WorldWideScience

Sample records for secondary organic aerosols

  1. Secondary organic aerosols: Formation potential and ambient data

    DEFF Research Database (Denmark)

    Barthelmie, R.J.; Pryor, S.C.

    1997-01-01

    Organic aerosols comprise a significant fraction of the total atmospheric particle loading and are associated with radiative forcing and health impacts. Ambient organic aerosol concentrations contain both a primary and secondary component. Herein, fractional aerosol coefficients (FAC) are used...... in conjunction with measurements of volatile organic compounds (VOC) to predict the formation potential of secondary organic aerosols (SOA) in the Lower Fraser Valley (LEV) of British Columbia. The predicted concentrations of SOA show reasonable accord with ambient aerosol measurements and indicate considerable...

  2. Volatile organic compounds and secondary organic aerosol in the Earth's atmosphere

    International Nuclear Information System (INIS)

    Galbally, Ian

    2007-01-01

    Full text: Recent research, when considered as a whole, suggests that a substantial fraction of both gas-phase and aerosol atmospheric organics have not been, or have very rarely been, directly measured. A review of the global budget for organic gases shows that we cannot account for the loss of approximately half the non-methane organic carbon entering the atmosphere. We suggest that this unaccounted-for loss most likely occurs through formation of secondary organic aerosols (SOAs), indicating that the source for these aerosols is an order of magnitude larger than current estimates. There is evidence that aged secondary organic aerosol can participate in both direct and indirect (cloud modifying) radiative forcing and that this influence may change with other global climate change. Even though our knowledge of the organic composition of the atmosphere is limited, these compounds clearly influence the reactive chemistry of the atmosphere and the formation, composition, and climate impact of aerosols A major challenge in the coming decade of atmospheric chemistry research will be to elucidate the sources, structure, chemistry, fate and influences of these clearly ubiquitous yet poorly constrained organic atmospheric constituents

  3. Predicting Thermal Behavior of Secondary Organic Aerosols

    Data.gov (United States)

    U.S. Environmental Protection Agency — Volume concentrations of secondary organic aerosol (SOA) are measured in 139 steady-state, single precursor hydrocarbon oxidation experiments after passing through a...

  4. Correlation of Secondary Organic Aerosol with Odd Oxygen in Mexico City

    Energy Technology Data Exchange (ETDEWEB)

    Herndon, Scott C.; Onasch, Timothy B.; Wood, Ezra C.; Kroll, Jesse H.; Canagaratna, M. R.; Jayne, John T.; Zavala, Miguel A.; Knighton, W. Berk; Mazzoleni, Claudio; Dubey, Manvendra K.; Ulbrich, Ingrid M.; Jimenez, Jose L.; Seila, Robert; de Gouw, Joost A.; de Foy, B.; Fast, Jerome D.; Molina, Luisa T.; Kolb, C. E.; Worsnop, Douglas R.

    2008-08-05

    Data collected from a mountain location within the Mexico City limits are used to demonstrate a correlation between secondary organic aerosol and odd-oxygen (O3 + NO2). Positive matrix factorization techniques are employed to separate organic aerosol components: hydrocarbon-like organic aerosol; oxidized-organic aerosol; and biomass burning organic aerosol. The measured hydrocarbon-like organic aerosol is correlated with urban CO (8±1) µg m-3 ppmv-1. The measured oxidized-organic aerosol is associated with photochemical oxidation products and correlates with odd-oxygen with an apparent slope of (70-120) µg m-3 ppmv-1. The dependence of the oxidized-organic aerosol to odd-oxygen correlation on the nature of the gas-phase hydrocarbon profile is discussed.

  5. Recent advances in understanding secondary organic aerosol: Implications for global climate forcing: Advances in Secondary Organic Aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Shrivastava, Manish [Pacific Northwest National Laboratory, Richland Washington USA; Cappa, Christopher D. [Department of Civil and Environmental Engineering, University of California, Davis California USA; Fan, Jiwen [Pacific Northwest National Laboratory, Richland Washington USA; Goldstein, Allen H. [Department of Environmental Science, Policy and Management and Department of Civil and Environmental Engineering, University of California, Berkeley California USA; Guenther, Alex B. [Department of Earth System Science, University of California, Irvine California USA; Jimenez, Jose L. [Cooperative Institute for Research in Environmental Sciences and Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder Colorado USA; Kuang, Chongai [Brookhaven National Laboratory, Upton New York USA; Laskin, Alexander [Pacific Northwest National Laboratory, Richland Washington USA; Martin, Scot T. [School of Engineering and Applied Sciences and Department of Earth and Planetary Sciences, Harvard University, Cambridge Massachusetts USA; Ng, Nga Lee [School of Chemical and Biomolecular Engineering and School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta Georgia USA; Petaja, Tuukka [Department of Physics, University of Helsinki, Helsinki Finland; Pierce, Jeffrey R. [Department of Atmospheric Science, Colorado State University, Fort Collins Colorado USA; Rasch, Philip J. [Pacific Northwest National Laboratory, Richland Washington USA; Roldin, Pontus [Department of Physics, Lund University, Lund Sweden; Seinfeld, John H. [Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena California USA; Shilling, John [Pacific Northwest National Laboratory, Richland Washington USA; Smith, James N. [Department of Earth System Science, University of California, Irvine California USA; Thornton, Joel A. [Department of Atmospheric Sciences, University of Washington, Seattle Washington USA; Volkamer, Rainer [Cooperative Institute for Research in Environmental Sciences and Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder Colorado USA; Wang, Jian [Brookhaven National Laboratory, Upton New York USA; Worsnop, Douglas R. [Aerodyne Research, Inc., Billerica Massachusetts USA; Zaveri, Rahul A. [Pacific Northwest National Laboratory, Richland Washington USA; Zelenyuk, Alla [Pacific Northwest National Laboratory, Richland Washington USA; Zhang, Qi [Department of Environmental Toxicology, University of California, Davis California USA

    2017-06-01

    Anthropogenic emissions and land-use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding pre-industrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features 1) influence estimates of aerosol radiative forcing and 2) can confound estimates of the historical response of climate to increases in greenhouse gases (e.g. the ‘climate sensitivity’). Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through a combination of laboratory and field measurements, yet current climate models typically do not comprehensively include all important SOA-relevant processes. Therefore, major gaps exist at present between current measurement-based knowledge on the one hand and model implementation of organic aerosols on the other. The critical review herein summarizes some of the important developments in understanding SOA formation that could potentially have large impacts on our understanding of aerosol radiative forcing and climate. We highlight the importance of some recently discovered processes and properties that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including: formation of extremely low-volatility organics in the gas-phase; isoprene epoxydiols (IEPOX) multi-phase chemistry; particle-phase oligomerization; and physical properties such as viscosity. In addition, this review also highlights some of the important processes that involve interactions between natural biogenic emissions and anthropogenic emissions, such as the role of sulfate and oxides of nitrogen (NOx) on SOA formation from biogenic volatile organic compounds. Studies that relate the observed evolution of organic aerosol

  6. Secondary organic material formed by methylglyoxal in aqueous aerosol mimics

    Directory of Open Access Journals (Sweden)

    N. Sareen

    2010-02-01

    Full Text Available We show that methylglyoxal forms light-absorbing secondary organic material in aqueous ammonium sulfate and ammonium nitrate solutions mimicking tropospheric aerosol particles. The kinetics were characterized using UV-Vis spectrophotometry. The results suggest that the bimolecular reaction of methylglyoxal with an ammonium or hydronium ion is the rate-limiting step for the formation of light-absorbing species, with kNH4+II=5×10−6 M−1 min−1 and kH3O+II≤10−3 M−1 min−1. Evidence of aldol condensation products and oligomeric species up to 759 amu was found using chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS. Tentative identifications of carbon-nitrogen species and a sulfur-containing compound were also made using Aerosol-CIMS. Aqueous solutions of methylglyoxal, with and without inorganic salts, exhibit significant surface tension depression. These observations add to the growing body of evidence that dicarbonyl compounds may form secondary organic material in the aerosol aqueous phase, and that secondary organic aerosol formation via heterogeneous processes may affect seed aerosol properties.

  7. Predicting Thermal Behavior of Secondary Organic Aerosols

    Science.gov (United States)

    Volume concentrations of steady-state secondary organic aerosol (SOA) were measured in 139 steadystate single precursor hydrocarbon oxidation experiments after passing through a temperature controlled inlet tube. Higher temperatures resulted in greater loss of particle volume, wi...

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

    Energy Technology Data Exchange (ETDEWEB)

    Seinfeld, John H. [California Inst. of Technology (CalTech), Pasadena, CA (United States)

    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.

  9. Secondary organic aerosol formation from biomass burning intermediates: phenol and methoxyphenols

    Directory of Open Access Journals (Sweden)

    L. D. Yee

    2013-08-01

    Full Text Available The formation of secondary organic aerosol from oxidation of phenol, guaiacol (2-methoxyphenol, and syringol (2,6-dimethoxyphenol, major components of biomass burning, is described. Photooxidation experiments were conducted in the Caltech laboratory chambers under low-NOx (2O2 as the OH source. Secondary organic aerosol (SOA yields (ratio of mass of SOA formed to mass of primary organic reacted greater than 25% are observed. Aerosol growth is rapid and linear with the primary organic conversion, consistent with the formation of essentially non-volatile products. Gas- and aerosol-phase oxidation products from the guaiacol system provide insight into the chemical mechanisms responsible for SOA formation. Syringol SOA yields are lower than those of phenol and guaiacol, likely due to novel methoxy group chemistry that leads to early fragmentation in the gas-phase photooxidation. Atomic oxygen to carbon (O : C ratios calculated from high-resolution-time-of-flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS measurements of the SOA in all three systems are ~ 0.9, which represent among the highest such ratios achieved in laboratory chamber experiments and are similar to that of aged atmospheric organic aerosol. The global contribution of SOA from intermediate volatility and semivolatile organic compounds has been shown to be substantial (Pye and Seinfeld, 2010. An approach to representing SOA formation from biomass burning emissions in atmospheric models could involve one or more surrogate species for which aerosol formation under well-controlled conditions has been quantified. The present work provides data for such an approach.

  10. Secondary organic aerosol formation through cloud processing of aromatic VOCs

    Science.gov (United States)

    Herckes, P.; Hutchings, J. W.; Ervens, B.

    2010-12-01

    Field observations have shown substantial concentrations (20-5,500 ng L-1) of aromatic volatile organic compounds (VOC) in cloud droplets. The potential generation of secondary organic aerosol mass through the processing of these anthropogenic VOCs was investigated through laboratory and modeling studies. Under simulated atmospheric laboratory conditions, in idealized solutions, benzene, toluene, ethylbenzene, and xylene (BTEX) degraded quickly in the aqueous phase. The degradation process yielded less volatile products which would contribute to new aerosol mass upon cloud evaporation. However, when realistic cloud solutions containing natural organic matter were used in the experiments, the reaction rates decreased with increasing organic carbon content. Kinetic data derived from these experiments were used as input to a multiphase box model in order to evaluate the secondary organic aerosol (SOA) mass formation potential of cloud processing of BTEX. Model results will be presented that quantify the SOA amounts from these aqueous phase pathways. The efficiency of this multiphase SOA source will be compared to SOA yields from the same aromatics as treated in traditional SOA models that are restricted to gas phase oxidation and subsequent condensation on particles.

  11. Cloud processing of organic compounds: Secondary organic aerosol and nitrosamine formation

    Science.gov (United States)

    Hutchings, James W., III

    Cloud processing of atmospheric organic compounds has been investigated through field studies, laboratory experiments, and numerical modeling. Observational cloud chemistry studies were performed in northern Arizona and fog studies in central Pennsylvania. At both locations, the cloud and fogs showed low acidity due to neutralization by soil dust components (Arizona) and ammonia (Pennsylvania). The field observations showed substantial concentrations (20-5500 ng•L -1) of volatile organic compounds (VOC) in the cloud droplets. The potential generation of secondary organic aerosol mass through the processing of these anthropogenic VOCs was investigated through laboratory and modeling studies. Under simulated atmospheric conditions, in idealized solutions, benzene, toluene, ethylbenzene, and xylene (BTEX) degraded quickly in the aqueous phase with half lives of approximately three hours. The degradation process yielded less volatile products which would contribute to new aerosol mass upon cloud evaporation. However, when realistic cloud solutions containing natural organic matter were used in the experiments, the reaction kinetics decreased with increasing organic carbon content, resulting in half lives of approximately 7 hours. The secondary organic aerosol (SUA) mass formation potential of cloud processing of BTEX was evaluated. SOA mass formation by cloud processing of BTEX, while strongly dependent on the atmospheric conditions, could contribute up to 9% of the ambient atmospheric aerosol mass, although typically ˜1% appears realistic. Field observations also showed the occurrence of N-nitrosodimethylamine (NDMA), a potent carcinogen, in fogs and clouds (100-340 ng•L -1). Laboratory studies were conducted to investigate the formation of NDMA from nitrous acid and dimethylamine in the homogeneous aqueous phase within cloud droplets. While NDMA was produced in the cloud droplets, the low yields (NDMA with partitioning to droplet must be the source of aqueous

  12. Organic aerosols

    International Nuclear Information System (INIS)

    Penner, J.E.

    1994-01-01

    Organic aerosols scatter solar radiation. They may also either enhance or decrease concentrations of cloud condensation nuclei. This paper summarizes observed concentrations of aerosols in remote continental and marine locations and provides estimates for the sources of organic aerosol matter. The anthropogenic sources of organic aerosols may be as large as the anthropogenic sources of sulfate aerosols, implying a similar magnitude of direct forcing of climate. The source estimates are highly uncertain and subject to revision in the future. A slow secondary source of organic aerosols of unknown origin may contribute to the observed oceanic concentrations. The role of organic aerosols acting as cloud condensation nuclei (CCN) is described and it is concluded that they may either enhance or decrease the ability of anthropogenic sulfate aerosols to act as CCN

  13. SECONDARY ORGANIC AEROSOL FORMATION FROM THE OXIDATION OF AROMATIC HYDROCARBONS IN THE PRESENCE OF DRY SUBMICRON AMMONIUM SULFATE AEROSOL

    Science.gov (United States)

    A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas-aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds ...

  14. Characterization of a large biogenic secondary organic aerosol event from eastern Canadian forests

    Science.gov (United States)

    Slowik, J. G.; Stroud, C.; Bottenheim, J. W.; Brickell, P. C.; Chang, R. Y.-W.; Liggio, J.; Makar, P. A.; Martin, R. V.; Moran, M. D.; Shantz, N. C.; Sjostedt, S. J.; van Donkelaar, A.; Vlasenko, A.; Wiebe, H. A.; Xia, A. G.; Zhang, J.; Leaitch, W. R.; Abbatt, J. P. D.

    2010-03-01

    Measurements of aerosol composition, volatile organic compounds, and CO are used to determine biogenic secondary organic aerosol (SOA) concentrations at a rural site 70 km north of Toronto. These biogenic SOA levels are many times higher than past observations and occur during a period of increasing temperatures and outflow from Northern Ontario and Quebec forests in early summer. A regional chemical transport model approximately predicts the event timing and accurately predicts the aerosol loading, identifying the precursors as monoterpene emissions from the coniferous forest. The agreement between the measured and modeled biogenic aerosol concentrations contrasts with model underpredictions for polluted regions. Correlations of the oxygenated organic aerosol mass with tracers such as CO support a secondary aerosol source and distinguish biogenic, pollution, and biomass burning periods during the field campaign. Using the Master Chemical Mechanism, it is shown that the levels of CO observed during the biogenic event are consistent with a photochemical source arising from monoterpene oxidation. The biogenic aerosol mass correlates with satellite measurements of regional aerosol optical depth, indicating that the event extends across the eastern Canadian forest. This regional event correlates with increased temperatures, indicating that temperature-dependent forest emissions can significantly affect climate through enhanced direct optical scattering and higher cloud condensation nuclei numbers.

  15. Organic molecular composition of marine aerosols over the Arctic Ocean in summer: contributions of primary emission and secondary aerosol formation

    Directory of Open Access Journals (Sweden)

    P. Q. Fu

    2013-02-01

    Full Text Available Organic molecular composition of marine aerosol samples collected during the MALINA cruise in the Arctic Ocean was investigated by gas chromatography/mass spectrometry. More than 110 individual organic compounds were determined in the samples and were grouped into different compound classes based on the functionality and sources. The concentrations of total quantified organics ranged from 7.3 to 185 ng m−3 (mean 47.6 ng m−3, accounting for 1.8–11.0% (4.8% of organic carbon in the marine aerosols. Primary saccharides were found to be dominant organic compound class, followed by secondary organic aerosol (SOA tracers formed from the oxidation of biogenic volatile organic compounds (VOCs such as isoprene, α-pinene and β-caryophyllene. Mannitol, the specific tracer for airborne fungal spores, was detected as the most abundant organic species in the samples with a concentration range of 0.052–53.3 ng m−3 (9.2 ng m−3, followed by glucose, arabitol, and the isoprene oxidation products of 2-methyltetrols. Biomass burning tracers such as levoglucosan are evident in all samples with trace levels. On the basis of the tracer-based method for the estimation of fungal-spore OC and biogenic secondary organic carbon (SOC, we estimate that an average of 10.7% (up to 26.2% of the OC in the marine aerosols was due to the contribution of fungal spores, followed by the contribution of isoprene SOC (mean 3.8% and α-pinene SOC (2.9%. In contrast, only 0.19% of the OC was due to the photooxidation of β-caryophyllene. This study indicates that primary organic aerosols from biogenic emissions, both from long-range transport of mid-latitude aerosols and from sea-to-air emission of marine organics, as well as secondary organic aerosols formed from the photooxidation of biogenic VOCs are important factors controlling the organic chemical composition of marine aerosols in the Arctic Ocean.

  16. Atmospheric oxidation of isoprene and 1,3-Butadiene: influence of aerosol acidity and Relative humidity on secondary organic aerosol

    Science.gov (United States)

    The effects of acidic seed aerosols on the formation of secondary organic aerosol (SOA)have been examined in a number of previous studies, several of which have observed strong linear correlations between the aerosol acidity (measured as nmol H+ per m3 air s...

  17. Primary and Secondary Organic Marine Aerosol and Oceanic Biological Activity: Recent Results and New Perspectives for Future Studies

    Directory of Open Access Journals (Sweden)

    Matteo Rinaldi

    2010-01-01

    Full Text Available One of the most important natural aerosol systems at the global level is marine aerosol that comprises both organic and inorganic components of primary and secondary origin. The present paper reviews some new results on primary and secondary organic marine aerosol, achieved during the EU project MAP (Marine Aerosol Production, comparing them with those reported in the recent literature. Marine aerosol samples collected at the coastal site of Mace Head, Ireland, show a chemical composition trend that is influenced by the oceanic biological activity cycle, in agreement with other observations. Laboratory experiments show that sea-spray aerosol from biologically active sea water can be highly enriched in organics, and the authors highlight the need for further studies on the atmospheric fate of such primary organics. With regard to the secondary fraction of organic aerosol, the average chemical composition and molecular tracer (methanesulfonic-acid, amines distribution could be successfully characterized by adopting a multitechnique analytical approach.

  18. Real-time, controlled OH-initiated oxidation of biogenic secondary organic aerosol

    Directory of Open Access Journals (Sweden)

    J. G. Slowik

    2012-10-01

    Full Text Available The chemical complexity of atmospheric organic aerosol (OA requires novel methods for characterization of its components and description of its atmospheric processing-induced transformations. We present the first field deployment of the Toronto Photooxidation Tube (TPOT, a field-deployable flow reactor for the controlled exposure of ambient aerosol to OH radicals. The system alternates between sampling of (1 (unreacted ambient aerosol, (2 aerosol exposed to UV light and subjected to a ~4 to 10 °C temperature increase, and (3 aerosol that is oxidized by OH (in addition to the aforementioned UV exposure/temperature increase. This allows both characterization of the aging process and classification of aerosol in terms of its volatility and reaction-based properties. Summertime measurements by an aerosol mass spectrometer coupled to the TPOT were performed in the remote forest of western Canada, resulting in aerosol dominated by biogenic secondary organic aerosol. Volatilization/UV exposure resulted in an approximately 10 to 25% decrease in organic mass and resulted in a slight increase in oxygenation. OH oxidation resulted in a further organic mass decrease (additional ~25% and yielded an aerosol with O:C values comparable to those characteristic of low volatility, highly oxygenated OA. Most OH-induced changes occurred within ~3 day-equivalents of atmospheric processing, with further reactions generally proceeding at a greatly reduced rate. Positive matrix factorization (PMF analysis of the TPOT data yielded five factors. One factor is related to primary biomass burning organic aerosol, while the others describe oxygenated organic aerosol (OOA components in terms of reactivity and volatility: (1 volatile and reactive; (2 non-volatile and reactive; (3 non-volatile and reactive early-generation product; (4 non-volatile and non-reactive product. This PMF classification of aerosol components directly in terms of reactivity and volatility is enabled by

  19. Effect of acidic seed on biogenic secondary organic aerosol growth

    Science.gov (United States)

    Czoschke, Nadine M.; Jang, Myoseon; Kamens, Richard M.

    Secondary organic aerosol (SOA) growth in the presence of acid aerosols was studied in twin 500 l Teflon bags and in a 4 m flow reactor. In Teflon bags, isoprene, acrolein and α-pinene were all made to react individually with ozone and exposed to either acid or non-acid inorganic seed aerosols to determine the effect of acid-catalyzed heterogeneous reactions on SOA growth. α-Pinene and ozone were made to react in a flow reactor to assess the immediate effect of mixing an acid aerosol with SOA at high and low relative humidity levels. In all cases, exposure to acid seed aerosol increased the amount of SOA mass produced. Fourier transform infrared spectra of the SOA in acid systems confirmed the transformation of carbonyl functional groups through acid-catalyzed heterogeneous reactions when SOAs formed in acidic environments or were exposed to acidic aerosols. Organic products initially produced from ozonation in the gas phase partition onto the inorganic seed aerosol and react heterogeneously with an acid catalyst forming low vapor pressure products. These acid-catalyzed heterogeneous reactions are implicated in generating the increased SOA mass observed in acidic aerosol systems as they transform predominantly gas phase compounds of high volatility into low vapor pressure predominantly particle phase products.

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

    Science.gov (United States)

    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,...

  1. Secondary organic aerosol formation from in-use motor vehicle emissions using a potential aerosol mass reactor.

    Science.gov (United States)

    Tkacik, Daniel S; Lambe, Andrew T; Jathar, Shantanu; Li, Xiang; Presto, Albert A; Zhao, Yunliang; Blake, Donald; Meinardi, Simone; Jayne, John T; Croteau, Philip L; Robinson, Allen L

    2014-10-07

    Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ∼ 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ∼ 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas.

  2. Global modelling of secondary organic aerosol in the troposphere: a sensitivity analysis

    Directory of Open Access Journals (Sweden)

    K. Tsigaridis

    2003-01-01

    Full Text Available A global 3-dimensional chemistry/transport model able to describe O3, NOx, Volatile Organic Compounds (VOC, sulphur and NH3 chemistry has been extended to simulate the temporal and spatial distribution of primary and secondary carbonaceous aerosols in the troposphere focusing on Secondary Organic Aerosol (SOA formation. A number of global simulations have been performed to determine a possible range of annual global SOA production and investigate uncertainties associated with the model results. The studied uncertainties in the SOA budget have been evaluated to be in decreasing importance: the potentially irreversible sticking of the semi-volatile compounds on aerosols, the enthalpy of vaporization of these compounds, the partitioning of SOA on non-carbonaceous aerosols, the conversion of aerosols from hydrophobic to hydrophilic, the emissions of primary carbonaceous aerosols, the chemical fate of the first generation products and finally the activity coefficient of the condensable species. The large uncertainties associated with the emissions of VOC and the adopted simplification of chemistry have not been investigated in this study. Although not all sources of uncertainties have been investigated, according to our calculations, the above factors within the experimental range of variations could result to an overall uncertainty of about a factor of 20 in the global SOA budget. The global annual SOA production from biogenic VOC might range from 2.5 to 44.5 Tg of organic matter per year, whereas that from anthropogenic VOC ranges from 0.05 to 2.62 Tg of organic matter per year. These estimates can be considered as a lower limit, since partitioning on coarse particles like nitrate, dust or sea-salt, together with the partitioning and the dissociation of the semi-volatile products in aerosol water has been neglected. Comparison of model results to observations, where available, shows a better agreement for the upper budget estimates than for the

  3. Chemical and isotopic composition of secondary organic aerosol generated by alpha-pinene ozonolysis

    NARCIS (Netherlands)

    Meusinger, Carl; Dusek, Ulrike; King, Stephanie M.; Holzinger, Rupert; Rosenorn, Thomas; Sperlich, Peter; Julien, Maxime; Remaud, Gerald S.; Bilde, Merete; Rockmann, Thomas; Johnson, Matthew S.

    2017-01-01

    Secondary organic aerosol (SOA) plays a central role in air pollution and climate. However, the description of the sources and mechanisms leading to SOA is elusive despite decades of research. While stable isotope analysis is increasingly used to constrain sources of ambient aerosol, in many cases

  4. Secondary organic aerosol formation from fossil fuel sources contribute majority of summertime organic mass at Bakersfield

    Science.gov (United States)

    Secondary organic aerosols (SOA), known to form in the atmosphere from oxidation of volatile organic compounds (VOCs) emitted by anthropogenic and biogenic sources, are a poorly understood but substantial component of atmospheric particles. In this study, we examined the chemic...

  5. Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

    Directory of Open Access Journals (Sweden)

    J. Ofner

    2012-07-01

    Full Text Available Reactive halogen species (RHS, such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA and organic aerosol derived from biomass-burning (BBOA has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols.

    Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy, changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  6. Formation of secondary organic aerosol coating on black carbon particles near vehicular emissions

    Science.gov (United States)

    Lee, Alex K. Y.; Chen, Chia-Li; Liu, Jun; Price, Derek J.; Betha, Raghu; Russell, Lynn M.; Zhang, Xiaolu; Cappa, Christopher D.

    2017-12-01

    Black carbon (BC) emitted from incomplete combustion can result in significant impacts on air quality and climate. Understanding the mixing state of ambient BC and the chemical characteristics of its associated coatings is particularly important to evaluate BC fate and environmental impacts. In this study, we investigate the formation of organic coatings on BC particles in an urban environment (Fontana, California) under hot and dry conditions using a soot-particle aerosol mass spectrometer (SP-AMS). The SP-AMS was operated in a configuration that can exclusively detect refractory BC (rBC) particles and their coatings. Using the -log(NOx / NOy) ratio as a proxy for photochemical age of air masses, substantial formation of secondary organic aerosol (SOA) coatings on rBC particles was observed due to active photochemistry in the afternoon, whereas primary organic aerosol (POA) components were strongly associated with rBC from fresh vehicular emissions in the morning rush hours. There is also evidence that cooking-related organic aerosols were externally mixed from rBC. Positive matrix factorization and elemental analysis illustrate that most of the observed SOA coatings were freshly formed, providing an opportunity to examine SOA coating formation on rBCs near vehicular emissions. Approximately 7-20 wt % of secondary organic and inorganic species were estimated to be internally mixed with rBC on average, implying that rBC is unlikely the major condensation sink of SOA in this study. Comparison of our results to a co-located standard high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurement suggests that at least a portion of SOA materials condensed on rBC surfaces were chemically different from oxygenated organic aerosol (OOA) particles that were externally mixed with rBC, although they could both be generated from local photochemistry.

  7. High formation of secondary organic aerosol from the photo-oxidation of toluene

    OpenAIRE

    L. Hildebrandt; N. M. Donahue; S. N. Pandis

    2009-01-01

    Toluene and other aromatics have long been viewed as the dominant anthropogenic secondary organic aerosol (SOA) precursors, but the SOA mass yields from toluene reported in previous studies vary widely. Experiments conducted in the Carnegie Mellon University environmental chamber to study SOA formation from the photo-oxidation of toluene show significantly larger SOA production than parameterizations employed in current air-quality models. Aerosol mass yields depend on experimental co...

  8. Ubiquitous influence of wildfire emissions and secondary organic aerosol on summertime atmospheric aerosol in the forested Great Lakes region

    Science.gov (United States)

    Gunsch, Matthew J.; May, Nathaniel W.; Wen, Miao; Bottenus, Courtney L. H.; Gardner, Daniel J.; VanReken, Timothy M.; Bertman, Steven B.; Hopke, Philip K.; Ault, Andrew P.; Pratt, Kerri A.

    2018-03-01

    Long-range aerosol transport affects locations hundreds of kilometers from the point of emission, leading to distant particle sources influencing rural environments that have few major local sources. Source apportionment was conducted using real-time aerosol chemistry measurements made in July 2014 at the forested University of Michigan Biological Station near Pellston, Michigan, a site representative of the remote forested Great Lakes region. Size-resolved chemical composition of individual 0.5-2.0 µm particles was measured using an aerosol time-of-flight mass spectrometer (ATOFMS), and non-refractory aerosol mass less than 1 µm (PM1) was measured with a high-resolution aerosol mass spectrometer (HR-AMS). The field site was influenced by air masses transporting Canadian wildfire emissions and urban pollution from Milwaukee and Chicago. During wildfire-influenced periods, 0.5-2.0 µm particles were primarily aged biomass burning particles (88 % by number). These particles were heavily coated with secondary organic aerosol (SOA) formed during transport, with organics (average O/C ratio of 0.8) contributing 89 % of the PM1 mass. During urban-influenced periods, organic carbon, elemental carbon-organic carbon, and aged biomass burning particles were identified, with inorganic secondary species (ammonium, sulfate, and nitrate) contributing 41 % of the PM1 mass, indicative of atmospheric processing. With current models underpredicting organic carbon in this region and biomass burning being the largest combustion contributor to SOA by mass, these results highlight the importance for regional chemical transport models to accurately predict the impact of long-range transported particles on air quality in the upper Midwest, United States, particularly considering increasing intensity and frequency of Canadian wildfires.

  9. Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Zaveri, Rahul A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Shilling, John E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Zelenyuk, Alla [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Div.; Liu, Jiumeng [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Bell, David M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Div.; Paul Scherrer Inst. (PSI), Villigen (Switzerland). Lab. of Atmospheric Chemistry; D’Ambro, Emma L. [Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences and Dept. of Chemistry; Gaston, Cassandra J. [Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences; Univ. of Miami, Miami, FL (United States). Rosenstiel School of Marine and Atmospheric Science; Thornton, Joel A. [Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences and Dept. of Chemistry; Laskin, Alexander [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry; Lin, Peng [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry; Wilson, Jacqueline [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Div.; Easter, Richard C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Wang, Jian [Brookhaven National Lab. (BNL), Upton, NY (United States). Environmental & Climate Sciences Dept.; Bertram, Allan K. [Univ. of British Columbia, Vancouver, BC (Canada). Dept. of Chemistry; Martin, Scot T. [Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences (SEAS) and Dept. of Earth and Planetary Sciences; Seinfeld, John H. [California Inst. of Technology (CalTech), Pasadena, CA (United States). Div. of Chemistry and Chemical Engineering and Div. of Engineering and Applied Science; Worsnop, Douglas R. [Aerodyne Research, Billerica, MA (United States). Center for Aerosol and Cloud Chemistry

    2017-12-15

    Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversibly reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.

  10. Evaluating Simulated Primary Anthropogenic and Biomass Burning Organic Aerosols during MILAGRO: Implications for Assessing Treatments of Secondary Organic Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Fast, Jerome D.; Aiken, Allison; Allan, James D.; Alexander, M. L.; Campos, Teresa; Canagaratna, Manjula R.; Chapman, Elaine G.; DeCarlo, Peter; de Foy, B.; Gaffney, Jeffrey; de Gouw, Joost A.; Doran, J. C.; Emmons, L.; Hodzic, Alma; Herndon, Scott C.; Huey, L. G.; Jayne, John T.; Jimenez, Jose L.; Kleinman, Lawrence I.; Kuster, W. C.; Marley, Nancy A.; Russell, Lynn M.; Ochoa, Carlos; Onasch, Timothy B.; Pekour, Mikhail S.; Song, Chen; Ulbrich, Ingrid M.; Warneke, Carsten; Welsh-Bon, Daniel; Wiedinmyer, Christine; Worsnop, Douglas R.; Yu, Xiao-Ying; Zaveri, Rahul A.

    2009-08-31

    Simulated primary organic aerosols (POA), as well as other particulates and trace gases, in the vicinity of Mexico City are evaluated using measurements collected during the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) field campaigns. Since the emission inventories and dilution will affect predictions of total organic matter and consequently total particulate matter, our objective is to assess the uncertainties in predicted POA before testing and evaluating the performance of secondary organic aerosol (SOA) treatments. Carbon monoxide (CO) is well simulated on most days both over the city and downwind, indicating that transport and mixing processes were usually consistent with the meteorological conditions observed during MILAGRO. Predicted and observed elemental carbon (EC) in the city was similar, but larger errors occurred at remote locations since the CO/EC emission ratios in the national emission inventory were lower than in the metropolitan emission inventory. Components of organic aerosols derived from Positive Matrix Factorization and data from several Aerodyne Aerosol Mass Spectrometer instruments deployed both at ground sites and on research aircraft are used to evaluate the model. Predicted POA was consistently lower than the measured organic matter at the ground sites, which is consistent with the expectation that SOA should be a large fraction of the total organic matter mass. A much better agreement was found when predicted POA was compared with the sum of "primary anthropogenic" and "primary biomass burning" components on days with relatively low biomass burning, suggesting that the overall magnitude of primary organic particulates released was reasonable. The predicted POA was greater than the total observed organic matter when the aircraft flew directly downwind of large fires, suggesting that biomass burning emission estimates from some large fires may be too high. Predicted total observed organic carbon (TOOC) was

  11. Secondary organic aerosol in the global aerosol – chemical transport model Oslo CTM2

    Directory of Open Access Journals (Sweden)

    I. S. A. Isaksen

    2007-11-01

    Full Text Available The global chemical transport model Oslo CTM2 has been extended to include the formation, transport and deposition of secondary organic aerosol (SOA. Precursor hydrocarbons which are oxidised to form condensible species include both biogenic species such as terpenes and isoprene, as well as species emitted predominantly by anthropogenic activities (toluene, m-xylene, methylbenzene and other aromatics. A model simulation for 2004 gives an annual global SOA production of approximately 55 Tg. Of this total, 2.5 Tg is found to consist of the oxidation products of anthropogenically emitted hydrocarbons, and about 15 Tg is formed by the oxidation products of isoprene. The global production of SOA is increased to about 69 Tg yr−1 by allowing semi-volatile species to partition to ammonium sulphate aerosol. This brings modelled organic aerosol values closer to those observed, however observations in Europe remain significantly underestimated. Allowing SOA to partition into ammonium sulphate aerosol increases the contribution of anthropogenic SOA from about 4.5% to 9.4% of the total production. Total modelled organic aerosol (OA values are found to represent a lower fraction of the measured values in winter (when primary organic aerosol (POA is the dominant OA component than in summer, which may be an indication that estimates of POA emissions are too low. Additionally, for measurement stations where the summer OA values are higher than in winter, the model generally underestimates the increase in summertime OA. In order to correctly model the observed increase in OA in summer, additional SOA sources or formation mechanisms may be necessary. The importance of NO3 as an oxidant of SOA precursors is found to vary regionally, causing up to 50%–60% of the total amount of SOA near the surface in polluted regions and less than 25% in more remote areas, if the yield of condensible oxidation products for β-pinene is used for NO3 oxidation of all terpenes

  12. Cloud condensation nuclei activity of aliphatic amine secondary aerosol

    Science.gov (United States)

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The resulting particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate ...

