; Spindler, Christian; Bohn, Birger; Brauers, Theo; Dorn, Hans P.; Fuchs, Hendrik; Tillmann, Ralf; Wahner, Andreas; Saathoff, Harald; Naumann, Karl-Heinz; Möhler, Ottmar; Leisner, Thomas; Müller, Lars; Reinnig, Marc-Christopher; Hoffmann, Thorsten; Salo, Kent; Hallquist, Mattias; Frosch, Mia; Bilde, Merete; Tritscher, Torsten; Barmet, Peter; Praplan, Arnaud P.; DeCarlo, Peter F.; Dommen, Josef; Prévôt, Andre S.H.; Baltensperger, Urs

    2012-01-01

    The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models. PMID:22869714

  5. 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.

  6. 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...

  7. 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

  8. Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene

    PubMed Central

    Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

    2017-01-01

    The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m3 smog chamber. The presence of FeSO4 or Fe2(SO4)3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO4 or (NH4)2SO4. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO4 or Fe2(SO4)3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation. PMID:28059151

  9. Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene

    NASA Astrophysics Data System (ADS)

    Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

    2017-01-01

    The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m3 smog chamber. The presence of FeSO4 or Fe2(SO4)3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO4 or (NH4)2SO4. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO4 or Fe2(SO4)3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.

  10. Proposal for all-optical generation of multiple-frequency millimeter-wave signals for RoF system with multiple base stations using FWM in SOA.

    PubMed

    Zhang, Chongfu; Wang, Leyang; Qiu, Kun

    2011-07-18

    An approach for the multiple-frequency millimeter-wave (mm-wave) signals generation is proposed and demonstrated, specifically, which can be applied to a radio-over-fiber (RoF) system with multiple base stations (BSs). In this scheme, optical double sideband (ODSB) modulation is achieved using a Mach-Zehnder modulator (MZM) to generate the two-sideband signals. New frequencies of the optical signals are obtained by using four-wave mixing (FWM) in a semiconductor optical amplifier (SOA). At the BSs, two different frequencies are achieved using a comb optical filter (COF), and which then input a photodiode (PD) to generate the mm-wave signals with the frequencies of 20, 40 or 60 GHz for different BSs, by mixing of these frequencies components. Experimental results verify that the proposed multiple-frequency mm-wave signals generation scheme for a RoF system with multiple base stations can work properly.

  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. Assessment of the Aerosol Generation and Toxicity of Carbon Nanotubes

    PubMed Central

    O’Shaughnessy, Patrick T.; Adamcakova-Dodd, Andrea; Altmaier, Ralph; Thorne, Peter S.

    2014-01-01

    Current interest in the pulmonary toxicity of carbon nanotubes (CNTs) has resulted in a need for an aerosol generation system that is capable of consistently producing a CNT aerosol at a desired concentration level. This two-part study was designed to: (1) assess the properties of a commercially-available aerosol generator when producing an aerosol from a purchased powder supply of double-walled carbon nanotubes (DWCNTs); and (2) assess the pulmonary sub-acute toxicity of DWCNTs in a murine model during a 5-day (4 h/day) whole-body exposure. The aerosol generator, consisting of a novel dustfeed mechanism and venturi ejector was determined to be capable of producing a DWCNT consistently over a 4 h exposure period at an average level of 10.8 mg/m3. The count median diameter was 121 nm with a geometric standard deviation of 2.04. The estimated deposited dose was 32 µg/mouse. The total number of cells in bronchoalveolar lavage (BAL) fluid was significantly (p < 0.01) increased in exposed mice compared to controls. Similarly, macrophages in BAL fluid were significantly elevated in exposed mice, but not neutrophils. All animals exposed to CNT and euthanized immediately after exposure had changes in the lung tissues showing acute inflammation and injury; however these pathological changes resolved two weeks after the exposure.

  13. Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NO x photooxidation system

    NASA Astrophysics Data System (ADS)

    Lu, Zifeng; Hao, Jiming; Takekawa, Hideto; Hu, Lanhua; Li, Junhua

    High concentrations (>15 μm 3 cm -3) of CaSO 4, Ca(NO 3) 2 and (NH 4) 2SO 4 were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO 4 and aqueous Ca(NO 3) 2), even at elevated concentrations. The presence of high concentrations of (NH 4) 2SO 4 aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH 4) 2SO 4 on SOA yield is found to be positively correlated with the (NH 4) 2SO 4 surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH 4) 2SO 4 seed aerosols.

  14. 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.

  15. 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

  16. To what extent can biogenic SOA be controlled?

    PubMed

    Carlton, Annmarie G; Pinder, Robert W; Bhave, Prakash V; Pouliot, George A

    2010-05-01

    The implicit assumption that biogenic secondary organic aerosol (SOA) is natural and can not be controlled hinders effective air quality management. Anthropogenic pollution facilitates transformation of naturally emitted volatile organic compounds (VOCs) to the particle phase, enhancing the ambient concentrations of biogenic secondary organic aerosol (SOA). It is therefore conceivable that some portion of ambient biogenic SOA can be removed by controlling emissions of anthropogenic pollutants. Direct measurement of the controllable fraction of biogenic SOA is not possible, but can be estimated through 3-dimensional photochemical air quality modeling. To examine this in detail, 22 CMAQ model simulations were conducted over the continental U.S. (August 15 to September 4, 2003). The relative contributions of five emitted pollution classes (i.e., NO(x), NH(3), SO(x), reactive non methane carbon (RNMC) and primary carbonaceous particulate matter (PCM)) on biogenic SOA were estimated by removing anthropogenic emissions of these pollutants, one at a time and all together. Model results demonstrate a strong influence of anthropogenic emissions on predicted biogenic SOA concentrations, suggesting more than 50% of biogenic SOA in the eastern U.S. can be controlled. Because biogenic SOA is substantially enhanced by controllable emissions, classification of SOA as biogenic or anthropogenic based solely on VOC origin is not sufficient to describe the controllable fraction.

  17. 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....

  18. 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.

  19. 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

  20. Real-time continuous characterization of secondary organic aerosol derived from isoprene epoxydiols in downtown Atlanta, Georgia, using the Aerodyne Aerosol Chemical Speciation Monitor.

    PubMed

    Budisulistiorini, Sri Hapsari; Canagaratna, Manjula R; Croteau, Philip L; Marth, Wendy J; Baumann, Karsten; Edgerton, Eric S; Shaw, Stephanie L; Knipping, Eladio M; Worsnop, Douglas R; Jayne, John T; Gold, Avram; Surratt, Jason D

    2013-06-04

    Real-time continuous chemical measurements of fine aerosol were made using an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) during summer and fall 2011 in downtown Atlanta, Georgia. Organic mass spectra measured by the ACSM were analyzed by positive matrix factorization (PMF), yielding three conventional factors: hydrocarbon-like organic aerosol (HOA), semivolatile oxygenated organic aerosol (SV-OOA), and low-volatility oxygenated organic aerosol (LV-OOA). An additional OOA factor that contributed to 33 ± 10% of the organic mass was resolved in summer. This factor had a mass spectrum that strongly correlated (r(2) = 0.74) to that obtained from laboratory-generated secondary organic aerosol (SOA) derived from synthetic isoprene epoxydiols (IEPOX). Time series of this additional factor is also well correlated (r(2) = 0.59) with IEPOX-derived SOA tracers from filters collected in Atlanta but less correlated (r(2) < 0.3) with a methacrylic acid epoxide (MAE)-derived SOA tracer, α-pinene SOA tracers, and a biomass burning tracer (i.e., levoglucosan), and primary emissions. Our analyses suggest IEPOX as the source of this additional factor, which has some correlation with aerosol acidity (r(2) = 0.3), measured as H(+) (nmol m(-3)), and sulfate mass loading (r(2) = 0.48), consistent with prior work showing that these two parameters promote heterogeneous chemistry of IEPOX to form SOA.

  1. 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.

  2. Molecular characterization of nitrogen and sulfur containing compounds in night-time SOA

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    The oxidation of volatile organic compounds (VOCs) leads to the formation of low volatile organic compounds that can form secondary organic aerosol (SOA). Studies in the past showed that laboratory generated and ambient SOA are made of polar molecules with O/C ratios generally greater than 0.5. More recent studies have shown that SOA compounds can contain heteroatoms mainly sulfur and nitrogen atoms. Offline chemical analysis with high-resolution mass spectrometers and fragmentation experiments has shown that sulphur containing compounds are mainly organosulfates and nitrogen containing species are aromatic heterocyclic compounds such as imidazole and nitrated aromatic compounds such as nitrophenols. In addition to these, SOA compounds containing both sulfur and nitrogen have been reported from the analysis of ambient organic aerosol, rainwater, fog and cloud samples. Based on the mass spectrometric evidence these compounds are attributed to nitrooxy-organosulfates originating from isoprene and monoterpenes. Although these compounds are ubiquitously detected in the ambient samples, reports about their detection in laboratory generated SOA are scares and their formation mechanisms are not well understood. In the present study, we investigated the formation of sulfur and nitrogen containing SOA species in the oxidation of biogenic VOCs. Photooxidation and night-time oxidation experiments were performed in a smog chamber to produce SOA samples. The laboratory generated SOA samples were analysed with UPLC-IMS-TOFMS (Ultra Performance Liquid Chromatography coupled to Ion Mobility Spectrometry and Time of Flight Mass Spectrometry). The presence of highly acidic sulphate seed particles (pH0) did not promote the formation of compounds with chemical formula of C10H17NO7S- and m/z value of 294.0653, indicating that the formation mechanisms of these compounds unlikely involve the ring opening reactions of epoxides and subsequent sulfation reactions. On the other hand, their

  3. Chamber studies of SOA formation from aromatic hydrocarbons: observation of limited glyoxal uptake

    NASA Astrophysics Data System (ADS)

    Nakao, S.; Liu, Y.; Tang, P.; Chen, C.-L.; Zhang, J.; Cocker, D. R., III

    2012-05-01

    This study evaluates the significance of glyoxal acting as an intermediate species leading to secondary organic aerosol (SOA) formation from aromatic hydrocarbon photooxidation under humid conditions. Rapid SOA formation from glyoxal uptake onto aqueous (NH4)2SO4 seed particles is observed in agreement with previous studies; however, glyoxal did not partition significantly to SOA (with or without aqueous seed) during aromatic hydrocarbon photooxidation within an environmental chamber (RH less than 80%). Rather, glyoxal influences SOA formation by raising hydroxyl (OH) radical concentrations. Four experimental approaches supporting this conclusion are presented in this paper: (1) increased SOA formation and decreased SOA volatility in the toluene + NOx photooxidation system with additional glyoxal was reproduced by matching OH radical concentrations through H2O2 addition; (2) glyoxal addition to SOA seed formed from toluene + NOx photooxidation did not increase SOA volume under dark; (3) SOA formation from toluene + NOx photooxidation with and without deliquesced (NH4)2SO4 seed resulted in similar SOA growth, consistent with a minor contribution from glyoxal uptake onto deliquesced seed and organic coatings; and (4) the fraction of a C4H9+ fragment (observed by Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer, HR-ToF-AMS) in SOA from 2-tert-butylphenol (BP) oxidation was unchanged in the presence of additional glyoxal despite enhanced SOA formation. This study suggests that glyoxal uptake onto aerosol during the oxidation of aromatic hydrocarbons is more limited than previously thought.

  4. Water absorption by secondary organic aerosol and its effect on inorganic aerosol behavior

    SciTech Connect

    Ansari, A.S.; Pandis, S.N.

    2000-01-01

    The hygroscopic nature of atmospheric aerosol has generally been associated with its inorganic fraction. In this study, a group contribution method is used to predict the water absorption of secondary organic aerosol (SOA). Compared against growth measurements of mixed inorganic-organic particles, this method appears to provide a first-order approximation in predicting SOA water absorption. The growth of common SOA species is predicted to be significantly less than common atmospheric inorganic salts such as (NH{sub 4}){sub 2}SO{sub 4} and NaCl. Using this group contribution method as a tool in predicting SOA water absorption, an integrated modeling approach is developed combining available SOA and inorganic aerosol models to predict overall aerosol behavior. The effect of SOA on water absorption and nitrate partitioning between the gas and aerosol phases is determined. On average, it appears that SOA accounts for approximately 7% of total aerosol water and increases aerosol nitrate concentrations by approximately 10%. At high relative humidity and low SOA mass fractions, the role of SOA in nitrate partitioning and its contribution to total aerosol water is negligible. However, the water absorption of SOA appears to be less sensitive to changes in relative humidity than that of inorganic species, and thus at low relative humidity and high SOA mass fraction concentrations, SOA is predicted to account for approximately 20% of total aerosol water and a 50% increase in aerosol nitrate concentrations. These findings could improve the results of modeling studies where aerosol nitrate has often been underpredicted.

  5. 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

  6. Characterization of aerosols containing Legionella generated upon nebulization.

    PubMed

    Allegra, Séverine; Leclerc, Lara; Massard, Pierre André; Girardot, Françoise; Riffard, Serge; Pourchez, Jérémie

    2016-09-27

    Legionella pneumophila is, by far, the species most frequently associated with Legionnaires' disease (LD). Human infection occurs almost exclusively by aerosol inhalation which places the bacteria in juxtaposition with alveolar macrophages. LD risk management is based on controlling water quality by applying standardized procedures. However, to gain a better understanding of the real risk of exposure, there is a need (i) to investigate under which conditions Legionella may be aerosolized and (ii) to quantify bacterial deposition into the respiratory tract upon nebulization. In this study, we used an original experimental set-up that enables the generation of aerosol particles containing L. pneumophila under various conditions. Using flow cytometry in combination with qPCR and culture, we determined (i) the size of the aerosols and (ii) the concentration of viable Legionella forms that may reach the thoracic region. We determined that the 0.26-2.5 μm aerosol size range represents 7% of initial bacterial suspension. Among the viable forms, 0.7% of initial viable bacterial suspension may reach the pulmonary alveoli. In conclusion, these deposition profiles can be used to standardize the size of inoculum injected in any type of respiratory tract model to obtain new insights into the dose response for LD.

  7. Characterization of aerosols containing Legionella generated upon nebulization

    PubMed Central

    Allegra, Séverine; Leclerc, Lara; Massard, Pierre André; Girardot, Françoise; Riffard, Serge; Pourchez, Jérémie

    2016-01-01

    Legionella pneumophila is, by far, the species most frequently associated with Legionnaires’ disease (LD). Human infection occurs almost exclusively by aerosol inhalation which places the bacteria in juxtaposition with alveolar macrophages. LD risk management is based on controlling water quality by applying standardized procedures. However, to gain a better understanding of the real risk of exposure, there is a need (i) to investigate under which conditions Legionella may be aerosolized and (ii) to quantify bacterial deposition into the respiratory tract upon nebulization. In this study, we used an original experimental set-up that enables the generation of aerosol particles containing L. pneumophila under various conditions. Using flow cytometry in combination with qPCR and culture, we determined (i) the size of the aerosols and (ii) the concentration of viable Legionella forms that may reach the thoracic region. We determined that the 0.26–2.5 μm aerosol size range represents 7% of initial bacterial suspension. Among the viable forms, 0.7% of initial viable bacterial suspension may reach the pulmonary alveoli. In conclusion, these deposition profiles can be used to standardize the size of inoculum injected in any type of respiratory tract model to obtain new insights into the dose response for LD. PMID:27671446

  8. Characterization of aerosols containing Legionella generated upon nebulization

    NASA Astrophysics Data System (ADS)

    Allegra, Séverine; Leclerc, Lara; Massard, Pierre André; Girardot, Françoise; Riffard, Serge; Pourchez, Jérémie

    2016-09-01

    Legionella pneumophila is, by far, the species most frequently associated with Legionnaires’ disease (LD). Human infection occurs almost exclusively by aerosol inhalation which places the bacteria in juxtaposition with alveolar macrophages. LD risk management is based on controlling water quality by applying standardized procedures. However, to gain a better understanding of the real risk of exposure, there is a need (i) to investigate under which conditions Legionella may be aerosolized and (ii) to quantify bacterial deposition into the respiratory tract upon nebulization. In this study, we used an original experimental set-up that enables the generation of aerosol particles containing L. pneumophila under various conditions. Using flow cytometry in combination with qPCR and culture, we determined (i) the size of the aerosols and (ii) the concentration of viable Legionella forms that may reach the thoracic region. We determined that the 0.26–2.5 μm aerosol size range represents 7% of initial bacterial suspension. Among the viable forms, 0.7% of initial viable bacterial suspension may reach the pulmonary alveoli. In conclusion, these deposition profiles can be used to standardize the size of inoculum injected in any type of respiratory tract model to obtain new insights into the dose response for LD.