  13. Organic nitrate and secondary organic aerosol yield from NO3 oxidation of β-pinene evaluated using a gas-phase kinetics/aerosol partitioning model

    Directory of Open Access Journals (Sweden)

    H.-P. Dorn

    2009-02-01

    Full Text Available The yields of organic nitrates and of secondary organic aerosol (SOA particle formation were measured for the reaction NO3+β-pinene under dry and humid conditions in the atmosphere simulation chamber SAPHIR at Research Center Jülich. These experiments were conducted at low concentrations of NO3 (NO3+N2O5pvap~5×10−6 Torr (6.67×10−4 Pa, which constrains speculation about the oxidation mechanism and chemical identity of the organic nitrate. Once formed the SOA in this system continues to evolve, resulting in measurable aerosol volume decrease with time. The observations of high aerosol yield from NOx-dependent oxidation of monoterpenes provide an example of a significant anthropogenic source of SOA from biogenic hydrocarbon precursors. Estimates of the NO3+β-pinene SOA source strength for California and the globe indicate that NO3 reactions with monoterpenes are likely an important source (0.5–8% of the global total of organic aerosol on regional and global scales.

  14. Updated aerosol module and its application to simulate secondary organic aerosols during IMPACT campaign May 2008

    Directory of Open Access Journals (Sweden)

    Y. P. Li

    2013-07-01

    Full Text Available The formation of Secondary organic aerosol (SOA was simulated with the Secondary ORGanic Aerosol Model (SORGAM by a classical gas-particle partitioning concept, using the two-product model approach, which is widely used in chemical transport models. In this study, we extensively updated SORGAM including three major modifications: firstly, we derived temperature dependence functions of the SOA yields for aromatics and biogenic VOCs (volatile organic compounds, based on recent chamber studies within a sophisticated mathematic optimization framework; secondly, we implemented the SOA formation pathways from photo oxidation (OH initiated of isoprene; thirdly, we implemented the SOA formation channel from NO3-initiated oxidation of reactive biogenic hydrocarbons (isoprene and monoterpenes. The temperature dependence functions of the SOA yields were validated against available chamber experiments, and the updated SORGAM with temperature dependence functions was evaluated with the chamber data. Good performance was found with the normalized mean error of less than 30%. Moreover, the whole updated SORGAM module was validated against ambient SOA observations represented by the summed oxygenated organic aerosol (OOA concentrations abstracted from aerosol mass spectrometer (AMS measurements at a rural site near Rotterdam, the Netherlands, performed during the IMPACT campaign in May 2008. In this case, we embedded both the original and the updated SORGAM module into the EURopean Air pollution and Dispersion-Inverse Model (EURAD-IM, which showed general good agreements with the observed meteorological parameters and several secondary products such as O3, sulfate and nitrate. With the updated SORGAM module, the EURAD-IM model also captured the observed SOA concentrations reasonably well especially those during nighttime. In contrast, the EURAD-IM model before update underestimated the observations by a factor of up to 5. The large improvements of the modeled

  15. Secondary sulfate is internally mixed with sea spray aerosol and organic aerosol in the winter Arctic

    Science.gov (United States)

    Kirpes, Rachel M.; Bondy, Amy L.; Bonanno, Daniel; Moffet, Ryan C.; Wang, Bingbing; Laskin, Alexander; Ault, Andrew P.; Pratt, Kerri A.

    2018-03-01

    Few measurements of aerosol chemical composition have been made during the winter-spring transition (following polar sunrise) to constrain Arctic aerosol-cloud-climate feedbacks. Herein, we report the first measurements of individual particle chemical composition near Utqiaġvik (Barrow), Alaska, in winter (seven sample days in January and February 2014). Individual particles were analyzed by computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM-EDX, 24 847 particles), Raman microspectroscopy (300 particles), and scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS, 290 particles). Sea spray aerosol (SSA) was observed in all samples, with fresh and aged SSA comprising 99 %, by number, of 2.5-7.5 µm diameter particles, 65-95 % from 0.5-2.5 µm, and 50-60 % from 0.1-0.5 µm, indicating SSA is the dominant contributor to accumulation and coarse-mode aerosol during the winter. The aged SSA particles were characterized by reduced chlorine content with 94 %, by number, internally mixed with secondary sulfate (39 %, by number, internally mixed with both nitrate and sulfate), indicative of multiphase aging reactions during transport. There was a large number fraction (40 % of 1.0-4.0 µm diameter particles) of aged SSA during periods when particles were transported from near Prudhoe Bay, consistent with pollutant emissions from the oil fields participating in atmospheric processing of aerosol particles. Organic carbon and sulfate particles were observed in all samples and comprised 40-50 %, by number, of 0.1-0.4 µm diameter particles, indicative of Arctic haze influence. Soot was internally mixed with organic and sulfate components. All sulfate was mixed with organic carbon or SSA particles. Therefore, aerosol sources in the Alaskan Arctic and resulting aerosol chemical mixing states need to be considered when predicting aerosol climate effects, particularly cloud

  16. Substantial secondary organic aerosol formation in a coniferous forest: observations of both day- and nighttime chemistry

    OpenAIRE

    A. K. Y. Lee; J. P. D. Abbatt; W. R. Leaitch; S.-M. Li; S. J. Sjostedt; S. J. Sjostedt; J. J. B. Wentzell; J. Liggio; A. M. Macdonald

    2016-01-01

    Substantial biogenic secondary organic aerosol (BSOA) formation was investigated in a coniferous forest mountain region at Whistler, British Columbia. A largely biogenic aerosol growth episode was observed, providing a unique opportunity to investigate BSOA formation chemistry in a forested environment with limited influence from anthropogenic emissions. Positive matrix factorization of aerosol mass spectrometry (AMS) measurement identifie...

  17. Aerosol composition and sources during the Chinese Spring Festival: fireworks, secondary aerosol, and holiday effects

    Science.gov (United States)

    Jiang, Q.; Sun, Y. L.; Wang, Z.; Yin, Y.

    2015-06-01

    Aerosol particles were characterized by an Aerodyne aerosol chemical speciation monitor along with various collocated instruments in Beijing, China, to investigate the role of fireworks (FW) and secondary aerosol in particulate pollution during the Chinese Spring Festival of 2013. Three FW events, exerting significant and short-term impacts on fine particles (PM2.5), were observed on the days of Lunar New Year, Lunar Fifth Day, and Lantern Festival. The FW were shown to have a large impact on non-refractory potassium, chloride, sulfate, and organics in submicron aerosol (PM1), of which FW organics appeared to be emitted mainly in secondary, with its mass spectrum resembling that of secondary organic aerosol (SOA). Pollution events (PEs) and clean periods (CPs) alternated routinely throughout the study. Secondary particulate matter (SPM = SOA + sulfate + nitrate + ammonium) dominated the total PM1 mass on average, accounting for 63-82% during nine PEs in this study. The elevated contributions of secondary species during PEs resulted in a higher mass extinction efficiency of PM1 (6.4 m2 g-1) than during CPs (4.4 m2 g-1). The Chinese Spring Festival also provides a unique opportunity to study the impact of reduced anthropogenic emissions on aerosol chemistry in the city. Primary species showed ubiquitous reductions during the holiday period with the largest reduction being in cooking organic aerosol (OA; 69%), in nitrogen monoxide (54%), and in coal combustion OA (28%). Secondary sulfate, however, remained only slightly changed, and the SOA and the total PM2.5 even slightly increased. Our results have significant implications for controlling local primary source emissions during PEs, e.g., cooking and traffic activities. Controlling these factors might have a limited effect on improving air quality in the megacity of Beijing, due to the dominance of SPM from regional transport in aerosol particle composition.

  18. Light absorption of secondary organic aerosol: Composition and contribution of nitro-aromatic compounds

    Science.gov (United States)

    Secondary organic aerosol (SOA) might affect the atmospheric radiation balance through absorbing light at shorter visible and UV wavelengths. However, the composition and optical properties of light-absorbing SOA is poorly understood. In this work, SOA filter samples were collect...

  19. Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

    Science.gov (United States)

    Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen; Goldstein, Allen H.; Guenther, Alex B.; Jimenez, Jose L.; Kuang, Chongai; Laskin, Alexander; Martin, Scot T.; Ng, Nga Lee; Petaja, Tuukka; Pierce, Jeffrey R.; Rasch, Philip J.; Roldin, Pontus; Seinfeld, John H.; Shilling, John; Smith, James N.; Thornton, Joel A.; Volkamer, Rainer; Wang, Jian; Worsnop, Douglas R.; Zaveri, Rahul A.; Zelenyuk, Alla; Zhang, Qi

    2017-06-01

    Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process-related interactions, so that these processes can be accurately represented in atmospheric chemistry-climate models.

  20. Modeling organic aerosols during MILAGRO: importance of biogenic secondary organic aerosols

    Directory of Open Access Journals (Sweden)

    A. Hodzic

    2009-09-01

    Full Text Available 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 contain 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 one-step oxidation of anthropogenic (i.e. aromatics, alkanes, biogenic (i.e. monoterpenes and isoprene, and biomass-burning SOA precursors and their partitioning into both organic and aqueous phases. Conservative assumptions are made for uncertain parameters to maximize the amount of SOA produced by the model. 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, with a factor of 2–10 model underestimate. When only anthropogenic SOA precursors were considered, the model was able to reproduce within a factor of two the sharp increase in OOA concentrations during the late morning at both urban and near-urban locations but the discrepancy increases rapidly later in the day, consistent with previous results, and is especially obvious when the column-integrated SOA mass is considered instead of the surface concentration. The increase in the missing SOA mass in the afternoon coincides with the sharp drop in POA

  1. Uptake of Alkylamines on Dicarboxylic Acids Relevant to Secondary Organic Aerosol Formation

    Science.gov (United States)

    Marrero-Ortiz, W.; Secrest, J.; Zhang, R.

    2017-12-01

    Aerosols play a critical role in climate directly by scattering and absorbing solar radiation, and indirectly by functioning as cloud condensation nuclei (CCN); both represent the largest uncertainties in climate predictions. New particle formation contributes significantly to CCN production; however, the mechanisms related to particle nucleation and growth processes are not well understood. Organic acids are atmospherically abundant, and their neutralization by low molecular weight amines may result in the formation of stable low volatility aminium salt products contributing to the growth of secondary organic aerosols and even the alteration of the aerosol properties. The acid-base neutralization of particle phase succinic acid and tartaric acid by low molecular weight aliphatic amines, i.e. methylamine, dimethylamine, and trimethylamine, has been investigated by employing a low-pressure fast flow reactor at 298K with an ion drift - chemical ionization mass spectrometer (ID-CIMS). The heterogeneous uptake is time dependent and influenced by organic acids functionality, alkylamines basicity, and steric effect. The implications of our results to atmospheric nanoparticle growth will be discussed.

  2. Mixing of secondary organic aerosols versus relative humidity

    Science.gov (United States)

    Ye, Qing; Robinson, Ellis Shipley; Ding, Xiang; Ye, Penglin

    2016-01-01

    Atmospheric aerosols exert a substantial influence on climate, ecosystems, visibility, and human health. Although secondary organic aerosols (SOA) dominate fine-particle mass, they comprise myriad compounds with uncertain sources, chemistry, and interactions. SOA formation involves absorption of vapors into particles, either because gas-phase chemistry produces low-volatility or semivolatile products that partition into particles or because more-volatile organics enter particles and react to form lower-volatility products. Thus, SOA formation involves both production of low-volatility compounds and their diffusion into particles. Most chemical transport models assume a single well-mixed phase of condensing organics and an instantaneous equilibrium between bulk gas and particle phases; however, direct observations constraining diffusion of semivolatile organics into particles containing SOA are scarce. Here we perform unique mixing experiments between SOA populations including semivolatile constituents using quantitative, single-particle mass spectrometry to probe any mass-transfer limitations in particles containing SOA. We show that, for several hours, particles containing SOA from toluene oxidation resist exchange of semivolatile constituents at low relative humidity (RH) but start to lose that resistance above 20% RH. Above 40% RH, the exchange of material remains constant up to 90% RH. We also show that dry particles containing SOA from α-pinene ozonolysis do not appear to resist exchange of semivolatile compounds. Our interpretation is that in-particle diffusion is not rate-limiting to mass transfer in these systems above 40% RH. To the extent that these systems are representative of ambient SOA, we conclude that diffusion limitations are likely not common under typical ambient boundary layer conditions. PMID:27791066

  3. Mixing of secondary organic aerosols versus relative humidity.

    Science.gov (United States)

    Ye, Qing; Robinson, Ellis Shipley; Ding, Xiang; Ye, Penglin; Sullivan, Ryan C; Donahue, Neil M

    2016-10-24

    Atmospheric aerosols exert a substantial influence on climate, ecosystems, visibility, and human health. Although secondary organic aerosols (SOA) dominate fine-particle mass, they comprise myriad compounds with uncertain sources, chemistry, and interactions. SOA formation involves absorption of vapors into particles, either because gas-phase chemistry produces low-volatility or semivolatile products that partition into particles or because more-volatile organics enter particles and react to form lower-volatility products. Thus, SOA formation involves both production of low-volatility compounds and their diffusion into particles. Most chemical transport models assume a single well-mixed phase of condensing organics and an instantaneous equilibrium between bulk gas and particle phases; however, direct observations constraining diffusion of semivolatile organics into particles containing SOA are scarce. Here we perform unique mixing experiments between SOA populations including semivolatile constituents using quantitative, single-particle mass spectrometry to probe any mass-transfer limitations in particles containing SOA. We show that, for several hours, particles containing SOA from toluene oxidation resist exchange of semivolatile constituents at low relative humidity (RH) but start to lose that resistance above 20% RH. Above 40% RH, the exchange of material remains constant up to 90% RH. We also show that dry particles containing SOA from α-pinene ozonolysis do not appear to resist exchange of semivolatile compounds. Our interpretation is that in-particle diffusion is not rate-limiting to mass transfer in these systems above 40% RH. To the extent that these systems are representative of ambient SOA, we conclude that diffusion limitations are likely not common under typical ambient boundary layer conditions.

  4. Large contribution of fossil fuel derived secondary organic carbon to water soluble organic aerosols in winter haze in China

    Science.gov (United States)

    Zhang, Yan-Lin; El-Haddad, Imad; Huang, Ru-Jin; Ho, Kin-Fai; Cao, Jun-Ji; Han, Yongming; Zotter, Peter; Bozzetti, Carlo; Daellenbach, Kaspar R.; Slowik, Jay G.; Salazar, Gary; Prévôt, André S. H.; Szidat, Sönke

    2018-03-01

    Water-soluble organic carbon (WSOC) is a large fraction of organic aerosols (OA) globally and has significant impacts on climate and human health. The sources of WSOC remain very uncertain in polluted regions. Here we present a quantitative source apportionment of WSOC, isolated from aerosols in China using radiocarbon (14C) and offline high-resolution time-of-flight aerosol mass spectrometer measurements. Fossil emissions on average accounted for 32-47 % of WSOC. Secondary organic carbon (SOC) dominated both the non-fossil and fossil derived WSOC, highlighting the importance of secondary formation to WSOC in severe winter haze episodes. Contributions from fossil emissions to SOC were 61 ± 4 and 50 ± 9 % in Shanghai and Beijing, respectively, significantly larger than those in Guangzhou (36 ± 9 %) and Xi'an (26 ± 9 %). The most important primary sources were biomass burning emissions, contributing 17-26 % of WSOC. The remaining primary sources such as coal combustion, cooking and traffic were generally very small but not negligible contributors, as coal combustion contribution could exceed 10 %. Taken together with earlier 14C source apportionment studies in urban, rural, semi-urban and background regions in Asia, Europe and the USA, we demonstrated a dominant contribution of non-fossil emissions (i.e., 75 ± 11 %) to WSOC aerosols in the Northern Hemisphere; however, the fossil fraction is substantially larger in aerosols from East Asia and the eastern Asian pollution outflow, especially during winter, due to increasing coal combustion. Inclusion of our findings can improve a modelling of effects of WSOC aerosols on climate, atmospheric chemistry and public health.

  5. Characterization of Halyomorpha halys (brown marmorated stink bug) biogenic volatile organic compound emissions and their role in secondary organic aerosol formation.

    Science.gov (United States)

    Solomon, Danielle; Dutcher, Dabrina; Raymond, Timothy

    2013-11-01

    The formation of aerosols is a key component in understanding cloud formation in the context of radiative forcings and global climate modeling. Biogenic volatile organic compounds (BVOCs) are a significant source of aerosols, yet there is still much to be learned about their structures, sources, and interactions. The aims of this project were to identify the BVOCs found in the defense chemicals of the brown marmorated stink bug Halymorpha halys and quantify them using gas chromatography-mass spectrometry (GC/MS) and test whether oxidation of these compounds by ozone-promoted aerosol and cloud seed formation. The bugs were tested under two conditions: agitation by asphyxiation and direct glandular exposure. Tridecane, 2(5H)-furanone 5-ethyl, and (E)-2-decenal were identified as the three most abundant compounds. H. halys were also tested in the agitated condition in a smog chamber. It was found that in the presence of 100-180 ppm ozone, secondary aerosols do form. A scanning mobility particle sizer (SMPS) and a cloud condensation nuclei counter (CCNC) were used to characterize the secondary aerosols that formed. This reaction resulted in 0.23 microg/ bug of particulate mass. It was also found that these secondary organic aerosol particles could act as cloud condensation nuclei. At a supersaturation of 1%, we found a kappa value of 0.09. Once regional populations of these stink bugs stablilize and the populations estimates can be made, the additional impacts of their contribution to regional air quality can be calculated.

  6. The impact of building recirculation rates on secondary organic aerosols generated by indoor chemistry

    DEFF Research Database (Denmark)

    Zuraimi, M.S.; Weschler, Charles J.; Tham, K.W.

    2007-01-01

    Numerous investigators have documented increases in the concentrations of airborne particles as a consequence of ozone/terpene reactions in indoor environments. This study examines the effect of building recirculation rates on the concentrations of secondary organic aerosol (SOA) resulting from r...

  7. Secondary organic aerosol formation from a large number of reactive man-made organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Derwent, Richard G., E-mail: r.derwent@btopenworld.com [rdscientific, Newbury, Berkshire (United Kingdom); Jenkin, Michael E. [Atmospheric Chemistry Services, Okehampton, Devon (United Kingdom); Utembe, Steven R.; Shallcross, Dudley E. [School of Chemistry, University of Bristol, Bristol (United Kingdom); Murrells, Tim P.; Passant, Neil R. [AEA Environment and Energy, Harwell International Business Centre, Oxon (United Kingdom)

    2010-07-15

    A photochemical trajectory model has been used to examine the relative propensities of a wide variety of volatile organic compounds (VOCs) emitted by human activities to form secondary organic aerosol (SOA) under one set of highly idealised conditions representing northwest Europe. This study applied a detailed speciated VOC emission inventory and the Master Chemical Mechanism version 3.1 (MCM v3.1) gas phase chemistry, coupled with an optimised representation of gas-aerosol absorptive partitioning of 365 oxygenated chemical reaction product species. In all, SOA formation was estimated from the atmospheric oxidation of 113 emitted VOCs. A number of aromatic compounds, together with some alkanes and terpenes, showed significant propensities to form SOA. When these propensities were folded into a detailed speciated emission inventory, 15 organic compounds together accounted for 97% of the SOA formation potential of UK man made VOC emissions and 30 emission source categories accounted for 87% of this potential. After road transport and the chemical industry, SOA formation was dominated by the solvents sector which accounted for 28% of the SOA formation potential.

  8. Small molecules as tracers in atmospheric secondary organic aerosol

    Science.gov (United States)

    Yu, Ge

    Secondary organic aerosol (SOA), formed from in-air oxidation of volatile organic compounds, greatly affects human health and climate. Although substantial research has been devoted to SOA formation and evolution, the modeled and lab-generated SOA are still low in mass and degree of oxidation compared to ambient measurements. In order to compensate for these discrepancies, the aqueous processing pathway has been brought to attention. The atmospheric waters serve as aqueous reaction media for dissolved organics to undergo further oxidation, oligomerization, or other functionalization reactions, which decreases the vapor pressure while increasing the oxidation state of carbon atoms. Field evidence for aqueous processing requires the identification of tracer products such as organosulfates. We synthesized the standards for two organosulfates, glycolic acid sulfate and lactic acid sulfate, in order to measure their aerosol-state concentration from five distinct locations via filter samples. The water-extracted filter samples were analyzed by LC-MS. Lactic acid sulfate and glycolic acid sulfate were detected in urban locations in the United States, Mexico City, and Pakistan with varied concentrations, indicating their potential as tracers. We studied the aqueous processing reaction between glyoxal and nitrogen-containing species such as ammonium and amines exclusively by NMR spectrometry. The reaction products formic acid and several imidazoles along with the quantified kinetics were reported. The brown carbon generated from these reactions were quantified optically by UV-Vis spectroscopy. The organic-phase reaction between oxygen molecule and alkenes photosensitized by alpha-dicarbonyls were studied in the same manner. We observed the fast kinetics transferring alkenes to epoxides under simulated sunlight. Statistical estimations indicate a very effective conversion of aerosol-phase alkenes to epoxides, potentially forming organosulfates in a deliquescence event and

  9. Quantitative evaluation of emission controls on primary and secondary organic aerosol sources during Beijing 2008 Olympics

    Directory of Open Access Journals (Sweden)

    S. Guo

    2013-08-01

    Full Text Available To assess the primary and secondary sources of fine organic aerosols after the aggressive implementation of air pollution controls during the 2008 Beijing Olympic Games, 12 h PM2.5 values were measured at an urban site at Peking University (PKU and an upwind rural site at Yufa during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region summer field campaign. The average PM2.5 concentrations were 72.5 ± 43.6 μg m−3 and 64.3 ± 36.2 μg m−3 (average ± standard deviation, below as the same at PKU and Yufa, respectively, showing the lowest concentrations in recent years. Combining the results from a CMB (chemical mass balance model and secondary organic aerosol (SOA tracer-yield model, five primary and four secondary fine organic aerosol sources were compared with the results from previous studies in Beijing. The relative contribution of mobile sources to PM2.5 concentrations was increased in 2008, with diesel engines contributing 16.2 ± 5.9% and 14.5 ± 4.1% and gasoline vehicles contributing 10.3 ± 8.7% and 7.9 ± 6.2% to organic carbon (OC at PKU and Yufa, respectively. Due to the implementation of emission controls, the absolute OC concentrations from primary sources were reduced during the Olympics, and the contributions from secondary formation of OC represented a larger relative source of fine organic aerosols. Compared with the non-controlled period prior to the Olympics, primary vehicle contributions were reduced by 30% at the urban site and 24% at the rural site. The reductions in coal combustion contributions were 57% at PKU and 7% at Yufa. Our results demonstrate that the emission control measures implemented in 2008 significantly alleviated the primary organic particle pollution in and around Beijing. However, additional studies are needed to provide a more comprehensive assessment of the emission control effectiveness on SOA formation.

  10. Direct Observations of Isoprene Secondary Organic Aerosol Formation in Ambient Cloud Droplets

    Science.gov (United States)

    Zelenyuk, A.; Bell, D.; Thornton, J. A.; Fast, J. D.; Shrivastava, M. B.; Berg, L. K.; Imre, D. G.; Mei, F.; Shilling, J.; Suski, K. J.; Liu, J.; Tomlinson, J. M.; Wang, J.

    2017-12-01

    Multiphase chemistry of isoprene photooxidation products has been shown to be one of the major sources of secondary organic aerosol (SOA) in the atmosphere. A number of recent studies indicate that aqueous aerosol phase provides a medium for reactive uptake of isoprene photooxidation products, and in particular, isomeric isoprene epoxydiols (IEPOX), with reaction rates and yields being dependent on aerosol acidity, water content, sulfate concentration, and organic coatings. However, very few studies focused on chemistry occurring within actual cloud droplets. We will present data acquired during recent Holistic Interactions of Shallow Clouds, Aerosols, and Land Ecosystems (HI-SCALE) Campaign, which provide direct evidence for IEPOX-SOA formation in cloud droplets. Single particle mass spectrometer, miniSPLAT, and a high-resolution, time-of-flight aerosol mass spectrometer were used to characterize the composition of aerosol particles and cloud droplet residuals, while a high-resolution, time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) was used to characterize gas-phase compounds. We find that the composition of cloud droplet residuals was markedly different than that of aerosol particles sampled outside the cloud. Cloud droplet residuals were comprised of individual particles with high relative fractions of sulfate and nitrate and significant fraction of particles with mass spectra that are nearly identical to those of laboratory-generated IEPOX-SOA particles. The observed cloud-induced formation of IEPOX-SOA was accompanied by simultaneous decrease in measured concentrations of IEPOX and other gas-phase isoprene photooxidation products. Ultimately, the combined cloud, aerosol, and gas-phase measurements conducted during HI-SCALE will be used to develop and evaluate model treatments of aqueous-phase isoprene SOA formation.

  11. Secondary organic aerosol importance in the future atmosphere

    International Nuclear Information System (INIS)

    Tsigaridis, K.; Kanakidou, M.

    2007-01-01

    In order to investigate the secondary organic aerosol (SOA) response to changes in biogenic volatile organic compounds (VOC) emissions in the future atmosphere and how important will SOA be relative to the major anthropogenic aerosol component (sulfate), the global three-dimensional chemistry/transport model TM3 has been used. Emission estimates of biogenic VOC (BVOC) and anthropogenic gases and particles from the literature for the year 2100 have been adopted. According to our present-day model simulations, isoprene oxidation produces 4.6 Tg SOA yr -1 , that is less than half of the 12.2 Tg SOA yr -1 formed by the oxidation of other BVOC. In the future, nitrate radicals and ozone become more important than nowadays, but remain minor oxidants for both isoprene and aromatics. SOA produced by isoprene is estimated to almost triple, whereas the production from other BVOC more than triples. The calculated future SOA burden change, from 0.8 Tg at present to 2.0 Tg in the future, is driven by changes in emissions, oxidant levels and pre-existing particles. The non-linearity in SOA formation and the involved chemical and physical feedbacks prohibit the quantitative attribution of the computed changes to the above-mentioned individual factors. In 2100, SOA burden is calculated to exceed that of sulfate, indicating that SOA might become more important than nowadays. These results critically depend on the biogenic emissions and thus are subject to the high uncertainty associated with these emissions estimated due to the insufficient knowledge on plant response to carbon dioxide changes. Nevertheless, they clearly indicate that the change in oxidants and primary aerosol caused by human activities can contribute as much as the change in BVOC emissions to the increase of the biogenic SOA production in the future atmosphere. (authors)

  12. Potential of secondary aerosol formation from Chinese gasoline engine exhaust.

    Science.gov (United States)

    Du, Zhuofei; Hu, Min; Peng, Jianfei; Guo, Song; Zheng, Rong; Zheng, Jing; Shang, Dongjie; Qin, Yanhong; Niu, He; Li, Mengren; Yang, Yudong; Lu, Sihua; Wu, Yusheng; Shao, Min; Shuai, Shijin

    2018-04-01

    Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds (VOCs). However, little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4-5hr simulation, which was estimated to represent more than 10days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol (SOA) production was 426±85mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China. Copyright © 2017. Published by Elsevier B.V.

  13. Formation of secondary organic aerosols from gas-phase emissions of heated cooking oils

    Directory of Open Access Journals (Sweden)

    T. Liu

    2017-06-01

    Full Text Available Cooking emissions can potentially contribute to secondary organic aerosol (SOA but remain poorly understood. In this study, formation of SOA from gas-phase emissions of five heated vegetable oils (i.e., corn, canola, sunflower, peanut and olive oils was investigated in a potential aerosol mass (PAM chamber. Experiments were conducted at 19–20 °C and 65–70 % relative humidity (RH. The characterization instruments included a scanning mobility particle sizer (SMPS and a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS. The efficiency of SOA production, in ascending order, was peanut oil, olive oil, canola oil, corn oil and sunflower oil. The major SOA precursors from heated cooking oils were related to the content of monounsaturated fat and omega-6 fatty acids in cooking oils. The average production rate of SOA, after aging at an OH exposure of 1. 7 × 1011 molecules cm−3 s, was 1. 35 ± 0. 30 µg min−1, 3 orders of magnitude lower compared with emission rates of fine particulate matter (PM2. 5 from heated cooking oils in previous studies. The mass spectra of cooking SOA highly resemble field-derived COA (cooking-related organic aerosol in ambient air, with R2 ranging from 0.74 to 0.88. The average carbon oxidation state (OSc of SOA was −1.51 to −0.81, falling in the range between ambient hydrocarbon-like organic aerosol (HOA and semi-volatile oxygenated organic aerosol (SV-OOA, indicating that SOA in these experiments was lightly oxidized.

  14. A large source of low-volatility secondary organic aerosol

    DEFF Research Database (Denmark)

    Ehn, Mikael; Thornton, Joel A.; Kleist, Einhard

    2014-01-01

    radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed...... particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate...... the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form...

  15. Humidity influence on gas-particle phase partitioning of α-pinene + O3 secondary organic aerosol

    Science.gov (United States)

    Prisle, N. L.; Engelhart, G. J.; Bilde, M.; Donahue, N. M.

    2010-01-01

    Water vapor uptake to particles could potentially affect organic-aerosol mass in three ways: first, water in the organic phase could reduce organic (equilibrium) partial pressures according to Raoult's law; second, an aqueous phase could attract water soluble organics according to Henry's law; finally, deliquescence of inorganic particle cores could mix the organic and inorganic particle phases, significantly diluting the organics and again reducing organic partial pressures according to Raoult's law. We present experiments using initially dry α-pinene + ozone secondary organic aerosol (SOA) on ammonium sulfate (AS) seeds at atmospheric concentrations in a smog chamber. After SOA formation, the chamber relative humidity is increased steadily by addition of steam to near 100%. Little subsequent SOA mass growth is observed, suggesting that none of these potential effects play a strong role in this system.

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

    Directory of Open Access Journals (Sweden)

    E. M. Knipping

    2011-02-01

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

  17. Secondary organic aerosol: a comparison between foggy and nonfoggy days.

    Science.gov (United States)

    Kaul, D S; Gupta, Tarun; Tripathi, S N; Tare, V; Collett, J L

    2011-09-01

    Carbonaceous species, meteorological parameters, trace gases, and fogwater chemistry were measured during winter in the Indian city of Kanpur to study secondary organic aerosol (SOA) during foggy and clear (nonfoggy) days. Enhanced SOA production was observed during fog episodes. It is hypothesized that aqueous phase chemistry in fog drops is responsible for increasing SOA production. SOA concentrations on foggy days exceeded those on clear days at all times of day; peak foggy day SOA concentrations were observed in the evening vs peak clear day SOA concentrations which occurred in the afternoon. Changes in biomass burning emissions on foggy days were examined because of their potential to confound estimates of SOA production based on analysis of organic to elemental carbon (OC/EC) ratios. No evidence of biomass burning influence on SOA during foggy days was found. Enhanced oxidation of SO(2) to sulfate during foggy days was observed, possibly causing the regional aerosol to become more acidic. No evidence was found in this study, either, for effects of temperature or relative humidity on SOA production. In addition to SOA production, fogs can also play an important role in cleaning the atmosphere of carbonaceous aerosols. Preferential scavenging of water-soluble organic carbon (WSOC) by fog droplets was observed. OC was found to be enriched in smaller droplets, limiting the rate of OC deposition by droplet sedimentation. Lower EC concentrations were observed on foggy days, despite greater stagnation and lower mixing heights, suggesting fog scavenging and removal of EC was active as well.

  18. Gasoline emissions dominate over diesel in formation of secondary organic aerosol mass

    Science.gov (United States)

    Bahreini, R.; Middlebrook, A. M.; de Gouw, J. A.; Warneke, C.; Trainer, M.; Brock, C. A.; Stark, H.; Brown, S. S.; Dube, W. P.; Gilman, J. B.; Hall, K.; Holloway, J. S.; Kuster, W. C.; Perring, A. E.; Prevot, A. S. H.; Schwarz, J. P.; Spackman, J. R.; Szidat, S.; Wagner, N. L.; Weber, R. J.; Zotter, P.; Parrish, D. D.

    2012-03-01

    Although laboratory experiments have shown that organic compounds in both gasoline fuel and diesel engine exhaust can form secondary organic aerosol (SOA), the fractional contribution from gasoline and diesel exhaust emissions to ambient SOA in urban environments is poorly known. Here we use airborne and ground-based measurements of organic aerosol (OA) in the Los Angeles (LA) Basin, California made during May and June 2010 to assess the amount of SOA formed from diesel emissions. Diesel emissions in the LA Basin vary between weekdays and weekends, with 54% lower diesel emissions on weekends. Despite this difference in source contributions, in air masses with similar degrees of photochemical processing, formation of OA is the same on weekends and weekdays, within the measurement uncertainties. This result indicates that the contribution from diesel emissions to SOA formation is zero within our uncertainties. Therefore, substantial reductions of SOA mass on local to global scales will be achieved by reducing gasoline vehicle emissions.

  19. Large contribution of fossil fuel derived secondary organic carbon to water soluble organic aerosols in winter haze in China

    Directory of Open Access Journals (Sweden)

    Y.-L. Zhang

    2018-03-01

    Full Text Available Water-soluble organic carbon (WSOC is a large fraction of organic aerosols (OA globally and has significant impacts on climate and human health. The sources of WSOC remain very uncertain in polluted regions. Here we present a quantitative source apportionment of WSOC, isolated from aerosols in China using radiocarbon (14C and offline high-resolution time-of-flight aerosol mass spectrometer measurements. Fossil emissions on average accounted for 32–47 % of WSOC. Secondary organic carbon (SOC dominated both the non-fossil and fossil derived WSOC, highlighting the importance of secondary formation to WSOC in severe winter haze episodes. Contributions from fossil emissions to SOC were 61 ± 4 and 50 ± 9 % in Shanghai and Beijing, respectively, significantly larger than those in Guangzhou (36 ± 9 % and Xi'an (26 ± 9 %. The most important primary sources were biomass burning emissions, contributing 17–26 % of WSOC. The remaining primary sources such as coal combustion, cooking and traffic were generally very small but not negligible contributors, as coal combustion contribution could exceed 10 %. Taken together with earlier 14C source apportionment studies in urban, rural, semi-urban and background regions in Asia, Europe and the USA, we demonstrated a dominant contribution of non-fossil emissions (i.e., 75 ± 11 % to WSOC aerosols in the Northern Hemisphere; however, the fossil fraction is substantially larger in aerosols from East Asia and the eastern Asian pollution outflow, especially during winter, due to increasing coal combustion. Inclusion of our findings can improve a modelling of effects of WSOC aerosols on climate, atmospheric chemistry and public health.