  9. Contribution of carbonyl photochemistry to aging of atmospheric secondary organic aerosol.

    PubMed

    Mang, Stephen A; Henricksen, Dana K; Bateman, Adam P; Andersen, Mads P Sulbaek; Blake, Donald R; Nizkorodov, Sergey A

    2008-09-11

    The photodegradation of secondary organic aerosol (SOA) material by actinic UV radiation was investigated. SOA was generated via the dark reaction of ozone and d-limonene, collected onto quartz-fiber filters, and exposed to wavelength-tunable radiation. Photochemical production of CO was monitored in situ by infrared cavity ring-down spectroscopy. A number of additional gas-phase products of SOA photodegradation were observed by gas chromatography, including methane, ethene, acetaldehyde, acetone, methanol, and 1-butene. The absorption spectrum of SOA material collected onto CaF2 windows was measured and compared with the photolysis action spectrum for the release of CO, a marker for Norrish type-I photocleavage of carbonyls. Both spectra had a band at approximately 300 nm corresponding to the overlapping n --> pi* transitions in nonconjugated carbonyls. The effective extinction coefficient of freshly prepared SOA was estimated to be on the order of 15 L mol(-1) cm(-1) at 300 nm, implying one carbonyl group in every SOA constituent. The absorption by the SOA material slowly increased in the visible and near-UV during storage of SOA in open air in the dark, presumably as a result of condensation reactions that increased the degree of conjugation in the SOA constituents. These observations suggest that photolysis of carbonyl functional groups represents a significant sink for monoterpene SOA compounds in the troposphere, with an estimated lifetime of several hours over the continental United States.

  10. 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.

  11. 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...

  12. 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.

  13. 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.

  14. 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.

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

    PubMed

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

    2013-06-04

    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 water-soluble SOA generated from two monoterpenes, limonene and α-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 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 λexcitation = 420 ± 50 nm and λemission = 475 ± 38 nm. The window of the strongest fluorescence shifted to λexcitation = 320 ± 25 nm and λemission = 425 ± 38 nm for the α-pinene-derived SOA. Both regions overlap with the EEM spectra of some of the fluorophores found in primary biological aerosols. Despite the low quantum yield, the aged SOA particles may have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

  16. 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.

  17. Characterisation of aerosol combustible mixtures generated using condensation process

    NASA Astrophysics Data System (ADS)

    Saat, Aminuddin; Dutta, Nilabza; Wahid, Mazlan A.

    2012-06-01

    An accidental release of a liquid flammable substance might be formed as an aerosol (droplet and vapour mixture). This phenomenon might be due to high pressure sprays, pressurised liquid leaks and through condensation when hot vapour is rapidly cooled. Such phenomena require a fundamental investigation of mixture characterisation prior to any subsequent process such as evaporation and combustion. This paper describes characterisation study of droplet and vapour mixtures generated in a fan stirred vessel using condensation technique. Aerosol of isooctane mixtures were generated by expansion from initially a premixed gaseous fuel-air mixture. The distribution of droplets within the mixture was characterised using laser diagnostics. Nearly monosized droplet clouds were generated and the droplet diameter was defined as a function of expansion time. The effect of changes in pressure, temperature, fuel-air fraction and expansion ratio on droplet diameter was evaluated. It is shown that aerosol generation by expansion was influenced by the initial pressure and temperature, equivalence ratio and expansion rates. All these parameters affected the onset of condensation which in turn affected the variation in droplet diameter.

  18. 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.

  19. 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

  20. Analysis of the hygroscopic and volatile properties of ammonium sulphate seeded and un-seeded SOA particles

    NASA Astrophysics Data System (ADS)

    Meyer, N. K.; Duplissy, J.; Gysel, M.; Metzger, A.; Dommen, J.; Weingartner, E.; Alfarra, M. R.; Fletcher, C.; Good, N.; McFiggans, G.; Jonsson, Ã. M.; Hallquist, M.; Baltensperger, U.; Ristovski, Z. D.

    2008-05-01

    The volatile and hygroscopic properties of ammonium sulphate seeded and un-seeded secondary organic aerosol (SOA) derived from the photo-oxidation of atmospherically relevant concentrations of α-pinene were studied. The seed particles were electrospray generated ammonium sulphate ((NH4)2SO4) having diameters of approximately 33 nm with a quasi-mono-disperse size distribution (geometric standard deviation σg=1.3). The volatile and hygroscopic properties of both seeded and unseeded SOA were simultaneously measured with a VH-TDMA (volatility - hygroscopicity tandem differential mobility analyzer). VH-TDMA measurements of unseeded SOA show a decrease in the hygroscopic growth (HGF) factor for increased volatilisation temperatures such that the more volatile compounds appear to be more hygroscopic. This is opposite to the expected preferential evaporation of more volatile but less hygroscopic material, but could also be due to enhanced oligomerisation occurring at the higher temperature in the thermodenuder. In addition, HGF measurements of seeded SOA were measured as a function of time at two relative humidities, below (RH 75%) and above (RH 85%) the deliquescence relative humidity (DRH) of the pure ammonium sulphate seeds. As these measurements were conducted during the onset phase of photo-oxidation, during particle growth, they enabled us to find the dependence of the HGF as a function of the volume fraction of the SOA coating. HGF's measured at RH of 85% showed a continuous decrease as the SOA coating thickness increased. The measured growth factors show good agreements with ZSR predictions indicating that, at these RH values, there are only minor solute-solute interactions. At 75% RH, as the SOA fraction increased, a rapid increase in the HGF was observed indicating that an increasing fraction of the (NH4)2SO4 is subject to a phase transition, going into solution, with an increasing volume fraction of SOA. To our knowledge this is the first time that SOA derived

  1. 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...

  2. 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...

  3. 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.

  4. 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

  5. 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

  6. Modeling Organic Aerosols during MILAGRO: Application of the CHIMERE Model and Importance of Biogenic Secondary Organic Aerosols

    SciTech Connect

    Hodzic, Alma; Jimenez, Jose L.; Madronich, Sasha; Aiken, Allison; Bessagnet, Bertrand; Curci, Gabriele; Fast, Jerome D.; Lamarque, J.-F.; Onasch, Timothy B.; Roux, Gregory; Schauer, James J.; Stone, Elizabeth A.

    2009-09-22

    The meso-scale chemistry-transport model CHIMERE is used to assess our understanding of major sources and formation processes leading to a fairly large amount of organic aerosols [OA, including primary OA (POA) and secondary OA (SOA)] observed in Mexico City during the MILAGRO field project (March 2006). Chemical analyses of submicron aerosols from aerosol mass spectrometers (AMS) indicate that organic particles found in the Mexico City basin have a large fraction of oxygenated organic species (OOA), which have strong correspondence with SOA, and that their production actively continues downwind of the city. The SOA formation is modeled here by 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 lower than the measured total OA. Fairly good agreement is found between predicted and observed POA within the city suggesting that anthropogenic and biomass burning emissions are reasonably captured. Consistent with previous studies in Mexico City, large discrepancies are encountered for SOA species, with a factor of 5-10 model underestimate. When only anthropogenic SOA precursors were considered, the model was able to reproduce within a factor of two 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 nighttime discrepancies were not significantly reduced when greatly enhanced partitioning to the aerosol phase was assumed. Model sensitivity results suggest that observed nighttime SOA concentrations are strongly influenced by the regional background (~2µg/m3) from biogenic origin, which is transported

  7. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Yee, L. D.; Schilling, K.; Loza, C. L.; Craven, J. S.; Zuend, A.; Ziemann, P. J.; Seinfeld, J.

    2013-12-01

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosol (SOA). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multi-generation gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a mid-experiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. The results of the current work have a number of implications for SOA models. While the dynamics of an aerosol size distribution reflects the mechanism of growth, we demonstrate here that it provides a key constraint in interpreting laboratory and ambient SOA formation. This work, although carried out specifically for the long chain alkane, dodecane, is expected to be widely applicable to other major classes of SOA precursors. SOA consists of a myriad of organic compounds containing various functional groups, which can generally undergo heterogeneous/multiphase reactions forming low-volatility products such as oligomers and other high molecular mass compounds. If particle-phase chemistry is indeed

  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.

    2015-02-01

    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.

  9. Sensitivity analysis of simulated SOA loadings using a variance-based statistical approach: SENSITIVITY ANALYSIS OF SOA

    SciTech Connect

    Shrivastava, Manish; Zhao, Chun; Easter, Richard C.; Qian, Yun; Zelenyuk, Alla; Fast, Jerome D.; Liu, Ying; Zhang, Qi; Guenther, Alex

    2016-04-08

    We investigate the sensitivity of secondary organic aerosol (SOA) loadings simulated by a regional chemical transport model to 7 selected tunable model parameters: 4 involving emissions of anthropogenic and biogenic volatile organic compounds, anthropogenic semi-volatile and intermediate volatility organics (SIVOCs), and NOx, 2 involving dry deposition of SOA precursor gases, and one involving particle-phase transformation of SOA to low volatility. We adopt a quasi-Monte Carlo sampling approach to effectively sample the high-dimensional parameter space, and perform a 250 member ensemble of simulations using a regional model, accounting for some of the latest advances in SOA treatments based on our recent work. We then conduct a variance-based sensitivity analysis using the generalized linear model method to study the responses of simulated SOA loadings to the tunable parameters. Analysis of SOA variance from all 250 simulations shows that the volatility transformation parameter, which controls whether particle-phase transformation of SOA from semi-volatile SOA to non-volatile is on or off, is the dominant contributor to variance of simulated surface-level daytime SOA (65% domain average contribution). We also split the simulations into 2 subsets of 125 each, depending on whether the volatility transformation is turned on/off. For each subset, the SOA variances are dominated by the parameters involving biogenic VOC and anthropogenic SIVOC emissions. Furthermore, biogenic VOC emissions have a larger contribution to SOA variance when the SOA transformation to non-volatile is on, while anthropogenic SIVOC emissions have a larger contribution when the transformation is off. NOx contributes less than 4.3% to SOA variance, and this low contribution is mainly attributed to dominance of intermediate to high NOx conditions throughout the simulated domain. The two parameters related to dry deposition of SOA precursor gases also have very low contributions to SOA variance

  10. In vitro exposure to isoprene-derived secondary organic aerosol by direct deposition and its effects on COX-2 and IL-8 gene expression

    NASA Astrophysics Data System (ADS)

    Arashiro, Maiko; Lin, Ying-Hsuan; Sexton, Kenneth G.; Zhang, Zhenfa; Jaspers, Ilona; Fry, Rebecca C.; Vizuete, William G.; Gold, Avram; Surratt, Jason D.

    2016-11-01

    Atmospheric oxidation of isoprene, the most abundant non-methane hydrocarbon emitted into Earth's atmosphere primarily from terrestrial vegetation, is now recognized as a major contributor to the global secondary organic aerosol (SOA) burden. Anthropogenic pollutants significantly enhance isoprene SOA formation through acid-catalyzed heterogeneous chemistry of epoxide products. Since isoprene SOA formation as a source of fine aerosol is a relatively recent discovery, research is lacking on evaluating its potential adverse effects on human health. The objective of this study was to examine the effect of isoprene-derived SOA on inflammation-associated gene expression in human lung cells using a direct deposition exposure method. We assessed altered expression of inflammation-related genes in human bronchial epithelial cells (BEAS-2B) exposed to isoprene-derived SOA generated in an outdoor chamber facility. Measurements of gene expression of known inflammatory biomarkers interleukin 8 (IL-8) and cyclooxygenase 2 (COX-2) in exposed cells, together with complementary chemical measurements, showed that a dose of 0.067 µg cm-2 of SOA from isoprene photooxidation leads to statistically significant increases in IL-8 and COX-2 mRNA levels. Resuspension exposures using aerosol filter extracts corroborated these findings, supporting the conclusion that isoprene-derived SOA constituents induce the observed changes in mRNA levels. The present study is an attempt to examine the early biological responses of isoprene SOA exposure in human lung cells.

  11. Optical Properties and Aging of Light Absorbing Secondary Organic Aerosol

    SciTech Connect

    Liu, Jiumeng; Lin, Peng; Laskin, Alexander; Laskin, Julia; Kathmann, Shawn M.; Wise, Matthew E.; Caylor, Ryan; Imholt, Felisha; Selimovic, Vanessa; Shilling, John E.

    2016-10-14

    The light-absorbing organic aerosol (OA), commonly referred to as “brown carbon (BrC)”, has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various VOC precursors, NOx concentrations, photolysis time and relative humidity (RH) on the light absorption of selected secondary organic aerosols (SOA). Light absorption of chamber generated SOA samples, especially aromatic SOA, was found to increase with NOx concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficients (MAC) value is observed from toluene SOA products formed under high NOx conditions at moderate RH, in which nitro-aromatics were previously identified as the major light absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organonitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible and UV light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed-SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.

  12. Effect of Humidity on the Composition of Isoprene Photooxidation Secondary Organic Aerosol

    SciTech Connect

    Nguyen, Tran B.; Roach, Patrick J.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Serguei

    2011-07-18

    The effect of relative humidity (RH) on the composition and concentrations of gas-phase products and secondary organic aerosol (SOA) generated from the photooxidation of isoprene under high-NOx conditions was investigated. The yields of most gas-phase products were the same regardless of initial water vapor concentration with exception of hydroxyacetone and glycolaldehyde, which were considerably affected by RH. A significant change was observed in the SOA composition, with many unique condensed-phase products formed under humid (90% RH) vs. dry (<2% RH) conditions, without any observable effect on the rate and extent of the SOA mass growth.

  13. 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

  14. Design and performance of 10-Gb/s L-band REAM-SOA for OLT Transmitter in next generation access networks.

    PubMed

    Lee, Dong-Hun; Jeong, Jong Sool; Kim, Ki-Soo; Kim, Hyun-Soo; Kim, Dong Churl; Park, Mi-Ran; Han, Yong-Tak; Kwon, Oh Kee; Kwon, O-Kyun

    2015-02-09

    We present a 10-Gb/s L-band reflective electro-absorption modulator integrated with a semiconductor optical amplifier (REAM-SOA) having improved transmission performance at very low input power of seed light. To decrease the input power of seed light, the absorption characteristics of the REAM are adjusted to reduce the amplified spontaneous emission light returned into the SOA, suppressing the gain saturation effect of the SOA. At a considerably low input power of -16 dBm, the REAM-SOA exhibits a low transmission penalty of about 1.2 dB after 50-km SMF transmission. Over a wide input power range from -16 dBm to 5 dBm, a penalty of less than 1.6 dB is achieved at 50-km transmission.

  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.

  16. Integrable high order UWB pulse photonic generator based on cross phase modulation in a SOA-MZI.

    PubMed

    Moreno, Vanessa; Rius, Manuel; Mora, José; Muriel, Miguel A; Capmany, José

    2013-09-23

    We propose and experimentally demonstrate a potentially integrable optical scheme to generate high order UWB pulses. The technique is based on exploiting the cross phase modulation generated in an InGaAsP Mach-Zehnder interferometer containing integrated semiconductor optical amplifiers, and is also adaptable to different pulse modulation formats through an optical processing unit which allows to control of the amplitude, polarity and time delay of the generated taps.

  17. Constraining uncertainties in particle-wall deposition correction during SOA formation in chamber experiments

    NASA Astrophysics Data System (ADS)

    Nah, Theodora; McVay, Renee C.; Pierce, Jeffrey R.; Seinfeld, John H.; Ng, Nga L.

    2017-02-01

    The effect of vapor-wall deposition on secondary organic aerosol (SOA) formation has gained significant attention; however, uncertainties in experimentally derived SOA mass yields due to uncertainties in particle-wall deposition remain. Different approaches have been used to correct for particle-wall deposition in SOA formation studies, each having its own set of assumptions in determining the particle-wall loss rate. In volatile and intermediate-volatility organic compound (VOC and IVOC) systems in which SOA formation is governed by kinetically limited growth, the effect of vapor-wall deposition on SOA mass yields can be constrained by using high surface area concentrations of seed aerosol to promote the condensation of SOA-forming vapors onto seed aerosol instead of the chamber walls. However, under such high seed aerosol levels, the presence of significant coagulation may complicate the particle-wall deposition correction. Here, we present a model framework that accounts for coagulation in chamber studies in which high seed aerosol surface area concentrations are used. For the α-pinene ozonolysis system, we find that after accounting for coagulation, SOA mass yields remain approximately constant when high seed aerosol surface area concentrations ( ≥ 8000 µm2 cm-3) are used, consistent with our prior study (Nah et al., 2016) showing that α-pinene ozonolysis SOA formation is governed by quasi-equilibrium growth. In addition, we systematically assess the uncertainties in the calculated SOA mass concentrations and yields between four different particle-wall loss correction methods over the series of α-pinene ozonolysis experiments. At low seed aerosol surface area concentrations (< 3000 µm2 cm-3), the SOA mass yields at peak SOA growth obtained from the particle-wall loss correction methods agree within 14 %. However, at high seed aerosol surface area concentrations ( ≥ 8000 µm2 cm-3), the SOA mass yields at peak SOA growth obtained from different particle

  18. Secondary Organic Aerosol Formation from the Ozonolysis of Cycloalkenes

    NASA Astrophysics Data System (ADS)

    Keywood, M.; Varutbangkul, V.; Gao, S.; Brechtel, F.; Bahreini, R.; Flagan, R. C.; Seinfeld, J. H.