  20. Regional modeling of carbonaceous aerosols over Europe-focus on secondary organic aerosols

    International Nuclear Information System (INIS)

    Bessagnet, B.; Menut, L.; Curci, G.; Hodzic, A.; Guillaume, B.; Liousse, C.; Moukhtar, S.; Pun, B.; Seigneur, C.; Schulz, M.

    2008-01-01

    In this study, an improved and complete secondary organic aerosols (SOA) chemistry scheme was implemented in the CHIMERE model. The implementation of isoprene chemistry for SOA significantly improves agreement between long series of simulated and observed particulate matter concentrations. While simulated organic carbon concentrations are clearly improved at elevated sites by adding the SOA scheme, time correlation are impaired at low level sites in Portugal, Italy and Slovakia. At several sites a clear underestimation by the CHIMERE model is noticed in wintertime possibly due to missing wood burning emissions as shown in previous modeling studies. In Europe, the CHIMERE model gives yearly average SOA concentrations ranging from 0.5 μg m -3 in the Northern Europe to 4 μg m -3 over forested regions in Spain, France, Germany and Italy. In addition, our work suggests that during the highest fire emission periods, fires can be the dominant source of primary organic carbon over the Mediterranean Basin, but the SOA contribution from fire emissions is low. Isoprene chemistry has a strong impact on SOA formation when using current available kinetic schemes. (authors)

  1. Identification of secondary aerosol precursors emitted by an aircraft turbofan

    Science.gov (United States)

    Kılıç, Doğuşhan; El Haddad, Imad; Brem, Benjamin T.; Bruns, Emily; Bozetti, Carlo; Corbin, Joel; Durdina, Lukas; Huang, Ru-Jin; Jiang, Jianhui; Klein, Felix; Lavi, Avi; Pieber, Simone M.; Rindlisbacher, Theo; Rudich, Yinon; Slowik, Jay G.; Wang, Jing; Baltensperger, Urs; Prévôt, Andre S. H.

    2018-05-01

    Oxidative processing of aircraft turbine-engine exhausts was studied using a potential aerosol mass (PAM) chamber at different engine loads corresponding to typical flight operations. Measurements were conducted at an engine test cell. Organic gases (OGs) and particle emissions pre- and post-PAM were measured. A suite of instruments, including a proton-transfer-reaction mass spectrometer (PTR-MS) for OGs, a multigas analyzer for CO, CO2, NOx, and an aerosol mass spectrometer (AMS) for nonrefractory particulate matter (NR-PM1) were used. Total aerosol mass was dominated by secondary aerosol formation, which was approximately 2 orders of magnitude higher than the primary aerosol. The chemical composition of both gaseous and particle emissions were also monitored at different engine loads and were thrust-dependent. At idling load (thrust 2.5-7 %), more than 90 % of the secondary particle mass was organic and could mostly be explained by the oxidation of gaseous aromatic species, e.g., benzene; toluene; xylenes; tri-, tetra-, and pentamethyl-benzene; and naphthalene. The oxygenated-aromatics, e.g., phenol, furans, were also included in this aromatic fraction and their oxidation could alone explain up to 25 % of the secondary organic particle mass at idling loads. The organic fraction decreased with thrust level, while the inorganic fraction increased. At an approximated cruise load sulfates comprised 85 % of the total secondary particle mass.

  2. Secondary organic aerosol from VOC mixtures in an oxidation flow reactor

    Science.gov (United States)

    Ahlberg, Erik; Falk, John; Eriksson, Axel; Holst, Thomas; Brune, William H.; Kristensson, Adam; Roldin, Pontus; Svenningsson, Birgitta

    2017-07-01

    The atmospheric organic aerosol is a tremendously complex system in terms of chemical content. Models generally treat the mixtures as ideal, something which has been questioned owing to model-measurement discrepancies. We used an oxidation flow reactor to produce secondary organic aerosol (SOA) mixtures containing oxidation products of biogenic (α-pinene, myrcene and isoprene) and anthropogenic (m-xylene) volatile organic compounds (VOCs). The resulting volume concentration and chemical composition was measured using a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. The SOA mass yield of the mixtures was compared to a partitioning model constructed from single VOC experiments. The single VOC SOA mass yields with no wall-loss correction applied are comparable to previous experiments. In the mixtures containing myrcene a higher yield than expected was produced. We attribute this to an increased condensation sink, arising from myrcene producing a significantly higher number of nucleation particles compared to the other precursors. Isoprene did not produce much mass in single VOC experiments but contributed to the mass of the mixtures. The effect of high concentrations of isoprene on the OH exposure was found to be small, even at OH reactivities that previously have been reported to significantly suppress OH exposures in oxidation flow reactors. Furthermore, isoprene shifted the particle size distribution of mixtures towards larger sizes, which could be due to a change in oxidant dynamics inside the reactor.

  3. High formation of secondary organic aerosol from the photo-oxidation of toluene

    Directory of Open Access Journals (Sweden)

    L. Hildebrandt

    2009-05-01

    Full Text Available Toluene and other aromatics have long been viewed as the dominant anthropogenic secondary organic aerosol (SOA precursors, but the SOA mass yields from toluene reported in previous studies vary widely. Experiments conducted in the Carnegie Mellon University environmental chamber to study SOA formation from the photo-oxidation of toluene show significantly larger SOA production than parameterizations employed in current air-quality models. Aerosol mass yields depend on experimental conditions: yields are higher under higher UV intensity, under low-NOx conditions and at lower temperatures. The extent of oxidation of the aerosol also varies with experimental conditions, consistent with ongoing, progressive photochemical aging of the toluene SOA. Measurements using a thermodenuder system suggest that the aerosol formed under high- and low-NOx conditions is semi-volatile. These results suggest that SOA formation from toluene depends strongly on ambient conditions. An approximate parameterization is proposed for use in air-quality models until a more thorough treatment accounting for the dynamic nature of this system becomes available.

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

    Science.gov (United States)

    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...

  5. Gas phase precursors to anthropogenic secondary organic aerosol: detailed observations of 1,3,5-trimethylbenzene photooxidation

    Directory of Open Access Journals (Sweden)

    K. P. Wyche

    2009-01-01

    Full Text Available A series of photooxidation experiments were conducted in an atmospheric simulation chamber in order to investigate the oxidation mechanism and secondary organic aerosol (SOA formation potential of the model anthropogenic gas phase precursor, 1,3,5-trimethylbenzene. Alongside specific aerosol measurements, comprehensive gas phase measurements, primarily by Chemical Ionisation Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS, were carried out to provide detailed insight into the composition and behaviour of the organic components of the gas phase matrix during SOA formation. An array of gas phase organic compounds was measured during the oxidation process, including several previously unmeasured primary bicyclic compounds possessing various functional groups. Analysis of results obtained during this study implies that these peroxide bicyclic species along with a series of ring opening products and organic acids contribute to SOA growth. The effect of varying the VOC/NOx ratio on SOA formation was explored, as was the effect of acid seeding. It was found that low NOx conditions favour more rapid aerosol formation and a higher aerosol yield, a result that implies a role for organic peroxides in the nucleation process and SOA growth.

  6. Identification of secondary aerosol precursors emitted by an aircraft turbofan

    Directory of Open Access Journals (Sweden)

    D. Kılıç

    2018-05-01

    Full Text Available Oxidative processing of aircraft turbine-engine exhausts was studied using a potential aerosol mass (PAM chamber at different engine loads corresponding to typical flight operations. Measurements were conducted at an engine test cell. Organic gases (OGs and particle emissions pre- and post-PAM were measured. A suite of instruments, including a proton-transfer-reaction mass spectrometer (PTR-MS for OGs, a multigas analyzer for CO, CO2, NOx, and an aerosol mass spectrometer (AMS for nonrefractory particulate matter (NR-PM1 were used. Total aerosol mass was dominated by secondary aerosol formation, which was approximately 2 orders of magnitude higher than the primary aerosol. The chemical composition of both gaseous and particle emissions were also monitored at different engine loads and were thrust-dependent. At idling load (thrust 2.5–7 %, more than 90 % of the secondary particle mass was organic and could mostly be explained by the oxidation of gaseous aromatic species, e.g., benzene; toluene; xylenes; tri-, tetra-, and pentamethyl-benzene; and naphthalene. The oxygenated-aromatics, e.g., phenol, furans, were also included in this aromatic fraction and their oxidation could alone explain up to 25 % of the secondary organic particle mass at idling loads. The organic fraction decreased with thrust level, while the inorganic fraction increased. At an approximated cruise load sulfates comprised 85 % of the total secondary particle mass.

  7. Regional modeling of carbonaceous aerosols over Europe-focus on secondary organic aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Bessagnet, B. [INERIS, Inst Nat Env Indust Risques, F-60550 Verneuil en Halatte, (France); Menut, L. [Ecole Poltechnique, Inst Pierre Simon Laplace, Lab Meteorol Dyn, F-91128 Palaiseau, (France); Curci, G. [Univ degli Studi dell' Aquila, CETEMPS, 67010 Coppito - L' Aquila, (Italy); Hodzic, A. [NCAR, Nat Center for Atmosph Research, Boulder, 80301, CO, (United States); Guillaume, B.; Liousse, C. [LA/OMP, Lab Aerol/Observ Midi-Pyrenees, F-31400 Toulouse, (France); Moukhtar, S. [York Univ, Centre Atmosph Chem, Toronto, (Italy); Pun, B.; Seigneur, C. [Atmosph and Environ Research, San Ramon, CA 94583, (United States); Schulz, M. [CEA-CNRS-UVSQ, IPSL, Lab Sciences Climat et Environm, F-91191 Gif sur Yvette, (France)

    2008-07-01

    In this study, an improved and complete secondary organic aerosols (SOA) chemistry scheme was implemented in the CHIMERE model. The implementation of isoprene chemistry for SOA significantly improves agreement between long series of simulated and observed particulate matter concentrations. While simulated organic carbon concentrations are clearly improved at elevated sites by adding the SOA scheme, time correlation are impaired at low level sites in Portugal, Italy and Slovakia. At several sites a clear underestimation by the CHIMERE model is noticed in wintertime possibly due to missing wood burning emissions as shown in previous modeling studies. In Europe, the CHIMERE model gives yearly average SOA concentrations ranging from 0.5 {mu}g m{sup -3} in the Northern Europe to 4 {mu}g m{sup -3} over forested regions in Spain, France, Germany and Italy. In addition, our work suggests that during the highest fire emission periods, fires can be the dominant source of primary organic carbon over the Mediterranean Basin, but the SOA contribution from fire emissions is low. Isoprene chemistry has a strong impact on SOA formation when using current available kinetic schemes. (authors)

  8. Estimating the direct and indirect effects of secondary organic aerosols using ECHAM5-HAM

    Directory of Open Access Journals (Sweden)

    D. O'Donnell

    2011-08-01

    Full Text Available Secondary organic aerosol (SOA has been introduced into the global climate-aerosol model ECHAM5/HAM. The SOA module handles aerosols originating from both biogenic and anthropogenic sources. The model simulates the emission of precursor gases, their chemical conversion into condensable gases, the partitioning of semi-volatile condenable species into the gas and aerosol phases. As ECHAM5/HAM is a size-resolved model, a new method that permits the calculation of partitioning of semi-volatile species between different size classes is introduced. We compare results of modelled organic aerosol concentrations against measurements from extensive measurement networks in Europe and the United States, running the model with and without SOA. We also compare modelled aerosol optical depth against measurements from the AERONET network of grond stations. We find that SOA improves agreement between model and measurements in both organic aerosol mass and aerosol optical depth, but does not fully correct the low bias that is present in the model for both of these quantities. Although many models now include SOA, any overall estimate of the direct and indirect effects of these aerosols is still lacking. This paper makes a first step in that direction. The model is applied to estimate the direct and indirect effects of SOA under simulated year 2000 conditions. The modelled SOA spatial distribution indicates that SOA is likely to be an important source of free and upper tropospheric aerosol. We find a negative shortwave (SW forcing from the direct effect, amounting to −0.31 Wm−2 on the global annual mean. In contrast, the model indicates a positive indirect effect of SOA of +0.23 Wm−2, arising from the enlargement of particles due to condensation of SOA, together with an enhanced coagulation sink of small particles. In the longwave, model results are a direct effect of +0.02 Wm−2 and an indirect effect of −0.03 Wm−2

  9. Modeling of secondary organic aerosol yields from laboratory chamber data

    Directory of Open Access Journals (Sweden)

    M. N. Chan

    2009-08-01

    Full Text Available Laboratory chamber data serve as the basis for constraining models of secondary organic aerosol (SOA formation. Current models fall into three categories: empirical two-product (Odum, product-specific, and volatility basis set. The product-specific and volatility basis set models are applied here to represent laboratory data on the ozonolysis of α-pinene under dry, dark, and low-NOx conditions in the presence of ammonium sulfate seed aerosol. Using five major identified products, the model is fit to the chamber data. From the optimal fitting, SOA oxygen-to-carbon (O/C and hydrogen-to-carbon (H/C ratios are modeled. The discrepancy between measured H/C ratios and those based on the oxidation products used in the model fitting suggests the potential importance of particle-phase reactions. Data fitting is also carried out using the volatility basis set, wherein oxidation products are parsed into volatility bins. The product-specific model is most likely hindered by lack of explicit inclusion of particle-phase accretion compounds. While prospects for identification of the majority of SOA products for major volatile organic compounds (VOCs classes remain promising, for the near future empirical product or volatility basis set models remain the approaches of choice.

  10. Heterogeneous conversion of NO2 on secondary organic aerosol surfaces: A possible source of nitrous acid (HONO in the atmosphere?

    Directory of Open Access Journals (Sweden)

    R. Bröske

    2003-01-01

    Full Text Available The heterogeneous conversion of NO2 on different secondary organic aerosols (SOA was investigated with the focus on a possible formation of nitrous acid (HONO. In one set of experiments different organic aerosols were produced in the reactions of O3 with alpha-pinene, limonene or catechol and OH radicals with toluene or limonene, respectively. The aerosols were sampled on filters and exposed to humidified NO2  mixtures under atmospheric conditions. The estimated upper limits for the uptake coefficients of NO2  and the reactive uptake coefficients NO2  -> HONO are in the range of 10-6 and 10-7, respectively. The integrated HONO formation for 1 h reaction time was 13 cm-2 geometrical surface and 17 g-1 particle mass. In a second set of experiments the conversion of NO2 into HONO in the presence of organic particles was carried out in an aerosol flow tube under atmospheric conditions. In this case the aerosols were produced in the reaction of O3 with beta-pinene, limonene or catechol, respectively. The upper limits for the reactive uptake coefficients NO2 -> HONO were in the range of 7 x 10-7 - 9 x 10-6. The results from the present study show that heterogeneous formation of nitrous acid on secondary organic aerosols (SOA is unimportant for the atmosphere.

  11. The formation, properties and impact of secondary organic aerosol: current and emerging issues

    Directory of Open Access Journals (Sweden)

    J. Wildt

    2009-07-01

    Full Text Available Secondary organic aerosol (SOA accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

  12. Evaluation of the Volatility Basis-Set Approach for Modeling Primary and Secondary Organic Aerosol in the Mexico City Metropolitan Area

    Science.gov (United States)

    Tsimpidi, A. P.; Karydis, V. A.; Pandis, S. N.; Zavala, M.; Lei, W.; Molina, L. T.

    2007-12-01

    Anthropogenic air pollution is an increasingly serious problem for public health, agriculture, and global climate. Organic material (OM) contributes ~ 20-50% to the total fine aerosol mass at continental mid-latitudes. Although OM accounts for a large fraction of PM2.5 concentration worldwide, the contributions of primary and secondary organic aerosol have been difficult to quantify. In this study, new primary and secondary organic aerosol modules were added to PMCAMx, a three dimensional chemical transport model (Gaydos et al., 2007), for use with the SAPRC99 chemistry mechanism (Carter, 2000; ENVIRON, 2006) based on recent smog chamber studies (Robinson et al., 2007). The new modeling framework is based on the volatility basis-set approach (Lane et al., 2007): both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The emission inventory, which uses as starting point the MCMA 2004 official inventory (CAM, 2006), is modified and the primary organic aerosol (POA) emissions are distributed by volatility based on dilution experiments (Robinson et al., 2007). Sensitivity tests where POA is considered as nonvolatile and POA and SOA as chemically reactive are also described. In all cases PMCAMx is applied in the Mexico City Metropolitan Area during March 2006. The modeling domain covers a 180x180x6 km region in the MCMA with 3x3 km grid resolution. The model predictions are compared with Aerodyne's Aerosol Mass Spectrometry (AMS) observations from the MILAGRO Campaign. References Robinson, A. L.; Donahue, N. M.; Shrivastava, M. K.; Weitkamp, E. A.; Sage, A. M.; Grieshop, A. P.; Lane, T. E.; Pandis, S. N.; Pierce, J. R., 2007. Rethinking organic aerosols: semivolatile emissions and photochemical aging. Science 315, 1259-1262. Gaydos, T. M.; Pinder, R. W.; Koo, B.; Fahey, K. M.; Pandis, S. N., 2007. Development and application of a three- dimensional aerosol

  13. Secondary organic aerosols. Chemical aging, hygroscopicity, and cloud droplet activation

    Energy Technology Data Exchange (ETDEWEB)

    Buchholz, Angela

    2011-07-06

    Atmospheric aerosols have an important impact on the radiation balance, and thus, on the climate of the Earth. Aerosol particles scatter and absorb incoming solar and terrestrial radiation. Apart from this direct effect, aerosol particles act as cloud condensation nuclei (CCN), thereby greatly influencing the microphysics of clouds. Secondary organic aerosols (SOA) are an important fraction of the total aerosol mass. In many environments these organic compounds are mainly products of the oxidation of biogenic volatile organic compounds (VOC). In this study the hygroscopic growth and CCN activation of biogenic SOA were investigated which was formed by the oxidation of VOC with O{sub 3} and photochemically formed OH radicals under low NO{sub x} conditions. For this purpose, a complex mixture of VOC emitted by boreal tree species as gas-phase precursors was used in the Juelich Plant Atmosphere Chamber (JPAC). In long-term studies in the atmosphere simulation chamber SAPHIR {alpha}-pinene or a defined mixture of {alpha}-pinene, {beta}-pinene, limonene, ocimene, {delta}-3-carene served as precursors. Initial precursor concentrations between 40 and 1000 ppbC were investigated. The observed SOA particles were slightly hygroscopic with an average hygroscopicity parameter {kappa}(CCN) = 0.10 {+-} 0.02 and {kappa}(90%RH) = 0.05 {+-} 0.01. Closure between hygroscopic growth and CCN activation data could be achieved allowing either surface tension reduction, limited solubility, or non-ideality of the solution in the droplet. The SOA solutions in equilibrium with RH <95% are possible highly non-ideal. Therefore the organic-water interaction were investigated by applying the UNIFAC model. Calculations for surrogate compounds exhibited the same strong concentration (i.e. RH) dependence of {kappa} at sub-saturation. The growth curves could be fitted and CCN activation predicted by assuming a binary mixture of water and one hypothetical organic compound. The occurrence of

  14. Molecular structure impacts on secondary organic aerosol formation from glycol ethers

    Science.gov (United States)

    Li, Lijie; Cocker, David R.

    2018-05-01

    Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA

  15. Experiments probing the influence of air exchange rates on secondary organic aerosols derived from indoor chemistry

    DEFF Research Database (Denmark)

    Weschler, Charles J.; Shields, H.C.

    2003-01-01

    Reactions between ozone and terpenes have been shown to increase the concentrations of submicron particles in indoor settings. The present study was designed to examine the influence of air exchange rates on the concentrations of these secondary organic aerosols as well as on the evolution...

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

    Directory of Open Access Journals (Sweden)

    R. C. Flagan

    2007-10-01

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

  17. Evidence for a significant proportion of Secondary Organic Aerosol from isoprene above a maritime tropical forest

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    N. H. Robinson

    2011-02-01

    Full Text Available Isoprene is the most abundant non-methane biogenic volatile organic compound (BVOC, but the processes governing secondary organic aerosol (SOA formation from isoprene oxidation are only beginning to become understood and selective quantification of the atmospheric particulate burden remains difficult. Organic aerosol above a tropical rainforest located in Danum Valley, Borneo, Malaysia, a high isoprene emission region, was studied during Summer 2008 using Aerosol Mass Spectrometry and offline detailed characterisation using comprehensive two dimensional gas chromatography. Observations indicate that a substantial fraction (up to 15% by mass of atmospheric sub-micron organic aerosol was observed as methylfuran (MF after thermal desorption. This observation was associated with the simultaneous measurements of established gas-phase isoprene oxidation products methylvinylketone (MVK and methacrolein (MACR. Observations of MF were also made during experimental chamber oxidation of isoprene. Positive matrix factorisation of the AMS organic mass spectral time series produced a robust factor which accounts for an average of 23% (0.18 μg m−3, reaching as much as 53% (0.50 μg m−3 of the total oraganic loading, identified by (and highly correlated with a strong MF signal. Assuming that this factor is generally representative of isoprene SOA, isoprene derived aerosol plays a significant role in the region. Comparisons with measurements from other studies suggest this type of isoprene SOA plays a role in other isoprene dominated environments, albeit with varying significance.

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

    DEFF Research Database (Denmark)

    Mang, Stephen A.; Henricksen, Dana K.; Bateman, Adam P.

    2008-01-01

    of freshly prepared SOA was estimated to be on the order of' 15 L mol(-1) cm(-1) at 300 rim, 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......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...

  19. Secondary organic aerosol origin in an urban environment: influence of biogenic and fuel combustion precursors.

    Science.gov (United States)

    Minguillón, M C; Pérez, N; Marchand, N; Bertrand, A; Temime-Roussel, B; Agrios, K; Szidat, S; van Drooge, B; Sylvestre, A; Alastuey, A; Reche, C; Ripoll, A; Marco, E; Grimalt, J O; Querol, X

    2016-07-18

    Source contributions of organic aerosol (OA) are still not fully understood, especially in terms of quantitative distinction between secondary OA formed from anthropogenic precursors vs. that formed from natural precursors. In order to investigate the OA origin, a field campaign was carried out in Barcelona in summer 2013, including two periods characterized by low and high traffic conditions. Volatile organic compound (VOC) concentrations were higher during the second period, especially aromatic hydrocarbons related to traffic emissions, which showed a marked daily cycle peaking during traffic rush hours, similarly to black carbon (BC) concentrations. Biogenic VOC (BVOC) concentrations showed only minor changes from the low to the high traffic period, and their intra-day variability was related to temperature and solar radiation cycles, although a decrease was observed for monoterpenes during the day. The organic carbon (OC) concentrations increased from the first to the second period, and the fraction of non-fossil OC as determined by (14)C analysis increased from 43% to 54% of the total OC. The combination of (14)C analysis and Aerosol Chemical Speciation Monitor (ACSM) OA source apportionment showed that the fossil OC was mainly secondary (>70%) except for the last sample, when the fossil secondary OC only represented 51% of the total fossil OC. The fraction of non-fossil secondary OC increased from 37% of total secondary OC for the first sample to 60% for the last sample. This enhanced formation of non-fossil secondary OA (SOA) could be attributed to the reaction of BVOC precursors with NOx emitted from road traffic (or from its nocturnal derivative nitrate that enhances night-time semi-volatile oxygenated OA (SV-OOA)), since NO2 concentrations increased from 19 to 42 μg m(-3) from the first to the last sample.

  20. Experiments probing the influence of air exchange rates on secondary organic aerosols derived from indoor chemistry

    DEFF Research Database (Denmark)

    Weschler, Charles J.; Shields, H.C.

    2003-01-01

    Reactions between ozone and terpenes have been shown to increase the concentrations of submicron particles in indoor settings. The present study was designed to examine the influence of air exchange rates on the concentrations of these secondary organic aerosols as well as on the evolution of the...

  1. Determination of the biogenic secondary organic aerosol fraction in the boreal forest by NMR spectroscopy

    Directory of Open Access Journals (Sweden)

    E. Finessi

    2012-01-01

    Full Text Available The study investigates the sources of fine organic aerosol (OA in the boreal forest, based on measurements including both filter sampling (PM1 and online methods and carried out during a one-month campaign held in Hyytiälä, Finland, in spring 2007. Two aerosol mass spectrometers (Q-AMS, ToF-AMS were employed to measure on-line concentrations of major non-refractory aerosol species, while the water extracts of the filter samples were analyzed by nuclear magnetic resonance (NMR spectroscopy for organic functional group characterization of the polar organic fraction of the aerosol. AMS and NMR spectra were processed separately by non-negative factorization algorithms, in order to apportion the main components underlying the submicrometer organic aerosol composition and depict them in terms of both mass fragmentation patterns and functional group compositions.

    The NMR results supported the AMS speciation of oxidized organic aerosol (OOA into two main fractions, which could be generally labelled as more and less oxidized organics. The more oxidized component was characterized by a mass spectrum dominated by the m/z 44 peak, and in parallel by a NMR spectrum showing aromatic and aliphatic backbones highly substituted with oxygenated functional groups (carbonyls/carboxyls and hydroxyls. Such component, contributing on average 50% of the OA mass throughout the observing period, was associated with pollution outbreaks from the Central Europe. The less oxidized component was enhanced in concomitance with air masses originating from the North-to-West sector, in agreement with previous investigations conducted at this site. NMR factor analysis was able to separate two distinct components under the less oxidized fraction of OA. One of these NMR-factors was associated with the formation of terrestrial biogenic secondary organic aerosol (BSOA, based on the comparison with spectral profiles obtained from laboratory experiments of

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

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    J. F. Hamilton

    2009-06-01

    Full Text Available 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.

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

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    J. Liu

    2016-10-01

    Full Text Available 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.

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Science.gov (United States)

    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.

  6. Synthesis and Surface-Specific Analysis of Molecular Constituents Relevant to Biogenic Secondary Organic Aerosol Material

    Science.gov (United States)

    Be, A. G.; Upshur, M. A.; Chase, H. M.; Geiger, F.; Thomson, R. J.

    2017-12-01

    Secondary organic aerosol (SOA) particles formed from the oxidation of biogenic volatile organic compounds (BVOCs) remain a principal, yet elusive, class of airborne particulate matter that impacts the Earth's radiation budget. Given the characteristic molecular complexity comprising biogenic SOA particles, chemical information selective to the gas-aerosol interface may be valuable in the investigation of such systems, as surface considerations likely dictate the phenomena driving particle evolution mechanisms and climate effects. In particular, cloud activation processes may be parameterized using the surface tension depression that coincides with partitioning of surface-active organic species to the gas-droplet interface. However, the extent to which surface chemical processes, such as cloud droplet condensation, are influenced by the chemical structure and reactivity of individual surface-active molecules in SOA particles is largely unknown. We seek to study terpene-derived organic species relevant to the surfaces of biogenic SOA particles via synthesis of putative oxidation products followed by analysis using surface-selective physicochemical measurements. Using dynamic surface tension measurements, considerable differences are observed in the surface tension depression of aqueous pendant droplets that contain synthetically prepared ozonolysis products derived from abundant terpene precursors. Furthermore, sum frequency generation spectroscopy is utilized for comparison of the surface vibrational spectral responses of synthesized reference compounds with those observed for laboratory aerosol toward probing the surface composition of SOA material. Such ongoing findings highlight the underlying importance of molecular structure and reactivity when considering the surface chemistry of biogenic terpene-derived atmospheric aerosols.

  7. Characterization of biogenic secondary organic aerosols using statistical methods; Charakterisierung Biogener Sekundaerer Organischer Aerosole mit Statistischen Methoden

    Energy Technology Data Exchange (ETDEWEB)

    Spindler, Christian

    2010-07-01

    Atmospheric aerosols have important influence on the radiation balance of the Earth, on visibility and human health. Secondary organic aerosol is formed from gas-to-particle conversion of oxidized volatile organic compounds. A dominant fraction of the gases originates from plant emissions, making biogenic secondary organic aerosol (BSOA) an especially important constituent of the atmosphere. Knowing the chemical composition of BSOA particles is crucial for a thorough understanding of aerosol processes in the environment. In this work, the chemical composition of BSOA particles was measured with aerosol mass spectrometry and analyzed with statistical methods. The experimental part of the work comprises process studies of the formation and aging of biogenic aerosols in simulation chambers. Using a plant chamber, real tree emissions were used to produce particles in a way close to conditions in forest environments. In the outdoor chamber SAPHIR, OH-radicals were produced from the photooxidation of ozone under illumination with natural sunlight. Here, BSOA was produced from defined mixtures of mono- and sesquiterpenes that represent boreal forest emissions. A third kind of experiments was performed in the indoor chamber AIDA. Here, particles were produced from ozonolysis of single monoterpenes and aged by condensing OH-oxidation products. Two aerosol mass spectrometers (AMS) were used to measure the chemical composition of the particles. One of the instruments is equipped with a quadrupole mass spectrometer providing unit mass resolution. The second instrument contains a time-of-flight mass spectrometer and provides mass resolution sufficient to distinguish different fragments with the same nominal mass. Aerosol mass spectra obtained with these instruments are strongly fragmented due to electron impact ionization of the evaporated molecules. In addition, typical BSOA mass spectra are very similar to each other. In order to get a more detailed knowledge about the mass

  8. Bounce behavior of freshly nucleated biogenic secondary organic aerosol particles

    Directory of Open Access Journals (Sweden)

    A. Virtanen

    2011-08-01

    Full Text Available The assessment of the climatic impacts and adverse health effects of atmospheric aerosol particles requires detailed information on particle properties. However, very limited information is available on the morphology and phase state of secondary organic aerosol (SOA particles. The physical state of particles greatly affects particulate-phase chemical reactions, and thus the growth rates of newly formed atmospheric aerosol. Thus verifying the physical phase state of SOA particles gives new and important insight into their formation, subsequent growth, and consequently potential atmospheric impacts. According to our recent study, biogenic SOA particles produced in laboratory chambers from the oxidation of real plant emissions as well as in ambient boreal forest atmospheres can exist in a solid phase in size range >30 nm. In this paper, we extend previously published results to diameters in the range of 17–30 nm. The physical phase of the particles is studied by investigating particle bounce properties utilizing electrical low pressure impactor (ELPI. We also investigate the effect of estimates of particle density on the interpretation of our bounce observations. According to the results presented in this paper, particle bounce clearly decreases with decreasing particle size in sub 30 nm size range. The comparison measurements by ammonium sulphate and investigation of the particle impaction velocities strongly suggest that the decreasing bounce is caused by the differences in composition and phase of large (diameters greater than 30 nm and smaller (diameters between 17 and 30 nm particles.

  9. Evidence of aqueous secondary organic aerosol formation from biogenic emissions in the North American Sonoran Desert.

    Science.gov (United States)

    Youn, Jong-Sang; Wang, Zhen; Wonaschütz, Anna; Arellano, Avelino; Betterton, Eric A; Sorooshian, Armin

    2013-07-16

    This study examines the role of aqueous secondary organic aerosol formation in the North American Sonoran Desert as a result of intense solar radiation, enhanced moisture, and biogenic volatile organic compounds (BVOCs). The ratio of water-soluble organic carbon (WSOC) to organic carbon (OC) nearly doubles during the monsoon season relative to other seasons of the year. When normalized by mixing height, the WSOC enhancement during monsoon months relative to preceding dry months (May-June) exceeds that of sulfate by nearly a factor of 10. WSOC:OC and WSOC are most strongly correlated with moisture parameters, temperature, and concentrations of O 3 and BVOCs. No positive relationship was identified between WSOC or WSOC:OC and anthropogenic tracers such as CO over a full year. This study points at the need for further work to understand the effect of BVOCs and moisture in altering aerosol properties in understudied desert regions.

  10. Laboratory studies of the chemical composition and cloud condensation nuclei (CCN activity of secondary organic aerosol (SOA and oxidized primary organic aerosol (OPOA

    Directory of Open Access Journals (Sweden)

    A. T. Lambe

    2011-09-01

    Full Text Available Secondary organic aerosol (SOA and oxidized primary organic aerosol (OPOA were produced in laboratory experiments from the oxidation of fourteen precursors representing atmospherically relevant biogenic and anthropogenic sources. The SOA and OPOA particles were generated via controlled exposure of precursors to OH radicals and/or O3 in a Potential Aerosol Mass (PAM flow reactor over timescales equivalent to 1–20 days of atmospheric aging. Aerosol mass spectra of SOA and OPOA were measured with an Aerodyne aerosol mass spectrometer (AMS. The fraction of AMS signal at m/z = 43 and m/z = 44 (f43, f44, the hydrogen-to-carbon (H/C ratio, and the oxygen-to-carbon (O/C ratio of the SOA and OPOA were obtained, which are commonly used to characterize the level of oxidation of oxygenated organic aerosol (OOA. The results show that PAM-generated SOA and OPOA can reproduce and extend the observed f44f43 composition beyond that of ambient OOA as measured by an AMS. Van Krevelen diagrams showing H/C ratio as a function of O/C ratio suggest an oxidation mechanism involving formation of carboxylic acids concurrent with fragmentation of carbon-carbon bonds. Cloud condensation nuclei (CCN activity of PAM-generated SOA and OPOA was measured as a function of OH exposure and characterized as a function of O/C ratio. CCN activity of the SOA and OPOA, which was characterized in the form of the hygroscopicity parameter κorg, ranged from 8.4×10−4 to 0.28 over measured O/C ratios ranging from 0.05 to 1.42. This range of κorg and O/C ratio is significantly wider than has been previously obtained. To first order, the κorg-to-O/C relationship is well represented by a linear function of the form κorg = (0.18±0.04 ×O/C + 0.03, suggesting that a simple, semi-empirical parameterization of OOA hygroscopicity and

  11. Effect of humidity on the composition of isoprene photooxidation secondary organic aerosol

    Directory of Open Access Journals (Sweden)

    T. B. Nguyen

    2011-07-01

    Full Text Available 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. Experiments were performed with hydrogen peroxide as the OH precursor and in the absence of seed aerosol. The relative 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 detectable effect on the rate and extent of the SOA mass growth. There is a 40 % reduction in the number and relative abundance of distinct particle-phase nitrogen-containing organic compounds (NOC detected by high resolution mass spectrometry. The suppression of condensation reactions, which produce water as a product, is the most important chemical effect of the increased RH. For example, the total signal from oligomeric esters of 2-methylglyceric acid was reduced by about 60 % under humid conditions and the maximum oligomer chain lengths were reduced by 7–11 carbons. Oligomers formed by addition mechanisms, without direct involvement of water, also decreased at elevated RH but to a much smaller extent. The observed reduction in the extent of condensation-type oligomerization at high RH may have substantial impact on the phase characteristics and hygroscopicity of the isoprene aerosol. The reduction in the amount of organic nitrates in the particle phase has implications for understanding the budget of NOC compounds.

  12. Modeling Secondary Organic Aerosol Formation From Emissions of Combustion Sources

    Science.gov (United States)

    Jathar, Shantanu Hemant

    Atmospheric aerosols exert a large influence on the Earth's climate and cause adverse public health effects, reduced visibility and material degradation. Secondary organic aerosol (SOA), defined as the aerosol mass arising from the oxidation products of gas-phase organic species, accounts for a significant fraction of the submicron atmospheric aerosol mass. Yet, there are large uncertainties surrounding the sources, atmospheric evolution and properties of SOA. This thesis combines laboratory experiments, extensive data analysis and global modeling to investigate the contribution of semi-volatile and intermediate volatility organic compounds (SVOC and IVOC) from combustion sources to SOA formation. The goals are to quantify the contribution of these emissions to ambient PM and to evaluate and improve models to simulate its formation. To create a database for model development and evaluation, a series of smog chamber experiments were conducted on evaporated fuel, which served as surrogates for real-world combustion emissions. Diesel formed the most SOA followed by conventional jet fuel / jet fuel derived from natural gas, gasoline and jet fuel derived from coal. The variability in SOA formation from actual combustion emissions can be partially explained by the composition of the fuel. Several models were developed and tested along with existing models using SOA data from smog chamber experiments conducted using evaporated fuel (this work, gasoline, fischertropschs, jet fuel, diesels) and published data on dilute combustion emissions (aircraft, on- and off-road gasoline, on- and off-road diesel, wood burning, biomass burning). For all of the SOA data, existing models under-predicted SOA formation if SVOC/IVOC were not included. For the evaporated fuel experiments, when SVOC/IVOC were included predictions using the existing SOA model were brought to within a factor of two of measurements with minor adjustments to model parameterizations. Further, a volatility

  13. Secondary organic aerosol formation and composition from the photo-oxidation of methyl chavicol (estragole)

    Science.gov (United States)

    Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Muñoz, A.; Vázquez, M.; Borrás, E.; Ródenas, M.

    2014-06-01

    The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound (VOC) that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high-performance liquid chromatography mass spectrometry (HPLC-ITMS), high-performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18 and 29% for an initial VOC mixing ratio of 212 and 460 ppbv (parts per billion by volume) respectively; using a VOC:NOx ratio of ~5:1. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high-resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro-functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O:C ratios, where functionalisation rather than fragmentation is mainly observed as a result of the stability of the ring. The SOA species observed can be characterised as semi-volatile to low-volatility oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.

  14. Is the gas-particle partitioning in alpha-pinene secondary organic aerosol reversible?

    Science.gov (United States)

    Grieshop, Andrew P.; Donahue, Neil M.; Robinson, Allen L.

    2007-07-01

    This paper discusses the reversibility of gas-particle partitioning in secondary organic aerosol (SOA) formed from α-pinene ozonolysis in a smog chamber. Previously, phase partitioning has been studied quantitatively via SOA production experiments and qualitatively by perturbing temperature and observing particle evaporation. In this work, two methods were used to isothermally dilute the SOA: an external dilution sampler and an in-chamber technique. Dilution caused some evaporation of SOA, but repartitioning took place on a time scale of tens of minutes to hours-consistent with an uptake coefficient on the order of 0.001-0.01. However, given sufficient time, α-pinene SOA repartitions reversibly based on comparisons with data from conventional SOA yield experiments. Further, aerosol mass spectrometer (AMS) data indicate that the composition of SOA varies with partitioning. These results suggest that oligomerization observed in high-concentration laboratory experiments may be a reversible process and underscore the complexity of the kinetics of formation and evaporation of SOA.

  15. The effects of isoprene and NOx on secondary organic aerosols formed through reversible and irreversible uptake to aerosol water

    Science.gov (United States)

    El-Sayed, Marwa M. H.; Ortiz-Montalvo, Diana L.; Hennigan, Christopher J.

    2018-01-01

    Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11 h after isoprene concentrations, with maxima at a time lag of 9 h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NOx / isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NOx oxidation products may be responsible for these effects. The observed relationships with NOx and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NOx levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles.

  16. Secondary organic aerosol formation from road vehicle emissions

    Science.gov (United States)

    Pieber, Simone M.; Platt, Stephen M.; El Haddad, Imad; Zardini, Alessandro A.; Suarez-Bertoa, Ricardo; Slowik, Jay G.; Huang, Ru-Jin; Hellebust, Stig; Temime-Roussel, Brice; Marchand, Nicolas; Drinovec, Luca; Mocnik, Grisa; Baltensperger, Urs; Astorga, Covadogna; Prévôt, André S. H.

    2014-05-01

    Organic aerosol particles (OA) are a major fraction of the submicron particulate matter. OA consists of directly emitted primary (POA) and secondary OA (SOA). SOA is formed in-situ in the atmosphere via the reaction of volatile organic precursors. The partitioning of SOA species depends not only on the exposure to oxidants, but for instance also on temperature, relative humidity (RH), and the absorptive mass chemical composition (presence of inorganics) and concentration. Vehicle exhaust is a known source of POA and likely contributes to SOA formation in urban areas [1;2]. This has recently been estimated by (i) analyzing ambient data from urban areas combined with fuel consumption data [3], (ii) by examining the chemical composition of raw fuels [4], or (iii) smog chamber studies [5, 6]. Contradictory and thus somewhat controversial results in the relative quantity of SOA from diesel vs. gasoline vehicle exhaust were observed. In order to elucidate the impact of variable ambient conditions on the potential SOA formation of vehicle exhaust, and its relation to the emitted gas phase species, we studied SOA formed from the exhaust of passenger cars and trucks as a function of fuel and engine type (gasoline, diesel) at different temperatures (T 22 vs. -7oC) and RH (40 vs. 90%), as well as with different levels of inorganic salt concentrations. The exhaust was sampled at the tailpipe during regulatory driving cycles on chassis dynamometers, diluted (200 - 400x) and introduced into the PSI mobile smog chamber [6], where the emissions were subjected to simulated atmospheric ageing. Particle phase instruments (HR-ToF-AMS, aethalometers, CPC, SMPS) and gas phase instruments (PTR-TOF-MS, CO, CO2, CH4, THC, NH3 and other gases) were used online during the experiments. We found that gasoline emissions, because of cold starts, were generally larger than diesel, especially during cold temperatures driving cycles. Gasoline vehicles also showed the highest SOA formation

  17. How important is organic aerosol hygroscopicity to aerosol indirect forcing?

    International Nuclear Information System (INIS)

    Liu Xiaohong; Wang Jian

    2010-01-01

    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 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 (represented by a single parameter 'κ' ) of POA and SOA. Our model simulation indicates that in the present-day (PD) condition changing the 'κ' value of POA from 0 to 0.1 increases the number concentration of cloud condensational nuclei (CCN) at supersaturation S = 0.1% by 40-80% over the POA source regions, while changing the 'κ' value of SOA by ± 50% (from 0.14 to 0.07 and 0.21) changes the CCN concentration within 40%. There are disproportionally larger changes in CCN concentration in the pre-industrial (PI) condition. Due to the stronger impact of organics hygroscopicity on CCN and cloud droplet number concentration at PI condition, global annual mean anthropogenic aerosol indirect forcing (AIF) between PD and PI conditions reduces with the increase of the hygroscopicity of organics. Global annual mean AIF varies by 0.4 W m -2 in the sensitivity runs with the control run of - 1.3 W m -2 , highlighting the need for improved understanding of organics hygroscopicity and its representation in global models.

  18. Heterogeneous ice nucleation and phase transition of viscous α-pinene secondary organic aerosol

    Science.gov (United States)

    Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Virtanen, Annele; Stratmann, Frank

    2016-04-01

    There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate deposition ice nucleation and thus influence cirrus cloud properties. Global model simulations of monoterpene SOA particles suggest that viscous biogenic SOA are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle (INP) budget. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles at the CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN (Ignatius et al., 2015, Järvinen et al., 2015). In the CLOUD chamber, the SOA particles were produced from the ozone initiated oxidation of α-pinene at temperatures in the range from -38 to -10° C at 5-15 % relative humidity with respect to water (RHw) to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. As the RHw was increased to between 35 % at -10° C and 80 % at -38° C, a transition to spherical shape was observed with a new in-situ optical method. This transition confirms previous modelling of the viscosity transition conditions. The ice nucleation ability of SOA particles was investigated with a new continuous flow diffusion chamber SPIN (Spectrometer for Ice Nuclei) for different SOA particle sizes. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA in the deposition mode for ice saturation ratios between 1.3 and 1.4, significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -36.5 and -38.3° C ranged from 6 to 20 % and did not depend on the particle surface area. References Ignatius, K. et al., Heterogeneous ice

  19. [Estimate of the formation potential of secondary organic aerosol in Beijing summertime].

    Science.gov (United States)

    Lü, Zi-Feng; Hao, Ji-Ming; Duan, Jing-Chun; Li, Jun-Hua

    2009-04-15

    Fractional aerosol coefficients (FAC) are used in conjunction with measurements of volatile organic compounds (VOC) during ozone episodes to estimate the formation potential of secondary organic aerosols (SOA) in the summertime of Beijing. The estimation is based on the actual atmospheric conditions of Beijing, and benzene and isoprene are considered as the precursors of SOA. The results show that 31 out of 70 measured VOC species are SOA precursors, and the total potential SOA formation is predicted to be 8.48 microg/m3, which accounts for 30% of fine organic particle matter. Toluene, xylene, pinene, ethylbenzene and n-undecane are the 5 largest contributors to SOA production and account for 20%, 22%, 14%, 9% and 4% of total SOA production, respectively. The anthropogenic aromatic compounds, which yield 76% of the calculated SOA, are the major source of SOA. The biogenic alkenes, alkanes and carbonyls produce 16%, 7% and 1% of SOA formation, respectively. The major components of produced SOA are expected to be aromatic compounds, aliphatic acids, carbonyls and aliphatic nitrates, which contribute to 72%, 14%, 11% and 3% of SOA mass, respectively. The SOA precursors have relatively low atmospheric concentrations and low ozone formation potential. Hence, SOA formation potential of VOC species, in addition to their atmospheric concentrations and ozone formation potential, should be considered in policy making process of VOCs control.

  20. Estimated effects of temperature on secondary organic aerosol concentrations.

    Science.gov (United States)

    Sheehan, P E; Bowman, F M

    2001-06-01

    The temperature-dependence of secondary organic aerosol (SOA) concentrations is explored using an absorptive-partitioning model under a variety of simplified atmospheric conditions. Experimentally determined partitioning parameters for high yield aromatics are used. Variation of vapor pressures with temperature is assumed to be the main source of temperature effects. Known semivolatile products are used to define a modeling range of vaporization enthalpy of 10-25 kcal/mol-1. The effect of diurnal temperature variations on model predictions for various assumed vaporization enthalpies, precursor emission rates, and primary organic concentrations is explored. Results show that temperature is likely to have a significant influence on SOA partitioning and resulting SOA concentrations. A 10 degrees C decrease in temperature is estimated to increase SOA yields by 20-150%, depending on the assumed vaporization enthalpy. In model simulations, high daytime temperatures tend to reduce SOA concentrations by 16-24%, while cooler nighttime temperatures lead to a 22-34% increase, compared to constant temperature conditions. Results suggest that currently available constant temperature partitioning coefficients do not adequately represent atmospheric SOA partitioning behavior. Air quality models neglecting the temperature dependence of partitioning are expected to underpredict peak SOA concentrations as well as mistime their occurrence.

  1. Formation of secondary organic aerosol from isoprene oxidation over Europe

    Directory of Open Access Journals (Sweden)

    M. Karl

    2009-09-01

    Full Text Available The role of isoprene as a precursor to secondary organic aerosol (SOA over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr−1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of organic matter (OM during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC emissions from vegetation. However, during winter, our model strongly underestimates OM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr−1. The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  3. Substantial secondary organic aerosol formation in a coniferous forest: observations of both day- and nighttime chemistry

    Directory of Open Access Journals (Sweden)

    A. K. Y. Lee

    2016-06-01

    Full Text Available Substantial biogenic secondary organic aerosol (BSOA formation was investigated in a coniferous forest mountain region in Whistler, British Columbia. A largely biogenic aerosol growth episode was observed, providing a unique opportunity to investigate BSOA formation chemistry in a forested environment with limited influence from anthropogenic emissions. Positive matrix factorization of aerosol mass spectrometry (AMS measurement identified two types of BSOA (BSOA-1 and BSOA-2, which were primarily generated by gas-phase oxidation of monoterpenes and perhaps sesquiterpenes. The temporal variations of BSOA-1 and BSOA-2 can be explained by gas–particle partitioning in response to ambient temperature and the relative importance of different oxidation mechanisms between day and night. While BSOA-1 arises from gas-phase ozonolysis and nitrate radical chemistry at night, BSOA-2 is likely less volatile than BSOA-1 and consists of products formed via gas-phase oxidation by OH radical and ozone during the day. Organic nitrates produced through nitrate radical chemistry can account for 22–33 % of BSOA-1 mass at night. The mass spectra of BSOA-1 and BSOA-2 have higher values of the mass fraction of m/z 91 (f91 compared to the background organic aerosol. Using f91 to evaluate BSOA formation pathways in this unpolluted, forested region, heterogeneous oxidation of BSOA-1 is a minor production pathway of BSOA-2.

  4. Impact of human presence on secondary organic aerosols derived from ozone-initiated chemistry in a simulated office environment

    DEFF Research Database (Denmark)

    Fadeyi, Moshood O.; Weschler, Charles J.; Tham, Kwok W.

    2013-01-01

    's reactions with various indoor pollutants. The present study examines this possibility for secondary organic aerosols (SOA) derived from ozone-initiated chemistry with limonene, a commonly occurring indoor terpene. The experiments were conducted at realistic ozone and limonene concentrations in a 240 m3...

  5. Characterization of Secondary Organic Aerosol Precursors Using Two-Dimensional Gas-Chromatography

    Science.gov (United States)

    Roskamp, M.; Lou, W.; Pankow, J. F.; Harley, P. C.; Turnipseed, A.; Barsanti, K. C.

    2012-12-01

    The oxidation of volatile organic compounds (VOCs) plays a role in both regional and global air quality. However, field and laboratory research indicate that the body of knowledge around the identities, quantities and oxidation processes of these compounds in the ambient atmosphere is still incomplete (e.g., Goldstein & Galbally, 2007; Robinson et al., 2009). VOCs emitted to the atmosphere largely are of biogenic origin (Guenther et al., 2006), and many studies of ambient secondary organic aerosol (SOA) suggest that SOA is largely of biogenic origin (albeit closely connected to anthropogenic activities, e.g., de Gouw and Jimenez, 2009). Accurate modeling of SOA levels and properties will require a more complete understanding of biogenic VOCs (BOCs) and their atmospheric oxidation products. For example, satellite measurements indicate that biogenic VOC emissions are two to three times greater than levels currently included in models (Heald et al., 2010). Two-dimensional gas chromatography (GC×GC) is a powerful analytical technique that shows much promise in advancing the state-of-knowledge regarding BVOCs and their role in SOA formation. In this work, samples were collected during BEACHON-RoMBAS (Bio-hydro-atmosphere Interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study) in July and August of 2011. The field site was a Ponderosa Pine forest near Woodland, CO, inside the Manitou Experimental Forest, which is operated by the US Forest Service. The area is characteristic of the central Rocky Mountains and trace gas monitoring indicates that little anthropogenic pollution is transported from the nearby urban areas (Kim et al. 2010 and references therein). Ambient and enclosure samples were collected on ATD (adsorption/thermal desorption) cartridges and analyzed for BVOCs using two-dimensional gas chromatography (GC×GC) with time of flight mass spectrometry (TOFMS) and flame ionized detection (FID). Measurements of

  6. Modeling reactive ammonia uptake by secondary organic aerosol in CMAQ: application to the continental US

    OpenAIRE

    S. Zhu; J. R. Horne; J. Montoya-Aguilera; M. L. Hinks; S. A. Nizkorodov; D. Dabdub

    2018-01-01

    Ammonium salts such as ammonium nitrate and ammonium sulfate constitute an important fraction of the total fine particulate matter (PM2.5) mass. While the conversion of inorganic gases into particulate-phase sulfate, nitrate, and ammonium is now well understood, there is considerable uncertainty over interactions between gas-phase ammonia and secondary organic aerosols (SOAs). Observations have confirmed that ammonia can react with carbonyl compounds in SOA, forming nitrogen...

  7. Secondary organic aerosols over oceans via oxidation of isoprene and monoterpenes from Arctic to Antarctic.

    Science.gov (United States)

    Hu, Qi-Hou; Xie, Zhou-Qing; Wang, Xin-Ming; Kang, Hui; He, Quan-Fu; Zhang, Pengfei

    2013-01-01

    Isoprene and monoterpenes are important precursors of secondary organic aerosols (SOA) in continents. However, their contributions to aerosols over oceans are still inconclusive. Here we analyzed SOA tracers from isoprene and monoterpenes in aerosol samples collected over oceans during the Chinese Arctic and Antarctic Research Expeditions. Combined with literature reports elsewhere, we found that the dominant tracers are the oxidation products of isoprene. The concentrations of tracers varied considerably. The mean average values were approximately one order of magnitude higher in the Northern Hemisphere than in the Southern Hemisphere. High values were generally observed in coastal regions. This phenomenon was ascribed to the outflow influence from continental sources. High levels of isoprene could emit from oceans and consequently have a significant impact on marine SOA as inferred from isoprene SOA during phytoplankton blooms, which may abruptly increase up to 95 ng/m³ in the boundary layer over remote oceans.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    DEFF Research Database (Denmark)

    Frosch, M.; Bilde, Merete; Nenes, A.

    2013-01-01

    In a series of smog chamber experiments, the cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) generated from ozonolysis of beta-caryophyllene was characterized by determining the CCN derived hygroscopicity parameter, kappa(CCN), from experimental data. Two types of CCN...... in experiments without an OH scavenger (i.e. where OH was produced during ozonolysis). In other experiments, lights were turned on, either without or with the addition of HONO (OH source). This led to the formation of more CCN active SOA. SOA was aged up to 30 h through exposure to ozone and (in experiments...... with no OH scavenger present) to OH. In all experiments, the derived kappa(CCN) consistently increased with time after initial injection of beta-caryophyllene, showing that chemical ageing increases the CCN activity of beta-caryophyllene SOA. kappa(CCN) was also observed to depend on supersaturation, which...

  10. Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

    Science.gov (United States)

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for...

  11. Primary and secondary organic aerosol origin by combined gas-particle phase source apportionment

    Directory of Open Access Journals (Sweden)

    M. Crippa

    2013-08-01

    Full Text Available Secondary organic aerosol (SOA, a prominent fraction of particulate organic mass (OA, remains poorly constrained. Its formation involves several unknown precursors, formation and evolution pathways and multiple natural and anthropogenic sources. Here a combined gas-particle phase source apportionment is applied to wintertime and summertime data collected in the megacity of Paris in order to investigate SOA origin during both seasons. This was possible by combining the information provided by an aerosol mass spectrometer (AMS and a proton transfer reaction mass spectrometer (PTR-MS. A better constrained apportionment of primary OA (POA sources is also achieved using this methodology, making use of gas-phase tracers. These tracers made possible the discrimination between biogenic and continental/anthropogenic sources of SOA. We found that continental SOA was dominant during both seasons (24–50% of total OA, while contributions from photochemistry-driven SOA (9% of total OA and marine emissions (13% of total OA were also observed during summertime. A semi-volatile nighttime component was also identified (up to 18% of total OA during wintertime. This approach was successfully applied here and implemented in a new source apportionment toolkit.

  12. Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields

    Directory of Open Access Journals (Sweden)

    A. W. Rollins

    2009-09-01

    Full Text Available Alkyl nitrates and secondary organic aerosol (SOA produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber chamber. A 16 h dark experiment was conducted with temperatures at 289–301 K, and maximum concentrations of 11 ppb isoprene, 62.4 ppb O3 and 31.1 ppb NOx. We find the yield of nitrates is 70±8% from the isoprene + NO3 reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO3 is 40±20%. We find an effective rate constant for reaction of NO3 with the group of first generation oxidation products to be 7×10−14 molecule−1 cm3 s−1. At the low total organic aerosol concentration in the chamber (max=0.52 μg m−3 we observed a mass yield (ΔSOA mass/Δisoprene mass of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.7% while the further oxidation of the initial products leads to a yield of 14% (defined as ΔSOA/Δisoprene2x where Δisoprene2x is the mass of isoprene which reacted twice with NO3. The SOA yield of 14% is consistent with equilibrium partitioning of highly functionalized C5 products of isoprene oxidation.

  13. Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds

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    V. Varutbangkul

    2006-01-01

    Full Text Available A series of experiments has been conducted in the Caltech indoor smog chamber facility to investigate the water uptake properties of aerosol formed by oxidation of various organic precursors. Secondary organic aerosol (SOA from simple and substituted cycloalkenes (C5-C8 is produced in dark ozonolysis experiments in a dry chamber (RH~5%. Biogenic SOA from monoterpenes, sesquiterpenes, and oxygenated terpenes is formed by photooxidation in a humid chamber (~50% RH. Using the hygroscopicity tandem differential mobility analyzer (HTDMA, we measure the diameter-based hygroscopic growth factor (GF of the SOA as a function of time and relative humidity. All SOA studied is found to be slightly hygroscopic, with smaller water uptake than that of typical inorganic aerosol substances. The aerosol water uptake increases with time early in the experiments for the cycloalkene SOA, but decreases with time for the sesquiterpene SOA. This behavior could indicate competing effects between the formation of more highly oxidized polar compounds (more hygroscopic, and formation of longer-chained oligomers (less hygroscopic. All SOA also exhibit a smooth water uptake with RH with no deliquescence or efflorescence. The water uptake curves are found to be fitted well with an empirical three-parameter functional form. The measured pure organic GF values at 85% RH are between 1.09–1.16 for SOA from ozonolysis of cycloalkenes, 1.01–1.04 for sesquiterpene photooxidation SOA, and 1.06–1.10 for the monoterpene and oxygenated terpene SOA. The GF of pure SOA (GForg in experiments in which inorganic seed aerosol is used is determined by assuming volume-weighted water uptake (Zdanovskii-Stokes-Robinson or 'ZSR' approach and using the size-resolved organic mass fraction measured by the Aerodyne Aerosol Mass Spectrometer. Knowing the water content associated with the inorganic fraction yields GForg values. However, for each precursor, the GForg values computed from different

  14. Formation of secondary organic aerosol in the Paris pollution plume and its impact on surrounding regions

    Science.gov (United States)

    Zhang, Q. J.; Beekmann, M.; Freney, E.; Sellegri, K.; Pichon, J. M.; Schwarzenboeck, A.; Colomb, A.; Bourrianne, T.; Michoud, V.; Borbon, A.

    2015-12-01

    Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plumes of megacities can affect regional air quality. In the framework of the FP7/EU MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) project, an intensive campaign was launched in the greater Paris region in July 2009. The major objective was to quantify different sources of organic aerosol (OA) within a megacity and in its plume. In this study, we use airborne measurements aboard the French ATR-42 aircraft to evaluate the regional chemistry-transport model CHIMERE within and downwind of the Paris region. Two mechanisms of secondary OA (SOA) formation are used, both including SOA formation from oxidation and chemical aging of primary semivolatile and intermediate volatility organic compounds (SI-SOA) in the volatility basis set (VBS) framework. As for SOA formed from traditional VOC (volatile organic compound) precursors (traditional SOA), one applies chemical aging in the VBS framework adopting different SOA yields for high- and low-NOx environments, while another applies a single-step oxidation scheme without chemical aging. Two emission inventories are used for discussion of emission uncertainties. The slopes of the airborne OA levels versus Ox (i.e., O3 + NO2) show SOA formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. The simulated slopes were overestimated slightly by factors of 1.1, 1.7 and 1.3 with respect to those observed for the three airborne measurements, when the most realistic "high-NOx" yields for traditional SOA formation in the VBS scheme are used in the model. In addition, these slopes are relatively stable from one day to another, which suggests that they are characteristic for the given megacity plume environment. The configuration with increased primary

  15. Direct radiative feedback due to biogenic secondary organic aerosol estimated from boreal forest site observations

    International Nuclear Information System (INIS)

    Lihavainen, Heikki; Asmi, Eija; Aaltonen, Veijo; Makkonen, Ulla; Kerminen, Veli-Matti

    2015-01-01

    We used more than five years of continuous aerosol measurements to estimate the direct radiative feedback parameter associated with the formation of biogenic secondary organic aerosol (BSOA) at a remote continental site at the edge of the boreal forest zone in Northern Finland. Our upper-limit estimate for this feedback parameter during the summer period (ambient temperatures above 10 °C) was −97 ± 66 mW m −2 K −1 (mean ± STD) when using measurements of the aerosol optical depth (f AOD ) and −63 ± 40 mW m −2 K −1 when using measurements of the ‘dry’ aerosol scattering coefficient at the ground level (f σ ). Here STD represents the variability in f caused by the observed variability in the quantities used to derive the value of f. Compared with our measurement site, the magnitude of the direct radiative feedback associated with BSOA is expected to be larger in warmer continental regions with more abundant biogenic emissions, and even larger in regions where biogenic emissions are mixed with anthropogenic pollution. (letter)

  16. Effect of relative humidity on soot - secondary organic aerosol mixing: A case study from the Soot Aerosol Aging Study (PNNL-SAAS)

    Science.gov (United States)

    Sharma, N.; China, S.; Zaveri, R. A.; Shilling, J. E.; Pekour, M. S.; Liu, S.; Aiken, A. C.; Dubey, M. K.; Wilson, J. M.; Zelenyuk, A.; OBrien, R. E.; Moffet, R.; Gilles, M. K.; Gourihar, K.; Chand, D.; Sedlacek, A. J., III; Subramanian, R.; Onasch, T. B.; Laskin, A.; Mazzoleni, C.

    2014-12-01

    Atmospheric processing of fresh soot particles emitted by anthropogenic as well as natural sources alters their physical and chemical properties. For example, fresh and aged soot particles interact differently with incident solar radiation, resulting in different overall radiation budgets. Varying atmospheric chemical and meteorological conditions can result in complex soot mixing states. The Soot Aerosol Aging Study (SAAS) was conducted at the Pacific Northwest National Laboratory in November 2013 and January 2014 as a step towards understanding the evolution of mixing state of soot and its impact on climate-relevant properties. Aging experiments on diesel soot were carried out in a controlled laboratory chamber, and the effects of condensation and coagulation processes were systematically explored in separate sets of experiments. In addition to online measurement of aerosol properties, aerosol samples were collected for offline single particle analysis to investigate the evolution of the morphology, elemental composition and fine structure of sample particles from different experiments. Condensation experiments focused on the formation of α-pinene secondary organic aerosol on diesel soot aerosol seeds. Experiments were conducted to study the aging of soot under dry (RH < 2%) and humid conditions (RH ~ 80%). We present an analysis of the morphology of soot, its evolution, and its correlation with optical properties, as the condensation of α-pinene SOA is carried out for the two different RH conditions. The analysis was performed by using scanning electron microscopy, transmission electron microscopy, scanning transmission x-ray microscopy and atomic force microscopy for single particle characterization. In addition, particle size, mass, composition, shape, and density were characterized in-situ, as a function of organics condensed on soot seeds, using single particle mass spectrometer.

  17. Secondary Organic Aerosol Formation from Acetylene (C2H2: seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase

    Directory of Open Access Journals (Sweden)

    P. J. Ziemann

    2009-03-01

    Full Text Available The lightest Non Methane HydroCarbon (NMHC, i.e., acetylene (C2H2 is found to form secondary organic aerosol (SOA. Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosols, mild acidification with sulphuric acid (SA, 3organic mass portion of the seed, but increased linearly with liquid water content (LWC of the seed. For fixed LWC, YSOA varied by more than a factor of five. Water soluble organic carbon (WSOC photochemistry in the liquid water associated with internally mixed inorganic/WSOC seed aerosols is found responsible for this seed effect. WSOC photochemistry enhances the SOA source from CHOCHO, while seeds containing amino acids (AA and/or SA showed among the lowest of all YSOA values, and largely suppress the photochemical enhancement on the rate of CHOCHO uptake. Our results give first evidence for the importance of heterogeneous photochemistry of CHOCHO in SOA formation, and identify a potential bias in the currently available YSOA data for other SOA precursor NMHCs. We demonstrate that SOA formation via the aqueous phase is not limited to cloud droplets, but proceeds also in the absence of clouds, i.e., does not stop once a cloud droplet evaporates. Atmospheric models need to be expanded to include SOA formation from WSOC photochemistry of CHOCHO, and possibly other α-dicarbonyls, in aqueous aerosols.

  18. Diurnally resolved particulate and VOC measurements at a rural site: indication of significant biogenic secondary organic aerosol formation

    Science.gov (United States)

    Sjostedt, S. J.; Slowik, J. G.; Brook, J. R.; Chang, R. Y.-W.; Mihele, C.; Stroud, C. A.; Vlasenko, A.; Abbatt, J. P. D.

    2011-06-01

    We report simultaneous measurements of volatile organic compound (VOC) mixing ratios including C6 to C8 aromatics, isoprene, monoterpenes, acetone and organic aerosol mass loadings at a rural location in southwestern Ontario, Canada by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) and Aerosol Mass Spectrometry (AMS), respectively. During the three-week-long Border Air Quality and Meteorology Study in June-July 2007, air was sampled from a range of sources, including aged air from the polluted US Midwest, direct outflow from Detroit 50 km away, and clean air with higher biogenic input. After normalization to the diurnal profile of CO, a long-lived tracer, diurnal analyses show clear photochemical loss of reactive aromatics and production of oxygenated VOCs and secondary organic aerosol (SOA) during the daytime. Biogenic VOC mixing ratios increase during the daytime in accord with their light- and temperature-dependent sources. Long-lived species, such as hydrocarbon-like organic aerosol and benzene show little to no photochemical reactivity on this timescale. From the normalized diurnal profiles of VOCs, an estimate of OH concentrations during the daytime, measured O3 concentrations, and laboratory SOA yields, we calculate integrated local organic aerosol production amounts associated with each measured SOA precursor. Under the assumption that biogenic precursors are uniformly distributed across the southwestern Ontario location, we conclude that such precursors contribute significantly to the total amount of SOA formation, even during the period of Detroit outflow. The importance of aromatic precursors is more difficult to assess given that their sources are likely to be localized and thus of variable impact at the sampling location.

  19. Particle size dependence of biogenic secondary organic aerosol molecular composition

    Science.gov (United States)

    Tu, Peijun; Johnston, Murray V.

    2017-06-01

    Formation of secondary organic aerosol (SOA) is initiated by the oxidation of volatile organic compounds (VOCs) in the gas phase whose products subsequently partition to the particle phase. Non-volatile molecules have a negligible evaporation rate and grow particles at their condensation rate. Semi-volatile molecules have a significant evaporation rate and grow particles at a much slower rate than their condensation rate. Particle phase chemistry may enhance particle growth if it transforms partitioned semi-volatile molecules into non-volatile products. In principle, changes in molecular composition as a function of particle size allow non-volatile molecules that have condensed from the gas phase (a surface-limited process) to be distinguished from those produced by particle phase reaction (a volume-limited process). In this work, SOA was produced by β-pinene ozonolysis in a flow tube reactor. Aerosol exiting the reactor was size-selected with a differential mobility analyzer, and individual particle sizes between 35 and 110 nm in diameter were characterized by on- and offline mass spectrometry. Both the average oxygen-to-carbon (O / C) ratio and carbon oxidation state (OSc) were found to decrease with increasing particle size, while the relative signal intensity of oligomers increased with increasing particle size. These results are consistent with oligomer formation primarily in the particle phase (accretion reactions, which become more favored as the volume-to-surface-area ratio of the particle increases). Analysis of a series of polydisperse SOA samples showed similar dependencies: as the mass loading increased (and average volume-to-surface-area ratio increased), the average O / C ratio and OSc decreased, while the relative intensity of oligomer ions increased. The results illustrate the potential impact that particle phase chemistry can have on biogenic SOA formation and the particle size range where this chemistry becomes important.

  20. Particle size dependence of biogenic secondary organic aerosol molecular composition

    Directory of Open Access Journals (Sweden)

    P. Tu

    2017-06-01

    Full Text Available Formation of secondary organic aerosol (SOA is initiated by the oxidation of volatile organic compounds (VOCs in the gas phase whose products subsequently partition to the particle phase. Non-volatile molecules have a negligible evaporation rate and grow particles at their condensation rate. Semi-volatile molecules have a significant evaporation rate and grow particles at a much slower rate than their condensation rate. Particle phase chemistry may enhance particle growth if it transforms partitioned semi-volatile molecules into non-volatile products. In principle, changes in molecular composition as a function of particle size allow non-volatile molecules that have condensed from the gas phase (a surface-limited process to be distinguished from those produced by particle phase reaction (a volume-limited process. In this work, SOA was produced by β-pinene ozonolysis in a flow tube reactor. Aerosol exiting the reactor was size-selected with a differential mobility analyzer, and individual particle sizes between 35 and 110 nm in diameter were characterized by on- and offline mass spectrometry. Both the average oxygen-to-carbon (O ∕ C ratio and carbon oxidation state (OSc were found to decrease with increasing particle size, while the relative signal intensity of oligomers increased with increasing particle size. These results are consistent with oligomer formation primarily in the particle phase (accretion reactions, which become more favored as the volume-to-surface-area ratio of the particle increases. Analysis of a series of polydisperse SOA samples showed similar dependencies: as the mass loading increased (and average volume-to-surface-area ratio increased, the average O ∕ C ratio and OSc decreased, while the relative intensity of oligomer ions increased. The results illustrate the potential impact that particle phase chemistry can have on biogenic SOA formation and the particle size range where this chemistry becomes

  1. Primary and secondary organic aerosols in summer 2016 in Beijing

    Science.gov (United States)

    Tang, Rongzhi; Wu, Zepeng; Li, Xiao; Wang, Yujue; Shang, Dongjie; Xiao, Yao; Li, Mengren; Zeng, Limin; Wu, Zhijun; Hallquist, Mattias; Hu, Min; Guo, Song

    2018-03-01

    To improve air quality, the Beijing government has employed several air pollution control measures since the 2008 Olympics. In order to investigate organic aerosol sources after the implementation of these measures, ambient fine particulate matter was collected at a regional site in Changping (CP) and an urban site at the Peking University Atmosphere Environment Monitoring Station (PKUERS) during the Photochemical Smog in China field campaign in summer 2016. Chemical mass balance (CMB) modeling and the tracer yield method were used to apportion primary and secondary organic sources. Our results showed that the particle concentration decreased significantly during the last few years. The apportioned primary and secondary sources explained 62.8 ± 18.3 and 80.9 ± 27.2 % of the measured OC at CP and PKUERS, respectively. Vehicular emissions served as the dominant source. Except for gasoline engine emissions, the contributions of all the other primary sources decreased. In addition, the anthropogenic SOC, i.e., toluene SOC, also decreased, implying that deducting primary emissions can reduce anthropogenic SOA. In contrast to the SOA from other regions in the world where biogenic SOA was dominant, anthropogenic SOA was the major contributor to SOA, implying that deducting anthropogenic VOC emissions is an efficient way to reduce SOA in Beijing. Back-trajectory cluster analysis results showed that high mass concentrations of OC were observed when the air mass was from the south. However, the contributions of different primary organic sources were similar, suggesting regional particle pollution. The ozone concentration and temperature correlated well with the SOA concentration. Different correlations between day and night samples suggested different SOA formation pathways. Significant enhancement of SOA with increasing particle water content and acidity was observed in our study, suggesting that aqueous-phase acid-catalyzed reactions may be the important SOA formation

  2. Molecular characterization of urban organic aerosol in tropical India: contributions of primary emissions and secondary photooxidation

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    P. Q. Fu

    2010-03-01

    Full Text Available Organic molecular composition of PM10 samples, collected at Chennai in tropical India, was studied using capillary gas chromatography/mass spectrometry. Fourteen organic compound classes were detected in the aerosols, including aliphatic lipids, sugar compounds, lignin products, terpenoid biomarkers, sterols, aromatic acids, hydroxy-/polyacids, phthalate esters, hopanes, Polycyclic Aromatic Hydrocarbons (PAHs, and photooxidation products from biogenic Volatile Organic Compounds (VOCs. At daytime, phthalate esters were found to be the most abundant compound class; however, at nighttime, fatty acids were the dominant one. Di-(2-ethylhexyl phthalate, C16 fatty acid, and levoglucosan were identified as the most abundant single compounds. The nighttime maxima of most organics in the aerosols indicate a land/sea breeze effect in tropical India, although some other factors such as local emissions and long-range transport may also influence the composition of organic aerosols. However, biogenic VOC oxidation products (e.g., 2-methyltetrols, pinic acid, 3-hydroxyglutaric acid and β-caryophyllinic acid showed diurnal patterns with daytime maxima. Interestingly, terephthalic acid was maximized at nighttime, which is different from those of phthalic and isophthalic acids. A positive relation was found between 1,3,5-triphenylbenzene (a tracer for plastic burning and terephthalic acid, suggesting that the field burning of municipal solid wastes including plastics is a significant source of terephthalic acid. Organic compounds were further categorized into several groups to clarify their sources. Fossil fuel combustion (24–43% was recognized as the most significant source for the total identified compounds, followed by plastic emission (16–33%, secondary oxidation (8.6–23%, and microbial/marine sources (7.2–17%. In contrast, the contributions of terrestrial plant waxes (5.9–11% and biomass burning (4.2–6.4% were relatively

  3. Secondary organic aerosol production from modern diesel engine emissions

    Directory of Open Access Journals (Sweden)

    S. Samy

    2010-01-01

    Full Text Available Secondary organic aerosol (SOA production was observed at significant levels in a series of modern diesel exhaust (DE aging experiments conducted at the European Outdoor Photoreactor/Simulation Chamber (EUPHORE. The greatest production occurred in DE with toluene addition experiments (>40%, followed by DE with HCHO (for OH radical generation experiments. A small amount of SOA (3% was observed for DE in dark with N2O5 (for NO3 radical production experiments. The analysis for a limited number (54 of polar organic compounds (POC was conducted to assess the composition of modern DE and the formation of photochemical transformation products. Distinct POC formation in light versus dark experiments suggests the role of OH initiated reactions in these chamber atmospheres. A trend of increasing concentrations of dicarboxylic acids in light versus dark experiments was observed when evaluated on a compound group basis. The four toluene addition experiments in this study were performed at different [tol]o/[NOx]o ratios and displayed an average SOA %yield (in relation to toluene of 5.3±1.6%, which is compared to past chamber studies that evaluated the impact of [tol]o/[NOx]o on SOA production in more simplified mixtures.