    2003-12-01

    Secondary organic aerosol (SOA) is ubiquitous in the atmosphere being present in both urban and remote locations and exerting influence on human health, visibility and climate. Despite its importance, our understanding of SOA formation still lacks essential elements, limiting our understanding of the effect of SOA on climate forcing. While there do exist experimental data on SOA yields from both biogenic and anthropogenic precursor compounds, it is difficult to extend these results to predict the aerosol-forming potential of precursor compounds not yet studied. In response to this, a series of chamber experiments were carried out in the Caltech Indoor Chamber Facility, where compounds from the cycloalkene and methyl-substituted cycloalkene families were oxidized by ozone in the dark. The reactions were carried out in dual 28 m3 teflon chambers at 20oC and relative humidity below 5%, in the presence of ammonium sulfate seed aerosol. Cyclohexane was used as a scavenger to prevent side oxidation reactions with OH radicals, generated during ozonolysis of the cycloalkene. While cycloalkenes may not be important precursors for SOA formation in the ambient atmosphere, the system was chosen for its simplicity relative to atmospherically relevant SOA precursors such as the biogenic monoterpenes and sesquiterpenes. Cycloalkenes may be seen as the simplified structures on which these more complicated compounds are based. The compounds reacted included the cycloalkenes: cyclopentene, cyclohexene, cycloheptene and cyclooctene, the methyl-substituted cycloalkenes: 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, 1-methy-1-cycloheptene and1-methyl-1-cylopentene, and other related classes of hydrocarbons: methylene cyclohexane and terpinolene. Data collected include aerosol yield, chemical composition and hygroscopic behaviour. The effect of the precursor hydrocarbon structure on these properties of the SOA will be discussed.

  19. 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.

  20. 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.

  1. 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 ...

  2. 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.

  3. 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

  4. Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle

    NASA Astrophysics Data System (ADS)

    Gordon, T. D.; Presto, A. A.; Nguyen, N. T.; Robertson, W. H.; Na, K.; Sahay, K. N.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

    2014-05-01

    Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices, including diesel particulate filters (DPFs), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOCs). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle,~Urban Dynamometer Driving Schedule, and creep + idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photooxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary PM emissions and SOA production from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after 3 h of oxidation at typical urban VOC / NOx ratios (3 : 1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the nonmethane organic gas emissions that could not be speciated using traditional one-dimensional gas chromatography. The

  5. 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

  6. 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.

  7. 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

  8. 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

  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. The water up-take of semisolid SOA particles

    NASA Astrophysics Data System (ADS)

    Pajunoja, A.; Lambe, A. T.; Hakala, J. P.; Rastak, N.; Hao, L.; Paramonov, M.; Hong, J.; Laaksonen, A. J.; Kulmala, M. T.; Massoli, P.; Onasch, T. B.; Donahue, N. M.; Riipinen, I.; Davidovits, P.; Worsnop, D. R.; Petäjä, T.; Virtanen, A.

    2014-12-01

    The dependence of aerosol particle hygroscopicity on particle composition is often represented with the single parameter k commonly used in global models to describe the hygroscopic properties of atmospheric aerosol particles. From the theoretical formulation of k the same value is expected for ideal solutes in both the sub- and supersaturated regimes as typically calculated from hygroscopicity tandem differential mobility analyser (HTDMA) and cloud condensation nuclei counter (CCNc) measurements respectively (i.e. k HGF and kCCN). Yet, a number of recent studies conducted on SOA indicate that the two measurements yield different k values (k HGF < kCCN). There are several studies discussing the behaviour but the underlying reasons are unresolved. To investigate this in more detailed, CCNc and HTDMA measurements were conducted to determine the effects of chemical composition, oxidation level, the phase state and RH on the associated water uptake properties of biogenic SOA particles formed from isoprene, a-pinene, and longifolene precursors. Pure SOA particles by OH and/or O3 oxidation of the gas-phase precursors were formed in a PAM (Potential Aerosol Mass) flow tube reactor. Hygroscopic growth factors (HGF) were measured by Hygroscopicity Tandem Differential Mobility Analyser (HTDMA) at RH range of 50-~95% and CCN activation by CCN counter. To investigate the physical phase of the particles the particle bounced fraction (BF) using an Aerosol Bounce Instrument (ABI) was also measured. SOA oxidation state and composition was measured by a c-ToF-AMS. Based on the measurements we suggest that at subsaturation conditions semi solid SOA particles take up water mostly via surface adsorption resulting a large discrepancy between the kHGF and kCCN values. By calculating the aerosol direct radiative effect (Wm-2) using our results we also show that ambiguity about the κ values has important implications for quantifying the climate effects of SOA in atmospheric models.

  11. 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.

  12. 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.

  13. 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.

  14. SOA: A Quality Attribute Perspective

    DTIC Science & Technology

    2011-06-23

    JMS) – CORBA … • Infrastructure services available to service providers and/or service consumers to perform common tasks or satisfy QoS requirements...Services is one technology for SOA implementation SOA and Quality Attributes SOA WS* Web Services CORBA REST Services and POX Key Class Realization

  15. 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

  16. SOA formation from partitioning and heterogeneous reactions: model study in the presence of inorganic species.

    PubMed

    Jang, Myoseon; Czoschke, Nadine M; Northcross, Amanda L; Cao, Gang; Shaof, David

    2006-05-01

    A predictive model for secondary organic aerosol (SOA) formation by both partitioning and heterogeneous reactions was developed for SOA created from ozonolysis of alpha-pinene in the presence of preexisting inorganic seed aerosols. SOA was created in a 2 m3 polytetrafluoroethylene film indoor chamber under darkness. Extensive sets of SOA experiments were conducted varying humidity, inorganic seed compositions comprising of ammonium sulfate and sulfuric acid, and amounts of inorganic seed mass. SOA mass was decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). The reaction rate constant for OM(H) production was subdivided into three categories (fast, medium, and slow) to consider different reactivity of organic products for the particle phase heterogeneous reactions. The influence of particle acidity on reaction rates was treated in a previous semiempirical model. Model OM(H) was developed with medium and strong acidic seed aerosols, and then extrapolated to OM(H) in weak acidic conditions, which are more relevant to atmospheric aerosols. To demonstrate the effects of preexisting glyoxal derivatives (e.g., glyoxal hydrate and dimer) on OM(H), SOA was created with a seed mixture comprising of aqueous glyoxal and inorganic species. Our results show that heterogeneous SOA formation was also influenced by preexisting reactive glyoxal derivatives.

  17. Recent activities in the Aerosol Generation and Transport Program

    SciTech Connect

    Adams, R.E.

    1984-01-01

    General statements may be made on the behavior of single-component and multi-component aerosols in the Nuclear Safety Pilot Plant vessel. The removal processes for U/sub 3/O/sub 8/, Fe/sub 2/O/sub 3/, and U/sub 3/O/sub 8/ + Fe/sub 2/O/sub 3/ aerosols are enhanced in a steam-air atmosphere. Steam-air seems to have little effect on removal of concrete aerosol from the vessel atmosphere. A steam-air environment causes a change in aerosol shape from chain-agglomerate to basically spherical for U/sub 3/O/sub 8/, Fe/sub 2/O/sub 3/, and U/sub 3/O/sub 8/ + Fe/sub 2/O/sub 3/ aerosol; for concrete the change in aerosol shape is from chain-agglomerate to partially spherical. The mass ratio of the individual components of a multi-component aerosol seems to have an observable influence on the resultant behavior of these aerosols in steam. The enhanced rate of removal of the U/sub 3/O/sub 8/, the Fe/sub 2/O/sub 3/, and the mixed U/sub 3/O/sub 8/ + Fe/sub 2/O/sub 3/ aerosols from the atmosphere of the NSPP vessel by steam-air is probably caused by the change in aerosol shape and the condensation of steam on the aerosol surfaces combining to increase the effect of gravitational settling. The apparent lack of an effect by steam-air on the removal rate of concrete aerosol could result from a differing physical/chemical response of the surfaces of this aerosol to condensing steam.

  18. Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Lewis, A. C.; Carey, T. J.; Wenger, J. C.; Garcia, E. Borrás. I.; Muñoz, A.

    2009-02-01

    Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1-5 TgC yr-1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

  19. Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Lewis, A. C.; Carey, T. J.; Wenger, J. C.; Garcia, E. Borrás. I.; Muñoz, A.

    2009-06-01

    Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1-5 TgC yr-1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

  20. Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle

    NASA Astrophysics Data System (ADS)

    Gordon, T. D.; Presto, A. A.; Nguyen, N. T.; Robertson, W. H.; Na, K.; Sahay, K. N.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

    2013-09-01

    Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices including diesel particulate filters (DPF), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOC). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle, Urban Dynamometer Driving Schedule, and creep+idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photo-oxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary and secondary fine particulate matter from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after three hours of oxidation at typical urban VOC : NOx ratios (3:1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the non-methane organic gas emissions that could not be speciated using traditional one-dimensional gas

  1. 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,...

  2. 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

  3. 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

  4. 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...

  5. 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).

  6. 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.

  7. Impacts of Oil and Gas Exploration Activities on SOA formation in the Colorado Front Range

    NASA Astrophysics Data System (ADS)

    Bahreini, R.; Vu, K. K. T.; Dingle, J. H.; Apel, E. C.; Blake, N. J.; Campos, T. L.; Cantrell, C. A.; Flocke, F. M.; Fried, A.; Herndon, S. C.; Hills, A. J.; Hornbrook, R. S.; Huey, L. G.; Kaser, L.; Mauldin, L.; Meinardi, S.; Montzka, D.; Nowak, J. B.; Richter, D.; Roscioli, J. R.; Schroeder, J.; Shertz, S.; Stell, M. H.; Tanner, D.; Tyndall, G. S.; Walega, J.; Weibring, P.; Weinheimer, A. J.

    2015-12-01

    Oil and gas exploration activities (O&G) in Wattenberg Field, located north of the Denver Metropolitan area, have expanded in the last few years. Although VOC emissions and the potential for ozone formation in the area from these sources have been studied previously, no information is available on the impact on secondary organic aerosol (SOA) formation. During the Front Range Air Pollution and Photochemistry Experiment (FRAPPE), airborne measurements of trace gases and aerosol composition were made in the northern Front Range during July-August 2014. We present analyses on evolution of organic aerosol (OA) and their precursors in order to assess the impact of urban vs. O&G emissions on SOA formation. Significant contribution of SOA to total OA was observed in pure urban and urban plumes mixed with O&G emissions. Under an OH-exposure of 2.8×1011 molecule cm-3 s, enhancement ratios of OA relative to carbon monoxide (ΔOA/ΔCO) increased by factors of ~3.6-5.4; however, (ΔSOA/ΔCO)urban+O&G was 87% higher than (ΔSOA/ΔCO)urban. Predicted ΔSOA/ΔCO values from the oxidation of C7-C11 alkanes, C6-C9 aromatics, and biogenics were about a factor of 10-15 too small compared to the measurements. Predicated alkane-derived SOA contributed to 38% (16%) of anthropogenic ΔSOA/ΔCO values in urban+O&G- (urban-) influenced air masses.

  8. 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...

  9. 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

  10. Aerosols

    Atmospheric Science Data Center

    2013-04-17

    ... article title:  Aerosols over Central and Eastern Europe     View Larger Image ... last weeks of March 2003, widespread aerosol pollution over Europe was detected by several satellite-borne instruments. The Multi-angle ...

  11. Optical properties and aging of light-absorbing secondary organic aerosol

    DOE PAGES

    Liu, Jiumeng; Lin, Peng; Laskin, Alexander; ...

    2016-10-14

    The light-absorbing organic aerosol (OA) commonly referred to as “brown carbon” (BrC) has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various volatile organic carbon (VOC) precursors, NOx concentrations, photolysis time, and relative humidity (RH) on the light absorptionmore » of selected secondary organic aerosols (SOA). Light absorption of chamber-generated SOA samples, especially aromatic SOA, was found to increase with NOx concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficient (MAC) value is observed from toluene SOA products formed under high-NOx conditions at moderate RH, in which nitro-aromatics were previously identified as the major light-absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organic nitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible (Vis) and ultraviolet (UV) light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.« less

  12. Optical properties and aging of light-absorbing secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Liu, Jiumeng; Lin, Peng; Laskin, Alexander; Laskin, Julia; Kathmann, Shawn M.; Wise, Matthew; Caylor, Ryan; Imholt, Felisha; Selimovic, Vanessa; Shilling, John E.

    2016-10-01

    The light-absorbing organic aerosol (OA) commonly referred to as "brown carbon" (BrC) has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various volatile organic carbon (VOC) precursors, NOx concentrations, photolysis time, and relative humidity (RH) on the light absorption of selected secondary organic aerosols (SOA). Light absorption of chamber-generated SOA samples, especially aromatic SOA, was found to increase with NOx concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficient (MAC) value is observed from toluene SOA products formed under high-NOx conditions at moderate RH, in which nitro-aromatics were previously identified as the major light-absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organic nitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible (Vis) and ultraviolet (UV) light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.

  13. 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.

  14. Satellite remote sensing of aerosols generated by the Island of Nauru

    NASA Astrophysics Data System (ADS)

    Henderson, Bradley G.; Chylek, Petr; Porch, William M.; Dubey, Manvendra K.

    2006-11-01

    We use imagery from the Multispectral Thermal Imager (MTI) to search for aerosols generated by the Island of Nauru, an island located in the tropical western Pacific Ocean. Nauru frequently displays linear cloud trails for many kilometers downwind of the island, and this study was intended to investigate the presence of aerosols as an aid to understanding those features. The study had three components: (1) a search for specific aerosol plumes, (2) a comparison of downwind and upwind aerosol loading to look for asymmetries, and (3) application of matched filters to increase the visibility of aerosol plumes. The plume search resulted in the finding of three aerosol plumes, two of which are presented as imagery and also radiance profiles. The comparison of downwind and upwind reflectance spectra demonstrated that the radiance is slightly higher downwind of the island, and the residual spectra (downwind minus upwind) have a spectrum consistent with sea salt aerosol. Application of clutter-matched filters to MTI imagery accentuated the upper (near source) sections of an aerosol plume when utilizing a single-scatter albedo signature for coarse-grained sea salt aerosol. We combine our observations with models from the literature to describe a simple mechanism by which Nauru aerosols are created by wave breaking and wind tearing of sea spray and then entrained by island-influenced wind motions.

  15. Micro-physical properties of carbonaceous aerosol particles generated by laser ablation of a graphite target

    NASA Astrophysics Data System (ADS)

    Ajtai, T.; Utry, N.; Pintér, M.; Tápai, Cs.; Kecskeméti, G.; Smausz, T.; Hopp, B.; Bozóki, Z.; Szabó, G.

    2014-09-01

    In this work the authors propose laser ablation as a highly versatile tool for carbonaceous aerosol generation. The generated carbonaceous particles can be used as a model aerosol for atmospheric black carbon. Various microphysical properties including mass concentration, size distribution and morphology of aerosol particles generated by laser ablation of a high purity graphite sample were investigated in detail. These measurements proved that the proposed method can be used to generate both primary particles and fractal aggregates with a high yield. As a further advantage of the method the size distribution of the generated aerosol can cover a wide range, and can be tuned accurately with laser fluence, the ambient composition or with the volumetric flow rate of the carrier gas.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. Constraining the properties of hydrocarbon oxidation products via SOA studies at high loadings

    NASA Astrophysics Data System (ADS)

    Hunter, J. F.; Carrasquillo, A. J.; Daumit, K. E.; Franklin, J. P.; Boulanger, K.; Cross, E. S.; Worsnop, D. R.; Kroll, J. H.

    2013-12-01

    The oxidation processes that lead to the formation of secondary organic aerosol (SOA) generate products with a spectrum of vapor pressures. In accordance with absorptive partitioning theory, only a fraction of these components will condense under typical experimental and atmospheric conditions at low to medium organic aerosol concentration (Coa). The more volatile products may go on to form additional aerosol or other oxidation products by serving as precursors in further oxidation chemistry. They may also serve as sinks for airborne organic carbon if they are lost to environmental surfaces prior to reaction. As Coa is increased, more volatile oxidation products will partition to the condensed phase, where they can be measured using conventional aerosol techniques. In the limit of very high Coa, the aerosol yield plateaus somewhere at or below an organic carbon yield of 100%. At a carbon yield of 100%, all of the carbon from the precursor is found in the condensed phase, with yields below 100% indicating that some carbon is still in the gas phase. This limit gives the yield of condensable carbon for a given precursor, and thereby the branching between pathways yielding condensable versus strictly gas-phase products. Experiments have been performed in which the Coa is systematically increased in order to approach this limit for various precursors. The precursors have been chosen across a variety of parent vapor pressures and structures, allowing the influence of these properties on the limiting yield to be assessed. The influence of ';trapping,' wherein products that are primarily condensed see their overall reaction rate decreased is also discussed. The primary effect of trapping on these experiments is that as Coa is increased, more volatile components are trapped in the condensed phase, leading to overall less oxidized and younger generation aerosol. The chemistry of the organic aerosol is evaluated using aerosol mass spectrometry, enabling the oxygen to carbon

  1. System for the continuous generation of phosphorous aerosols from Red Phosphorus-Butyl Rubber. Final report

    SciTech Connect

    Holmberg, R.W.; Moneyhun, J.H.; Gayle, T.M.

    1985-06-01

    A system for the continuous generation of phosphoric acid aerosols from burning Red Phosphorus-Butyl Rubber (RPBR) is described. The system is primarily intended for inhalation toxicology experiments using high aerosol concentrations (ca. 0.3 to 3 g/m/sup 3/), but is adaptable to other studies where a time independent concentration of the aerosol is desired in a flowing system. The RPBR formulation is softened by addition of a small amount of hexane and extruded at a controlled rate at high pressure through an orifice. A precision hydraulic extrusion system using a micrometer adjustable high pressure hydraulic pump has been developed to control the extrusion rate. The emerging filament is ignited and burned in a flowing air stream for delivery to chambers. In addition to the extrusion-combustion system for aerosol generation, devices for recovering the spent aerosol and for monitoring its concentration are described. 2 refs., 18 figs.

  2. Aerosol generation and distribution system for the Third International Cloud Condensation Nuclei Workshop

    NASA Technical Reports Server (NTRS)

    Katz, U.; Dea, J. Y.

    1981-01-01

    In order to obtain identical samples participating CCN instruments and aerosol characterizing equipment were located along and connected to a 8.2 cm diameter aluminum tube through which the test aerosols were pumped directly from the source at very slight overpressure. Of the total of 29 experiments, 18 were carried out with artificial NaCl or (NH4)2SO4 aerosols. These were generated from salt solutions by pneumatic atomizers of special design to ensure high constancy of the aerosol output concentration. In three experiments with insoluble CCN (AgI, paraffin wax) the aerosols were generated thermally. In some of the tests, an electrostatic classifier was used for narrowing the particle size distributions.

  3. Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

    NASA Astrophysics Data System (ADS)

    Gordon, T. D.; Presto, A. A.; May, A. A.; Nguyen, N. T.; Lipsky, E. M.; Donahue, N. M.; Gutierrez, A.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

    2014-05-01

    The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter (PM) after 3 h of oxidation inside the chamber at typical atmospheric oxidant levels (and 5 times the amount of SOA as primary PM after 5 × 106 molecules cm-3 h of OH exposure). Therefore, the contribution of light-duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photooxidizing exhaust from newer (LEV2) vehicles was a factor of 3 lower than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions (a factor of 11-15) in nonmethane organic gas emissions. These data suggest that a complex and nonlinear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the timescale of these experiments, the mixture of organic vapors

  4. Effects of inorganic seed aerosols on the particulate products of aged 1,3,5-trimethylbenzene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Huang, Mingqiang; Hao, Liqing; Cai, Shunyou; Gu, Xuejun; Zhang, Weixiong; Hu, Changjin; Wang, Zhenya; Fang, Li; Zhang, Weijun

    2017-03-01

    Inorganic aerosols such as (NH4)2SO4, NaNO3 and CaCl2 are commonly present in the Chinese urban atmosphere. They could significantly affect the formation and aging of ambient secondary organic aerosols (SOA), but the underlying mechanisms remain unknown. In this work we studied SOA formation from the photooxidation reaction of 1,3,5-trimethylbenzene (135-TMB) with 100 μg/m3 of the above three types of inorganic aerosols as seeds in a laboratory chamber. We focused on the aging products of SOA particles by exposing them to high levels of oxidizing hydroxyl radicals (OH). The particulate products of SOA were measured using an aerosol laser time-of-flight mass spectrometer (ALTOFMS) and Fuzzy C-Means (FCM) were applied to organic mass spectra for clustering. In the presence of (NH4)2SO4 seeds, 4-methyl-1H-imidazole, 4-methyl-imidazole-2-acetaldehyde and other imidazole derivative compounds formed from reactions of NH4+ with methylglyoxal were detected as new aged products. We also observed aromatic nitrogen-containing organic compounds as the major aged products in the presence of NaNO3 seeds as a consequence of reaction with OH and NO2 radicals, which were generated by UV irradiation of acidic aqueous nitrate, inducing nitration reactions with phenolic compounds. As CaCl2 has the strongest hygroscopic properties of the three salt particles tested, the greater water content on the surface of the aerosol may facilitate the condensing of more gas-phase organic acid products to the hygroscopic CaCl2 seeds, forming H+ ions that catalyze the heterogeneous reaction of aldehydes, products of photooxidation of 135-TMB, and forming high-molecular-weight (HMW) compounds. These results provide new insight into the aromatic SOA aging mechanisms.

  5. 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

  6. Efficient Isoprene Secondary Organic Aerosol Formation from a Non-IEPOX Pathway

    SciTech Connect

    Liu, Jiumeng; D’Ambro, Emma L.; Lee, Ben H.; Lopez-Hilfiker, Felipe D.; Zaveri, Rahul A.; Rivera-Rios, Jean C.; Keutsch, Frank N.; Iyer, Siddharth; Kurten, Theo; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.; Shilling, John E.; Thornton, Joel A.

    2016-09-20

    With a large global emission rate and high reactivity, isoprene has a profound effect upon atmospheric chemistry and composition. The atmospheric pathways by which isoprene converts to secondary organic aerosol (SOA) and how anthropogenic pollutants such as nitrogen oxides and sulfur affect this process are a subject of intense research because particles affect Earth’s climate and local air quality. In the absence of both nitrogen oxides and reactive aqueous seed particles, we measure SOA mass yields from isoprene photochemical oxidation of up to 15%, which are factors of 2, or more, higher than those typically used in coupled chemistry-climate models. SOA yield is initially constant with the addition of increasing amounts of nitric oxide (NO) but then sharply decreases for input concentrations above 10 ppbv. Online measurements of aerosol molecular composition show that the fate of second-generation RO2 radicals is key to understanding the efficient SOA formation and the NOx dependent yields described here and in the literature. These insights allow for improved quantitative estimates of SOA formation in the pre-industrial atmosphere and in biogenic-rich regions with limited anthropogenic impacts and suggest a more complex representation of NOx dependent SOA yields may be important in models.

  7. Easy Volcanic Aerosol (EVA v1.0): an idealized forcing generator for climate simulations

    NASA Astrophysics Data System (ADS)

    Toohey, Matthew; Stevens, Bjorn; Schmidt, Hauke; Timmreck, Claudia

    2016-11-01

    Stratospheric sulfate aerosols from volcanic eruptions have a significant impact on the Earth's climate. To include the effects of volcanic eruptions in climate model simulations, the Easy Volcanic Aerosol (EVA) forcing generator provides stratospheric aerosol optical properties as a function of time, latitude, height, and wavelength for a given input list of volcanic eruption attributes. EVA is based on a parameterized three-box model of stratospheric transport and simple scaling relationships used to derive mid-visible (550 nm) aerosol optical depth and aerosol effective radius from stratospheric sulfate mass. Precalculated look-up tables computed from Mie theory are used to produce wavelength-dependent aerosol extinction, single scattering albedo, and scattering asymmetry factor values. The structural form of EVA and the tuning of its parameters are chosen to produce best agreement with the satellite-based reconstruction of stratospheric aerosol properties following the 1991 Pinatubo eruption, and with prior millennial-timescale forcing reconstructions, including the 1815 eruption of Tambora. EVA can be used to produce volcanic forcing for climate models which is based on recent observations and physical understanding but internally self-consistent over any timescale of choice. In addition, EVA is constructed so as to allow for easy modification of different aspects of aerosol properties, in order to be used in model experiments to help advance understanding of what aspects of the volcanic aerosol are important for the climate system.

  8. Organosulfate formation in biogenic secondary organic aerosol.

    PubMed

    Surratt, Jason D; Gómez-González, Yadian; Chan, Arthur W H; Vermeylen, Reinhilde; Shahgholi, Mona; Kleindienst, Tadeusz E; Edney, Edward O; Offenberg, John H; Lewandowski, Michael; Jaoui, Mohammed; Maenhaut, Willy; Claeys, Magda; Flagan, Richard C; Seinfeld, John H

    2008-09-11

    Organosulfates of isoprene, alpha-pinene, and beta-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 series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (alpha-pinene, beta-pinene, d-limonene, l-limonene, alpha-terpinene, gamma-terpinene, terpinolene, Delta(3)-carene, and beta-phellandrene) and three monoterpenes (alpha-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, alpha-pinene, beta-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate

  9. 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.

  10. Photochemical aging of secondary organic aerosols: effects on hygroscopic growth and CCN activation

    NASA Astrophysics Data System (ADS)

    Buchholz, A.; Mentel, Th. F.; Tillmann, R.; Schlosser, E.; Mildenberger, K.; Clauss, T.; Henning, S.; Kiselev, A.; Stratmann, F.

    2009-04-01

    Plant emitted volatile organic carbons (VOCs) are a major precursor of secondary organic aerosols (SOA), an important constituent of atmospheric aerosols. The precursors are oxidized via ozonolysis, photooxidation, or by NO3 and form aerosol particles. Due to further oxidation of the organic matter the composition of the SOA may age with time. This will also change the hygroscopic growth (HG) and cloud condensation nuclei (CCN) activation of the particles. In this study we generated and aged SOA in the SAPHIR chamber at the Research Centre Juelich under near atmospheric conditions: natural sunlight, low precursor and O3 concentrations, and long reaction times. As precursor we used a mixture of 5 monoterpenes (MT) or 5 MT with 2 sesquiterpenes which had been identified as major constituents of plant emissions in previous experiments. Concentrations ranged between 4 and 100 ppb MT and the total reaction time was 36h. HG was measured at RH=10-97% by a Hygroscopic Tandem Differential Analyser (HTDMA, FZ Juelich) and at RH=97-99% by the Leipzig Aerosol Cloud Interaction Simulator (LACIS-mobile, IfT Leipzig). The agreement between HTDMA and LACIS-mobile data was generally good. CCN properties were measured with a continuous flow CCN Counter from DMT. SOA particles generated on a sunny day were more hygroscopic and had a lower activation diameter (Dcrit) than SOA formed under cloudy conditions. With aging it became more hygroscopic and Dcrit decreased. Sunlight enhanced this effect. But the change in HG and Dcrit due to aging was less than the difference between SOA generated under different conditions (i.e. sunny or cloudy). We did not observe a dependence of the HG on the precursor concentration.

  11. Chamber studies to simulate secondary organic aerosol formation from the Deepwater Horizon oil spill

    NASA Astrophysics Data System (ADS)

    Daumit, K. E.; Carrasquillo, A. J.; Cross, E. S.; Hunter, J. F.; Bahreini, R.; Middlebrook, A. M.; De Gouw, J. A.; Williams, L. R.; Worsnop, D. R.; Kroll, J. H.

    2011-12-01

    Because atmospheric organic species are generally emitted from a large number of sources, over wide spatial and temporal scales, it is generally challenging to ascribe ambient organic aerosol (OA) to the oxidation of specific secondary organic aerosol (SOA) precursors. However, the Deepwater Horizon (DWH) oil spill (April 20-July 15, 2010), provided the unique circumstance of a large, well-defined source of gas-phase organics introduced into a relatively clean atmosphere. Here we describe a laboratory simulation of SOA formation downwind of the DWH spill, via the oxidation of South Louisiana-light (SL) crude oil by OH radicals in an environmental chamber. Intermediate and semi-volatile fractions of the SL crude oil are vaporized and oxidized by gas-phase OH radicals (formed from the photolysis of HONO). The chemical composition is monitored as a function of OH exposure. When OH exposures are approximately matched, laboratory-generated SOA and OA measured downwind of the oil spill exhibit extremely similar aerosol mass spectra, in strong support of the hypothesis that the OA measured downwind of the DWH oil spill was secondary in nature. More generally, this agreement indicates that in cases when SOA precursors are well-constrained, chamber experiments can reasonably reproduce key properties of ambient OA. Results of chamber studies on sub-fractions of the SL crude oil, aimed at identifying the classes of oil components most responsible for SOA formation, will be discussed.

  12. Can Secondary Organic Aerosol Formed in Atmospheric Simulation Chamber Be Continuously Aging?

    NASA Astrophysics Data System (ADS)

    Qi, L.; Nakao, S.; Malloy, Q.; Warren, B.; Cocker, D.

    2009-12-01

    Recent smog chamber studies have found that the oxidative processing (i.e. aging) of organic aerosol affects the chemical and physical properties for both aromatic and terpene aerosol precursors. Evidence from laboratory experiments suggests that organic aerosol can be converted from a hydrophobic to a hydrophilic state with aging. Several possible chemical mechanisms have been proposed based on chamber studies from other research groups e.g. heterogeneous reaction at the particle surface. Previous experiments conducted in the UC Riverside/CE-CERT environment chamber have shown little evidence of particle aging in terms of changes in hygroscopic properties from α-pinene dark ozonolysis systems. In this study, we simulate chemical aging of carbonaceous aerosol generated from α-pinene ozonolysis, α-pinene photooxidation and m-xylene photooxidation with an emphasis on the further uptake of oxidants, the evolution of aerosol hygroscopicity, particle density and elemental chemical composition (C:O:H) estimated from aerosol mass spectra to further investigate chamber secondary organic aerosol (SOA) aging behavior. Experimental results indicate that the SOA formed from photooxidation systems do get more functionalized as the oxidative age process go while dark ozonolysis SOA do not show aging phenomena within the normal chamber experiment duration.

  13. 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

  14. 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

  15. SOA formation by biogenic and carbonyl compounds: data evaluation and application.

    PubMed

    Ervens, Barbara; Kreidenweis, Sonia M

    2007-06-01

    The organic fraction of atmospheric aerosols affects the physical and chemical properties of the particles and their role in the climate system. Current models greatly underpredict secondary organic aerosol (SOA) mass. Based on a compilation of literature studies that address SOA formation, we discuss different parameters that affect the SOA formation efficiency of biogenic compounds (alpha-pinene, isoprene) and aliphatic aldehydes (glyoxal, hexanal, octanal, hexadienal). Applying a simple model, we find that the estimated SOA mass after one week of aerosol processing under typical atmospheric conditions is increased by a few microg m(-3) (low NO(x) conditions). Acid-catalyzed reactions can create > 50% more SOA mass than processes under neutral conditions; however, other parameters such as the concentration ratio of organics/NO(x), relative humidity, and absorbing mass are more significant. The assumption of irreversible SOA formation not limited by equilibrium in the particle phase or by depletion of the precursor leads to unrealistically high SOA masses for some of the assumptions we made (surface vs volume controlled processes).