  4. Model analysis of secondary organic aerosol formation by glyoxal in laboratory studies: the case for photoenhanced chemistry.

    Science.gov (United States)

    Sumner, Andrew J; Woo, Joseph L; McNeill, V Faye

    2014-10-21

    The reactive uptake of glyoxal by atmospheric aerosols is believed to be a significant source of secondary organic aerosol (SOA). Several recent laboratory studies have been performed with the goal of characterizing this process, but questions remain regarding the effects of photochemistry on SOA growth. We applied GAMMA (McNeill et al. Environ. Sci. Technol. 2012, 46, 8075-8081), a photochemical box model with coupled gas-phase and detailed aqueous aerosol-phase chemistry, to simulate aerosol chamber studies of SOA formation by the uptake of glyoxal by wet aerosol under dark and irradiated conditions (Kroll et al. J. Geophys. Res. 2005, 110 (D23), 1-10; Volkamer et al. Atmos. Chem. Phys. 2009, 9, 1907-1928; Galloway et al. Atmos. Chem. Phys. 2009, 9, 3331- 306 3345 and Geophys. Res. Lett. 2011, 38, L17811). We find close agreement between simulated SOA growth and the results of experiments conducted under dark conditions using values of the effective Henry's Law constant of 1.3-5.5 × 10(7) M atm(-1). While irradiated conditions led to the production of some organic acids, organosulfates, and other oxidation products via well-established photochemical mechanisms, these additional product species contribute negligible aerosol mass compared to the dark uptake of glyoxal. Simulated results for irradiated experiments therefore fell short of the reported SOA mass yield by up to 92%. This suggests a significant light-dependent SOA formation mechanism that is not currently accounted for by known bulk photochemistry, consistent with recent laboratory observations of SOA production via photosensitizer chemistry.

  5. Modeling organic aerosol concentrations and properties during winter 2014 in the northwestern Mediterranean region

    OpenAIRE

    Chrit, Mounir; Sartelet, Karine; Sciare, Jean; Majdi, Marwa; Nicolas, José; Petit, Jean-Eudes; Dulac, François

    2018-01-01

    Organic aerosols are measured at a remote site (Ersa) on Corsica Cape in the northwestern Mediterranean basin during the Chemistry-Aerosol Mediterranean Experiment (CharMEx) winter campaign of 2014, when high organic concentrations from anthropogenic origin are observed. This work aims at representing the observed organic aerosol concentrations and properties (oxidation state) using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA) formation. Becau...

  6. Emissions of biogenic volatile organic compounds and subsequent photochemical production of secondary organic aerosol in mesocosm studies of temperate and tropical plant species

    Science.gov (United States)

    Wyche, K. P.; Ryan, A. C.; Hewitt, C. N.; Alfarra, M. R.; McFiggans, G.; Carr, T.; Monks, P. S.; Smallbone, K. L.; Capes, G.; Hamilton, J. F.; Pugh, T. A. M.; MacKenzie, A. R.

    2014-12-01

    Silver birch (Betula pendula) and three Southeast Asian tropical plant species (Ficus cyathistipula, Ficus benjamina and Caryota millis) from the pantropical fig and palm genera were grown in a purpose-built and environment-controlled whole-tree chamber. The volatile organic compounds emitted from these trees were characterised and fed into a linked photochemical reaction chamber where they underwent photo-oxidation under a range of controlled conditions (relative humidity or RH ~65-89%, volatile organic compound-to-NOx or VOC / NOx ~3-9 and NOx ~2 ppbV). Both the gas phase and the aerosol phase of the reaction chamber were monitored in detail using a comprehensive suite of on-line and off-line chemical and physical measurement techniques. Silver birch was found to be a high monoterpene and sesquiterpene but low isoprene emitter, and its emissions were observed to produce measurable amounts of secondary organic aerosol (SOA) via both nucleation and condensation onto pre-existing seed aerosol (YSOA 26-39%). In contrast, all three tropical species were found to be high isoprene emitters with trace emissions of monoterpenes and sesquiterpenes. In tropical plant experiments without seed aerosol there was no measurable SOA nucleation, but aerosol mass was shown to increase when seed aerosol was present. Although principally isoprene emitting, the aerosol mass produced from tropical fig was mostly consistent (i.e. in 78 out of 120 aerosol mass calculations using plausible parameter sets of various precursor specific yields) with condensation of photo-oxidation products of the minor volatile organic compounds (VOCs) co-emitted; no significant aerosol yield from condensation of isoprene oxidation products was required in the interpretations of the experimental results. This finding is in line with previous reports of organic aerosol loadings consistent with production from minor biogenic VOCs co-emitted with isoprene in principally isoprene-emitting landscapes in Southeast

  7. Cloud Processing of Secondary Organic Aerosol from Isoprene and Methacrolein Photooxidation.

    Science.gov (United States)

    Giorio, Chiara; Monod, Anne; Brégonzio-Rozier, Lola; DeWitt, Helen Langley; Cazaunau, Mathieu; Temime-Roussel, Brice; Gratien, Aline; Michoud, Vincent; Pangui, Edouard; Ravier, Sylvain; Zielinski, Arthur T; Tapparo, Andrea; Vermeylen, Reinhilde; Claeys, Magda; Voisin, Didier; Kalberer, Markus; Doussin, Jean-François

    2017-10-12

    Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth's changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on- and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25-32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of-flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15-20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.

  8. Variation in pH of Model Secondary Organic Aerosol during Liquid-Liquid Phase Separation.

    Science.gov (United States)

    Dallemagne, Magda A; Huang, Xiau Ya; Eddingsaas, Nathan C

    2016-05-12

    The majority of atmospheric aerosols consist of both organic and inorganic components. At intermediate relative humidity (RH), atmospheric aerosol can undergo liquid-liquid phase separation (LLPS) in which the organic and inorganic fractions segregate from each other. We have extended the study of LLPS to the effect that phase separation has on the pH of the overall aerosols and the pH of the individual phases. Using confocal microscopy and pH sensitive dyes, the pH of internally mixed model aerosols consisting of polyethylene glycol 400 and ammonium sulfate as well as the pH of the organic fraction during LLPS have been directly measured. During LLPS, the pH of the organic fraction was observed to increase to 4.2 ± 0.2 from 3.8 ± 0.1 under high RH when the aerosol was internally mixed. In addition, the high spatial resolution of the confocal microscope allowed us to characterize the composition of each of the phases, and we have observed that during LLPS the organic shell still contains large quantities of water and should be characterized as an aqueous organic-rich phase rather than simply an organic phase.

  9. Nitrate radical oxidation of γ-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields

    Science.gov (United States)

    Slade, Jonathan H.; de Perre, Chloé; Lee, Linda; Shepson, Paul B.

    2017-07-01

    Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield = 4(+1/-3) %, total ON yield = 14(+3/-2) %, and SOA yield ≤ 10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography-mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest.

  10. Chemical characterisation of atmospheric aerosols during a 2007 summer field campaign at Brasschaat, Belgium: sources and source processes of biogenic secondary organic aerosol

    Directory of Open Access Journals (Sweden)

    Y. Gómez-González

    2012-01-01

    Full Text Available Measurements of organic marker compounds and inorganic species were performed on PM2.5 aerosols from a Belgian forest site that is severely impacted by urban pollution ("De Inslag", Brasschaat, Belgium during a 2007 summer period within the framework of the "Formation mechanisms, marker compounds, and source apportionment for biogenic atmospheric aerosols (BIOSOL" project. The measured organic species included (i low-molecular weight (MW dicarboxylic acids (LMW DCAs, (ii methanesulfonate (MSA, (iii terpenoic acids originating from the oxidation of α-pinene, β-pinene, d-limonene and Δ3-carene, and (iv organosulfates related to secondary organic aerosol from the oxidation of isoprene and α-pinene. The organic tracers explained, on average, 5.3 % of the organic carbon (OC, of which 0.7 % was due to MSA, 3.4 % to LMW DCAs, 0.6 % to organosulfates, and 0.6 % to terpenoic acids. The highest atmospheric concentrations of most species were observed during the first five days of the campaign, which were characterised by maximum day-time temperatures >22 °C. Most of the terpenoic acids and the organosulfates peaked during day-time, consistent with their local photochemical origin. High concentrations of 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA and low concentrations of cis-pinonic acid were noted during the first five days of the campaign, indicative of an aged biogenic aerosol. Several correlations between organic species were very high (r>0.85, high (0.7<r<0.85, or substantial (0.5<r<0.7, suggesting that they are generated through similar formation pathways. Substantial correlations with temperature were found for OC, water-soluble OC, MBTCA, and several other organic species. MBTCA and terebic acid were highly correlated with the temperature (r>0.7 and showed an Arrhenius-type relationship, consistent with their formation through OH radical chemistry.

  11. Novel pathway of SO2 oxidation in the atmosphere: reactions with monoterpene ozonolysis intermediates and secondary organic aerosol

    Science.gov (United States)

    Ye, Jianhuai; Abbatt, Jonathan P. D.; Chan, Arthur W. H.

    2018-04-01

    Ozonolysis of monoterpenes is an important source of atmospheric biogenic secondary organic aerosol (BSOA). While enhanced BSOA formation has been associated with sulfate-rich conditions, the underlying mechanisms remain poorly understood. In this work, the interactions between SO2 and reactive intermediates from monoterpene ozonolysis were investigated under different humidity conditions (10 % vs. 50 %). Chamber experiments were conducted with ozonolysis of α-pinene or limonene in the presence of SO2. Limonene SOA formation was enhanced in the presence of SO2, while no significant changes in SOA yields were observed during α-pinene ozonolysis. Under dry conditions, SO2 primarily reacted with stabilized Criegee intermediates (sCIs) produced from ozonolysis, but at 50 % RH heterogeneous uptake of SO2 onto organic aerosol was found to be the dominant sink of SO2, likely owing to reactions between SO2 and organic peroxides. This SO2 loss mechanism to organic peroxides in SOA has not previously been identified in experimental chamber studies. Organosulfates were detected and identified using an electrospray ionization-ion mobility spectrometry-high-resolution time-of-flight mass spectrometer (ESI-IMS-TOF) when SO2 was present in the experiments. Our results demonstrate the synergistic effects between BSOA formation and SO2 oxidation through sCI chemistry and SO2 uptake onto organic aerosol and illustrate the importance of considering the chemistry of organic and sulfur-containing compounds holistically to properly account for their reactive sinks.

  12. Organic aerosol formation in citronella candle plumes

    OpenAIRE

    Bothe, Melanie; Donahue, Neil McPherson

    2010-01-01

    Citronella candles are widely used as insect repellants, especially outdoors in the evening. Because these essential oils are unsaturated, they have a unique potential to form secondary organic aerosol (SOA) via reaction with ozone, which is also commonly elevated on summer evenings when the candles are often in use. We investigated this process, along with primary aerosol emissions, by briefly placing a citronella tealight candle in a smog chamber and then adding ozone to the chamber. In rep...

  13. Secondary organic aerosol formation through fog processing of VOCs

    Science.gov (United States)

    Herckes, P.; Hutchings, J. W.

    2010-07-01

    Volatile Organic Compounds (VOCs) including benzene, toluene, ethylbenzene and xylenes (BTEX) have been determined in highly concentrated amounts (>1 ug/L) in intercepted clouds in northern Arizona (USA). These VOCs are found in concentrations much higher than predicted by partitioning alone. The reactivity of BTEX in the fog/cloud aqueous phase was investigated through laboratory studies. BTEX species showed fast degradation in the aqueous phase in the presence of peroxides and light. Observed half-lives ranged from three and six hours, substantially shorter than the respective gas phase half-lives (several days). The observed reaction rates were on the order of 1 ppb/min but decreased substantially with increasing concentrations of organic matter (TOC). The products of BTEX oxidation reactions were analyzed using HPLC-UV and LCMS. The first generation of products identified included phenol and cresols which correspond to the hydroxyl-addition reaction to benzene and toluene. Upon investigating of multi-generational products, smaller, less volatile species are predominant although a large variety of products is found. Most reaction products have substantially lower vapor pressure and will remain in the particle phase upon droplet evaporation. The SOA generation potential of cloud and fog processing of BTEX was evaluated using simple calculations and showed that in ideal situations these reactions could add up to 9% of the ambient aerosol mass. In more conservative scenarios, the contribution of the processing of BTEX was around 1% of ambient aerosol concentrations. Overall, cloud processing of VOC has the potential to contribute to the atmospheric aerosol mass. However, the contribution will depend upon many factors such as the irradiation, organic matter content in the droplets and droplet lifetime.

  14. Emission of intermediate, semi and low volatile organic compounds from traffic and their impact on secondary organic aerosol concentrations over Greater Paris

    Science.gov (United States)

    Sartelet, K.; Zhu, S.; Moukhtar, S.; André, M.; André, J. M.; Gros, V.; Favez, O.; Brasseur, A.; Redaelli, M.

    2018-05-01

    Exhaust particle emissions are mostly made of black carbon and/or organic compounds, with some of these organic compounds existing in both the gas and particle phases. Although emissions of volatile organic compounds (VOC) are usually measured at the exhaust, emissions in the gas phase of lower volatility compounds (POAvapor) are not. However, these gas-phase emissions may be oxidised after emission and enhance the formation of secondary organic aerosols (SOA). They are shown here to contribute to most of the SOA formation in Central Paris. POAvapor emissions are usually estimated from primary organic aerosol emissions in the particle phase (POA). However, they could also be estimated from VOC emissions for both gasoline and diesel vehicles using previously published measurements from chamber measurements. Estimating POAvapor from VOC emissions and ageing exhaust emissions with a simple model included in the Polyphemus air-quality platform compare well to measurements of SOA formation performed in chamber experiments. Over Greater Paris, POAvapor emissions estimated using POA and VOC emissions are compared using the HEAVEN bottom-up traffic emissions model. The impact on the simulated atmospheric concentrations is then assessed using the Polyphemus/Polair3D chemistry-transport model. Estimating POAvapor emissions from VOC emissions rather than POA emissions lead to lower emissions along motorway axes (between -50% and -70%) and larger emissions in urban areas (up to between +120% and +140% in Central Paris). The impact on total organic aerosol concentrations (gas plus particle) is lower than the impact on emissions: between -8% and 25% along motorway axes and in urban areas respectively. Particle-phase organic concentrations are lower when POAvapor emissions are estimated from VOC than POA emissions, even in Central Paris where the total organic aerosol concentration is higher, because of different assumptions on the emission volatility distribution, stressing the

  15. Modeling the gas-particle partitioning of secondary organic aerosol: the importance of liquid-liquid phase separation

    Directory of Open Access Journals (Sweden)

    A. Zuend

    2012-05-01

    Full Text Available The partitioning of semivolatile organic compounds between the gas phase and aerosol particles is an important source of secondary organic aerosol (SOA. Gas-particle partitioning of organic and inorganic species is influenced by the physical state and water content of aerosols, and therefore ambient relative humidity (RH, as well as temperature and organic loading levels. We introduce a novel combination of the thermodynamic models AIOMFAC (for liquid mixture non-ideality and EVAPORATION (for pure compound vapor pressures with oxidation product information from the Master Chemical Mechanism (MCM for the computation of gas-particle partitioning of organic compounds and water. The presence and impact of a liquid-liquid phase separation in the condensed phase is calculated as a function of variations in relative humidity, organic loading levels, and associated changes in aerosol composition. We show that a complex system of water, ammonium sulfate, and SOA from the ozonolysis of α-pinene exhibits liquid-liquid phase separation over a wide range of relative humidities (simulated from 30% to 99% RH. Since fully coupled phase separation and gas-particle partitioning calculations are computationally expensive, several simplified model approaches are tested with regard to computational costs and accuracy of predictions compared to the benchmark calculation. It is shown that forcing a liquid one-phase aerosol with or without consideration of non-ideal mixing bears the potential for vastly incorrect partitioning predictions. Assuming an ideal mixture leads to substantial overestimation of the particulate organic mass, by more than 100% at RH values of 80% and by more than 200% at RH values of 95%. Moreover, the simplified one-phase cases stress two key points for accurate gas-particle partitioning calculations: (1 non-ideality in the condensed phase needs to be considered and (2 liquid-liquid phase separation is a consequence of considerable deviations

  16. Organic aerosol formation during the atmospheric degradation of toluene.

    Science.gov (United States)

    Hurley, M D; Sokolov, O; Wallington, T J; Takekawa, H; Karasawa, M; Klotz, B; Barnes, I; Becker, K H

    2001-04-01

    Organic aerosol formation during the atmospheric oxidation of toluene was investigated using smog chamber systems. Toluene oxidation was initiated by the UV irradiation of either toluene/air/NOx or toluene/air/CH3ONO/NO mixtures. Aerosol formation was monitored using scanning mobility particle sizers and toluene loss was monitored by in-situ FTIR spectroscopy or GC-FID techniques. The experimental results show that the reaction of OH radicals, NO3 radicals and/or ozone with the first generation products of toluene oxidation are sources of organic aerosol during the atmospheric oxidation of toluene. The aerosol results fall into two groups, aerosol formed in the absence and presence of ozone. An analytical expression for aerosol formation is developed and values are obtained for the yield of the aerosol species. In the absence of ozone the aerosol yield, defined as aerosol formed per unit toluene consumed once a threshold for aerosol formation has been exceeded, is 0.075 +/- 0.004. In the presence of ozone the aerosol yield is 0.108 +/- 0.004. This work provides experimental evidence and a simple theory confirming the formation of aerosol from secondary reactions.

  17. Laboratory studies of monoterpene secondary organic aerosol formation and evolution

    Science.gov (United States)

    Thornton, J. A.; D'Ambro, E.; Zhao, Y.; Lee, B. H.; Pye, H. O. T.; Schobesberger, S.; Shilling, J.; Liu, J.

    2017-12-01

    We have conducted a series of chamber experiments to study the molecular composition and properties of secondary organic aerosol (SOA) formed from monoterpenes under a range of photochemical and dark conditions. We connect variations in the SOA mass yield to molecular composition and volatility, and use a detailed Master Chemical Mechanism (MCM) based chemical box model with dynamic gas-particle partitioning to examine the importance of various peroxy radical reaction mechanisms in setting the SOA yield and properties. We compare the volatility distribution predicted by the model to that inferred from isothermal room-temperature evaporation experiments using the FIGAERO-CIMS where SOA particles collected on a filter are allowed to evaporate under humidified pure nitrogen flow stream for up to 24 hours. We show that the combination of results requires prompt formation of low volatility SOA from predominantly gas-phase mechanisms, with important differences between monoterpenes (alpha-Pinene and delta-3-Carene) followed by slower non-radical particle phase chemistry that modulates both the chemical and physical properties of the SOA. Implications for the regional evolution of atmospheric monoterpene SOA are also discussed.

  18. Secondary aerosols from power plant effluents: delivery and in vivo detection systems

    International Nuclear Information System (INIS)

    Parks, N.J.; Raabe, O.G.; Bradley, E.; Raub, J.

    1976-01-01

    An experimental system is described for the generation of radiolabeled monodisperse aerosols, which are physico-chemically analogous to aerosols produced as secondary products of gaseous fossil fuel power plant emissions of SO 2 and NO 2 . The experimental system for inhalation exposure of non-human primates to these particles and the in vivo determination of systemic distribution and target organs is discussed

  19. Modeling biogenic secondary organic aerosol (BSOA) formation from monoterpene reactions with NO3: A case study of the SOAS campaign using CMAQ

    Science.gov (United States)

    Qin, Momei; Hu, Yongtao; Wang, Xuesong; Vasilakos, Petros; Boyd, Christopher M.; Xu, Lu; Song, Yu; Ng, Nga Lee; Nenes, Athanasios; Russell, Armistead G.

    2018-07-01

    Monoterpenes react with nitrate radicals (NO3), contributing substantially to nighttime organic aerosol (OA) production. In this study, the role of reactions of monoterpenes + NO3 in forming biogenic secondary organic aerosol (BSOA) was examined using the Community Multiscale Air Quality (CMAQ) model, with extended emission profiles of biogenic volatile organic compounds (BVOCs), species-specific representations of BSOA production from individual monoterpenes and updated aerosol yields for monoterpene + NO3. The model results were compared to detailed measurements from the Southern Oxidants and Aerosol Study (SOAS) at Centreville, Alabama. With the more detailed model, monoterpene-derived BSOA increased by ∼1 μg m-3 at night, accounting for one-third of observed less-oxidized oxygenated OA (LO-OOA), more closely agreeing with observations (lower error, stronger correlation). Implementation of a multigenerational oxidation approach resulted in the model capturing elevated OA episodes. With the aging model, aged semi-volatile organic compounds (ASVOCs) contributed over 60% of the monoterpene-derived BSOA, followed by SOA formation via nitrate radical chemistry, making up to 34% of that formed at night. Among individual monoterpenes, β-pinene and limonene contributed most to the monoterpene-derived BSOA from nighttime reactions.

  20. Primary and secondary organic aerosols in summer 2016 in Beijing

    Directory of Open Access Journals (Sweden)

    R. Tang

    2018-03-01

    Full Text Available To improve air quality, the Beijing government has employed several air pollution control measures since the 2008 Olympics. In order to investigate organic aerosol sources after the implementation of these measures, ambient fine particulate matter was collected at a regional site in Changping (CP and an urban site at the Peking University Atmosphere Environment Monitoring Station (PKUERS during the Photochemical Smog in China field campaign in summer 2016. Chemical mass balance (CMB modeling and the tracer yield method were used to apportion primary and secondary organic sources. Our results showed that the particle concentration decreased significantly during the last few years. The apportioned primary and secondary sources explained 62.8 ± 18.3 and 80.9 ± 27.2 % of the measured OC at CP and PKUERS, respectively. Vehicular emissions served as the dominant source. Except for gasoline engine emissions, the contributions of all the other primary sources decreased. In addition, the anthropogenic SOC, i.e., toluene SOC, also decreased, implying that deducting primary emissions can reduce anthropogenic SOA. In contrast to the SOA from other regions in the world where biogenic SOA was dominant, anthropogenic SOA was the major contributor to SOA, implying that deducting anthropogenic VOC emissions is an efficient way to reduce SOA in Beijing. Back-trajectory cluster analysis results showed that high mass concentrations of OC were observed when the air mass was from the south. However, the contributions of different primary organic sources were similar, suggesting regional particle pollution. The ozone concentration and temperature correlated well with the SOA concentration. Different correlations between day and night samples suggested different SOA formation pathways. Significant enhancement of SOA with increasing particle water content and acidity was observed in our study, suggesting that aqueous-phase acid-catalyzed reactions may be

  1. The SOA/VOC/NOx system: an explicit model of secondary organic aerosol formation

    Directory of Open Access Journals (Sweden)

    S. Madronich

    2007-11-01

    Full Text Available Our current understanding of secondary organic aerosol (SOA formation is limited by our knowledge of gaseous secondary organics involved in gas/particle partitioning. The objective of this study is to explore (i the potential for products of multiple oxidation steps contributing to SOA, and (ii the evolution of the SOA/VOC/NOx system. We developed an explicit model based on the coupling of detailed gas-phase oxidation schemes with a thermodynamic condensation module. Such a model allows prediction of SOA mass and speciation on the basis of first principles. The SOA/VOC/NOx system is studied for the oxidation of 1-octene under atmospherically relevant concentrations. In this study, gaseous oxidation of octene is simulated to lead to SOA formation. Contributors to SOA formation are shown to be formed via multiple oxidation steps of the parent hydrocarbon. The behaviour of the SOA/VOC/NOx system simulated using the explicit model agrees with general tendencies observed during laboratory chamber experiments. This explicit modelling of SOA formation appears as a useful exploratory tool to (i support interpretations of SOA formation observed in laboratory chamber experiments, (ii give some insights on SOA formation under atmospherically relevant conditions and (iii investigate implications for the regional/global lifetimes of the SOA.

  2. A new oxidation flow reactor for measuring secondary aerosol formation of rapidly changing emission sources

    Science.gov (United States)

    Simonen, Pauli; Saukko, Erkka; Karjalainen, Panu; Timonen, Hilkka; Bloss, Matthew; Aakko-Saksa, Päivi; Rönkkö, Topi; Keskinen, Jorma; Dal Maso, Miikka

    2017-04-01

    Oxidation flow reactors (OFRs) or environmental chambers can be used to estimate secondary aerosol formation potential of different emission sources. Emissions from anthropogenic sources, such as vehicles, often vary on short timescales. For example, to identify the vehicle driving conditions that lead to high potential secondary aerosol emissions, rapid oxidation of exhaust is needed. However, the residence times in environmental chambers and in most oxidation flow reactors are too long to study these transient effects ( ˜ 100 s in flow reactors and several hours in environmental chambers). Here, we present a new oxidation flow reactor, TSAR (TUT Secondary Aerosol Reactor), which has a short residence time ( ˜ 40 s) and near-laminar flow conditions. These improvements are achieved by reducing the reactor radius and volume. This allows studying, for example, the effect of vehicle driving conditions on the secondary aerosol formation potential of the exhaust. We show that the flow pattern in TSAR is nearly laminar and particle losses are negligible. The secondary organic aerosol (SOA) produced in TSAR has a similar mass spectrum to the SOA produced in the state-of-the-art reactor, PAM (potential aerosol mass). Both reactors produce the same amount of mass, but TSAR has a higher time resolution. We also show that TSAR is capable of measuring the secondary aerosol formation potential of a vehicle during a transient driving cycle and that the fast response of TSAR reveals how different driving conditions affect the amount of formed secondary aerosol. Thus, TSAR can be used to study rapidly changing emission sources, especially the vehicular emissions during transient driving.

  3. High-time resolved measurements of biogenic and anthropogenic secondary organic aerosol precursors and products in urban air

    Science.gov (United States)

    Flores, Rosa M.; Doskey, Paul V.

    2016-04-01

    Volatile organic compounds (VOCs), which are present in the atmosphere entirely in the gas phase are directly emitted by biogenic (~1089 Tg yr-1) and anthropogenic sources (~185 Tg yr-1). However, the sources and molecular speciation of intermediate VOCs (IVOCs), which are for the most part also present almost entirely in the gas phase, are not well characterized. The VOCs and IVOCs participate in reactions that form ozone and semivolatile OC (SVOC) that partition into the aerosol phase. Formation and evolution of secondary organic aerosol (SOA) are part of a complex dynamic process that depends on the molecular speciation and concentration of VOCs, IVOCs, primary organic aerosol (POA), and the level of oxidants (NO3, OH, O3). The current lack of understanding of OA properties and their impact on radiative forcing, ecosystems, and human health is partly due to limitations of models to predict SOA production on local, regional, and global scales. More accurate forecasting of SOA production requires high-temporal resolution measurement and molecular characterization of SOA precursors and products. For the subject study, the IVOCs and aerosol-phase organic matter were collected using the high-volume sampling technique and were analyzed by multidimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-ToFMS). The IVOCs included terpenes, terpenoids, n-alkanes, branched alkanes, isoprenoids, alkylbenzenes, cycloalkylbenzenes, PAH, alkyl PAH, and an unresolved complex mixture (UCM). Diurnal variations of OA species containing multiple oxygenated functionalities and selected SOA tracers of isorprene, α-pinene, toluene, cyclohexene, and n-dodecane oxidation were also quantified. The data for SOA precursor and oxidation products presented here will be useful for evaluating the ability of molecular-specific SOA models to forecast SOA production in and downwind of urban areas.

  4. submitter Observation of viscosity transition in α-pinene secondary organic aerosol

    CERN Document Server

    Järvinen, Emma; Nichman, Leonid; Kristensen, Thomas B; Fuchs, Claudia; Hoyle, Christopher R; Höppel, Niko; Corbin, Joel C; Craven, Jill; Duplissy, Jonathan; Ehrhart, Sebastian; El Haddad, Imad; Frege, Carla; Gordon, Hamish; Jokinen, Tuija; Kallinger, Peter; Kirkby, Jasper; Kiselev, Alexei; Naumann, Karl-Heinz; Petäjä, Tuukka; Pinterich, Tamara; Prevot, Andre S H; Saathoff, Harald; Schiebel, Thea; Sengupta, Kamalika; Simon, Mario; Slowik, Jay G; Tröstl, Jasmin; Virtanen, Annele; Vochezer, Paul; Vogt, Steffen; Wagner, Andrea C; Wagner, Robert; Williamson, Christina; Winkler, Paul M; Yan, Chao; Baltensperger, Urs; Donahue, Neil M; Flagan, Rick C; Gallagher, Martin; Hansel, Armin; Kulmala, Markku; Stratmann, Frank; Worsnop, Douglas R; Möhler, Ottmar; Leisner, Thomas; Schnaiter, Martin

    2016-01-01

    Under certain conditions, secondary organic aerosol (SOA) particles can exist in the atmosphere in an amorphous solid or semi-solid state. To determine their relevance to processes such as ice nucleation or chemistry occurring within particles requires knowledge of the temperature and relative humidity (RH) range for SOA to exist in these states. In the Cosmics Leaving Outdoor Droplets (CLOUD) experiment at The European Organisation for Nuclear Research (CERN), we deployed a new in situ optical method to detect the viscous state of α-pinene SOA particles and measured their transition from the amorphous highly viscous state to states of lower viscosity. The method is based on the depolarising properties of laboratory-produced non-spherical SOA particles and their transformation to non-depolarising spherical particles at relative humidities near the deliquescence point. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. A transition to a spherical shape w...

  5. An interfacial mechanism for cloud droplet formation on organic aerosols.

    Science.gov (United States)

    Ruehl, Christopher R; Davies, James F; Wilson, Kevin R

    2016-03-25

    Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depression by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation. Copyright © 2016, American Association for the Advancement of Science.

  6. Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

    Science.gov (United States)

    Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

    2016-03-10

    Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

  7. submitter Heterogeneous ice nucleation of viscous secondary organic aerosol produced from ozonolysis of α-pinene

    CERN Document Server

    Ignatius, Karoliina; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R; Duplissy, Jonathan; Garimella, Sarvesh; Dias, Antonio; Frege, Carla; Höppel, Niko; Tröstl, Jasmin; Wagner, Robert; Yan, Chao; Amorim, Antonio; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M; Gallagher, Martin W; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Tomé, Antonio; Virtanen, Annele; Worsnop, Douglas; Stratmann, Frank

    2016-01-01

    There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from −38 to −10 ◦C at 5–15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fraction...

  8. The impact of recirculation, ventilation and filters on secondary organic aerosols generated by indoor chemistry

    DEFF Research Database (Denmark)

    Fadeyi, M.O.; Weschler, Charles J.; Tham, K.W.

    2009-01-01

    This study examined the impact of recirculation rates (7 and 14 h(-1)), ventilation rates (1 and 2 h(-1)), and filtration on secondary organic aerosols (SOAs) generated by ozone of outdoor origin reacting with limonene of indoor origin. Experiments were conducted within a recirculating air handling......, but this was more than offset by the increased dilution of SOA derived from ozone-initiated chemistry. The presence of a particle filter (new or used) strikingly lowered SOA number and mass concentrations compared with conditions when no filter was present. Even though the particle filter in this study had only 35...

  9. Chemical and microphysical properties of the aerosol during foggy and nonfoggy episodes: a relationship between organic and inorganic content of the aerosol

    Science.gov (United States)

    Kaul, D. S.; Gupta, T.; Tripathi, S. N.

    2012-06-01

    An extensive field measurement during winter was carried out at a site located in the Indo-Gangetic Plain (IGP) which gets heavily influenced by the fog during winter almost every year. The chemical and microphysical properties of the aerosols during foggy and nonfoggy episodes and chemical composition of the fogwater are presented. Positive matrix factorization (PMF) as a tool for the source apportionment was employed to understand the sources of pollution. Four major sources viz. biomass burning, refractory, secondary and mineral dust were identified. Aerosols properties during foggy episodes were heavily influenced by almost all the sources and they caused considerable loading of almost all the organic and inorganic species during the period. The biomass generated aerosols were removed from the atmosphere by scavenging during foggy episodes. The wet removal of almost all the species by the fog droplets was observed. The K+, water soluble organic carbon (WSOC), water soluble inorganic carbon (WSIC) and NO3- were most heavily scavenged among the species and their concentrations consequently became lower than the nonfoggy episode concentrations. The production of secondary inorganic aerosol, mainly sulfate and ammonium, during foggy episodes was considerably higher than nitrate which was rather heavily scavenged and removed by the fog droplets. The fogwater analysis showed that dissolved inorganic species play a vital role in processing of organic carbon such as the formation of organo-sulfate and organo-nitrate inside the fog droplets. The formation of organo-sulfate and organo-nitrate in aerosol and the influence of acidity on the secondary organic aerosol (SOA) formation were rather found to be negligible. The study average inorganic component of the aerosol was considerably higher than the carbonaceous component during both foggy and nonfoggy episode. The secondary production of the aerosol changed the microphysical properties of aerosol which was reflected by

  10. Evaluation of the atmospheric significance of multiphase reactions in atmospheric secondary organic aerosol formation

    Directory of Open Access Journals (Sweden)

    Gelencsér

    2005-01-01

    Full Text Available In a simple conceptual cloud-aerosol model the mass of secondary organic aerosol (SOA that may be formed in multiphase reaction in an idealized scenario involving two cloud cycles separated with a cloud-free period is evaluated. The conditions are set to those typical of continental clouds, and each parameter used in the model calculations is selected as a mean of available observational data of individual species for which the multiphase SOA formation route has been established. In the idealized setting gas and aqueous-phase reactions are both considered, but only the latter is expected to yield products of sufficiently low volatility to be retained by aerosol particles after the cloud dissipates. The key variable of the model is the Henry-constant which primarily determines how important multiphase reactions are relative to gas-phase photooxidation processes. The precursor considered in the model is assumed to already have some affinity to water, i.e. it is a compound having oxygen-containing functional group(s. As a principal model output an aerosol yield parameter is calculated for the multiphase SOA formation route as a function of the Henry-constant, and has been found to be significant already above H~103 M atm-1. Among the potential precursors that may be eligible for this mechanism based on their Henry constants, there are a suite of oxygenated compounds such as primary oxidation products of biogenic and anthropogenic hydrocarbons, including, for example, pinonaldehyde. Finally, the analogy of multiphase SOA formation to in-cloud sulfate production is exploited.

  11. Laboratory Studies of the Reactive Chemistry and Changing CCN Properties of Secondary Organic Aerosol, Including Model Development

    Energy Technology Data Exchange (ETDEWEB)

    Scot Martin

    2013-01-31

    The chemical evolution of secondary-organic-aerosol (SOA) particles and how this evolution alters their cloud-nucleating properties were studied. Simplified forms of full Koehler theory were targeted, specifically forms that contain only those aspects essential to describing the laboratory observations, because of the requirement to minimize computational burden for use in integrated climate and chemistry models. The associated data analysis and interpretation have therefore focused on model development in the framework of modified kappa-Koehler theory. Kappa is a single parameter describing effective hygroscopicity, grouping together several separate physicochemical parameters (e.g., molar volume, surface tension, and van't Hoff factor) that otherwise must be tracked and evaluated in an iterative full-Koehler equation in a large-scale model. A major finding of the project was that secondary organic materials produced by the oxidation of a range of biogenic volatile organic compounds for diverse conditions have kappa values bracketed in the range of 0.10 +/- 0.05. In these same experiments, somewhat incongruently there was significant chemical variation in the secondary organic material, especially oxidation state, as was indicated by changes in the particle mass spectra. Taken together, these findings then support the use of kappa as a simplified yet accurate general parameter to represent the CCN activation of secondary organic material in large-scale atmospheric and climate models, thereby greatly reducing the computational burden while simultaneously including the most recent mechanistic findings of laboratory studies.

  12. High secondary aerosol contribution to particulate pollution during haze events in China

    Science.gov (United States)

    Huang, Ru-Jin; Zhang, Yanlin; Bozzetti, Carlo; Ho, Kin-Fai; Cao, Jun-Ji; Han, Yongming; Daellenbach, Kaspar R.; Slowik, Jay G.; Platt, Stephen M.; Canonaco, Francesco; Zotter, Peter; Wolf, Robert; Pieber, Simone M.; Bruns, Emily A.; Crippa, Monica; Ciarelli, Giancarlo; Piazzalunga, Andrea; Schwikowski, Margit; Abbaszade, Gülcin; Schnelle-Kreis, Jürgen; Zimmermann, Ralf; An, Zhisheng; Szidat, Sönke; Baltensperger, Urs; Haddad, Imad El; Prévôt, André S. H.

    2014-10-01

    Rapid industrialization and urbanization in developing countries has led to an increase in air pollution, along a similar trajectory to that previously experienced by the developed nations. In China, particulate pollution is a serious environmental problem that is influencing air quality, regional and global climates, and human health. In response to the extremely severe and persistent haze pollution experienced by about 800 million people during the first quarter of 2013 (refs 4, 5), the Chinese State Council announced its aim to reduce concentrations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 micrometres) by up to 25 per cent relative to 2012 levels by 2017 (ref. 6). Such efforts however require elucidation of the factors governing the abundance and composition of PM2.5, which remain poorly constrained in China. Here we combine a comprehensive set of novel and state-of-the-art offline analytical approaches and statistical techniques to investigate the chemical nature and sources of particulate matter at urban locations in Beijing, Shanghai, Guangzhou and Xi'an during January 2013. We find that the severe haze pollution event was driven to a large extent by secondary aerosol formation, which contributed 30-77 per cent and 44-71 per cent (average for all four cities) of PM2.5 and of organic aerosol, respectively. On average, the contribution of secondary organic aerosol (SOA) and secondary inorganic aerosol (SIA) are found to be of similar importance (SOA/SIA ratios range from 0.6 to 1.4). Our results suggest that, in addition to mitigating primary particulate emissions, reducing the emissions of secondary aerosol precursors from, for example, fossil fuel combustion and biomass burning is likely to be important for controlling China's PM2.5 levels and for reducing the environmental, economic and health impacts resulting from particulate pollution.

  13. Characterization of aerosol photooxidation flow reactors: heterogeneous oxidation, secondary organic aerosol formation and cloud condensation nuclei activity measurements

    Directory of Open Access Journals (Sweden)

    A. T. Lambe

    2011-03-01

    Full Text Available Motivated by the need to develop instrumental techniques for characterizing organic aerosol aging, we report on the performance of the Toronto Photo-Oxidation Tube (TPOT and Potential Aerosol Mass (PAM flow tube reactors under a variety of experimental conditions. The PAM system was designed with lower surface-area-to-volume (SA/V ratio to minimize wall effects; the TPOT reactor was designed to study heterogeneous aerosol chemistry where wall loss can be independently measured. The following studies were performed: (1 transmission efficiency measurements for CO2, SO2, and bis(2-ethylhexyl sebacate (BES particles, (2 H2SO4 yield measurements from the oxidation of SO2, (3 residence time distribution (RTD measurements for CO2, SO2, and BES particles, (4 aerosol mass spectra, O/C and H/C ratios, and cloud condensation nuclei (CCN activity measurements of BES particles exposed to OH radicals, and (5 aerosol mass spectra, O/C and H/C ratios, CCN activity, and yield measurements of secondary organic aerosol (SOA generated from gas-phase OH oxidation of m-xylene and α-pinene. OH exposures ranged from (2.0 ± 1.0 × 1010 to (1.8 ± 0.3 × 1012 molec cm−3 s. Where applicable, data from the flow tube reactors are compared with published results from the Caltech smog chamber. The TPOT yielded narrower RTDs. However, its transmission efficiency for SO2 was lower than that for the PAM. Transmission efficiency for BES and H2SO4 particles was size-dependent and was similar for the two flow tube designs. Oxidized BES particles had similar O/C and H/C ratios and CCN activity at OH exposures greater than 1011 molec cm−3 s, but different CCN activity at lower OH exposures. The O/C ratio, H/C ratio, and yield of m-xylene and α-pinene SOA was strongly affected by reactor design and

  14. Ammonium addition (and aerosol pH) has a dramatic impact on the volatility and yield of glyoxal secondary organic aerosol.

    Science.gov (United States)

    Ortiz-Montalvo, Diana L; Häkkinen, Silja A K; Schwier, Allison N; Lim, Yong B; McNeill, V Faye; Turpin, Barbara J

    2014-01-01

    Glyoxal is an important precursor to secondary organic aerosol (SOA) formed through aqueous chemistry in clouds, fogs, and wet aerosols, yet the gas-particle partitioning of the resulting mixture is not well understood. This work characterizes the volatility behavior of the glyoxal precursor/product mix formed after aqueous hydroxyl radical oxidation and droplet evaporation under cloud-relevant conditions for 10 min, thus aiding the prediction of SOA via this pathway (SOACld). This work uses kinetic modeling for droplet composition, droplet evaporation experiments and temperature-programmed desorption aerosol-chemical ionization mass spectrometer analysis of gas-particle partitioning. An effective vapor pressure (p'L,eff) of ∼10(-7) atm and an enthalpy of vaporization (ΔHvap,eff) of ∼70 kJ/mol were estimated for this mixture. These estimates are similar to those of oxalic acid, which is a major product. Addition of ammonium until the pH reached 7 (with ammonium hydroxide) reduced the p'L,eff to 80 kJ/mol, at least in part via the formation of ammonium oxalate. pH 7 samples behaved like ammonium oxalate, which has a vapor pressure of ∼10(-11) atm. We conclude that ammonium addition has a large effect on the gas-particle partitioning of the mixture, substantially enhancing the yield of SOACld from glyoxal.

  15. Mass yields of secondary organic aerosols from the oxidation of α-pinene and real plant emissions

    Directory of Open Access Journals (Sweden)

    J. N. Smith

    2011-02-01

    Full Text Available Biogenic volatile organic compounds (VOCs are a significant source of global secondary organic aerosol (SOA; however, quantifying their aerosol forming potential remains a challenge. This study presents smog chamber laboratory work, focusing on SOA formation via oxidation of the emissions of two dominant tree species from boreal forest area, Scots pine (Pinus sylvestris L. and Norway spruce (Picea abies, by hydroxyl radical (OH and ozone (O3. Oxidation of α-pinene was also studied as a reference system. Tetramethylethylene (TME and 2-butanol were added to control OH and O3 levels, thereby allowing SOA formation events to be categorized as resulting from either OH-dominated or O3-initiated chemistry. SOA mass yields from α-pinene are consistent with previous studies while the yields from the real plant emissions are generally lower than that from α-pinene, varying from 1.9% at an aerosol mass loading of 0.69 μg m−3 to 17.7% at 26.0 μg m−3. Mass yields from oxidation of real plant emissions are subject to the interactive effects of the molecular structures of plant emissions and their reaction chemistry with OH and O3, which lead to variations in condensable product volatility. SOA formation can be reproduced with a two-product gas-phase partitioning absorption model in spite of differences in the source of oxidant species and product volatility in the real plant emission experiments. Condensable products from OH-dominated chemistry showed a higher volatility than those from O3-initiated systems during aerosol growth stage. Particulate phase products became less volatile via aging process which continued after input gas-phase oxidants had been completely consumed.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  17. The Secondary Organic Aerosol Processor (SOAP v1.0) model: a unified model with different ranges of complexity based on the molecular surrogate approach

    Science.gov (United States)

    Couvidat, F.; Sartelet, K.

    2015-04-01

    In this paper the Secondary Organic Aerosol Processor (SOAP v1.0) model is presented. This model determines the partitioning of organic compounds between the gas and particle phases. It is designed to be modular with different user options depending on the computation time and the complexity required by the user. This model is based on the molecular surrogate approach, in which each surrogate compound is associated with a molecular structure to estimate some properties and parameters (hygroscopicity, absorption into the aqueous phase of particles, activity coefficients and phase separation). Each surrogate can be hydrophilic (condenses only into the aqueous phase of particles), hydrophobic (condenses only into the organic phases of particles) or both (condenses into both the aqueous and the organic phases of particles). Activity coefficients are computed with the UNIFAC (UNIversal Functional group Activity Coefficient; Fredenslund et al., 1975) thermodynamic model for short-range interactions and with the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) parameterization for medium- and long-range interactions between electrolytes and organic compounds. Phase separation is determined by Gibbs energy minimization. The user can choose between an equilibrium representation and a dynamic representation of organic aerosols (OAs). In the equilibrium representation, compounds in the particle phase are assumed to be at equilibrium with the gas phase. However, recent studies show that the organic aerosol is not at equilibrium with the gas phase because the organic phases could be semi-solid (very viscous liquid phase). The condensation-evaporation of organic compounds could then be limited by the diffusion in the organic phases due to the high viscosity. An implicit dynamic representation of secondary organic aerosols (SOAs) is available in SOAP with OAs divided into layers, the first layer being at the center of the particle (slowly

  18. Preliminary characterization of submicron secondary aerosol in the amazon forest - ATTO station

    Science.gov (United States)

    Carbone, S.; Ferreira De Brito, J.; Andreae, M. O.; Pöhlker, C.; Chi, X.; Saturno, J.; Barbosa, H. M.; Artaxo, P.

    2014-12-01

    Biogenic secondary organic aerosol particles are investigated in the Amazon in the context of the GoAmazon Project. The forest naturally emits a large number of gaseous compounds; they are called the volatile organic compounds (VOCs). They are emitted through processes that are not totally understood. Part of those gaseous compounds are converted into aerosol particles, which affect the biogeochemical cycles, the radiation balance, the mechanisms involving cloud formation and evolution, among few other important effects. In this study the aerosol life-cycle is investigated at the ATTO station, which is located about 150 km northeast of Manaus, with emphasis on the natural organic component and its impacts in the ecosystem. To achieve these objectives physical and chemical aerosol properties have been investigated, such as the chemical composition with aerosol chemical speciation monitor (ACSM), nanoparticle size distribution (using the SMPS - Scanning Mobility Particle Sizer), optical properties with measurements of scattering and absorption (using nephelometers and aethalometers). Those instruments have been operating continuously since February 2014 together with trace gases (O3, CO2, CO, SO2 and NOx) analyzers and additional meteorological instruments. On average PM1 (the sum of black carbon, organic and inorganic ions) totalized 1.0±0.3 μg m-3, where the organic fraction was dominant (75%). During the beginning of the dry season (July/August) the organic aerosol presented a moderate oxygenated character with the oxygen to carbon ratio (O:C) of 0.7. In the wet season some episodes containing significant amount of chloride and backward wind trajectories suggest aerosol contribution from the Atlantic Ocean. A more comprehensive analysis will include an investigation of the different oxidized fractions of the organic aerosol and optical properties.

  19. a Study of the Origin of Atmospheric Organic Aerosols

    Science.gov (United States)

    Hildemann, Lynn Mary

    1990-01-01

    predictions and ambient concentrations that could be due to atmospheric chemical reaction are discussed. An upper limit on the amount of secondary organic aerosol present is estimated based on the difference between the acidic organic aerosol present in ambient samples versus that due to primary emissions as computed by the model. Finally, several hypotheses concerning the origin of the organic aerosol are proposed.

  20. Simulating secondary organic aerosol from missing diesel-related intermediate-volatility organic compound emissions during the Clean Air for London (ClearfLo campaign

    Directory of Open Access Journals (Sweden)

    R. Ots

    2016-05-01

    Full Text Available We present high-resolution (5 km  ×  5 km atmospheric chemical transport model (ACTM simulations of the impact of newly estimated traffic-related emissions on secondary organic aerosol (SOA formation over the UK for 2012. Our simulations include additional diesel-related intermediate-volatility organic compound (IVOC emissions derived directly from comprehensive field measurements at an urban background site in London during the 2012 Clean Air for London (ClearfLo campaign. Our IVOC emissions are added proportionally to VOC emissions, as opposed to proportionally to primary organic aerosol (POA as has been done by previous ACTM studies seeking to simulate the effects of these missing emissions. Modelled concentrations are evaluated against hourly and daily measurements of organic aerosol (OA components derived from aerosol mass spectrometer (AMS measurements also made during the ClearfLo campaign at three sites in the London area. According to the model simulations, diesel-related IVOCs can explain on average  ∼  30 % of the annual SOA in and around London. Furthermore, the 90th percentile of modelled daily SOA concentrations for the whole year is 3.8 µg m−3, constituting a notable addition to total particulate matter. More measurements of these precursors (currently not included in official emissions inventories is recommended. During the period of concurrent measurements, SOA concentrations at the Detling rural background location east of London were greater than at the central London location. The model shows that this was caused by an intense pollution plume with a strong gradient of imported SOA passing over the rural location. This demonstrates the value of modelling for supporting the interpretation of measurements taken at different sites or for short durations.

  1. Observational evidence for pollution-influenced selective uptake contributing to biogenic secondary organic aerosols in the southeastern U.S.

    Science.gov (United States)

    Liu, J.; Russell, L. M.; Lee, A. K. Y.; McKinney, K. A.; Surratt, J. D.; Ziemann, P. J.

    2017-08-01

    During the 2013 Southern Oxidant and Aerosol Study, aerosol mass spectrometer measurements of submicron mass and single particles were taken at Look Rock, Tennessee. Their concentrations increased during multiday stagnation events characterized by low wind, little rain, and increased daytime isoprene emissions. Organic mass (OM) sources were apportioned as 42% "vehicle-related" and 54% biogenic secondary organic aerosol (bSOA), with the latter including "sulfate-related bSOA" that correlated to sulfate (r = 0.72) and "nitrate-related bSOA" that correlated to nitrate (r = 0.65). Single-particle mass spectra showed three composition types that corresponded to the mass-based factors with spectra cosine similarity of 0.93 and time series correlations of r > 0.4. The vehicle-related OM with m/z 44 was correlated to black carbon, "sulfate-related bSOA" was on particles with high sulfate, and "nitrate-related bSOA" was on all particles. The similarity of the m/z spectra (cosine similarity = 0.97) and the time series correlation (r = 0.80) of the "sulfate-related bSOA" to the sulfate-containing single-particle type provide evidence for particle composition contributing to selective uptake of isoprene oxidation products onto particles that contain sulfate from power plants.

  2. Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

    Directory of Open Access Journals (Sweden)

    B. Ervens

    2010-09-01

    Full Text Available This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a oligomers, (b nitrogen-containing products, (c photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud chemistry for the same conditions (liquid water content, particle size.

    The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated process is the major SOA formation pathway forming ∼5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt. During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 < pH < 7.

    Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend

  3. Formation and toxicological effect of secondary organic aerosols%二次有机气溶胶的形成及其毒理效应

    Institute of Scientific and Technical Information of China (English)

    曹军骥; 李建军

    2016-01-01

    Background, aim, and scope Along with the rapid development of Chinese economy, pollutants derived from increasing usage of fossil fuels and biofuels, as well as emissions from waste incineration and dust have been causing serious air pollution problems in many areas of China. Particular matter (PM), especially anthropogenic aerosols, emitted from various sources may alter regional atmospheric stability, and are of significant impact on climate change and human health. Comparing with PM10 (aerodynamic diameter≤10 μm), ifne particle (PM2.5, aerodynamic diameter≤2.5 μm) do more damage to human health. Organic matter (OM), an important chemical composition of ifne particle, takes 20%—90% of the ifne particles, has a signiifcant impact on air pollution and haze event which is happening in China, and has become a frontier of atmospheric chemistry research area. Consisting with many toxic compounds, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organic amines and so on, organic aerosol is harmful for human health. Many in-vitro and in-vito studies of biological toxicity were focused on the primary particulate matters emitted directly from the pollution sources, however, attention for the formation and toxicity of secondary organic aerosols (SOA) are really scarce and therefore urgent.Materials and methods Taking PAHs, amines, and biogenic terpenes as examples, in order to improve the understanding on health damage of SOA pollution, this article brielfy reviewed the formation and bio-toxicity effects of speciifc group of SOA, and focused on the rising toxicity of the products comparing with their parent compounds.Results (1) Polycyclic aromatic hydrocarbons (PAHs). Because of the mutagenic, teratogenic and carcinogenic properties, PAHs has focused a great deal of attention from scientiifc researchers and is considered as one of the most important organic pollutants in the atmosphere. Parent PAHs in the aerosols can undergo a

  4. Characterization of urban aerosol using aerosol mass spectrometry and proton nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Cleveland, M. J.; Ziemba, L. D.; Griffin, R. J.; Dibb, J. E.; Anderson, C. H.; Lefer, B.; Rappenglück, B.

    2012-07-01

    Particulate matter was measured during August and September of 2006 in Houston as part of the Texas Air Quality Study II Radical and Aerosol Measurement Project. Aerosol size and composition were determined using an Aerodyne quadrupole aerosol mass spectrometer. Aerosol was dominated by sulfate (4.1 ± 2.6 μg m-3) and organic material (5.5 ± 4.0 μg m-3), with contributions of organic material from both primary (˜32%) and secondary (˜68%) sources. Secondary organic aerosol appears to be formed locally. In addition, 29 aerosol filter samples were analyzed using proton nuclear magnetic resonance (1H NMR) spectroscopy to determine relative concentrations of organic functional groups. Houston aerosols are less oxidized than those observed elsewhere, with smaller relative contributions of carbon-oxygen double bonds. These particles do not fit 1H NMR source apportionment fingerprints for identification of secondary, marine, and biomass burning organic aerosol, suggesting that a new fingerprint for highly urbanized and industrially influenced locations be established.

  5. Relating hygroscopicity and composition of organic aerosol particulate matter

    CERN Document Server

    Duplissy, J; Prevot, A S H; Barmpadimos, I; Jimenez, J L; Gysel, M; Worsnop, D R; Aiken, A C; Tritscher, T; Canagaratna, M R; Collins, D R; Alfarra, M R; Metzger, A; Tomlinson, J; DeCarlo, P F; Weingartner, E; Baltensperger, U

    2011-01-01

    A hygroscopicity tandem differential mobility analyzer (HTDMA) was used to measure the water uptake (hygroscopicity) of secondary organic aerosol (SOA) formed during the chemical and photochemical oxidation of several organic precursors in a smog chamber. Electron ionization mass spectra of the non-refractory submicron aerosol were simultaneously determined with an aerosol mass spectrometer (AMS), and correlations between the two different signals were investigated. SOA hygroscopicity was found to strongly correlate with the relative abundance of the ion signal m/z 44 expressed as a fraction of total organic signal (f(44)). m/z 44 is due mostly to the ion fragment CO(2)(+) for all types of SOA systems studied, and has been previously shown to strongly correlate with organic O/C for ambient and chamber OA. The analysis was also performed on ambient OA from two field experiments at the remote site Jungfrau-joch, and the megacity Mexico City, where similar results were found. A simple empirical linear relation b...

  6. Speciation of organic aerosols in the Saharan Air Layer and in the free troposphere westerlies

    Directory of Open Access Journals (Sweden)

    M. I. García

    2017-07-01

    Full Text Available We focused this research on the composition of the organic aerosols transported in the two main airflows of the subtropical North Atlantic free troposphere: (i the Saharan Air Layer – the warm, dry and dusty airstream that expands from North Africa to the Americas at subtropical and tropical latitudes – and (ii the westerlies, which flow from North America over the North Atlantic at mid- and subtropical latitudes. We determined the inorganic compounds (secondary inorganic species and elemental composition, elemental carbon and the organic fraction (bulk organic carbon and organic speciation present in the aerosol collected at Izaña Observatory,  ∼  2400 m a.s.l. on the island of Tenerife. The concentrations of all inorganic and almost all organic compounds were higher in the Saharan Air Layer than in the westerlies, with bulk organic matter concentrations within the range 0.02–4.0 µg m−3. In the Saharan Air Layer, the total aerosol population was by far dominated by dust (93 % of bulk mass, which was mixed with secondary inorganic pollutants ( <  5 % and organic matter ( ∼  1.5 %. The chemical speciation of the organic aerosols (levoglucosan, dicarboxylic acids, saccharides, n-alkanes, hopanes, polycyclic aromatic hydrocarbons and those formed after oxidation of α-pinene and isoprene, determined by gas chromatography coupled with mass spectrometry accounted for 15 % of the bulk organic matter (determined by the thermo-optical transmission technique; the most abundant organic compounds were saccharides (associated with surface soils, secondary organic aerosols linked to oxidation of biogenic isoprene (SOA ISO and dicarboxylic acids (linked to several primary sources and SOA. When the Saharan Air Layer shifted southward, Izaña was within the westerlies stream and organic matter accounted for  ∼  28 % of the bulk mass of aerosols. In the westerlies, the organic aerosol species determined

  7. Secondary organic aerosol production from pinanediol, a semi-volatile surrogate for first-generation oxidation products of monoterpenes

    Science.gov (United States)

    Ye, Penglin; Zhao, Yunliang; Chuang, Wayne K.; Robinson, Allen L.; Donahue, Neil M.

    2018-05-01

    We have investigated the production of secondary organic aerosol (SOA) from pinanediol (PD), a precursor chosen as a semi-volatile surrogate for first-generation oxidation products of monoterpenes. Observations at the CLOUD facility at CERN have shown that oxidation of organic compounds such as PD can be an important contributor to new-particle formation. Here we focus on SOA mass yields and chemical composition from PD photo-oxidation in the CMU smog chamber. To determine the SOA mass yields from this semi-volatile precursor, we had to address partitioning of both the PD and its oxidation products to the chamber walls. After correcting for these losses, we found OA loading dependent SOA mass yields from PD oxidation that ranged between 0.1 and 0.9 for SOA concentrations between 0.02 and 20 µg m-3, these mass yields are 2-3 times larger than typical of much more volatile monoterpenes. The average carbon oxidation state measured with an aerosol mass spectrometer was around -0.7. We modeled the chamber data using a dynamical two-dimensional volatility basis set and found that a significant fraction of the SOA comprises low-volatility organic compounds that could drive new-particle formation and growth, which is consistent with the CLOUD observations.

  8. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    Directory of Open Access Journals (Sweden)

    M. F. Heringa

    2012-02-01

    Full Text Available Organic aerosol (OA represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 μm mass. Secondary organic aerosol (SOA is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS and compared to SOA from α-pinene.

    The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production.

    Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25–0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions.

    The HR data of the four sources could be clustered and separated using

  9. Time-resolved analysis of primary volatile emissions and secondary aerosol formation potential from a small-scale pellet boiler

    Science.gov (United States)

    Czech, Hendryk; Pieber, Simone M.; Tiitta, Petri; Sippula, Olli; Kortelainen, Miika; Lamberg, Heikki; Grigonyte, Julija; Streibel, Thorsten; Prévôt, André S. H.; Jokiniemi, Jorma; Zimmermann, Ralf

    2017-06-01

    Small-scale pellet boilers and stoves became popular as a wood combustion appliance for domestic heating in Europe, North America and Asia due to economic and environmental aspects. Therefore, an increasing contribution of pellet boilers to air pollution is expected despite their general high combustion efficiency. As emissions of primary organic aerosol (POA) and permanent gases of pellet boilers are well investigated, the scope of this study was to investigate the volatile organic emissions and the formation potential of secondary aerosols for this type of appliance. Fresh and aged emissions were analysed by a soot-particle aerosol time-of-flight mass spectrometry (SP-AMS) and the molecular composition of the volatile precursors with single-photon ionisation time-of-flight mass spectrometry (SPI-TOFMS) at different pellet boiler operation conditions. Organic emissions in the gas phase were dominated by unsaturated hydrocarbons while wood-specific VOCs, e.g. phenolic species or substituted furans, were only detected during the starting phase. Furthermore, organic emissions in the gas phase were found to correlate with fuel grade and combustion technology in terms of secondary air supply. Secondary organic aerosols of optimised pellet boiler conditions (OPT, state-of-the-art combustion appliance) and reduced secondary air supply (RSA, used as a proxy for pellet boilers of older type) were studied by simulating atmospheric ageing in a Potential Aerosol Mass (PAM) flow reactor. Different increases in OA mass (55% for OPT, 102% for RSA), associated with higher average carbon oxidation state and O:C, could be observed in a PAM chamber experiment. Finally, it was found that derived SOA yields and emission factors were distinctly lower than reported for log wood stoves.

  10. Effect of Pellet Boiler Exhaust on Secondary Organic Aerosol Formation from α-Pinene.

    Science.gov (United States)

    Kari, Eetu; Hao, Liqing; Yli-Pirilä, Pasi; Leskinen, Ari; Kortelainen, Miika; Grigonyte, Julija; Worsnop, Douglas R; Jokiniemi, Jorma; Sippula, Olli; Faiola, Celia L; Virtanen, Annele

    2017-02-07

    Interactions between anthropogenic and biogenic emissions, and implications for aerosol production, have raised particular scientific interest. Despite active research in this area, real anthropogenic emission sources have not been exploited for anthropogenic-biogenic interaction studies until now. This work examines these interactions using α-pinene and pellet boiler emissions as a model test system. The impact of pellet boiler emissions on secondary organic aerosol (SOA) formation from α-pinene photo-oxidation was studied under atmospherically relevant conditions in an environmental chamber. The aim of this study was to identify which of the major pellet exhaust components (including high nitrogen oxide (NO x ), primary particles, or a combination of the two) affected SOA formation from α-pinene. Results demonstrated that high NO x concentrations emitted by the pellet boiler reduced SOA yields from α-pinene, whereas the chemical properties of the primary particles emitted by the pellet boiler had no effect on observed SOA yields. The maximum SOA yield of α-pinene in the presence of pellet boiler exhaust (under high-NO x conditions) was 18.7% and in the absence of pellet boiler exhaust (under low-NO x conditions) was 34.1%. The reduced SOA yield under high-NO x conditions was caused by changes in gas-phase chemistry that led to the formation of organonitrate compounds.

  11. Degradation of indoor limonene by outdoor ozone: A cascade of secondary organic aerosols.

    Science.gov (United States)

    Rösch, Carolin; Wissenbach, Dirk K; Franck, Ulrich; Wendisch, Manfred; Schlink, Uwe

    2017-07-01

    In indoor air, terpene-ozone reactions can form secondary organic aerosols (SOA) in a transient process. 'Real world' measurements conducted in a furnished room without air conditioning were modelled involving the indoor background of airborne particulate matter, outdoor ozone infiltrated by natural ventilation, repeated transient limonene evaporations, and different subsequent ventilation regimes. For the given setup, we disentangled the development of nucleated, coagulated, and condensed SOA fractions in the indoor air and calculated the time dependence of the aerosol mass fraction (AMF) by means of a process model. The AMF varied significantly between 0.3 and 5.0 and was influenced by the ozone limonene ratio and the background particles which existed prior to SOA formation. Both influencing factors determine whether nucleation or adsorption processes are preferred; condensation is strongly intensified by particulate background. The results provide evidence that SOA levels in natural indoor environments can surpass those known from chamber measurements. An indicator for the SOA forming potential of limonene was found to be limona ketone. Multiplying its concentration (in μg/m 3 ) by 450(±100) provides an estimate of the concentration of the reacted limonene. This can be used to detect a high particle formation potential due to limonene pollution, e.g. in epidemiological studies considering adverse health effects of indoor air pollutants. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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

  13. Partitioning phase preference for secondary organic aerosol in an urban atmosphere

    Science.gov (United States)

    Chang, Wayne Li-Wen

    Secondary organic aerosol (SOA) comprises a significant portion of atmospheric particular matter (PM). The impact of PM on both human health and global climate has long been recognized. Despite its importance, there are still many unanswered questions regarding the formation and evolution of SOA in the atmosphere. This study uses a modeling approach to understand the preferred partitioning behavior of SOA species into aqueous or organic condensed phases. More specifically, this work uses statistical analyses of approximately 24,000 data values for each variable from a state-of-the-art 3-D airshed model. Spatial and temporal distributions of fractions of SOA residing in the aqueous phase (fAQ) in the South Coast Air Basin of California are presented. Typical values of fAQ within the basin near the surface range from 5 to 80%. Results show that the distribution of fAQ values is inversely proportional to the total SOA loading. Further analysis accounting for various meteorological parameters indicates that large fAQ values are the results of aqueous-phase SOA insensitivity to the ambient conditions; while organic-phase SOA concentrations are dramatically reduced under unfavorable SOA formation conditions, aqueous-phase SOA level remains relatively unchanged, thus increasing fAQ at low SOA loading. Diurnal variations of fAQ near the surface are also observed: it tends to be larger during daytime hours than nighttime hours. When examining the vertical gradient of fAQ, largest values are found at heights above the surface layer. In summary, one must consider SOA in both organic and aqueous phases for proper regional and global SOA budget estimation.

  14. Open burning of rice, corn and wheat straws: primary emissions, photochemical aging, and secondary organic aerosol formation

    Science.gov (United States)

    Fang, Zheng; Deng, Wei; Zhang, Yanli; Ding, Xiang; Tang, Mingjin; Liu, Tengyu; Hu, Qihou; Zhu, Ming; Wang, Zhaoyi; Yang, Weiqiang; Huang, Zhonghui; Song, Wei; Bi, Xinhui; Chen, Jianmin; Sun, Yele; George, Christian; Wang, Xinming

    2017-12-01

    Agricultural residues are among the most abundant biomass burned globally, especially in China. However, there is little information on primary emissions and photochemical evolution of agricultural residue burning. In this study, indoor chamber experiments were conducted to investigate primary emissions from open burning of rice, corn and wheat straws and their photochemical aging as well. Emission factors of NOx, NH3, SO2, 67 non-methane hydrocarbons (NMHCs), particulate matter (PM), organic aerosol (OA) and black carbon (BC) under ambient dilution conditions were determined. Olefins accounted for > 50 % of the total speciated NMHCs emission (2.47 to 5.04 g kg-1), indicating high ozone formation potential of straw burning emissions. Emission factors of PM (3.73 to 6.36 g kg-1) and primary organic carbon (POC, 2.05 to 4.11 gC kg-1), measured at dilution ratios of 1300 to 4000, were lower than those reported in previous studies at low dilution ratios, probably due to the evaporation of semi-volatile organic compounds under high dilution conditions. After photochemical aging with an OH exposure range of (1.97-4.97) × 1010 molecule cm-3 s in the chamber, large amounts of secondary organic aerosol (SOA) were produced with OA mass enhancement ratios (the mass ratio of total OA to primary OA) of 2.4-7.6. The 20 known precursors could only explain 5.0-27.3 % of the observed SOA mass, suggesting that the major precursors of SOA formed from open straw burning remain unidentified. Aerosol mass spectrometry (AMS) signaled that the aged OA contained less hydrocarbons but more oxygen- and nitrogen-containing compounds than primary OA, and carbon oxidation state (OSc) calculated with AMS resolved O / C and H / C ratios increased linearly (p < 0.001) with OH exposure with quite similar slopes.