  16. Sensitivity analysis of simulated SOA loadings using a variance-based statistical approach

    NASA Astrophysics Data System (ADS)

    Shrivastava, Manish; Zhao, Chun; Easter, Richard C.; Qian, Yun; Zelenyuk, Alla; Fast, Jerome D.; Liu, Ying; Zhang, Qi; Guenther, Alex

    2016-06-01

    We investigate the sensitivity of secondary organic aerosol (SOA) loadings simulated by a regional chemical transport model to seven selected model parameters using a modified volatility basis-set (VBS) approach: four involving emissions of anthropogenic and biogenic volatile organic compounds, anthropogenic semivolatile and intermediate volatility organics (SIVOCs), and NOx; two involving dry deposition of SOA precursor gases, and one involving particle-phase transformation of SOA to low volatility. We adopt a quasi-Monte Carlo sampling approach to effectively sample the high-dimensional parameter space, and perform a 250 member ensemble of simulations using a regional model, accounting for some of the latest advances in SOA treatments based on our recent work. We then conduct a variance-based sensitivity analysis using the generalized linear model method to study the responses of simulated SOA loadings to the model parameters. Analysis of SOA variance from all 250 simulations shows that the volatility transformation parameter, which controls whether or not SOA that starts as semivolatile is rapidly transformed to nonvolatile SOA by particle-phase processes such as oligomerization and/or accretion, is the dominant contributor to variance of simulated surface-level daytime SOA (65% domain average contribution). We also split the simulations into two subsets of 125 each, depending on whether the volatility transformation is turned on/off. For each subset, the SOA variances are dominated by the parameters involving biogenic VOC and anthropogenic SIVOC emissions. Furthermore, biogenic VOC emissions have a larger contribution to SOA variance when the SOA transformation to nonvolatile is on, while anthropogenic SIVOC emissions have a larger contribution when the transformation is off. NOx contributes less than 4.3% to SOA variance, and this low contribution is mainly attributed to dominance of intermediate to high NOx conditions throughout the simulated domain. However

  17. 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

  18. On the mixing and evaporation of secondary organic aerosol components.

    PubMed

    Loza, Christine L; Coggon, Matthew M; Nguyen, Tran B; Zuend, Andreas; Flagan, Richard C; Seinfeld, John H

    2013-06-18

    The physical state and chemical composition of an organic aerosol affect its degree of mixing and its interactions with condensing species. We present here a laboratory chamber procedure for studying the effect of the mixing of organic aerosol components on particle evaporation. The procedure is applied to the formation of secondary organic aerosol (SOA) from α-pinene and toluene photooxidation. SOA evaporation is induced by heating the chamber aerosol from room temperature (25 °C) to 42 °C over 7 h and detected by a shift in the peak diameter of the SOA size distribution. With this protocol, α-pinene SOA is found to be more volatile than toluene SOA. When SOA is formed from the two precursors sequentially, the evaporation behavior of the SOA most closely resembles that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA resembles a core of SOA from the initial precursor coated by a layer of SOA from the second precursor. Such a core-and-shell configuration of the organic aerosol phases implies limited mixing of the SOA from the two precursors on the time scale of the experiments, consistent with a high viscosity of at least one of the phases.

  19. 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.

  20. 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.

  1. Measuring Aerosols Generated Inside Armoured Vehicles Perforated by Depleted Uranium Ammunition

    SciTech Connect

    Parkhurst, MaryAnn

    2003-01-01

    In response to questions raised after the Gulf War about the health significance of exposure to depleted uranium (DU), a study was initiated to provide an improved scientific basis for assessment of possible health effects of soldiers in vehicles struck by these munitions. As part of this experimental 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 characterized. The aerosol sampling system designed for these tests consisted of filter cassettes, cascade impactors, a five-stage cyclone, and a moving filter. Aerosols collected were analyzed for uranium concentration and particle size distribution as a function of time. The aerosol samples were also analyzed for uranium oxide phases, particle morphology, and in vitro solubility. These data will provide input for use in future prospective and retrospective dose and health risk assessments of DU aerosols.

  2. 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.

  3. 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.

  4. 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.

  5. 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...

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

    SciTech Connect

    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.

  7. Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

    NASA Astrophysics Data System (ADS)

    Gordon, T. D.; Presto, A. A.; May, A. A.; Nguyen, N. T.; Lipsky, E. M.; Donahue, N. M.; Gutierrez, A.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

    2013-09-01

    The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter after three hours of oxidation inside the chamber at typical atmospheric oxidant levels. Therefore, the contribution of light duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photo-oxidizing exhaust from newer (LEV1 and LEV2) vehicles was only modestly lower (38%) than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions in non-methane organic gas emissions. These data suggest that a complex and non-linear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the time scale of these experiments, the mixture of organic vapors emitted by newer vehicles appear to be more efficient (higher yielding) in producing SOA than

  8. Influence of non-ideality on condensation to aerosol

    NASA Astrophysics Data System (ADS)

    Compernolle, S.; Ceulemans, K.; Müller, J.-F.

    2009-02-01

    Secondary organic aerosol (SOA) is a complex mixture of water and organic molecules. Its composition is determined by the presence of semi-volatile or non-volatile compounds, their saturation vapor pressure and activity coefficient. The activity coefficient is a non-ideality effect and is a complex function of SOA composition. In a previous publication, the detailed chemical mechanism (DCM) for α-pinene oxidation and subsequent aerosol formation BOREAM was presented. In this work, we investigate with this DCM the impact of non-ideality by simulating smog chamber experiments for α-pinene degradation and aerosol formation and taking the activity coefficient into account of all molecules in the aerosol phase. Several versions of the UNIFAC method are tested for this purpose, and missing parameters for e.g. hydroperoxides and nitrates are inferred from fittings to activity coefficient data generated using the SPARC model. Alternative approaches to deal with these missing parameters are also tested, as well as an activity coefficient calculation method based on Hansen solubility parameters (HSP). It turns out that for most experiments, non-ideality has only a limited impact on the interaction between the organic molecules, and therefore on SOA yields and composition, when water uptake is ignored. The reason is that often, the activity coefficient is on average close to 1 and, specifically for high-VOC experiments, partitioning is not very sensitive on the activity coefficient because the equilibrium is shifted strongly towards condensation. Still, for ozonolysis experiments with low amounts of volatile organic carbon (low-VOC), the UNIFAC parameterization of Raatikainen et al. leads to significantly higher SOA yields (by up to a factor 1.6) compared to the ideal case and to other parameterizations. Water uptake is model dependent, in the order: ideal > UNIFAC-Raatikainen > UNIFAC-Peng > UNIFAC-Hansen ≍ UNIFAC-Magnussen ≍ UNIFAC-Ming. In the absence of salt

  9. 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

  10. 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...

  11. Size distribution of chromate paint aerosol generated in a bench-scale spray booth.

    PubMed

    Sabty-Daily, Rania A; Hinds, William C; Froines, John R

    2005-01-01

    Spray painters are potentially exposed to aerosols containing hexavalent chromium [Cr(VI)] via inhalation of chromate-based paint sprays. Evaluating the particle size distribution of a paint spray aerosol, and the variables that may affect this distribution, is necessary to determine the site and degree of respiratory deposition and the damage that may result from inhaled Cr(VI)-containing paint particles. This study examined the effect of spray gun atomization pressure, aerosol generation source and aerosol aging on the size distribution of chromate-based paint overspray aerosols generated in a bench-scale paint spray booth. The study also determined the effect of particle bounce inside a Marple personal cascade impactor on measured size distributions of paint spray aerosols. Marple personal cascade impactors with a modified inlet were used for sample collection. The data indicated that paint particle bounce did not occur inside the cascade impactors sufficiently to affect size distribution when using uncoated stainless steel or PVC substrate sampling media. A decrease in paint aerosol mass median aerodynamic diameter (MMAD) from 8.2 to 7.0 mum was observed as gun atomization pressure increased from 6 to 10 psi. Overspray aerosols were sampled at two locations in the spray booth. A downstream sampling position simulated the exposure of a worker standing between the painted surface and exhaust, a situation encountered in booths with multiple workers. The measured mean MMAD was 7.2 mum. The distance between the painted surface and sampler was varied to sample oversprays of varying ages between 2.8 and 7.7 s. Age was not a significant factor for determining MMAD. Overspray was sampled at a 90 degrees position to simulate a worker standing in front of the surface being painted with air flowing to the worker's side, a common situation in field applications. The resulting overspray MMAD averaged 5.9 mum. Direct-spray aerosols were sampled at ages from 5.3 to 11.7 s

  12. 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.

  13. 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

  14. 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

  15. SOA formation potential of emissions from soil and leaf litter.

    PubMed

    Faiola, Celia L; Vanderschelden, Graham S; Wen, Miao; Elloy, Farah C; Cobos, Douglas R; Watts, Richard J; Jobson, B Thomas; Vanreken, Timothy M

    2014-01-21

    Soil and leaf litter are significant global sources of small oxidized volatile organic compounds, VOCs (e.g., methanol and acetaldehyde). They may also be significant sources of larger VOCs that could act as precursors to secondary organic aerosol (SOA) formation. To investigate this, soil and leaf litter samples were collected from the University of Idaho Experimental Forest and transported to the laboratory. There, the VOC emissions were characterized and used to drive SOA formation via dark, ozone-initiated reactions. Monoterpenes dominated the emission profile with emission rates as high as 228 μg-C m(-2) h(-1). The composition of the SOA produced was similar to biogenic SOA formed from oxidation of ponderosa pine emissions and α-pinene. Measured soil and litter monoterpene emission rates were compared with modeled canopy emissions. Results suggest surface soil and litter monoterpene emissions could range from 12 to 136% of canopy emissions in spring and fall. Thus, emissions from leaf litter may potentially extend the biogenic emissions season, contributing to significant organic aerosol formation in the spring and fall when reduced solar radiation and temperatures reduce emissions from living vegetation.

  16. 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.

  17. 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.

  18. Direct radiative effect due to brownness in organic carbon aerosols generated from biomass combustion

    NASA Astrophysics Data System (ADS)

    Rathod, T. D.; Sahu, S. K.; Tiwari, M.; Pandit, G. G.

    2016-12-01

    We report the enhancement in the direct radiative effect due the presence of Brown carbon (BrC) as a part of organic carbon aerosols. The optical properties of organic carbon aerosols generated from pyrolytic combustion of mango tree wood (Magnifera Indica) and dung cake at different temperatures were considered. Mie codes were used to calculate absorption and scattering coefficients coupled with experimentally derived imaginary complex refractive index. The direct radiative effect (DRE) for sampled organic carbon aerosols was estimated using a wavelength dependent radiative transfer equation. The BrC DRE was estimated taking virtually non absorbing organic aerosols as reference. The BrC DRE from wood and dung cake was compared at different combustion temperatures and conditions. The BrC contributed positively to the direct top of the atmosphere radiative effect. Dung cake generated BrC aerosols were found to be strongly light absorbing as compared to BrC from wood combustion. It was noted that radiative effects of BrC from wood depended on its generation temperature and conditions. For BrC aerosols from dung cake such strong dependence was not observed. The average BrC aerosol DRE values were 1.53±0.76 W g-1 and 17.84±6.45 W g-1 for wood and dung cake respectively. The DRE contribution of BrC aerosols came mainly (67-90%) from visible light absorption though they exhibited strong absorption in shorter wavelengths of the UV-visible spectrum.

  19. 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.

  20. 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...

  1. 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...

  2. 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.

  3. 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.

  4. 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.

  5. Uncertainties in SOA simulations due to meteorological uncertainties in Mexico City during MILAGRO-2006 field campaign

    NASA Astrophysics Data System (ADS)

    Bei, N.; Li, G.; Molina, L. T.

    2013-05-01

    The purpose of the present study is to investigate the uncertainties in simulating secondary organic aerosol (SOA) in Mexico City metropolitan area (MCMA) due to meteorological initial uncertainties using the WRF-CHEM model through ensemble simulations. The simulated periods (24 and 29 March 2006) represent two typical meteorological episodes ("Convection-South" and "Convection-North", respectively) in the Mexico City basin during the MILAGRO-2006 field campaign. The organic aerosols are simulated using a non-traditional SOA model including the volatility basis-set modeling method and the contributions from glyoxal and methylglyoxal. Model results demonstrate that uncertainties in meteorological initial conditions have significant impacts on SOA simulations, including the peak time concentrations, the horizontal distributions, and the temporal variations. The ensemble spread of the simulated peak SOA at T0 can reach up to 4.0 μg m-3 during the daytime, which is around 35% of the ensemble mean. Both the basin wide wind speed and the convergence area affect the magnitude and the location of the simulated SOA concentrations inside the Mexico City basin. The wind speed, especially during the previous midnight and the following early morning, influences the magnitude of the peak SOA concentration through ventilation. The surface horizontal convergence zone generally determines the area with high SOA concentrations. The magnitude of the ensemble spreads may vary with different meteorological episodes but the ratio of the ensemble spread to mean does not change significantly.

  6. Uncertainties in SOA simulations due to meteorological uncertainties in Mexico City during MILAGRO-2006 field campaign

    NASA Astrophysics Data System (ADS)

    Bei, N.; Li, G.; Molina, L. T.

    2012-12-01

    The purpose of the present study is to investigate the uncertainties in simulating secondary organic aerosol (SOA) in Mexico City metropolitan area (MCMA) due to meteorological initial uncertainties using the WRF-CHEM model through ensemble simulations. The simulated periods (24 and 29 March 2006) represent two typical meteorological episodes ("Convection-South" and "Convection-North", respectively) in the Mexico City basin during the MILAGRO-2006 field campaign. The organic aerosols are simulated using a non-traditional SOA model including the volatility basis-set modeling method and the contributions from glyoxal and methylglyoxal. Model results demonstrate that uncertainties in meteorological initial conditions have significant impacts on SOA simulations, including the peak time concentrations, the horizontal distributions, and the temporal variations. The ensemble spread of the simulated peak SOA at T0 can reach up to 4.0 μg m-3 during the daytime, which is around 35% of the ensemble mean. Both the basin wide wind speed and the convergence area affect the magnitude and the location of the simulated SOA concentrations inside the Mexico City basin. The wind speed, especially during the previous midnight and the following early morning, influences the magnitude of the peak SOA concentration through ventilation. The surface horizontal convergence zone generally determines the area with high SOA concentrations. The magnitude of the ensemble spreads may vary with different meteorological episodes but the ratio of the ensemble spread to mean does not change significantly.

  7. Uncertainties in SOA simulations due to meteorological uncertainties in Mexico City during MILAGRO-2006 field campaign

    NASA Astrophysics Data System (ADS)

    Bei, N.; Li, G.; Molina, L. T.

    2012-07-01

    The purpose of the present study is to investigate the uncertainties in simulating secondary organic aerosol (SOA) in Mexico City metropolitan area (MCMA) due to meteorological initial uncertainties using the WRF-CHEM model through ensemble simulations. The simulated periods (24 and 29 March 2006) represent two typical meteorological episodes ("Convection-South" and "Convection-North", respectively) in the Mexico City basin during the MILAGRO-2006 field campaign. The organic aerosols are simulated using a non-traditional SOA model including the volatility basis-set modeling method and the contributions from glyoxal and methylglyoxal. Model results demonstrate that uncertainties in meteorological initial conditions have significant impacts on SOA simulations, including the peak time concentrations, the horizontal distributions, and the temporal variations. The ensemble spread of the simulated peak SOA at T0 can reach up to 4.0 µg m-3 during the daytime, which is around 35% of the ensemble mean. Both the basin wide wind speed and the convergence area affect the magnitude and the location of the simulated SOA concentrations inside the Mexico City basin. The wind speed, especially during the previous midnight and the following early morning, influences the magnitude of the peak SOA concentration through ventilation. The surface horizontal convergence zone generally determines the area with high SOA concentrations. The magnitude of the ensemble spreads may vary with different meteorological episodes but has same significance compared to the ensemble mean.

  8. Possibility of blood and hepatitis B contamination through aerosols generated during debonding procedures.

    PubMed

    Toroglu, Mustafa Serdar; Bayramoglu, Ozlem; Yarkin, Fugen; Tuli, Abdullah

    2003-10-01

    The primary purpose of this study was to investigate the presence of blood or blood elements in aerosols generated during the debonding procedures. The presence of three hepatitis B carriers in the study group led us to investigate the possibility of hepatitis B virus (HBV) contamination through aerosols, which was the secondary purpose of the study. The study group consisted of 26 patients who had a mean age of 16 +/- 2 years. Collection of aerosol samples was done using a saliva ejector that fit on the handle of the high-speed dental instrument and was attached to a mobile evacuator. A second evacuator was used to remove and collect excess fluid accumulated in the patient's mouth. The guaiac method was used to investigate the presence of occult blood in aerosol and in excess fluid samples. Serum, excess fluid, and aerosol samples of three hepatitis B carriers were tested by enzyme-linked immunosorbent assay for detecting hepatitis B surface antigen (HBsAg) and by polymerase chain reaction for detecting HBV-deoxyribonucleic acid (DNA). Blood was found in all the aerosols and in excess fluid samples. HBsAg was detected in excess fluid samples of the two hepatitis B carriers, whereas HBV-DNA was detected in only one of the excess fluid samples. HBsAg and HBV-DNA were detected in aerosol sample of only one hepatitis B carrier. The results of this study showed that aerosols generated during the debonding procedure should always be considered as potential hazards to health.

  9. 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...

  10. 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/...

  11. Aerosol generation and circulation in the shore zone of a Large Alpine lake - 2 - Aerosol distributions over Lake Tahoe, CA

    NASA Astrophysics Data System (ADS)

    VanCuren, R.; Pederson, J.; Lashgari, A.; Dolislager, L.; McCauley, E.

    2012-01-01

    The temporal, spatial, and size-distribution patterns of particles in ambient air over 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 to the surface of the lake. 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 and particle emissions driven by cycles of human activity near the shore. These effects were observed to be highly localized. Highest concentrations were found just offshore from urbanized areas, especially shoreline centers of activity; lowest concentrations were found along undeveloped shoreline; low-to-intermediate concentrations were measured over the middle areas of the lake. The on-lake data reported here indicate that aerosols over the lake, and thus dry deposition to the lake, are dominated by the same processes that control onshore emissions, and that the impact is strongest in the near shore areas of the lake.

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

    DOE PAGES

    Lambe, A. T.; Chhabra, P. S.; Onasch, T. B.; ...

    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

  13. A novel micropump droplet generator for aerosol drug delivery: Design simulations.

    PubMed

    Su, Guoguang; Longest, P Worth; Pidaparti, Ramana M

    2010-11-19

    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.

  14. 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

  15. 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.

  16. Contributions of toluene and alpha-pinene to SOA formed in an irradiated toluene/alpha-pinene/NO(x)/ air mixture: comparison of results using 14C content and SOA organic tracer methods.

    PubMed

    Offenberg, John H; Lewis, Charles W; Lewandowski, Michael; Jaoui, Mohammed; Kleindienst, Tadeusz E; Edney, Edward O

    2007-06-01

    An organic tracer method, recently proposed for estimating individual contributions of toluene and alpha-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydrocarbon, toluene, and the biogenic monoterpene, alpha-pinene, was irradiated in air in the presence of NO(x) to form SOA. The contributions of toluene and alpha-pinene to the total SOA concentration, calculated using the organic tracer method, were compared with those obtained with a more direct 14C content method. In the study, SOA to SOC ratios of 2.07 +/- 0.08 and 1.41 +/- 0.04 were measured for toluene and (alpha-pinene SOA, respectively. The individual tracer-based SOA contributions of 156 microg m(-3) for toluene and 198 microg m(-)3 for alpha-pinene, which together accounted for 82% of the gravimetrically determined total SOA concentration, compared well with the 14C values of 182 and 230 microg m(-3) measured for the respective SOA precursors. While there are uncertainties associated with the organic tracer method, largely due to the chemical complexity of SOA forming chemical mechanisms, the results of this study suggest the organic tracer method may serve as a useful tool for determining whether a precursor hydrocarbon is a major SOA contributor.

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

    DOE PAGES

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; ...

    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

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

    DOE PAGES

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; ...

    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

  19. 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.

  20. 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.

  1. 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.

  2. Enhancement of the deposition of ultrafine secondary organic aerosols by the negative air ion and the effect of relative humidity.

    PubMed

    Yu, Kuo-Pin

    2012-11-01

    Deposition is an important process for the removal of aerosol particles. Negative air ion (NAI) generators can charge the ultrafine airborne particles and enhance their deposition rate. However, many NAI generators may also emit ozone and increase the concentration of particles in the presence of biogenic volatile organic compounds owing to the secondary organic aerosol (SOA) production. To validate the effectiveness of NAI generator the authors investigated the enhancement effect of an NAI generator on the deposition of the ultrafine SOAs generated from the ozonolysis of d-limonene in a test chamber under controlled ventilation rate and relative humidity (RH). The experimental results demonstrated that compared with other effects, including the gravity, particle eddy diffusion, and the Brownian diffusion, the effect of NAIs is the most dominate one on the deposition of SOA particles onto the wall surface in the near-wall region (<1 cm away from the wall). According to these experiments, the tested NAI generator could efficiently enhance the deposition rate by an enhancement factor ranging from 8.17 +/- 0.38 to 25.3 +/- 1.1, with a low ozone production rate. This NAI generator had better performance on the deposition of the SOAs with smaller particle sizes and it performed even better under higher RH. The enhancement effect of the NAI generator was related to its high NAI production and electric field strength.

  3. 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.

  4. 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

  5. Computer-automated silica aerosol generator and animal inhalation exposure system.

    PubMed

    McKinney, Walter; Chen, Bean; Schwegler-Berry, Diane; Frazer, Dave G

    2013-06-01

    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 20 mg/m(3), for durations lasting up to 8 h. 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/m(3) 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 <10 min during the beginning phase of an exposure. This exposure system provided a highly automated tool for conducting inhalation toxicology studies involving silica particles.

  6. New liquid aerosol generation devices: systems that force pressurized liquids through nozzles.

    PubMed

    Geller, David E

    2002-12-01

    Over the past few decades, aerosol delivery devices have been relatively inefficient, wasteful, and difficult for patients to use. These drawbacks have been tolerated because the drugs available for inhalation have wide therapeutic margins and steep dose-response curves at low doses. Recently several forces have converged to drive innovation in the aerosol device industry: the ban on chlorofluorocarbon propellants in metered-dose inhalers, the need for more user-friendly devices, and the invention of expensive inhalable therapies for topical and systemic lung delivery. Numerous devices are in development to improve the efficiency, ease of use, and reproducibility of aerosol delivery to the lung, including systems that force liquid through a nozzle to form the aerosol cloud. The Respimat is a novel, compact, propellant-free, multi-dose inhaler that employs a spring to push drug solution through a nozzle, which generates a slow-moving aerosol. Deposition studies show that the Respimat can deliver 39-44% of a dose to the lungs. Clinical asthma and chronic obstructive pulmonary disease trials with bronchodilators show that the Respimat is 2-8 times as effective as a metered-dose inhaler. Respimat has been tested with bronchodilators and inhaled corticosteroids. The AERx device uses sophisticated electronics to deliver aerosol from a single-dose blister, using an integral, disposable nozzle array. The electronics control dose expression and titration, timing of aerosol generation with the breath, and provide feedback for proper inhalation technique. Lung deposition ranges from 50 to 80% of the loaded dose, with remarkable reproducibility. AERx has been tested with a variety of drugs, for both topical and systemic delivery, including rhDNase (dornase alfa), insulin, and opioids. These novel devices face competition from other technologies as well as financial and regulatory hurdles, but they both offer a marked improvement in the efficiency of pulmonary drug delivery.

  7. 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).

  8. Lake spray aerosol generation: a method for producing representative particles from freshwater wave breaking

    NASA Astrophysics Data System (ADS)

    May, Nathaniel W.; Axson, Jessica L.; Watson, Alexa; Pratt, Kerri A.; Ault, Andrew P.

    2016-09-01

    Wave-breaking action in bodies of freshwater produces atmospheric aerosols via a similar mechanism to sea spray aerosol (SSA) from seawater. The term lake spray aerosol (LSA) is proposed to describe particles formed by this mechanism, which have been observed over the Laurentian Great Lakes. Though LSA has been identified from size distribution measurements during a single measurement campaign, no measurements of LSA composition or relationship to bubble-bursting dynamics have been conducted. An LSA generator utilizing a plunging jet, similar to many SSA generators, was constructed for the generation of aerosol from freshwater samples and model salt solutions. To evaluate this new generator, bubble and aerosol number size distributions were measured for salt solutions representative of freshwater (CaCO3) and seawater (NaCl) at concentrations ranging from that of freshwater to seawater (0.05-35 g kg-1), synthetic seawater (inorganic), synthetic freshwater (inorganic), and a freshwater sample from Lake Michigan. Following validation of the bubble and aerosol size distributions using synthetic seawater, a range of salt concentrations were investigated. The systematic studies of the model salts, synthetic freshwater, and Lake Michigan sample indicate that LSA is characterized by a larger number size distribution mode diameter of 300 nm (lognormal), compared to seawater at 110 nm. Decreasing salt concentrations from seawater to freshwater led to greater bubble coalescence and formation of larger bubbles, which generated larger particles and lower aerosol number concentrations. This resulted in a bimodal number size distribution with a primary mode (180 ± 20 nm) larger than that of SSA, as well as a secondary mode (46 ± 6 nm) smaller than that of SSA. This new method for studying LSA under isolated conditions is needed as models, at present, utilize SSA parameterizations for freshwater systems, which do not accurately predict the different size distributions observed

  9. 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...

  10. 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

  11. 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...

  12. 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...

  13. 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 ...

  14. 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.

  15. Formation of Secondary Organic Aerosol from Non-traditional Intermediate Volatility Organic Compounds

    NASA Astrophysics Data System (ADS)

    Donahue, N. M.; Presto, A. A.; Robinson, A. L.; Kroll, J. H.; Worsnop, D. R.

    2009-04-01

    Secondary organic aerosol (SOA) formation from 'traditional' precursors such as monoterpenes and alkylbenzenes has received substantial attention for the past decade. These traditional sources have relatively high emissions into the atmosphere, but they are also relatively volatile. As a consequence, the oxidation products from those precursors must be more than one million times less volatile in order to form SOA. We have recently begun to investigate the role of 'nontraditional' SOA precursors with much lower volatility than the traditional precursors. These intermediate volatility organic compounds (IVOC) are typically co-emitted with traditional primary organic aerosol (POA) sources at elevated temperatures, including biomass burning and internal combustion processes. While their emissions are much lower than the traditional precursors, the volatility reduction required of the reaction products is much less drastic, making high-yield SOA formation much more likely. Here we describe the formation of SOA from two precursors in the CMU environmental chamber - heptadecane and pentacosane - under high- and low-NOx conditions. Analysis of the resulting SOA with a high-resolution aerosol mass spectrometer coupled to a thermodenuder allows us to asses the oxidation state and volatility distribution of the condensible products, revealing a high degree of oxidation under high-NOx conditions where most of the organics remain in the vapor phase for at least 2 generations of oxidation chemistry, but a lower (though progressive) degree of oxidation under other conditions. These results will be place in context using a two-dimensional volatility basis set that incorporates both the volatility distribution and oxidation state of complex organic mixtures.

  16. 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

  17. 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.

  18. [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.

  19. Measuring Aerosols Generated Inside Armoured Vehicles Perforated by Depleted Uranium Ammunition

    SciTech Connect

    Parkhurst, MaryAnn )

    2003-01-01

    In response to questions raised after the Gulf War about the health significance of exposure to depleted uranium (DU), the U.S. Department of Defense initiated a study designed to provide an improved scientific basis for assessment of possible health effects of 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 characterized. A robust sampling system was designed to collect aerosols in this difficult environment and to monitor continuously the sampler flow rates. Interior 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. These data 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.

  20. Characteristics and radiative impact of the aerosol generated by the Canberra firestorm of January 2003

    NASA Astrophysics Data System (ADS)

    Mitchell, R. M.; O'Brien, D. M.; Campbell, S. K.

    2006-01-01

    The extensive fires in southeastern Australia in January 2003 culminated in the Canberra firestorm of 18 January. The fires generated a pall of smoke that blanketed the Canberra area for the following week and affected the region for most of the following month. Analysis of Sun photometer data shows that aerosol optical depths τ500 > 7 were observed during the week following the firestorm. During the subsequent month the smoke aerosol dispersed, although background conditions (τ500 < 0.1) did not return until after significant rain in late February. Analysis of aerosol optical properties retrieved from sky radiance scans shows remarkably high single scattering albedo (ϖ440 ˜ 0.96) with only a small depression evident in the week following the firestorm. This indicates that the aerosols were significantly less absorbing than would be expected from smoke freshly generated by flaming combustion, possibly a result of inefficient combustion due to the extreme intensity of the fire, and marks them out as quite distinct from the more absorbing biomass burning aerosols encountered in the savannas of tropical Australia. The high single scattering albedo gave rise to mean radiative forcings of -50 W m-2 at the top of the atmosphere and -172 W m-2 at the surface during the week following the firestorm. Maximum heating rates are depressed by a factor of two at ϖ440 = 0.96 compared with ϖ440 = 0.88. Nevertheless, for plausible atmospheric profiles the large optical depths caused heating rates peaking at more than 10 K/day near the top of the smoke layer. The layer stabilized the lower troposphere through a combination of reduced surface heating and a positive gradient in heating rate through most of the layer. The enhanced stability suppressed surface temperatures and winds during the week following the firestorm, reducing the risk of renewed fire danger, and suggesting a useful role for aerosol effects in weather prediction models.

  1. Online Measurements and Modeling of Isoprene Photo-oxidation Products: Insights from the Laboratory and SOAS Field Campaign

    NASA Astrophysics Data System (ADS)

    D'Ambro, E.; Lopez-Hilfiker, F.; Mohr, C.; Gaston, C.; Lee, B. H.; Liu, J.; Lutz, A.; Hallquist, M.; Shilling, J.; Gold, A.; Zhang, Z.; Surratt, J. D.; Thornton, J. A.; Schobesberger, S.

    2015-12-01

    Isoprene, the most abundant non-methane volatile organic compound emitted globally, has the potential to produce large quantities of secondary organic aerosol (SOA) with implications for climate, air quality, and human health. However, much remains unknown about the mechanisms and processes that lead to isoprene derived SOA. We present measurements and modeling of a suite of newly detected compounds from isoprene oxidation from laboratory studies at the Pacific Northwest National Laboratory (PNNL) as well as in the atmosphere from the Southern Oxidant and Aerosol Study (SOAS) field campaign. Measurements were made with a high resolution time of flight chemical ionization mass spectrometer utilizing iodide adduct ionization coupled to the Filter Inlet for Gas and AEROsol (FIGAERO) for the simultaneous sampling of the gas and aerosol phases. In the PNNL chamber, isoprene photo-oxidation with dry neutral seed and IEPOX multiphase chemistry on aqueous particles was investigated at a variety of atmospherically relevant conditions. Isoprene photo-oxidation under high HO2 produced unexpectedly substantial SOA at a yield similar to but from a distinctly different mechanism than that from IEPOX uptake. The high HO2 chemistry also resulted in di hydroxy di hydroperoxides as a dominant component of the aerosol. By utilizing the same instrument and ion chemistry during both field and chamber experiments, together with an MCM-based model, we assess the degree to which the different mechanisms are operable in the atmosphere and relevant aerosol chemical and physical properties of the SOA such as volatility and oligomer content.

  2. How Important Is Organic Aerosol Hygroscopicity to Aerosol Indirect Forcing?

    SciTech Connect

    Liu, Xiaohong; Wang, Jian

    2010-12-07

    Organics are among the most abundant aerosol components in the atmosphere. However, there are still large uncertainties with emissions of primary organic aerosol (POA) and volatile organic compounds (VOCs) (precursor gases of secondary organic aerosol, SOA), formation and yield of SOA, and chemical and physical properties (e.g., hygroscopicity) of POA and SOA. All these may have significant impacts on aerosol direct and indirect forcing estimated from global models. In this study a modal aerosol module (MAM) in the NCAR Community Atmospheric Model (CAM) is used to examine sensitivities of aerosol indirect forcing to hygroscopicity (“κ” value) of POA and SOA. Our model simulation indicates that in the present-day condition changing “κ” value of POA from 0 to 0.1 increases the number concentration of cloud condensational nuclei (CCN) at supersaturation S=0.1% by 40-60% over the POA source regions, while changing “κ” value of SOA by ±50% (from 0.14 to 0.07 and 0.21) changes the CCN within 30%. Changes in the in-cloud droplet number concentrations (CDNC) are within 20% in most locations on the globe with the above changes in “κ” value of POA and SOA. Global annual mean anthropogenic aerosol indirect forcing (AIF) between present-day (PD) and pre-industrial (PI) conditions change by 0.4 W m-2 with the control run of -1.3 W m-2. AIF reduces with the increase hygroscopicity of organic aerosol, indicating the important role of natural organic aerosol in buffering the relative change of CDNC from PI to PD.

  3. 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

  4. 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.

  5. 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

    2016-04-23

    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.

  6. SOA formation from the atmospheric oxidation of 2-methyl-3-buten-2-ol and its implications for PM2.5

    NASA Astrophysics Data System (ADS)

    Jaoui, M.; Kleindienst, T. E.; Offenberg, J. H.; Lewandowski, M.; Lonneman, W. A.

    2012-02-01

    The formation of secondary organic aerosol (SOA) generated by irradiating 2-methyl-3-buten-2-ol (MBO) in the presence and/or absence of NOx, H2O2, and/or SO2 was examined. Experiments were conducted in smog chambers operated in either dynamic or static mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The structural characterization of gas and particulate products was investigated using BSTFA, BSTFA + PFBHA, and DNPH derivatization techniques followed by GC-MS and liquid chromatography analysis. This analysis showed the occurrence of more than 68 oxygenated organic compounds in the gas and particle phases, 28 of which were tentatively identified. The major components observed include 2,3-dihydroxyisopentanol (DHIP), 2-hydroxy-2-oxoisopentanol, 2,3-dihydroxy-3-methylbutanal, 2,3-dihydroxy-2-methylsuccinic acid, 2-hydroxy-2-methylpropanedioic acid, acetone, glyoxal, methylglyoxal, glycolaldehyde, and formaldehyde. Most of these oxygenated compounds were detected for the first time in this study. While measurements of the gas-phase photooxidation products have been made, the focus of this work has been an examination of the particle phase. SOA from some experiments was analyzed for the organic mass to organic carbon ratio (OM/OC), the effective enthalpy of vaporization (ΔHvapeff), and the aerosol yield. Additionally, aerosol size, volume, and number concentrations were measured by a Scanning Mobility Particle Sizer coupled to a Condensation Particle Counter system. The OM/OC ratio was 2.1 in the MBO/H2O2 system. The ΔHvapeff was 41 kJ mol-1, a value similar to that of isoprene SOA. The laboratory SOA yield measured in this study was 0.7% in MBO/H2O2 for an aerosol mass of 33 μg m-3. Secondary organic aerosol was found to be negligible under conditions with oxides of nitrogen (NOx) present. Time profiles and proposed reaction schemes are provided for selected compounds. The contribution of SOA products

  7. [Study on transformation mechanism of SOA from biogenic VOC under UV-B condition].