  15. Microphysical Properties of Single Secondary Organic Aerosol (SOA) Particles

    Science.gov (United States)

    Rovelli, Grazia; Song, Young-Chul; Pereira, Kelly; Hamilton, Jacqueline; Topping, David; Reid, Jonathan

    2017-04-01

    Secondary Organic Aerosols (SOA) deriving from the oxidation of volatile organic compounds (VOCs) can account for a substantial fraction of the overall atmospheric aerosol mass.[1] Therefore, the investigation of SOA microphysical properties is crucial to better comprehend their role in the atmospheric processes they are involved in. This works describes a single particle approach to accurately characterise the hygroscopic response, the optical properties and the gas-particle partitioning kinetics of water and semivolatile components for laboratory generated SOA. SOA was generated from the oxidation of different VOCs precursors (e.g. α-pinene, toluene) in a photo-chemical flow reactor, which consists of a temperature and relative humidity controlled 300 L polyvinyl fluoride bag. Known VOC, NOx and ozone concentrations are introduced in the chamber and UV irradiation is performed by means of a Hg pen-ray. SOA samples were collected with an electrical low pressure impactor, wrapped in aluminium foil and kept refrigerated at -20°C. SOA samples were extracted in a 1:1 water/methanol mixture. Single charged SOA particles were generated from the obtained solution using a microdispenser and confined within an electrodynamic balance (EDB), where they sit in a T (250-320 K) and RH (0-95%) controlled nitrogen flow. Suspended droplets are irradiated with a 532 nm laser and the evolving angularly resolved scattered light is used to keep track of changes in droplet size. One of the key features of this experimental approach is that very little SOA solution is required because of the small volumes needed to load the dispensers (evaporation kinetics experiments (CK-EDB) of suspended probe and sample droplets.[2] The variation of the refractive index of SOA droplets following to water or SVOCs evaporative loss was measured as a function of water activity by fitting the collected light scattering patterns with a generated Mie-Theory library of phase functions.[3] Long trapping

  16. Persistence of urban organic aerosols composition: Decoding their structural complexity and seasonal variability

    International Nuclear Information System (INIS)

    Matos, João T.V.; Duarte, Regina M.B.O.; Lopes, Sónia P.; Silva, Artur M.S.; Duarte, Armando C.

    2017-01-01

    Organic Aerosols (OAs) are typically defined as highly complex matrices whose composition changes in time and space. Focusing on time vector, this work uses two-dimensional nuclear magnetic resonance (2D NMR) techniques to examine the structural features of water-soluble (WSOM) and alkaline-soluble organic matter (ASOM) sequentially extracted from fine atmospheric aerosols collected in an urban setting during cold and warm seasons. This study reveals molecular signatures not previously decoded in NMR-related studies of OAs as meaningful source markers. Although the ASOM is less hydrophilic and structurally diverse than its WSOM counterpart, both fractions feature a core with heteroatom-rich branched aliphatics from both primary (natural and anthropogenic) and secondary origin, aromatic secondary organics originated from anthropogenic aromatic precursors, as well as primary saccharides and amino sugar derivatives from biogenic emissions. These common structures represent those 2D NMR spectral signatures that are present in both seasons and can thus be seen as an “annual background” profile of the structural composition of OAs at the urban location. Lignin-derived structures, nitroaromatics, disaccharides, and anhydrosaccharides signatures were also identified in the WSOM samples only from periods identified as smoke impacted, which reflects the influence of biomass-burning sources. The NMR dataset on the H–C molecules backbone was also used to propose a semi-quantitative structural model of urban WSOM, which will aid efforts for more realistic studies relating the chemical properties of OAs with their atmospheric behavior. - Highlights: • 2D NMR spectroscopy was used to decode urban organic aerosols. • Water and alkaline soluble components of urban organic aerosols have been compared. • Persistence of urban organic aerosols composition across different seasons. • Annual background profile of the structural features of urban organic aerosols. • Semi

  17. Field and Laboratory Studies of Atmospheric Organic Aerosol

    Science.gov (United States)

    Coggon, Matthew Mitchell

    of oxidized organic compounds contributed nearly an order of magnitude more cloud condensation nuclei (CCN) than less oxidized particles formed under cloudy conditions. The processing time necessary for particles to become CCN active was short ( 4 hr). Laboratory chamber experiments were also conducted to evaluate particle-phase processes influencing aerosol phase and composition. In one study, ammonium sulfate seed was coated with a layer of secondary organic aerosol (SOA) from toluene oxidation followed by a layer of SOA from α-pinene oxidation. The system exhibited different evaporative properties than ammonium sulfate seed initially coated with α-pinene SOA followed by a layer of toluene SOA. This behavior is consistent with a shell-and-core model and suggests limited mixing among different SOA types. Another study investigated the reactive uptake of isoprene epoxy diols (IEPOX) onto non-acidified aerosol. It was demonstrated that particle acidity has limited influence on organic aerosol formation onto ammonium sulfate seed, and that the chemical system is limited by the availability of nucleophiles such as sulfate. Flow tube experiments were conducted to examine the role of iron in the reactive uptake and chemical oxidation of glycolaldehyde. Aerosol particles doped with iron and hydrogen peroxide were mixed with gas-phase glycolaldehyde and photochemically aged in a custom-built flow reactor. Compared to particles free of iron, iron-doped aerosols significantly enhanced the oxygen to carbon (O/C) ratio of accumulated organic mass. The primary oxidation mechanism is suggested to be a combination of Fenton and photo-Fenton reactions which enhance particle-phase OH radical concentrations.

  18. Laboratory Experiments and Modeling for Interpreting Field Studies of Secondary Organic Aerosol Formation Using an Oxidation Flow Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez, Jose-Luis [Univ. of Colorado, Boulder, CO (United States)

    2016-02-01

    This grant was originally funded for deployment of a suite of aerosol instrumentation by our group in collaboration with other research groups and DOE/ARM to the Ganges Valley in India (GVAX) to study aerosols sources and processing. Much of the first year of this grant was focused on preparations for GVAX. That campaign was cancelled due to political reasons and with the consultation with our program manager, the research of this grant was refocused to study the applications of oxidation flow reactors (OFRs) for investigating secondary organic aerosol (SOA) formation and organic aerosol (OA) processing in the field and laboratory through a series of laboratory and modeling studies. We developed a gas-phase photochemical model of an OFR which was used to 1) explore the sensitivities of key output variables (e.g., OH exposure, O3, HO2/OH) to controlling factors (e.g., water vapor, external reactivity, UV irradiation), 2) develop simplified OH exposure estimation equations, 3) investigate under what conditions non-OH chemistry may be important, and 4) help guide design of future experiments to avoid conditions with undesired chemistry for a wide range of conditions applicable to the ambient, laboratory, and source studies. Uncertainties in the model were quantified and modeled OH exposure was compared to tracer decay measurements of OH exposure in the lab and field. Laboratory studies using OFRs were conducted to explore aerosol yields and composition from anthropogenic and biogenic VOC as well as crude oil evaporates. Various aspects of the modeling and laboratory results and tools were applied to interpretation of ambient and source measurements using OFR. Additionally, novel measurement methods were used to study gas/particle partitioning. The research conducted was highly successful and details of the key results are summarized in this report through narrative text, figures, and a complete list of publications acknowledging this grant.

  19. Particle mass yield in secondary organic aerosol formed by the dark ozonolysis of α-pinene

    Directory of Open Access Journals (Sweden)

    J. E. Shilling

    2008-04-01

    Full Text Available The yield of particle mass in secondary organic aerosol (SOA formed by dark ozonolysis was measured for 0.3–22.8 ppbv of reacted α-pinene. Most experiments were conducted using a continuous-flow chamber, allowing nearly constant SOA concentration and chemical composition for several days. For comparison, some experiments were also conducted in batch mode. Reaction conditions were 25°C, 40% RH, dry (NH4SO4 seed particles, and excess 1-butanol. The organic particle loading was independently measured by an aerosol mass spectrometer and a scanning mobility particle sizer, and the two measurements agreed well. The observations showed that SOA formation occurred for even the lowest reacted α-pinene concentration of 0.3 ppbv. The particle mass yield was 0.09 at 0.15 μg m−3, increasing to 0.27 at 40 μg m−3. Compared to some results reported in the literature, the yields were 80 to 100% larger for loadings above 2 μg m−3. At lower loadings, the yields had an offset of approximately +0.07 from those reported in the literature. To as low as 0.15 μm−3, the yield curve had no inflection point toward null yield, implying the formation of one or several products having vapor pressures below this value. These observations of increased yields, especially for low loadings, are potentially important for accurate prediction by chemical transport models of organic particle concentrations in the ambient atmosphere.

  20. Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

    Science.gov (United States)

    Wang, Shunyao; Ye, Jianhuai; Soong, Ronald; Wu, Bing; Yu, Legeng; Simpson, André J.; Chan, Arthur W. H.

    2018-03-01

    Owing to the complex nature and dynamic behaviors of secondary organic aerosol (SOA), its ability to cause oxidative stress (known as oxidative potential, or OP) and adverse health outcomes remains poorly understood. In this work, we probed the linkages between the chemical composition of SOA and its OP, and investigated impacts from various SOA evolution pathways, including atmospheric oligomerization, heterogeneous oxidation, and mixing with metal. SOA formed from photooxidation of the two most common polycyclic aromatic hydrocarbons (naphthalene and phenanthrene) were studied as model systems. OP was evaluated using the dithiothreitol (DTT) assay. The oligomer-rich fraction separated by liquid chromatography dominates DTT activity in both SOA systems (52 ± 10 % for naphthalene SOA (NSOA), and 56 ± 5 % for phenanthrene SOA (PSOA)). Heterogeneous ozonolysis of NSOA was found to enhance its OP, which is consistent with the trend observed in selected individual oxidation products. DTT activities from redox-active organic compounds and metals were found to be not additive. When mixing with highly redox-active metal (Cu), OP of the mixture decreased significantly for 1,2-naphthoquinone (42 ± 7 %), 2,3-dihydroxynaphthalene (35 ± 1 %), NSOA (50 ± 6 %), and PSOA (43 ± 4 %). Evidence from proton nuclear magnetic resonance (1H NMR) spectroscopy illustrates that such OP reduction upon mixing can be ascribed to metal-organic binding interactions. Our results highlight the role of aerosol chemical composition under atmospheric aging processes in determining the OP of SOA, which is needed for more accurate and explicit prediction of the toxicological impacts from particulate matter.

  1. Reactivity of liquid and semisolid secondary organic carbon with chloride and nitrate in atmospheric aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Bingbing [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); O' Brien, Rachel E. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of the Pacific, Stockton, CA (United States); Kelly, Stephen T. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Shilling, John E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Moffet, Ryan C. [Univ. of the Pacific, Stockton, CA (United States); Gilles, Mary K. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Laskin, Alexander [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-05-14

    Constituents of secondary organic carbon (SOC) in atmospheric aerosols are often mixed with inorganic components and compose a significant mass fraction of fine particulate matter in the atmosphere. Interactions between SOC and other condensed-phase species are not well understood. Here, we investigate the reactions of liquid-like and semi-solid SOC from ozonolysis of limonene (LSOC) and α-pinene (PSOC) with NaCl using a set of complementary micro-spectroscopic analyses. These reactions result in chloride depletion in the condensed phase, release of gaseous HCl, and formation of organic salts. The reactions attributed to acid displacement by SOC acidic components are driven by the high volatility of HCl. Similar reactions can take place in SOC/NaNO₃ particles. The results show that an increase in SOC mass fraction in the internally mixed SOC/NaCl particles leads to higher chloride depletion. Glass transition temperatures and viscosity of PSOC were estimated for atmospherically relevant conditions. Data show that the reaction extent depends on SOC composition, particle phase state and viscosity, mixing state, temperature, relative humidity (RH), and reaction time. LSOC shows slightly higher potential to deplete chloride than PSOC. Higher particle viscosity at low temperatures and RH can hinder these acid displacement reactions. Formation of organic salts from these overlooked reactions can alter particle physiochemical properties and may affect their reactivity and ability to act as cloud condensation and ice nuclei. The release and potential recycling of HCl and HNO₃ from reacted aerosol particles may have important implications for atmospheric chemistry.

  2. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: a kinetic study

    Science.gov (United States)

    Kroflič, Ana; Grgić, Irena

    2014-05-01

    It is well known that atmospheric aerosols play a crucial role in the Earth's climate and public health (Pöschl 2005). Despite a great effort invested in the studies of secondary organic aerosol (SOA) budget, composition, and its formation mechanisms, there is still a gap between field observations and atmospheric model predictions (Heald et al. 2005, Hallquist et al. 2009, and Lim et al. 2010). The insisting uncertainties surrounding SOA formation and aging thus gained an increasing interest in atmospheric aqueous phase chemistry; they call for more complex and time consuming studies at the environmentally relevant conditions allowing confident extrapolation to desired ambient conditions. In addition to the adverse health effects of atmospheric particulate matter (PM) as such, toxicity is also attributed to nitro-aromatic and other organic compounds which have already been detected in real aerosol samples (Traversi et al. 2009). Moreover, low-volatility aromatic derivatives are believed to form at least partly in the aerosol aqueous phase and not only in the gas phase from where they partition into water droplets (Ervens et al. 2011). Two nitro derivatives of biomass burning tracer guaiacol have recently been found in winter PM10 samples from the city of Ljubljana, Slovenia, and aqueous photonitration reaction was proposed as their possible production pathway (Kitanovski et al. 2012). In this study the kinetics of guaiacol nitration in aqueous solution was investigated in the presence of H2O2 and NO2¯ upon simulated solar irradiation (Xenon lamp, 300 W). During the experiment the DURAN® flask with the reaction mixture was held in the thermostated bath and thoroughly mixed. The reaction was monitored for 44 hours at different temperatures. Guaiacol and its main nitro-products (4-nitroguaiacol, 4-NG; 6-nitroguaiacol, 6-NG; and 4,6-dinitroguaiacol, 4,6-DNG) were quantified in every aliquot, taken from the reaction mixture, by use of high pressure liquid

  3. Oxidative potential of secondary organic aerosols produced from photooxidation of different hydrocarbons using outdoor chamber under ambient sunlight

    Science.gov (United States)

    Jiang, Huanhuan; Jang, Myoseon; Sabo-Attwood, Tara; Robinson, Sarah E.

    2016-04-01

    The oxidative potential of various secondary organic aerosols (SOA) was measured using dithiothreitol (DTT) assay to understand how organic aerosols react with cellular materials. SOA was produced via the photooxidation of four different hydrocarbons (toluene, 1,3,5-trimethylbenzene, isoprene and α-pinene) in the presence of NOx using a large outdoor photochemical smog chamber. The DTT consumption rate was normalized by the aerosol mass, which is expressed as DTTmass. Toluene SOA and isoprene SOA yielded higher DTTmass than 1,3,5-trimethylbenzene SOA or α-pinene SOA. In order to discover the correlation between the molecular structure and oxidative potential, the DTT responses of selected model compounds were also measured. Among them, conjugated aldehydes, quinones, and H2O2 showed considerable DTT response. To investigate the correlation between DTT response and cell responses in vitro, the expression of biological markers, i.e. IL-6, IL-8, and HMOX-1 were studied using small airway epithelial cells. Higher cellular expression of IL-8 was observed with toluene SOA exposure compared to 1,3,5-trimethylbenzene SOA exposure, which aligned with the results from DTT assay. Our study also suggests that within the urban atmosphere, the contribution of toluene SOA and isoprene SOA to the oxidative potential of ambient SOA will be more significant than that of α-pinene SOA.

  4. Secondary Organic Aerosol Produced from Aqueous Reactions of Phenols in Fog Drops and Deliquesced Particles

    Science.gov (United States)

    Smith, J.; Anastasio, C.

    2014-12-01

    The formation and evolution of secondary organic aerosol (SOA) in atmospheric condensed phases (i.e., aqueous SOA) can proceed rapidly, but relatively little is known of the important aqueous SOA precursors or their reaction pathways. In our work we are studying the aqueous SOA formed from reactions of phenols (phenol, guaiacol, and syringol), benzene-diols (catechol, resorcinol, and hydroquinone), and phenolic carbonyls (e.g., vanillin and syringaldehyde). These species are potentially important aqueous SOA precursors because they are released in large quantities from biomass burning, have high Henry's Law constants (KH = 103 -109 M-1 atm-1) and are rapidly oxidized. To evaluate the importance of aqueous reactions of phenols as a source of SOA, we first quantified the kinetics and SOA mass yields for 11 phenols reacting via direct photodegradation, hydroxyl radical (•OH), and with an excited organic triplet state (3C*). In the second step, which is the focus of this work, we use these laboratory results in a simple model of fog chemistry using conditions during a previously reported heavy biomass burning event in Bakersfield, CA. Our calculations indicate that under aqueous aerosol conditions (i.e., a liquid water content of 100 μg m-3) the rate of aqueous SOA production (RSOA(aq)) from phenols is similar to the rate in the gas phase. In contrast, under fog/cloud conditions the aqueous RSOA from phenols is 10 times higher than the rate in the gas phase. In both of these cases aqueous RSOA is dominated by the oxidation of phenols by 3C*, followed by direct photodegradation of phenolic carbonyls, and then •OH oxidation. Our results suggest that aqueous oxidation of phenols is a significant source of SOA during fog events and also during times when deliquesced aerosols are present.

  5. Primary emissions and secondary organic aerosol formation from the exhaust of a flex-fuel (ethanol) vehicle

    Science.gov (United States)

    Suarez-Bertoa, R.; Zardini, A. A.; Platt, S. M.; Hellebust, S.; Pieber, S. M.; El Haddad, I.; Temime-Roussel, B.; Baltensperger, U.; Marchand, N.; Prévôt, A. S. H.; Astorga, C.

    2015-09-01

    Incentives to use biofuels may result in increasing vehicular emissions of compounds detrimental to air quality. Therefore, regulated and unregulated emissions from a Euro 5a flex-fuel vehicle, tested using E85 and E75 blends (gasoline containing 85% and 75% of ethanol (vol/vol), respectively), were investigated at 22 and -7 °C over the New European Driving Cycle, at the Vehicle Emission Laboratory at the European Commission Joint Research Centre Ispra, Italy. Vehicle exhaust was comprehensively analyzed at the tailpipe and in a dilution tunnel. A fraction of the exhaust was injected into a mobile smog chamber to study the photochemical aging of the mixture. We found that emissions from a flex-fuel vehicle, fueled by E85 and E75, led to secondary organic aerosol (SOA) formation, despite the low aromatic content of these fuel blends. Emissions of regulated and unregulated compounds, as well as emissions of black carbon (BC) and primary organic aerosol (POA) and SOA formation were higher at -7 °C. The flex-fuel unregulated emissions, mainly composed of ethanol and acetaldehyde, resulted in very high ozone formation potential and SOA, especially at low temperature (860 mg O3 km-1 and up to 38 mg C kg-1). After an OH exposure of 10 × 106 cm-3 h, SOA mass was, on average, 3 times larger than total primary particle mass emissions (BC + POA) with a high O:C ratio (up to 0.7 and 0.5 at 22 and -7 °C, respectively) typical of highly oxidized mixtures. Furthermore, high resolution organic mass spectra showed high 44/43 ratios (ratio of the ions m/z 44 and m/z 43) characteristic of low-volatility oxygenated organic aerosol. We also hypothesize that SOA formation from vehicular emissions could be due to oxidation products of ethanol and acetaldehyde, both short-chain oxygenated VOCs, e.g. methylglyoxal and acetic acid, and not only from aromatic compounds.

  6. Fungal spores overwhelm biogenic organic aerosols in a midlatitudinal forest

    Directory of Open Access Journals (Sweden)

    C. Zhu

    2016-06-01

    Full Text Available Both primary biological aerosol particles (PBAPs and oxidation products of biogenic volatile organic compounds (BVOCs contribute significantly to organic aerosols (OAs in forested regions. However, little is known about their relative importance in diurnal timescales. Here, we report biomarkers of PBAP and secondary organic aerosols (SOAs for their diurnal variability in a temperate coniferous forest in Wakayama, Japan. Tracers of fungal spores, trehalose, arabitol and mannitol, showed significantly higher levels in nighttime than daytime (p < 0.05, resulting from the nocturnal sporulation under near-saturated relative humidity. On the contrary, BVOC oxidation products showed higher levels in daytime than nighttime, indicating substantial photochemical SOA formation. Using tracer-based methods, we estimated that fungal spores account for 45 % of organic carbon (OC in nighttime and 22 % in daytime, whereas BVOC oxidation products account for 15 and 19 %, respectively. To our knowledge, we present for the first time highly time-resolved results that fungal spores overwhelmed BVOC oxidation products in contributing to OA especially in nighttime. This study emphasizes the importance of both PBAPs and SOAs in forming forest organic aerosols.

  7. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    Science.gov (United States)

    Malloy, Q. G. J.; Qi, Li; Warren, B.; Cocker, D. R., III; Erupe, M. E.; Silva, P. J.

    2009-03-01

    Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

  8. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    Directory of Open Access Journals (Sweden)

    P. J. Silva

    2009-03-01

    Full Text Available Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<1% for all amines tested as detected by an aerosol mass spectrometer (AMS. We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

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

    Science.gov (United States)

    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 (grant funded by the Korea government (MEST) (No. 2011-01350000).

  10. Organic aerosol formation in citronella candle plumes.

    Science.gov (United States)

    Bothe, Melanie; Donahue, Neil McPherson

    2010-09-01

    Citronella candles are widely used as insect repellants, especially outdoors in the evening. Because these essential oils are unsaturated, they have a unique potential to form secondary organic aerosol (SOA) via reaction with ozone, which is also commonly elevated on summer evenings when the candles are often in use. We investigated this process, along with primary aerosol emissions, by briefly placing a citronella tealight candle in a smog chamber and then adding ozone to the chamber. In repeated experiments, we observed rapid and substantial SOA formation after ozone addition; this process must therefore be considered when assessing the risks and benefits of using citronella candle to repel insects.

  11. Measurement of the ambient organic aerosol volatility distribution: application during the Finokalia Aerosol Measurement Experiment (FAME-2008

    Directory of Open Access Journals (Sweden)

    B. H. Lee

    2010-12-01

    Full Text Available A variable residence time thermodenuder (TD was combined with an Aerodyne Aerosol Mass Spectrometer (AMS and a Scanning Mobility Particle Sizer (SMPS to measure the volatility distribution of aged organic aerosol in the Eastern Mediterranean during the Finokalia Aerosol Measurement Experiment in May of 2008 (FAME-2008. A new method for the quantification of the organic aerosol volatility distribution was developed combining measurements of all three instruments together with an aerosol dynamics model.

    Challenges in the interpretation of ambient thermodenuder-AMS measurements include the potential resistances to mass transfer during particle evaporation, the effects of particle size on the evaporated mass fraction, the changes in the AMS collection efficiency and particle density as the particles evaporate partially in the TD, and finally potential losses inside the TD. Our proposed measurement and data analysis method accounts for all of these problems combining the AMS and SMPS measurements.

    The AMS collection efficiency of the aerosol that passed through the TD was found to be approximately 10% lower than the collection efficiency of the aerosol that passed through the bypass. The organic aerosol measured at Finokalia is approximately 2 or more orders of magnitude less volatile than fresh laboratory-generated monoterpene (α-pinene, β-pinene and limonene under low NOx conditions secondary organic aerosol. This low volatility is consistent with its highly oxygenated AMS mass spectrum. The results are found to be highly sensitive to the mass accommodation coefficient of the evaporating species. This analysis is based on the assumption that there were no significant reactions taking place inside the thermodenuder.

  12. Increases to Biogenic Secondary Organic Aerosols from SO2 and NOx in the Southeastern US

    Science.gov (United States)

    Russell, L. M.; Liu, J.; Ruggeri, G.; Takahama, S.; Claflin, M. S.; Ziemann, P. J.; Lee, A.; Murphy, B.; Pye, H. O. T.; Ng, N. L.; McKinney, K. A.; Surratt, J. D.

    2017-12-01

    During the 2013 Southern Oxidant and Aerosol Study, Fourier Transform Infrared Spectroscopy (FTIR) and Aerosol Mass Spectrometer (AMS) measurements of submicron mass were collected at Look Rock, Tennessee, and Centreville, Alabama. The low NOx, low wind, little rain, and increased daytime isoprene emissions led to multi-day stagnation events at Look Rock that provided clear evidence of particle-phase sulfate enhancing biogenic secondary organic aerosol (bSOA) by selective uptake. Organic mass (OM) sources were apportioned as 42% "vehicle-related" and 54% bSOA, with the latter including "sulfate-related bSOA" that correlated to sulfate (r=0.72) and "nitrate-related bSOA" that correlated to nitrate (r=0.65). Single-particle mass spectra showed three composition types that corresponded to the mass-based factors with spectra cosine similarity of 0.93 and time series correlations of r>0.4. The vehicle-related OM with m/z 44 was correlated to black carbon, "sulfate-related bSOA" was on particles with high sulfate, and "nitrate-related bSOA" was on all particles. The similarity of the m/z spectra (cosine similarity=0.97) and the time series correlation (r=0.80) of the "sulfate-related bSOA" to the sulfate-containing single-particle type provide evidence for particle composition contributing to selective uptake of isoprene oxidation products onto particles that contain sulfate from power plants. Since Look Rock had much less NOx than Centreville, comparing the bSOA at the two sites provides an evaluation of the role of NOx for bSOA. CO and submicron sulfate and OM concentrations were 15-60 % higher at Centreville than at Look Rock but their time series had moderate correlations of r= 0.51, 0.54, and 0.47, respectively. However, NOx had no correlation (r=0.08) between the two sites. OM correlated with the higher NOx levels at Centreville but with O3 at Look Rock. OM sources identified by Positive Matrix Factorization had three very similar factors at both sites from FTIR

  13. The uptake of HO2 radicals to organic aerosols

    Science.gov (United States)

    Matthews, Pascale; Krapf, Manuel; Dommen, Josef; George, Ingrid; Whalley, Lisa; Ingham, Trevor; Baeza-Romero, Maria Teresa; Ammann, Markus; Heard, Dwayne

    2014-05-01

    HOx (OH + HO2) radicals are responsible for the majority of the oxidation in the troposphere and control the concentrations of many trace species in the atmosphere. There have been many field studies where the measured HO2 concentrations have been smaller than the concentration predicted by model calculations [1,2]. The difference has often been attributed to HO2 uptake by aerosols. Organics are a major component of aerosols accounting for 10 - 70 % of their mass [3]. However, there have been very few laboratory studies measuring HO2 uptake onto organic aerosols [4]. Uptake coefficients (γ) were measured for a range of aerosols using a Fluorescence Assay By Gas Expansion (FAGE) detector combined with an aerosol flow tube. HO2 was injected into the flow tube using a moveable injector which allowed first order HO2 decays to be measured along the flow tube both with and without aerosols. Laboratory generated aerosols were made using an atomiser or by homogeneous nucleation. Secondary organic aerosols (SOA) were made using the Paul Scherrer Institute smog chamber and also by means of a Potential Aerosol Mass (PAM) chamber. The total aerosol surface area was then measured using a Scanning Mobility Particle Sizer (SMPS). Experiments were carried out on aerosols containing glutaric acid, glyoxal, malonic acid, stearic acid, oleic acid and squalene. The HO2 uptake coefficients for these species were measured in the range of γ contained elevated levels of transition metal ions. For humic acid the uptake coefficient was highly dependent on humidity and this may be explained by the liquid water content of the aerosols. Measurements were also performed on copper doped aerosols containing different organics. An uptake coefficient of 0.23 ± 0.07 was measured for copper doped ammonium sulphate, however, this was reduced to 0.008 ± 0.009 when EDTA was added in a 1:1 ratio with copper and 0.003 ± 0.004 when oxalic acid was added in a 10:1 ratio with copper. SOA aerosols were

  14. Aqueous Oxidation of Green Leaf Volatiles as a Source of Secondary Organic Aerosol

    Science.gov (United States)

    Richards-Henderson, N. K.; Hansel, A.; Pham, A. T.; Vempati, H. S.; Valsaraj, K. T.; Anastasio, C.

    2013-12-01

    Vegetation emits volatile oxygenated hydrocarbons - the green leaf volatiles (GLVs) - which are formed from the biochemical conversion of linoleic and linolenic acids within plant cells. Stress or damage to vegetation can significantly elevate emission fluxes of these compounds, some of which are fairly water soluble. Aqueous-phase reactions of the GLVs with photochemically generated oxidants - such as hydroxyl radical (OH), singlet oxygen (1O2) and excited triplet states of organic compounds (3C*) _ might then form low-volatility products that can act as secondary organic aerosol (SOA). In order to determine if GLVs can be a significant source of secondary organic carbon in fogwater, studies of GLVs in laboratory solutions are needed to elucidate the oxidation kinetics and the corresponding SOA mass yields. In this study we are determining the second-order rate constants, and SOA mass yields, for five GLVs (cis-3-hexen-1-ol, cis-3-hexenylacetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol) reacting with OH,1O2 and 3C*. Experiments are performed at relevant fog water pHs, temperatures, and oxidant concentrations. Rate constants are determined using a relative rate approach in which the decay of GLVs and reference compounds are monitored as function of time by HPLC. The capacity of GLVs to form aqueous SOA was determined by following the formation of their decomposition products with HPLC-UV/DAD and HPLC-ESI/MS. SOA mass yields are measured gravimetrically from laboratory solutions containing atmospherically relevant concentrations of photooxidants and GLVs, and irradiated with simulated sunlight. We will use our results to assess the potential contribution of aqueous GLV reactions as a source of SOA in cloudy or foggy atmospheres.

  15. α-Pinene secondary organic aerosol at low temperature: chemical composition and implications for particle viscosity

    Science.gov (United States)

    Huang, Wei; Saathoff, Harald; Pajunoja, Aki; Shen, Xiaoli; Naumann, Karl-Heinz; Wagner, Robert; Virtanen, Annele; Leisner, Thomas; Mohr, Claudia

    2018-02-01

    Chemical composition, size distributions, and degree of oligomerization of secondary organic aerosol (SOA) from α-pinene (C10H16) ozonolysis were investigated for low-temperature conditions (223 K). Two types of experiments were performed using two simulation chambers at the Karlsruhe Institute of Technology: the Aerosol Preparation and Characterization (APC) chamber, and the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) chamber. Experiment type 1 simulated SOA formation at upper tropospheric conditions: SOA was generated in the AIDA chamber directly at 223 K at 61 % relative humidity (RH; experiment termed cold humid, CH) and for comparison at 6 % RH (experiment termed cold dry, CD) conditions. Experiment type 2 simulated SOA uplifting: SOA was formed in the APC chamber at room temperature (296 K) and warm dry, WD) or 21 % RH (experiment termed warm humid, WH) conditions, and then partially transferred to the AIDA chamber kept at 223 K, and 61 % RH (WDtoCH) or 30 % RH (WHtoCH), respectively. Precursor concentrations varied between 0.7 and 2.2 ppm α-pinene, and between 2.3 and 1.8 ppm ozone for type 1 and type 2 experiments, respectively. Among other instrumentation, a chemical ionization mass spectrometer (CIMS) coupled to a filter inlet for gases and aerosols (FIGAERO), deploying I- as reagent ion, was used for SOA chemical composition analysis. For type 1 experiments with lower α-pinene concentrations and cold SOA formation temperature (223 K), smaller particles of 100-300 nm vacuum aerodynamic diameter (dva) and higher mass fractions (> 40 %) of adducts (molecules with more than 10 carbon atoms) of α-pinene oxidation products were observed. For type 2 experiments with higher α-pinene concentrations and warm SOA formation temperature (296 K), larger particles ( ˜ 500 nm dva) with smaller mass fractions of adducts (models.

  16. Improving organic aerosol treatments in CESM/CAM5: Development, application, and evaluation

    Science.gov (United States)

    Glotfelty, Timothy; He, Jian; Zhang, Yang

    2017-06-01

    New treatments for organic aerosol (OA) formation have been added to a modified version of the CESM/CAM5 model (CESM-NCSU). These treatments include a volatility basis set treatment for the simulation of primary and secondary organic aerosols (SOAs), a simplified treatment for organic aerosol (OA) formation from glyoxal, and a parameterization representing the impact of new particle formation (NPF) of organic gases and sulfuric acid. With the inclusion of these new treatments, the concentration of oxygenated organic aerosol increases by 0.33 µg m-3 and that of primary organic aerosol (POA) decreases by 0.22 µg m-3 on global average. The decrease in POA leads to a reduction in the OA direct effect, while the increased OOA increases the OA indirect effects. Simulations with the new OA treatments show considerable improvement in simulated SOA, oxygenated organic aerosol (OOA), organic carbon (OC), total carbon (TC), and total organic aerosol (TOA), but degradation in the performance of HOA. In simulations of the current climate period, despite some deviations from observations, CESM-NCSU with the new OA treatments significantly improves the magnitude, spatial pattern, seasonal pattern of OC and TC, as well as, the speciation of TOA between POA and OOA. Sensitivity analysis reveals that the inclusion of the organic NPF treatment impacts the OA indirect effects by enhancing cloud properties. The simulated OA level and its impact on the climate system are most sensitive to choices in the enthalpy of vaporization and wet deposition of SVOCs, indicating that accurate representations of these parameters are critical for accurate OA-climate simulations.

  17. Seasonal variation of marine organic aerosols in the North Pacific Ocean

    Science.gov (United States)

    Fu, P.; Kawamura, K.

    2017-12-01

    Atmospheric aerosols were collected in the marine boundary layer during five marine cruises in the northern Pacific Ocean from October 1996 to July 1997. Organic molecular compositions of the marine aerosols were measured using gas chromatography/mass spectrometry (GC/MS). Higher concentrations of levoglucosan and its isomers, the biomass-burning tracers, were observed in the coastal regions than those in the central north Pacific. Seasonal trends of biomass burning tracers were found to be higher in fall-winter-spring than in summer, suggesting an enhanced influence of continental aerosols to the marine atmosphere during cold seasons when the westerlies prevail. However, the atmospheric levels of secondary organic aerosol (SOA) tracers from the photooxidation of isoprene and monoterpenes were higher in warm seasons than cold seasons, which are in accordance with the enhanced emissions of biogenic volatile organic compounds (BVOCs) in summer. Stable C isotope ratios of total carbon (δ13CTC) in the marine aerosols ranged from -28.5‰ to -23.6‰ (mean -26.4‰), suggesting an important input of terrestrial/continental aerosol particles. Stable N isotope ratios (2.6‰ to 12.9‰, mean 7.1‰) were found to be higher in the coastal regions than those in the open oceans, suggesting an enhanced emission of marine aerosols in the open oceans. The fluorescence properties of the water-soluble organic carbon (WSOC) in the marine aerosols conform the importance of marine emitted organics in the open ocean, especially during the high biological activity periods.

  18. MATRIX-VBS Condensing Organic Aerosols in an Aerosol Microphysics Model

    Science.gov (United States)

    Gao, Chloe Y.; Tsigaridis, Konstas; Bauer, Susanne E.

    2015-01-01

    The condensation of organic aerosols is represented in a newly developed box-model scheme, where its effect on the growth and composition of particles are examined. We implemented the volatility-basis set (VBS) framework into the aerosol mixing state resolving microphysical scheme Multiconfiguration Aerosol TRacker of mIXing state (MATRIX). This new scheme is unique and advances the representation of organic aerosols in models in that, contrary to the traditional treatment of organic aerosols as non-volatile in most climate models and in the original version of MATRIX, this new scheme treats them as semi-volatile. Such treatment is important because low-volatility organics contribute significantly to the growth of particles. The new scheme includes several classes of semi-volatile organic compounds from the VBS framework that can partition among aerosol populations in MATRIX, thus representing the growth of particles via condensation of low volatility organic vapors. Results from test cases representing Mexico City and a Finish forrest condistions show good representation of the time evolutions of concentration for VBS species in the gas phase and in the condensed particulate phase. Emitted semi-volatile primary organic aerosols evaporate almost completely in the high volatile range, and they condense more efficiently in the low volatility range.