    PubMed

    Li, Ying-Ying; Li, Xiang; Chen, Jian-Min

    2011-12-01

    A laboratory study was carried out to investigate the biogenic volatile organic compounds (BVOC) in a lab-made glass chamber. The secondary organic aerosol (SOA) products can be detected under the UV photooxidation of BVOC. Pelargonium x Citrenella was chosen as the target plant in this research because it can release a large amount of BVOCs. The predominant 7 alkene and ketol compounds were detected by using solid phase microextraction (SPME) sampling and gas chromatography/mass spectrometry (GC/MS) analysis. The photochemical experiment indicated that these BVOC can be rapidly oxidized into SOA under UV-B irradiation. A tandem differential mobility analyzer (TDMA) was used to measure the size distribution and the hygroscopicity of the SOA. The particle diameter was in the range of 50 nm to 320 nm. The high hygroscopicity of SOA was also obtained and the size increased from 1.05 to 1.11 during the wet experiment.

  8. High-NOx Photooxidation of n-Dodecane: Temperature Dependence of SOA Formation.

    PubMed

    Lamkaddam, Houssni; Gratien, Aline; Pangui, Edouard; Cazaunau, Mathieu; Picquet-Varrault, Bénédicte; Doussin, Jean-François

    2017-01-03

    The temperature and concentration dependence of secondary organic aerosol (SOA) yields has been investigated for the first time for the photooxidation of n-dodecane (C12H26) in the presence of NOx in the CESAM chamber (French acronym for "Chamber for Atmospheric Multiphase Experimental Simulation"). Experiments were performed with and without seed aerosol between 283 and 304.5 K. In order to quantify the SOA yields, a new parametrization is proposed to account for organic vapor loss to the chamber walls. Deposition processes were found to impact the aerosol yields by a factor from 1.3 to 1.8 between the lowest and the highest value. As with other photooxidation systems, experiments performed without seed and at low concentration of oxidant showed a lower SOA yield than other seeded experiments. Temperature did not significantly influence SOA formation in this study. This unforeseen behavior indicates that the SOA is dominated by sufficiently low volatility products for which a change in their partitioning due to temperature would not significantly affect the condensed quantities.

  9. 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.

  10. 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.

  11. Cloud droplet activity changes of soot aerosol upon smog chamber ageing

    NASA Astrophysics Data System (ADS)

    Wittbom, C.; Pagels, J. H.; Rissler, J.; Eriksson, A. C.; Carlsson, J. E.; Roldin, P.; Nordin, E. Z.; Nilsson, P. T.; Swietlicki, E.; Svenningsson, B.

    2014-04-01

    Particles containing soot, or black carbon, are generally considered to contribute to global warming. However, large uncertainties remain in the net climate forcing resulting from anthropogenic emissions of black carbon (BC), to a large extent due to the fact that BC is co-emitted with gases and primary particles, both organic and inorganic, and subject to atmospheric ageing processes. In this study, diesel exhaust particles and particles from a flame soot generator spiked with light aromatic secondary organic aerosol (SOA) precursors were processed by UV-radiation in a 6 m3 Teflon chamber in the presence of NOx. The time-dependent changes of the soot nanoparticle properties were characterised using a Cloud Condensation Nuclei Counter, an Aerosol Particle Mass Analyzer and a Soot Particle Aerosol Mass Spectrometer. The results show that freshly emitted soot particles do not activate into cloud droplets at supersaturations ≤ 2%, i.e. the black carbon core coated with primary organic aerosol (POA) from the exhaust is limited in hygroscopicity. Before the onset of UV radiation it is unlikely that any substantial SOA formation is taking place. An immediate change in cloud-activation properties occurs at the onset of UV exposure. This change in hygroscopicity is likely attributed to SOA formed from intermediate volatile organic compounds (IVOC) in the diesel engine exhaust. The change of cloud condensation nuclei (CCN) properties at the onset of UV radiation implies that the lifetime of soot particles in the atmosphere is affected by the access to sunlight, which differs between latitudes. The ageing of soot particles progressively enhances their ability to act as cloud condensation nuclei, due to changes in: (I) organic fraction of the particle, (II) chemical properties of this fraction (POA or SOA), (III) particle size, and (IV) particle morphology. Applying κ-Köhler theory, using a κSOA value of 0.13 (derived from independent input parameters describing the

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. Secondary organic aerosol from polycyclic aromatic hydrocarbons in Southeast Texas

    NASA Astrophysics Data System (ADS)

    Zhang, Hongliang; Ying, Qi

    2012-08-01

    Recent chamber studies show that low-volatility gas phase precursors such as polycyclic aromatic hydrocarbons (PAHs) can be a significant source of secondary organic aerosol (SOA). In this work, formation of SOA from the photo-oxidation products of PAHs is added to the SOA modeling framework of the Community Multiscale Air Quality (CMAQ) model to determine the regional distribution of SOA products from PAHs (PAH-SOA) and the contributions from sources in Southeast Texas during the Texas Air Quality Study 2006 (TexAQS 2006). Results show that PAHs released from anthropogenic sources can produce SOA mass as much as 10% of that from the traditional light aromatics or approximately 4% of total anthropogenic SOA. In areas under the influence of wildfire emissions, the amount of PAH-SOA can be as much as 50% of the SOA from light aromatics. A source-oriented modeling framework is adopted to determine the major sources of PAH-SOA by tracking the emitted PAHs and their oxidation products in the gas and aerosol phases from different sources separately. Among the eight sources (vehicles, solvent utilization, residential wood, industries, natural gas combustion, coal combustion, wildfire and other sources) that are tracked in the model, wildfire, vehicles, solvent and industries are the major sources of PAH-SOA. Coal and natural gas combustion appear to be less important in terms of their contributions to PAH-SOA.

  17. [Comparative studies of particle distribution range of aerosol cromolyn sodium generated by MDI systems].

    PubMed

    Gradoń, L; Sosnowski, T R

    1999-05-01

    Particles size distribution of the sodium cromoglycate preparations: CROPOZ PLUS and CROMOGEN EB generated with MDI and for under-pressure releasing methods were measured. Results of measurements indicate a significant repeatability of each sample properties. An average contribution of mass of the respirable fraction for both aerosolized pharmaceuticals is in the range of 40% of the generated dose. CROMOGEN EB with optimizer (spacer) gives a higher contribution of the respirable fraction--up to 50% of dose, with simultaneous lower value of the released mass of aerosol. Particles size distribution of CROPOZ PLUS within a respirable fraction indicates an efficient penetration and deposition of particles in the upper, central and peripheral parts of tracheobronchial tree (TB). High contribution of submicron particles of CROMOGEN EB with optimizer gives efficient penetration and deposition of these particles in the lungs.

  18. On the implications of aerosol liquid water and phase separation for organic aerosol mass

    NASA Astrophysics Data System (ADS)

    Pye, Havala O. T.; Murphy, Benjamin N.; Xu, Lu; Ng, Nga L.; Carlton, Annmarie G.; Guo, Hongyu; Weber, Rodney; Vasilakos, Petros; Wyat Appel, K.; Hapsari Budisulistiorini, Sri; Surratt, Jason D.; Nenes, Athanasios; Hu, Weiwei; Jimenez, Jose L.; Isaacman-VanWertz, Gabriel; Misztal, Pawel K.; Goldstein, Allen H.

    2017-01-01

    Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM / OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM / OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH > SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM / OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were highly water soluble and expected to contribute to water-soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night, but additional improvements in daytime organic aerosol are needed to close the model-measurement gap. When taking into account deviations from ideality, including both inorganic (when RH > SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from

  19. System for the continuous generation of phosphorus aerosol from red phosphorus - butyl rubber

    SciTech Connect

    Holmberg, R.W.; Moneyhun, J.H.

    1982-01-01

    Laboratory studies of Army smokes and obscurants often require that they be produced at known and uniform concentrations for a long period of time, and with properties that are comparable to those produced by the obscurant system in the field. In support of the toxicology program of the US Army Medical and Bioengineering Research and Development Laboratory, Fort Detrick, MD, we describe an extrusion-combustion generator that generates the phosphoric acid aerosol from a red phosphorus-butyl rubber (RPBR) formulation such as is deployed in a L8Al smoke grenade. The generator has been designed to produce aerosols of concentration from 0.25 to 5 g/m/sup 3/ in a one cubic meter chamber with an air throughput of 400 l/m, but can easily be adapted to other conditions. The generator design is based on the property that RPBR, suitably softened, can be extruded through a small orifice. The extruding filament burns, and the aerosol is produced, at a rate determined by the velocity of the filament emergence. In our implementation, the RPBR is softened by vapor phase absorption of hexane to 4% by weight. The material is compressed to form a cylindrical billet (1/2 inch diameter) and loaded into the extrusion cylinder for extrusion through a 2 mm orifice. A conventional hydraulic ram is used to provide the extrusion pressure. Hydraulic fluid is fed to it from a precision, high pressure metering pump. This fluid flow determines the rate at which the RPBR emerges from the dye. The filament is electrically ignited to burn in the air stream. It is sheathed in nitrogen gas as it emerges from the dye to prevent back combustion and to define the burning area. The aerosol concentration is monitored continuously using light scattering particle detectors whose response is linear with concentration.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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...

  5. SOA formation from the atmospheric oxidation of 2-methyl-3-buten-2-ol and its implications for PM2.5

    NASA Astrophysics Data System (ADS)

    Jaoui, M.; Kleindienst, T. E.; Offenberg, J. H.; Lewandowski, M.; Lonneman, W. A.

    2011-08-01

    The formation of secondary organic aerosol (SOA) generated by irradiating 2-methyl-3-buten-2-ol (MBO) in the presence and/or absence of NOx, H2O2, and/or SO2 was examined. Experiments were conducted in smog chambers operated either in dynamic or steady-state mode. A filter/denuder sampling system was used for simultaneously collecting gas and particle phase products. The structural characterization of gas and particulate products was investigated using BSTFA, BSTFA + PFBHA, and DNPH derivatization techniques followed by GC-MS and liquid chromatography analysis. This analysis showed the occurrence of more than 68 oxygenated organic compounds in the gas and particle phase, 28 of which were identified. The major components observed include 2,3-dihydroxyisopentanol (DHIP), 2-hydroxy-2-oxoisopentanol, 2,3-dihydroxy-3-methylbutanal, 2,3-dihydroxy-2-methylsuccinic acid, 2-hydroxy-2-methylpropanedioic acid, acetone, glyoxal, methylglyoxal, glycolaldehyde, and formaldehyde. Most of these oxygenated compounds were detected for the first time in this study. While measurements of the gas phase photooxidation products have been made, the focus of this work has been an examination of the particle phase. SOA from some experiments was analyzed for the organic mass to organic carbon ratio (OM/OC), the effective enthalpy of vaporization (ΔHvapeff), and the aerosol yield. Additionally, aerosol size, volume, and number concentrations were measured by a Scanning Mobility Particle Sizer coupled to a Condensation Particle Counter system. The OM/OC was found to be 2.1 in MBO/H2O2 system. The ΔHvapeff was 41 kJ mol-1, a value similar to that of isoprene SOA. The laboratory SOA yield measured in this study was found to be 0.7 % in MBO/H2O2 for an aerosol mass of 33 μg m-3. Time profiles and proposed reaction schemes are provided for selected compounds. The contribution of SOA products from MBO oxidation to ambient PM2.5 was investigated by analyzing a series of ambient PM2.5 samples

  6. 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.

  7. 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

    SciTech Connect

    Parkhurst, MaryAnn; 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.

  8. 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.

  9. Secondary organic aerosol formation from low-NO(x) photooxidation of dodecane: evolution of multigeneration gas-phase chemistry and aerosol composition.

    PubMed

    Yee, Lindsay D; Craven, Jill S; Loza, Christine L; Schilling, Katherine A; Ng, Nga Lee; Canagaratna, Manjula R; Ziemann, Paul J; Flagan, Richard C; Seinfeld, John H

    2012-06-21

    The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes.

  10. Rapid generation of protein aerosols and nanoparticles via surface acoustic wave atomization

    NASA Astrophysics Data System (ADS)

    Alvarez, Mar; Friend, James; Yeo, Leslie Y.

    2008-11-01

    We describe the fabrication of a surface acoustic wave (SAW) atomizer and show its ability to generate monodisperse aerosols and particles for drug delivery applications. In particular, we demonstrate the generation of insulin liquid aerosols for pulmonary delivery and solid protein nanoparticles for transdermal and gastrointestinal delivery routes using 20 MHz SAW devices. Insulin droplets around 3 µm were obtained, matching the optimum range for maximizing absorption in the alveolar region. A new approach is provided to explain these atomized droplet diameters by returning to fundamental physical analysis and considering viscous-capillary and inertial-capillary force balance rather than employing modifications to the Kelvin equation under the assumption of parametric forcing that has been extended to these frequencies in past investigations. In addition, we consider possible mechanisms by which the droplet ejections take place with the aid of high-speed flow visualization. Finally, we show that nanoscale protein particles (50-100 nm in diameter) were obtained through an evaporative process of the initial aerosol, the final size of which could be controlled merely by modifying the initial protein concentration. These results illustrate the feasibility of using SAW as a novel method for rapidly producing particles and droplets with a controlled and narrow size distribution.

  11. Formation and Processing of Secondary Organic Aerosol from Catechol as a Model for Atmospheric HULIS

    NASA Astrophysics Data System (ADS)

    Ofner, Johannes; Krüger, Heinz-Ulrich; Grothe, Hinrich; Zetzsch, Cornelius

    2010-05-01

    A particular fraction of the secondary organic aerosol (SOA) termed HUmic Like Substances (HULIS) attracted attention only recently in atmospheric aerosol, initiating a discourse about their aromaticity and other properties, such as reactivity and hygroscopicity. A major portion of HULIS originates from volatile organic compounds, which are formed by abiotic oxidation reactions involving mainly OH radicals, ozone, nitrogen oxides and possibly halogens. Subsequently, the particles provide surface for heterogeneous reactions with atmospheric trace gases. Thus, aerosol smog-chamber studies with appropriate precursors are needed to generate SOA with HULIS qualities in situ inside the smog chamber and study their possible interactions. Catechol and guaiacol were chosen as aromatic precursors for synthetic HULIS production. The SOA was produced in a 700 L aerosol smog chamber, equipped with a solar simulator. SOA formation from each precursor was investigated at simulated environmental conditions (humidity, light, and presence of oxidizers) and characterized with respect to HULIS properties by particle classifiers, Fourier Transform IR spectroscopy (by long-path absorption and attenuated total reflection), UV/VIS spectroscopy, high-resolution mass-spectroscopy and temperature-programmed-desorption mass-spectrometry. High-resolution imaging was obtained using Field Emission Gun Scanning Electron Microscopy (FEGSEM). After HULIS formation the aerosol particles were exposed to atmospheric halogen species to study their processing with those trace gases, released by sea salt-activation. Those investigations show that aromatic precursors like catechol and guaiacol are suitable to form synthetic HULIS for laboratory-scale measurements with physical and chemical properties described in literature. However, sunlight and relative humidity play a major role in particle production and composition of functional groups, which are the anchor points for heterogeneous atmospheric

  12. Kinetic analysis of competition between aerosol particle removal and generation by ionization air purifiers.

    PubMed

    Alshawa, Ahmad; Russell, Ashley R; Nizkorodov, Sergey A

    2007-04-01

    Ionization air purifiers are increasingly used to remove aerosol particles from indoor air. However, certain ionization air purifiers also emit ozone. Reactions between the emitted ozone and unsaturated volatile organic compounds (VOC) commonly found in indoor air produce additional respirable aerosol particles in the ultrafine (<0.1 microm) and fine (<2.5 microm) size domains. A simple kinetic model is used to analyze the competition between the removal and generation of particulate matter by ionization air purifiers under conditions of a typical residential building. This model predicts that certain widely used ionization air purifiers may actually increase the mass concentration of fine and ultrafine particulates in the presence of common unsaturated VOC, such as limonene contained in many household cleaning products. This prediction is supported by an explicit observation of ultrafine particle nucleation events caused by the addition of D-limonene to a ventilated office room equipped with a common ionization air purifier.

  13. 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.

  14. 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.

  15. Can secondary organic aerosol formed in an atmospheric simulation chamber continuously age?

    NASA Astrophysics Data System (ADS)

    Qi, Li; Nakao, Shunsuke; Malloy, Quentin; Warren, Bethany; Cocker, David R.

    2010-08-01

    This work investigates the oxidative aging process of SOA derived from select aromatic ( m-xylene) and biogenic (α-pinene) precursors within an environmental chamber. Simultaneous measurements of SOA hygroscopicity, volatility, particle density, and elemental chemical composition (C:O:H) reveal only slight particle aging for up to the first 16 h of formation. The chemical aging observed is consistent with SOA that is decreasing in volatility and increasing in O/C and hydrophilicity. Even after aging, the O/C (0.25 and 0.40 for α-pinene and m-xylene oxidation, respectively) was below the OOAI and OOAII ambient fractions measured by high-resolution aerosol mass spectra coupled with Positive Matrix Factorization (PMF). The rate of increase in O/C does not appear to be sufficient to achieve OOAI or OOAII levels of oxygenation within regular chamber experiment duration. No chemical aging was observed for SOA during dark α-pinene ozonolysis with a hydroxyl radical scavenger present. This finding is consistent with observations by other groups that SOA from this system is comprised of first generation products.

  16. Cloud condensation nucleus activity of secondary organic aerosol particles mixed with sulfate

    NASA Astrophysics Data System (ADS)

    King, Stephanie M.; Rosenoern, Thomas; Shilling, John E.; Chen, Qi; Martin, Scot T.

    2007-12-01

    The cloud condensation nucleus (CCN) activity of organic-sulfate particles was investigated using a steady-state environmental chamber. The organic component consisted of secondary organic aerosol (SOA) generated in the dark from 24 +/- 2 ppb α-pinene for conditions of 300 +/- 5 ppb ozone, 40 +/- 2% relative humidity, and 25 +/- 1°C, with the organic mass loading in the chamber ranging from 23 to 37 μg m-3. CCN analysis was performed for 80- to 150-nm particles having variable organic-sulfate volume fractions, which were estimated from the diameter of the organic-sulfate particle relative to that of the seed as well as independently from mass spectra. Critical supersaturation, which increased for greater SOA volume fraction and smaller particle diameter, was well predicted by a Köhler model having two components, one for ammonium sulfate and another for SOA. The entire data set could be successfully modeled by a single suite of effective chemical parameters for SOA. The results suggest that the effects of limited organic solubility in mixed SOA-sulfate particles may be reliably omitted in the treatment of cloud droplet formation.

  17. 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.

  18. 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.

  19. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols.

    PubMed

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-10-13

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

  20. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-10-01

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

  1. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

    PubMed Central

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-01-01

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks. PMID:27733773

  2. Updating CMAQ secondary organic aerosol properties relevant for aerosol water interactions

    EPA Science Inventory

    Properties of secondary organic aerosol (SOA) compounds in CMAQ are updated with state-of-the-science estimates from structure activity relationships to provide consistency among volatility, molecular weight, degree of oxygenation, and solubility/hygroscopicity. These updated pro...

  3. 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.

  4. Acid and organic aerosol coatings on magnetic nanoparticles increase iron concentrations in human airway epithelial cells.

    PubMed

    Ghio, Andrew J; Dailey, Lisa A; Richards, Judy H; Jang, Myoseon

    2009-07-01

    Numerous industrial applications for man-made nanoparticles have been proposed. Interactions of nanoparticles with agents in the atmosphere may impact human health. We tested the postulate that in vitro exposures of respiratory epithelial cells to airborne magnetic nanoparticles (MNP; Fe(3)O(4)) with and without a secondary organic aerosol (SOA) and an inorganic acid could affect iron homeostasis, oxidative stress, and interleukin (IL)-8 release. Cell iron concentrations were increased after exposures to MNP and values were further elevated with co-exposures to either SOA or inorganic acid. Increased expression of ferritin and elevated levels of RNA for DMT1, proteins for iron storage and transport respectively, followed MNP exposures, but values were significant for only those with co-exposures to inorganic acid and organic aerosols. Cell iron concentration corresponded to a measure of oxidative stress in the airway epithelial cells; MNP with co-exposures to SOA and inorganic acid increased both available metal and indices of oxidant generation. Finally, the release of a proinflammatory cytokine (i.e. IL-8) by the exposed cells similarly increased with cell iron concentration. We conclude that MNP can interact with a SOA and an inorganic acid to present metal in a catalytically reactive state to cultured respiratory cells. This produces an oxidative stress to affect a release of IL-8.

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

    DOE PAGES

    Hayes, P. L.; Carlton, A. G.; Baker, K. R.; ...

    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

  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.; 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

  7. 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

  8. Mapping PET-measured triamcinolone acetonide (TAA) aerosol distribution into deposition by airway generation.

    PubMed

    Lee, Z; Berridge, M S; Finlay, W H; Heald, D L

    2000-04-10

    The three dimensional (3D) distribution of inhaled drugs was measured using Positron Emission Tomography (PET) (Berridge, M.S, Muswick, G.J., Lee, Z., Leisure, G.L., Nelson, A.D., Muzic, R.F. Jr., Miraldi, F., Heald, D.L., 1997. PET evaluation of Azmacort(R) ([C-11]triamcinolone acetonide) dose administration. J. Nucl. Med. 38 (5) Suppl., 4-5). Data analysis was based upon regional ratios or penetration indices. To improve the analytical usefulness and objectivity, labeled drug from dynamic PET images was mapped into 23 airway generations following a general framework from a SPECT-based methodology (Fleming, J.S., Nassim, M.A., Hashish, A.H., Bailey, A.G. , Conway, J., Holgate, S., Halson, P., Moore, E., Martonen, T.B., 1995. Description of pulmonary deposition of radiolabeled aerosol by airway generation using a conceptual three dimensional model of lung morphology. J. Aerosol Med. 8, 341-356). A recently developed airway network model was used in this study. Quantitative PET scans of [C-11]triamcinolone acetonide distribution in the lung were determined following administration of Azmacort(R), a commercial metered dose inhaler with an integrated spacer device. Distributions at varying time periods after drug administration were investigated to explore the dynamics and kinetics of the aerosolized drug. Initially, deposition of labeled drug on conducting airways (generations 1-14) was found to be higher than those on acinar airways (generation 15-23), 64% versus 36%. The distribution pattern changed slowly with time. By 47 min, 51% of the dose remaining in the lung was found on conducting airways while 49% was on acinar airways. This study illustrates the value of PET imaging for the evaluation and design of drug formulations.

  9. Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

    NASA Astrophysics Data System (ADS)

    Kristensen, K.; Cui, T.; Zhang, H.; Gold, A.; Glasius, M.; Surratt, J. D.

    2014-04-01

    The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high-NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimers. A total of eight carboxylic acids and four dimers were identified, constituting between 8 and 12% of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimers was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NOx, with increased concentrations by a factor of two at higher RH (50-90%) relative to lower RH (30-50%). The increased formation of dimers correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimers. SOA mass yield did not influence the chemical composition of SOA formed from α-pinene ozonolysis with respect to

  10. Evaluation of the respiratory tract after acute exposure to a pyrotechnically generated aerosol fire suppressant.

    PubMed

    Smith, E A; Kimmel, E C; English, J H; Bowen, L E; Reboulet, J E; Carpenter, R L

    1997-01-01

    Fischer 344 rats (250-300 g) were exposed to the resulting aerosols from the pyrolysis of Spectrex Fire Extinguishant (SFE) Formulation A, a pyrotechnically generated aerosol fire suppressant, at a loading equivalent of 50 or 80 g m(-3) air for 15 or 60 min. Exposures were conducted in a 700-1 whole-body inhalation chamber under static conditions. The chamber atmosphere was analyzed for mass aerosol concentration and size distribution. Clinical observations were taken throughout the exposure. Animals were euthanized at 1 h, 6 h, 24 h, 7 days or 14 days post-exposure and underwent histopathological examination, enzyme analyses and wet/dry lung weight determination. No deaths occurred during the study. Animals exhibited signs of dyspnea, coughing, lack of coordination and lethargy during each exposure. These signs became more pronounced as the load and exposure length increased. No lesions were noted in the trachea, lung, heart or abdominal organs upon gross examination. A reversible pulmonary edema and olfactory necrosis were observed only in those animals exposed to an SFE loading equivalent to 80 g m(-3) for 60 min. Protein concentrations increased in the bronchoalveolar lavage but no changes in enzyme levels were observed. There was no significant difference between the control groups and the exposure groups for wet/dry lung weight determination.

  11. 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

  12. The effect of particle acidity on secondary organic aerosol formation from α-pinene photooxidation under atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Han, Yuemei; Stroud, Craig A.; Liggio, John; Li, Shao-Meng

    2016-11-01

    Secondary organic aerosol (SOA) formation from photooxidation of α-pinene has been investigated in a photochemical reaction chamber under varied inorganic seed particle acidity levels at moderate relative humidity. The effect of particle acidity on SOA yield and chemical composition was examined under high- and low-NOx conditions. The SOA yield (4.2-7.6 %) increased nearly linearly with the increase in particle acidity under high-NOx conditions. In contrast, the SOA yield (28.6-36.3 %) was substantially higher under low-NOx conditions, but its dependency on particle acidity was insignificant. A relatively strong increase in SOA yield (up to 220 %) was observed in the first hour of α-pinene photooxidation under high-NOx conditions, suggesting that SOA formation was more effective for early α-pinene oxidation products in the presence of fresh acidic particles. The SOA yield decreased gradually with the increase in organic mass in the initial stage (approximately 0-1 h) under high-NOx conditions, which is likely due to the inaccessibility to the acidity over time with the coating of α-pinene SOA, assuming a slow particle-phase diffusion of organic molecules into the inorganic seeds. The formation of later-generation SOA was enhanced by particle acidity even under low-NOx conditions when introducing acidic seed particles after α-pinene photooxidation, suggesting a different acidity effect exists for α-pinene SOA derived from later oxidation stages. This effect could be important in the atmosphere under conditions where α-pinene oxidation products in the gas-phase originating in forested areas (with low NOx and SOx) are transported to regions abundant in acidic aerosols such as power plant plumes or urban regions. The fraction of oxygen-containing organic fragments (CxHyO1+ 33-35 % and CxHyO2+ 16-17 %) in the total organics and the O / C ratio (0.52-0.56) of α-pinene SOA were lower under high-NOx conditions than those under low-NOx conditions (39-40, 17-19, and

  13. 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

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. 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

  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. 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.

  1. 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.

  2. Cloud droplet activity changes of soot aerosol upon smog chamber ageing

    NASA Astrophysics Data System (ADS)

    Wittbom, C.; Eriksson, A. C.; Rissler, J.; Carlsson, J. E.; Roldin, P.; Nordin, E. Z.; Nilsson, P. T.; Swietlicki, E.; Pagels, J. H.; Svenningsson, B.

    2014-09-01

    Particles containing soot, or black carbon, are generally considered to contribute to global warming. However, large uncertainties remain in the net climate forcing resulting from anthropogenic emissions of black carbon (BC), to a large extent due to the fact that BC is co-emitted with gases and primary particles, both organic and inorganic, and subject to atmospheric ageing processes. In this study, diesel exhaust particles and particles from a flame soot generator spiked with light aromatic secondary organic aerosol (SOA) precursors were processed by UV radiation in a 6 m3 Teflon chamber in the presence of NOx. The time-dependent changes of the soot nanoparticle properties were characterised using a Cloud Condensation Nuclei Counter, an Aerosol Particle Mass Analyzer and a Soot Particle Aerosol Mass Spectrometer. The results show that freshly emitted soot particles do not activate into cloud droplets at supersaturations ≤2%, i.e. the BC core coated with primary organic aerosol (POA) from the exhaust is limited in hygroscopicity. Before the onset of UV radiation it is unlikely that any substantial SOA formation is taking place. An immediate change in cloud-activation properties occurs at the onset of UV exposure. This change in hygroscopicity is likely attributed to SOA formed from intermediate volatility organic compounds (IVOCs) in the diesel engine exhaust. The change of cloud condensation nuclei (CCN) properties at the onset of UV radiation implies that the lifetime of soot particles in the atmosphere is affected by the access to sunlight, which differs between latitudes. The ageing of soot particles progressively enhances their ability to act as cloud condensation nuclei, due to changes in: (I) organic fraction of the particle, (II) chemical properties of this fraction (e.g. primary or secondary organic aerosol), (III) particle size, and (IV) particle morphology. Applying κ-Köhler theory, using a κSOA value of 0.13 (derived from independent input

  3. Optical Properties of Polymers Relevant to Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Marrero-Ortiz, W.; Gomez-Hernandez, M. E.; Xu, W.; Guo, S.; Zhang, R.

    2014-12-01

    Atmospheric aerosols play a critical role in climate directly by scattering and absorbing solar radiation and indirectly by modifying the cloud formation. Currently, the direct and indirect effects of aerosols represent the largest uncertainty in climate predictions models. Some aerosols are directly emitted, but the majority are formed in the atmosphere by the oxidation of gaseous precursors. However, the formation of aerosols at the molecular level is not fully characterized. Certain category of secondary organic aerosols (SOA), which represent a significant fraction of the total aerosol burden, can be light-absorbing, also known as brown carbon. However, the overall contribution of SOA to the brown carbon and the related climate forcing is poorly understood. Such incomplete understanding is due in part to the chemical complexity of SOA and the lack of knowledge regarding SOA formation, transformation, and optical properties. Based on previous laboratory experiments, field measurements, and modeling studies, it has been suggested that the polymers and oligomers play an important role in the SOA formation. Atmospheric polymers could be produced by the hydration or heterogeneous reactions of epoxides and small α-dicarbonyls. Their aqueous chemistry products have been shown to give light-absorbing and high molecular weight oligomeric species, which increase the SOA mass production and alter the direct and indirect effect of aerosols. In this paper, the aerosol chemistry of small α-dicarbonyl compounds with amines is investigated and the associated optical properties are measured using spectroscopic techniques. The differences between primary, secondary and tertiary amines with glyoxal and methylglyoxal are evaluated in terms of SOA browning efficiency. Atmospheric implications of our present work for understanding the formation of light-absorbing SOA will be presented, particularly in terms of the product distribution of light-absorbing SOA formed by aqueous phase

  4. Mechanisms of Formation of Secondary Organic Aerosols and Implications for Global Radiative Forcing

    SciTech Connect

    Seinfeld, John H.

    2011-12-02

    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. High speed cross-amplitude modulation in concatenated SOA-EAM-SOA.

    PubMed

    Cleary, Ciaran S; Manning, Robert J

    2012-06-18

    We observe a near-ideal high speed amplitude impulse response in an SOA-EAM-SOA configuration under optimum conditions. Full amplitude recovery times as low as 10 ps with modulation depths of 70% were observed in pump-probe measurements. System behavior could be controlled by the choice of signal wavelength, SOA current biases and EAM reverse bias voltages. Experimental data and impulse response modelling indicated that the slow tail in the gain response of first SOA was negated by a combination of cross-absorption modulation between pump and modulated CW probe, and self-gain modulation of the modulated CW probe in both the EAM and second SOA.

  6. Potential of Aerosol Liquid Water to Facilitate Organic Aerosol Formation: Assessing Knowledge Gaps about Precursors and Partitioning.

    PubMed

    Sareen, Neha; Waxman, Eleanor M; Turpin, Barbara J; Volkamer, Rainer; Carlton, Annmarie G

    2017-03-06

    Isoprene epoxydiol (IEPOX), glyoxal, and methylglyoxal are ubiquitous water-soluble organic gases (WSOGs) that partition to aerosol liquid water (ALW) and clouds to form aqueous secondary organic aerosol (aqSOA). Recent laboratory-derived Setschenow (or salting) coefficients suggest glyoxal's potential to form aqSOA is enhanced by high aerosol salt molality, or "salting-in". In the southeastern U.S., aqSOA is responsible for a significant fraction of ambient organic aerosol, and correlates with sulfate mass. However, the mechanistic explanation for this correlation remains elusive, and an assessment of the importance of different WSOGs to aqSOA is currently missing. We employ EPA's CMAQ model to the continental U.S. during the Southern Oxidant and Aerosol Study (SOAS) to compare the potential of glyoxal, methylglyoxal, and IEPOX to partition to ALW, as the initial step toward aqSOA formation. Among these three studied compounds, IEPOX is a dominant contributor, ∼72% on average in the continental U.S., to potential aqSOA mass due to Henry's Law constants and molecular weights. Glyoxal contributes significantly, and application of the Setschenow coefficient leads to a greater than 3-fold model domain average increase in glyoxal's aqSOA mass potential. Methylglyoxal is predicted to be a minor contributor. Acid or ammonium - catalyzed ring-opening IEPOX chemistry as well as sulfate-driven ALW and the associated molality may explain positive correlations between SOA and sulfate during SOAS and illustrate ways in which anthropogenic sulfate could regulate biogenic aqSOA formation, ways not presently included in atmospheric models but relevant to development of effective control strategies.

  7. 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.