  19. Chemical composition, sources and secondary processes of aerosols in Baoji city of northwest China

    Science.gov (United States)

    Wang, Y. C.; Huang, R.-J.; Ni, H. Y.; Chen, Y.; Wang, Q. Y.; Li, G. H.; Tie, X. X.; Shen, Z. X.; Huang, Y.; Liu, S. X.; Dong, W. M.; Xue, P.; Fröhlich, R.; Canonaco, F.; Elser, M.; Daellenbach, K. R.; Bozzetti, C.; El Haddad, I.; Prévôt, A. S. H.; Canagaratna, M. R.; Worsnop, D. R.; Cao, J. J.

    2017-06-01

    Particulate air pollution is a severe environmental problem in China, affecting visibility, air quality, climate and human health. However, previous studies focus mainly on large cities such as Beijing, Shanghai, and Guangzhou. In this study, an Aerodyne Aerosol Chemical Speciation Monitor was deployed in Baoji, a middle size inland city in northwest China from 26 February to 27 March 2014. The non-refractory submicron aerosol (NR-PM1) was dominated by organics (55%), followed by sulfate (16%), nitrate (15%), ammonium (11%) and chloride (3%). A source apportionment of the organic aerosol (OA) was performed with the Sofi (Source Finder) interface of ME-2 (Multilinear Engine), and six main sources/factors were identified and classified as hydrocarbon-like OA (HOA), cooking OA (COA), biomass burning OA (BBOA), coal combustion OA (CCOA), less oxidized oxygenated OA (LO-OOA) and more oxidized oxygenated OA (MO-OOA), which contributed 20%, 14%, 13%, 9%, 23% and 21% of total OA, respectively. The contribution of secondary components shows increasing trends from clean days to polluted days, indicating the importance of secondary aerosol formation processes in driving particulate air pollution. The formation of LO-OOA and MO-OOA is mainly driven by photochemical reactions, but significantly influenced by aqueous-phase chemistry during periods of low atmospheric oxidative capacity.

  20. 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

    Science.gov (United States)

    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...

  1. Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction

    Directory of Open Access Journals (Sweden)

    R. K. Pathak

    2007-07-01

    Full Text Available Existing parameterizations tend to underpredict the α-pinene aerosol mass fraction (AMF or yield by a factor of 2–5 at low organic aerosol concentrations (<5 µg m−3. A wide range of smog chamber results obtained at various conditions (low/high NOx, presence/absence of UV radiation, dry/humid conditions, and temperatures ranging from 15–40°C collected by various research teams during the last decade are used to derive new parameterizations of the SOA formation from α-pinene ozonolysis. Parameterizations are developed by fitting experimental data to a basis set of saturation concentrations (from 10−2 to 104 µg m−3 using an absorptive equilibrium partitioning model. Separate parameterizations for α-pinene SOA mass fractions are developed for: 1 Low NOx, dark, and dry conditions, 2 Low NOx, UV, and dry conditions, 3 Low NOx, dark, and high RH conditions, 4 High NOx, dark, and dry conditions, 5 High NOx, UV, and dry conditions. According to the proposed parameterizations the α-pinene SOA mass fractions in an atmosphere with 5 µg m−3 of organic aerosol range from 0.032 to 0.1 for reacted α-pinene concentrations in the 1 ppt to 5 ppb range.

  2. Heterogeneous ice nucleation of viscous secondary organic aerosol produced from ozonolysis of α-pinene

    Science.gov (United States)

    Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Garimella, Sarvesh; Dias, Antonio; Frege, Carla; Höppel, Niko; Tröstl, Jasmin; Wagner, Robert; Yan, Chao; Amorim, Antonio; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Tomé, Antonio; Virtanen, Annele; Worsnop, Douglas; Stratmann, Frank

    2016-05-01

    There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from -38 to -10 °C at 5-15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -39.0 and -37.2 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle budget.

  3. Primary and secondary aerosols in Beijing in winter: sources, variations and processes

    Science.gov (United States)

    Sun, Yele; Du, Wei; Fu, Pingqing; Wang, Qingqing; Li, Jie; Ge, Xinlei; Zhang, Qi; Zhu, Chunmao; Ren, Lujie; Xu, Weiqi; Zhao, Jian; Han, Tingting; Worsnop, Douglas R.; Wang, Zifa

    2016-07-01

    Winter has the worst air pollution of the year in the megacity of Beijing. Despite extensive winter studies in recent years, our knowledge of the sources, formation mechanisms and evolution of aerosol particles is not complete. Here we have a comprehensive characterization of the sources, variations and processes of submicron aerosols that were measured by an Aerodyne high-resolution aerosol mass spectrometer from 17 December 2013 to 17 January 2014 along with offline filter analysis by gas chromatography/mass spectrometry. Our results suggest that submicron aerosols composition was generally similar across the winter of different years and was mainly composed of organics (60 %), sulfate (15 %) and nitrate (11 %). Positive matrix factorization of high- and unit-mass resolution spectra identified four primary organic aerosol (POA) factors from traffic, cooking, biomass burning (BBOA) and coal combustion (CCOA) emissions as well as two secondary OA (SOA) factors. POA dominated OA, on average accounting for 56 %, with CCOA being the largest contributor (20 %). Both CCOA and BBOA showed distinct polycyclic aromatic hydrocarbons (PAHs) spectral signatures, indicating that PAHs in winter were mainly from coal combustion (66 %) and biomass burning emissions (18 %). BBOA was highly correlated with levoglucosan, a tracer compound for biomass burning (r2 = 0.93), and made a considerable contribution to OA in winter (9 %). An aqueous-phase-processed SOA (aq-OOA) that was strongly correlated with particle liquid water content, sulfate and S-containing ions (e.g. CH2SO2+) was identified. On average aq-OOA contributed 12 % to the total OA and played a dominant role in increasing oxidation degrees of OA at high RH levels (> 50 %). Our results illustrate that aqueous-phase processing can enhance SOA production and oxidation states of OA as well in winter. Further episode analyses highlighted the significant impacts of meteorological parameters on aerosol composition, size

  4. Primary and secondary aerosols in Beijing in winter: sources, variations and processes

    Directory of Open Access Journals (Sweden)

    Y. Sun

    2016-07-01

    Full Text Available Winter has the worst air pollution of the year in the megacity of Beijing. Despite extensive winter studies in recent years, our knowledge of the sources, formation mechanisms and evolution of aerosol particles is not complete. Here we have a comprehensive characterization of the sources, variations and processes of submicron aerosols that were measured by an Aerodyne high-resolution aerosol mass spectrometer from 17 December 2013 to 17 January 2014 along with offline filter analysis by gas chromatography/mass spectrometry. Our results suggest that submicron aerosols composition was generally similar across the winter of different years and was mainly composed of organics (60 %, sulfate (15 % and nitrate (11 %. Positive matrix factorization of high- and unit-mass resolution spectra identified four primary organic aerosol (POA factors from traffic, cooking, biomass burning (BBOA and coal combustion (CCOA emissions as well as two secondary OA (SOA factors. POA dominated OA, on average accounting for 56 %, with CCOA being the largest contributor (20 %. Both CCOA and BBOA showed distinct polycyclic aromatic hydrocarbons (PAHs spectral signatures, indicating that PAHs in winter were mainly from coal combustion (66 % and biomass burning emissions (18 %. BBOA was highly correlated with levoglucosan, a tracer compound for biomass burning (r2 = 0.93, and made a considerable contribution to OA in winter (9 %. An aqueous-phase-processed SOA (aq-OOA that was strongly correlated with particle liquid water content, sulfate and S-containing ions (e.g. CH2SO2+ was identified. On average aq-OOA contributed 12 % to the total OA and played a dominant role in increasing oxidation degrees of OA at high RH levels (> 50 %. Our results illustrate that aqueous-phase processing can enhance SOA production and oxidation states of OA as well in winter. Further episode analyses highlighted the significant impacts of meteorological parameters on

  5. Characterization of organic aerosols in Beirut, Lebanon

    International Nuclear Information System (INIS)

    Waked, Antoine

    2012-01-01

    The chemical composition of PM2.5 includes both organic and inorganic compounds. Organic compounds, which constitute a significant fraction of the PM2.5 mass, can be emitted directly as primary aerosol from sources such as fossil-fuel combustion, biomass burning, and natural biogenic emissions, or formed in the atmosphere via chemical reactions leading to secondary organic aerosol (SOA) formation. SOA, which account for 20 - 80 % of total organic aerosol, are currently a major source of uncertainty in air quality modeling. The identification and quantification of the chemical composition of the organic fraction of PM2.5 and its source apportionment are of great interest, especially in the Middle East region where data on organic aerosols are currently lacking. Lebanon, a small developing country in the Middle East region located on the eastern shore of the Mediterranean basin represents a good example for characterizing organic aerosols in this region. To address this issue, the air quality in Beirut (the capital city of Lebanon) was investigated with a focus on organic aerosols. First, an air pollutant emission inventory was developed for Lebanon with a spatial resolution of 5 km x 5 km and for Beirut with a spatial resolution of 1 km x 1 km. The results obtained show that the road transport sector is the major contributor to carbon monoxide (CO), nitrogen oxides (NO x ) and non-methane volatile organic compounds (VOC) emissions, whereas fossil fuel-fired power plants and large industrial plants are the major contributors to sulfur dioxide (SO 2 ) and primary particulate matter (PM) emissions. Then, two intensive 15-day measurement campaigns were conducted at a semi-urban site located in a Beirut suburb to characterize air pollutant concentrations. The first measurement campaign took place in July 2011 and the second in February 2012. Measurements included PM2.5, organic carbon (OC) and elemental carbon (EC) mass concentrations as well as a molecular

  6. Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

    Directory of Open Access Journals (Sweden)

    A. Hodzic

    2010-06-01

    Full Text Available It has been established that observed local and regional levels of secondary organic aerosols (SOA in polluted areas cannot be explained by the oxidation and partitioning of anthropogenic and biogenic VOC precursors, at least using current mechanisms and parameterizations. In this study, the 3-D regional air quality model CHIMERE is applied to estimate the potential contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic precursors (S/IVOC in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to include explicitly the volatility distribution of primary organic aerosols (POA, their gas-particle partitioning and the gas-phase oxidation of the vapors. Two recently proposed parameterizations, those of Robinson et al. (2007 ("ROB" and Grieshop et al. (2009 ("GRI" are compared and evaluated against surface and aircraft measurements. The 3-D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS data, and for the first time also with oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (2–4 times with respect to the previously published base case without S/IVOCs (Hodzic et al., 2009, both within and downwind of the city leading to much reduced discrepancies with the total OA measurements. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The predicted production from anthropogenic and biomass burning S/IVOC represents 40–60% of the total measured SOA at the surface during the day and is somewhat larger than that from commonly measured aromatic VOCs, especially at the T1 site at the edge of the city. The SOA production from the continued multi-generation S/IVOC oxidation products continues actively

  7. Improving organic aerosol treatments in CESM/CAM5: Development, application, and evaluation

    Science.gov (United States)

    Glotfelty, Timothy; He, Jian

    2017-01-01

    Abstract New treatments for organic aerosol (OA) formation have been added to a modified version of the CESM/CAM5 model (CESM‐NCSU). These treatments include a volatility basis set treatment for the simulation of primary and secondary organic aerosols (SOAs), a simplified treatment for organic aerosol (OA) formation from glyoxal, and a parameterization representing the impact of new particle formation (NPF) of organic gases and sulfuric acid. With the inclusion of these new treatments, the concentration of oxygenated organic aerosol increases by 0.33 µg m−3 and that of primary organic aerosol (POA) decreases by 0.22 µg m−3 on global average. The decrease in POA leads to a reduction in the OA direct effect, while the increased OOA increases the OA indirect effects. Simulations with the new OA treatments show considerable improvement in simulated SOA, oxygenated organic aerosol (OOA), organic carbon (OC), total carbon (TC), and total organic aerosol (TOA), but degradation in the performance of HOA. In simulations of the current climate period, despite some deviations from observations, CESM‐NCSU with the new OA treatments significantly improves the magnitude, spatial pattern, seasonal pattern of OC and TC, as well as, the speciation of TOA between POA and OOA. Sensitivity analysis reveals that the inclusion of the organic NPF treatment impacts the OA indirect effects by enhancing cloud properties. The simulated OA level and its impact on the climate system are most sensitive to choices in the enthalpy of vaporization and wet deposition of SVOCs, indicating that accurate representations of these parameters are critical for accurate OA‐climate simulations. PMID:29104733

  8. Experimental Characterization and Hygroscopicity Determination of Secondary Aerosol from D5 Cyclic Siloxane Oxidation

    Science.gov (United States)

    Stanier, C. O.; Janechek, N. J.; Bryngelson, N.; Marek, R. F.; Lersch, T.; Bunker, K.; Casuccio, G.; Brune, W. H.; Hornbuckle, K. C.

    2017-12-01

    Cyclic volatile methyl siloxanes are anthropogenic chemicals present in personal care products such as antiperspirants and lotions. These are volatile chemicals that are readily released into the atmosphere by product use. Due to their emission and relatively slow kinetics of their major transformation pathway, reaction with hydroxyl radicals (OH), these compounds are present in high concentrations in indoor environments and widespread in outdoor environments. Cyclic siloxane reaction with OH can lead to secondary organic aerosols, and due to the widespread prevalence of the parent compounds, may be an important source of ambient aerosols. Atmospheric aerosols have important influences to the climate by affecting the radiative balance and by serving as cloud condensation nuclei (CCN) which influence clouds. While the parent compounds have been well-studied, the oxidation products have received much less attention, with almost no ambient measurements or experimental physical property data. We report physical properties of aerosols generated by reacting the cyclic siloxane D5 with OH using a Potential Aerosol Mass (PAM) photochemical chamber. The particles were characterized by SMPS, imaging and elemental analysis using both Transmission Electron Microscopy and Scanning Transmission Electron Microscopy equipped with Energy Dispersive X-ray Spectroscopy systems (TEM-EDS and STEM-EDS), volatility measurements using Volatility Tandem Differential Mobility Analyzer (V-TDMA), and hygroscopicity measurements to determine CCN potential using a Droplet Measurement Technologies Cloud Condensation Nuclei Counter (DMT-CCN). Aerosol yield sensitivity to D5 and OH concentrations, residence time, and seed aerosols were analyzed. TEM-EDS and STEM-EDS analysis show spherical particle morphology with elemental composition consistent with aerosols derived from cyclic siloxane sources. Measured aerosol yields were 20-50% with typical aerosol concentrations 300,000 particles cm-3, up to

  9. Secondary organic aerosol from sesquiterpene and monoterpene emissions in the United States.

    Science.gov (United States)

    Sakulyanontvittaya, Tanarit; Guenther, Alex; Helmig, Detlev; Milford, Jana; Wiedinmyer, Christine

    2008-12-01

    Emissions of volatile organic compounds (VOC) from vegetation are believed to be a major source of secondary organic aerosol (SOA), which in turn comprises a large fraction of fine particulate matter in many areas. Sesquiterpenes are a class of biogenic VOC with high chemical reactivity and SOA yields. Sesquiterpenes have only recently been quantified in emissions from a wide variety of plants. In this study, a new sesquiterpene emission inventory is used to provide input to the Models-3 Community Multiscale Air Quality (CMAQ) model. CMAQ is used to estimate the contribution of sesquiterpenes and monoterpenes to SOA concentrations over the contiguous United States. The gas-particle partitioning module of CMAQ was modified to include condensable products of sesquiterpene oxidation and to update values of the enthalpy of vaporization. The resulting model predicts July monthly average surface concentrations of total SOA in the eastern U.S. ranging from about 0.2-0.8 microg m(-3). This is roughly double the amount of SOA produced in this region when sesquiterpenes are not included. Even with sesquiterpenes included, however, the model significantly underpredicts surface concentrations of particle-phase organic matter compared to observed values. Treating all SOA as capable of undergoing polymerization increases predicted monthly average surface concentrations in July to 0.4-1.2 microg m(-3), in closer agreement with observations. Using the original enthalpy of vaporization value in CMAQ in place of the values estimated from the recent literature results in predicted SOA concentrations of about 0.3-1.3 microg m(-3).

  10. Contributions of Organic Sources to Atmospheric Aerosol Particle Concentrations and Growth

    Science.gov (United States)

    Russell, L. M.

    2017-12-01

    Organic molecules are important contributors to aerosol particle mass and number concentrations through primary emissions as well as secondary growth in the atmosphere. New techniques for measuring organic aerosol components in atmospheric particles have improved measurements of this contribution in the last 20 years, including Scanning Transmission X-ray Microscopy Near Edge X-ray Absorption Fine Structure (STXM-NEXAFS), Fourier Transform Infrared spectroscopy (FTIR), and High-Resolution Aerosol Mass Spectrometry (AMS). STXM-NEXAFS individual aerosol particle composition illustrated the variety of morphology of organic components in marine aerosols, the inherent relationships between organic composition and shape, and the links between atmospheric aerosol composition and particles produced in smog chambers. This type of single particle microscopy has also added to size distribution measurements by providing evidence of how surface-controlled and bulk-controlled processes contribute to the growth of particles in the atmosphere. FTIR analysis of organic functional groups are sufficient to distinguish combustion, marine, and terrestrial organic particle sources and to show that each of those types of sources has a surprisingly similar organic functional group composition over four different oceans and four different continents. Augmenting the limited sampling of these off-line techniques with side-by-side inter-comparisons to online AMS provides complementary composition information and consistent quantitative attribution to sources (despite some clear method differences). Single-particle AMS techniques using light scattering and event trigger modes have now also characterized the types of particles found in urban, marine, and ship emission aerosols. Most recently, by combining with off-line techniques, single particle composition measurements have separated and quantified the contributions of organic, sulfate and salt components from ocean biogenic and sea spray

  11. A GCM study of organic matter in marine aerosol and its potential contribution to cloud drop activation

    Directory of Open Access Journals (Sweden)

    G. J. Roelofs

    2008-02-01

    Full Text Available With the global aerosol-climate model ECHAM5-HAM we investigate the potential influence of organic aerosol originating from the ocean on aerosol mass and chemical composition and the droplet concentration and size of marine clouds. We present sensitivity simulations in which the uptake of organic matter in the marine aerosol is prescribed for each aerosol mode with varying organic mass and mixing state, and with a geographical distribution and seasonality similar to the oceanic emission of dimethyl sulfide. Measurements of aerosol mass, aerosol chemical composition and cloud drop effective radius are used to assess the representativity of the model initializations. Good agreement with the measurements is obtained when organic matter is added to the Aitken, accumulation and coarse modes simultaneously. Representing marine organics in the model leads to higher cloud drop number concentrations and thus smaller cloud drop effective radii, and this improves the agreement with measurements. The mixing state of the organics and the other aerosol matter, i.e. internal or external depending on the formation process of aerosol organics, is an important factor for this. We estimate that globally about 75 Tg C yr−1 of organic matter from marine origin enters the aerosol phase, with comparable contributions from primary emissions and secondary organic aerosol formation.

  12. Source apportionment of size and time resolved trace elements and organic aerosols from an urban courtyard site in Switzerland

    Science.gov (United States)

    Richard, A.; Gianini, M. F. D.; Mohr, C.; Furger, M.; Bukowiecki, N.; Minguillón, M. C.; Lienemann, P.; Flechsig, U.; Appel, K.; Decarlo, P. F.; Heringa, M. F.; Chirico, R.; Baltensperger, U.; Prévôt, A. S. H.

    2011-09-01

    Time and size resolved data of trace elements were obtained from measurements with a rotating drum impactor (RDI) and subsequent X-ray fluorescence spectrometry. Trace elements can act as indicators for the identification of sources of particulate matter Switzerland. Eight different sources were identified for the three examined size ranges (PM1-0.1, PM2.5-1 and PM10-2.5): secondary sulfate, wood combustion, fire works, road traffic, mineral dust, de-icing salt, industrial and local anthropogenic activities. The major component was secondary sulfate for the smallest size range; the road traffic factor was found in all three size ranges. This trace element analysis is complemented with data from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS), assessing the PM1 fraction of organic aerosols. A separate PMF analysis revealed three factors related to three of the sources found with the RDI: oxygenated organic aerosol (OOA, related to inorganic secondary sulfate), hydrocarbon-like organic aerosol (HOA, related to road traffic) and biomass burning organic aerosol (BBOA), explaining 60 %, 22 % and 17 % of total measured organics, respectively. Since different compounds are used for the source classification, a higher percentage of the ambient PM10 mass concentration can be apportioned to sources by the combination of both methods.

  13. Exploring sources of biogenic secondary organic aerosol compounds using chemical analysis and the FLEXPART model

    Directory of Open Access Journals (Sweden)

    J. Martinsson

    2017-09-01

    Full Text Available Molecular tracers in secondary organic aerosols (SOAs can provide information on origin of SOA, as well as regional scale processes involved in their formation. In this study 9 carboxylic acids, 11 organosulfates (OSs and 2 nitrooxy organosulfates (NOSs were determined in daily aerosol particle filter samples from Vavihill measurement station in southern Sweden during June and July 2012. Several of the observed compounds are photo-oxidation products from biogenic volatile organic compounds (BVOCs. Highest average mass concentrations were observed for carboxylic acids derived from fatty acids and monoterpenes (12. 3 ± 15. 6 and 13. 8 ± 11. 6 ng m−3, respectively. The FLEXPART model was used to link nine specific surface types to single measured compounds. It was found that the surface category sea and ocean was dominating the air mass exposure (56 % but contributed to low mass concentration of observed chemical compounds. A principal component (PC analysis identified four components, where the one with highest explanatory power (49 % displayed clear impact of coniferous forest on measured mass concentration of a majority of the compounds. The three remaining PCs were more difficult to interpret, although azelaic, suberic, and pimelic acid were closely related to each other but not to any clear surface category. Hence, future studies should aim to deduce the biogenic sources and surface category of these compounds. This study bridges micro-level chemical speciation to air mass surface exposure at the macro level.

  14. Nuclear magnetic resonance spectroscopy for determining the functional content of organic aerosols: A review

    International Nuclear Information System (INIS)

    Chalbot, Marie-Cecile G.; Kavouras, Ilias G.

    2014-01-01

    The knowledge deficit of organic aerosol (OA) composition has been identified as the most important factor limiting our understanding of the atmospheric fate and implications of aerosol. The efforts to chemically characterize OA include the increasing utilization of nuclear magnetic resonance spectroscopy (NMR). Since 1998, the functional composition of different types, sizes and fractions of OA has been studied with one-dimensional, two-dimensional and solid state proton and carbon-13 NMR. This led to the use of functional group ratios to reconcile the most important sources of OA, including secondary organic aerosol and initial source apportionment using positive matrix factorization. Future research efforts may be directed towards the optimization of experimental parameters, detailed NMR experiments and analysis by pattern recognition methods to identify the chemical components, determination of the NMR fingerprints of OA sources and solid state NMR to study the content of OA as a whole. - Highlights: • Organic aerosol composition by 1 H- and 13 C-NMR spectroscopy. • NMR fingerprints of specific sources, types and sizes of organic aerosol. • Source reconciliation and apportionment using NMR spectroscopy. • Research priorities towards understanding organic aerosol composition and origin. - This review presents the recent advances on the characterization of organic aerosol composition using nuclear magnetic resonance spectroscopy

  15. Real time measurements of submicrometer aerosols in Seoul, Korea: Sources, characteristics, and processing of organic aerosols during winter time.

    Science.gov (United States)

    Kim, H.; Zhang, Q.

    2016-12-01

    Highly time-resolved chemical characterization of non-refractory submicrometer particulate matter (NR-PM1) was conducted in Seoul, the capital of Korea, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The measurements were performed during winter when persistent air quality problems associated with elevated PM concentrations were observed. The average NR-PM1 concentration was 27.5 µg m-3 and the average mass was dominated by organics (44%), followed by nitrate (24%) and sulfate (10%). Five distinct sources of organic aerosol (OA) were identified from positive matrix factorization (PMF) analysis of the AMS data: vehicle emissions represented by a hydrocarbon-like OA factor (HOA), cooking represented by a cooking OA factor (COA), wood combustion represented by a biomass burning OA factor (BBOA), and secondary aerosol formation in the atmosphere that is represented by a semi-volatile oxygenated OA factor (SVOOA) and a low volatile oxygenated OA factor (LVOOA). These factors, on average, contributed 16, 20, 23, 15 and 26% to the total OA mass, respectively, with primary organic aerosol (POA = HOA + COA + BBOA) accounting for 59% of the OA mass. On average, both primary emissions and secondary aerosol formation are important factors affecting air quality in Seoul during winter, contributing approximately equal. However, differences in the fraction of PM source and properties were observed between high and low loading PM period. For example, during stagnant period with low wind speed (WS) (0.99 ± 0.7 m/s) and high RH (71%), high PM loadings (43.6 ± 12.4 µg m-3) with enhanced fractions of nitrate (27%) and SVOOA (8%) were observed, indicating a strong influence from locally generated secondary aerosol. On the other hand, when low PM loadings (12.6 ± 7.1 µg m-3), which were commonly associated with high WS (1.8 ± 1.1 m/s) and low RH (50 %), were observed, the fraction of regional sources, such as sulfate (12%) and LVOOA (21

  16. CCN activity and droplet growth kinetics of fresh and aged monoterpene secondary organic aerosol

    Directory of Open Access Journals (Sweden)

    G. J. Engelhart

    2008-07-01

    Full Text Available The ability of secondary organic aerosol (SOA produced from the ozonolysis of α-pinene and monoterpene mixtures (α-pinene, β-pinene, limonene and 3-carene to become cloud droplets was investigated. A static CCN counter and a Scanning Mobility CCN Analyser (a Scanning Mobility Particle Sizer coupled with a Continuous Flow counter were used for the CCN measurements. Consistent with previous studies monoterpene SOA is quite active and would likely be a good source of cloud condensation nuclei (CCN in the atmosphere. A decrease in CCN activation diameter for α-pinene SOA of approximately 3 nm hr−1 was observed as the aerosol continued to react with oxidants. Hydroxyl radicals further oxidize the SOA particles thereby enhancing the particle CCN activity with time. The initial concentrations of ozone and monoterpene precursor (for concentrations lower than 40 ppb do not appear to affect the activity of the resulting SOA. Köhler Theory Analysis (KTA is used to infer the molar mass of the SOA sampled online and offline from atomized filter samples. The estimated average molar mass of online SOA was determined to be 180±55 g mol−1 (consistent with existing SOA speciation studies assuming complete solubility. KTA suggests that the aged aerosol (both from α-pinene and the mixed monoterpene oxidation is primarily water-soluble (around 65%. CCN activity measurements of the SOA mixed with (NH42SO4 suggest that the organic can depress surface tension by as much as 10 N m−1 (with respect to pure water. The droplet growth kinetics of SOA samples are similar to (NH42SO4, except at low supersaturation, where SOA tends to grow more slowly. The CCN activation diameter of α-pinene and mixed monoterpene SOA can be modelled to within 10–15% of experiments by a simple implementation of Köhler theory, assuming complete dissolution of the particles, no

  17. Observation of viscosity transition in α-pinene secondary organic aerosol

    Directory of Open Access Journals (Sweden)

    E. Järvinen

    2016-04-01

    Full Text Available Under certain conditions, secondary organic aerosol (SOA particles can exist in the atmosphere in an amorphous solid or semi-solid state. To determine their relevance to processes such as ice nucleation or chemistry occurring within particles requires knowledge of the temperature and relative humidity (RH range for SOA to exist in these states. In the Cosmics Leaving Outdoor Droplets (CLOUD experiment at The European Organisation for Nuclear Research (CERN, we deployed a new in situ optical method to detect the viscous state of α-pinene SOA particles and measured their transition from the amorphous highly viscous state to states of lower viscosity. The method is based on the depolarising properties of laboratory-produced non-spherical SOA particles and their transformation to non-depolarising spherical particles at relative humidities near the deliquescence point. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. A transition to a spherical shape was observed as the RH was increased to between 35 % at −10 °C and 80 % at −38 °C, confirming previous calculations of the viscosity-transition conditions. Consequently, α-pinene SOA particles exist in a viscous state over a wide range of ambient conditions, including the cirrus region of the free troposphere. This has implications for the physical, chemical, and ice-nucleation properties of SOA and SOA-coated particles in the atmosphere.

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

    Energy Technology Data Exchange (ETDEWEB)

    Madronich, Sasha [Univ. Corporation for Atmospheric Research, Boulder, CO (United States)

    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.

  19. Effects of NOx and SO2 on the secondary organic aerosol formation from photooxidation of α-pinene and limonene

    Science.gov (United States)

    Zhao, Defeng; Schmitt, Sebastian H.; Wang, Mingjin; Acir, Ismail-Hakki; Tillmann, Ralf; Tan, Zhaofeng; Novelli, Anna; Fuchs, Hendrik; Pullinen, Iida; Wegener, Robert; Rohrer, Franz; Wildt, Jürgen; Kiendler-Scharr, Astrid; Wahner, Andreas; Mentel, Thomas F.

    2018-02-01

    Anthropogenic emissions such as NOx and SO2 influence the biogenic secondary organic aerosol (SOA) formation, but detailed mechanisms and effects are still elusive. We studied the effects of NOx and SO2 on the SOA formation from the photooxidation of α-pinene and limonene at ambient relevant NOx and SO2 concentrations (NOx: leading to a lack of particle surface for the organics to condense on and thus a significant influence of vapor wall loss on SOA mass yield. By compensating for the suppressing effect on nucleation of NOx, SO2 also compensated for the suppressing effect on SOA yield. Aerosol mass spectrometer data show that increasing NOx enhanced nitrate formation. The majority of the nitrate was organic nitrate (57-77 %), even in low-NOx conditions (nitrate contributed 7-26 % of total organics assuming a molecular weight of 200 g mol-1. SOA from α-pinene photooxidation at high NOx had a generally lower hydrogen to carbon ratio (H / C), compared to low NOx. The NOx dependence of the chemical composition can be attributed to the NOx dependence of the branching ratio of the RO2 loss reactions, leading to a lower fraction of organic hydroperoxides and higher fractions of organic nitrates at high NOx. While NOx suppressed new particle formation and SOA mass formation, SO2 can compensate for such effects, and the combining effect of SO2 and NOx may have an important influence on SOA formation affected by interactions of biogenic volatile organic compounds (VOCs) with anthropogenic emissions.

  20. Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation

    Directory of Open Access Journals (Sweden)

    P. O. Wennberg

    2010-08-01

    Full Text Available Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene, the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA via methacrolein (a C4-unsaturated aldehyde under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232 is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(OOONO2 formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios (3–8, the SOA yields from isoprene high-NOx photooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

  1. Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation

    Science.gov (United States)

    Chan, A. W. H.; Chan, M. N.; Surratt, J. D.; Chhabra, P. S.; Loza, C. L.; Crounse, J. D.; Yee, L. D.; Flagan, R. C.; Wennberg, P. O.; Seinfeld, J. H.

    2010-08-01

    Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C4-unsaturated aldehyde) under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO2) formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios (3-8), the SOA yields from isoprene high-NOx photooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

  2. Contrasting organic aerosol particles from boreal and tropical forests during HUMPPA-COPEC-2010 and AMAZE-08 using coherent vibrational spectroscopy

    Directory of Open Access Journals (Sweden)

    C. J. Ebben

    2011-10-01

    Full Text Available We present the vibrational sum frequency generation spectra of organic particles collected in a boreal forest in Finland and a tropical forest in Brazil. These spectra are compared to those of secondary organic material produced in the Harvard Environmental Chamber. By comparing coherent vibrational spectra of a variety of terpene and olefin reference compounds, along with the secondary organic material synthesized in the environmental chamber, we show that submicron aerosol particles sampled in Southern Finland during HUMPPA-COPEC-2010 are composed to a large degree of material similar in chemical composition to synthetic α-pinene-derived material. For material collected in Brazil as part of AMAZE-08, the organic component is found to be chemically complex in the coarse mode but highly uniform in the fine mode. When combined with histogram analyses of the isoprene and monoterpene abundance recorded during the HUMPPA-COPEC-2010 and AMAZE-08 campaigns, the findings presented here indicate that if air is rich in monoterpenes, submicron-sized secondary aerosol particles that form under normal OH and O3 concentration levels can be described in terms of their hydrocarbon content as being similar to α-pinene-derived model secondary organic aerosol particles. If the isoprene concentration dominates the chemical composition of organic compounds in forest air, then the hydrocarbon component of secondary organic material in the submicron size range is not simply well-represented by that of isoprene-derived model secondary organic aerosol particles but is more complex. Throughout the climate-relevant size range of the fine mode, however, we find that the chemical composition of the secondary organic particle material from such air is invariant with size, suggesting that the particle growth does not change the chemical composition of the hydrocarbon component of the particles in a significant way.

  3. Formation of secondary aerosols from gasoline vehicle exhaust when mixing with SO2

    Directory of Open Access Journals (Sweden)

    T. Liu

    2016-01-01

    Full Text Available Sulfur dioxide (SO2 can enhance the formation of secondary aerosols from biogenic volatile organic compounds (VOCs, but its influence on secondary aerosol formation from anthropogenic VOCs, particularly complex mixtures like vehicle exhaust, remains uncertain. Gasoline vehicle exhaust (GVE and SO2, a typical pollutant from coal burning, are directly co-introduced into a smog chamber, in this study, to investigate the formation of secondary organic aerosols (SOA and sulfate aerosols through photooxidation. New particle formation was enhanced, while substantial sulfate was formed through the oxidation of SO2 in the presence of high concentration of SO2. Homogenous oxidation by OH radicals contributed a negligible fraction to the conversion of SO2 to sulfate, and instead the oxidation by stabilized Criegee intermediates (sCIs, formed from alkenes in the exhaust reacting with ozone, dominated the conversion of SO2. After 5 h of photochemical aging, GVE's SOA production factor revealed an increase by 60–200 % in the presence of high concentration of SO2. The increase could principally be attributed to acid-catalyzed SOA formation as evidenced by the strong positive linear correlation (R2 = 0.97 between the SOA production factor and in situ particle acidity calculated by the AIM-II model. A high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS resolved OA's relatively lower oxygen-to-carbon (O : C (0.44 ± 0.02 and higher hydrogen-to-carbon (H : C (1.40 ± 0.03 molar ratios for the GVE / SO2 mixture, with a significantly lower estimated average carbon oxidation state (OSc of −0.51 ± 0.06 than −0.19 ± 0.08 for GVE alone. The relative higher mass loading of OA in the experiments with SO2 might be a significant explanation for the lower SOA oxidation degree.

  4. Different roles of water in secondary organic aerosol formation from toluene and isoprene

    Science.gov (United States)

    Jia, Long; Xu, YongFu

    2018-06-01

    Roles of water in the formation of secondary organic aerosol (SOA) from the irradiations of toluene-NO2 and isoprene-NO2 were investigated in a smog chamber. Experimental results show that the yield of SOA from toluene almost doubled as relative humidity increased from 5 to 85 %, whereas the yield of SOA from isoprene under humid conditions decreased by 2.6 times as compared to that under dry conditions. The distinct difference of RH effects on SOA formation from toluene and isoprene is well explained with our experiments and model simulations. The increased SOA from humid toluene-NO2 irradiations is mainly contributed by O-H-containing products such as polyalcohols formed from aqueous reactions. The major chemical components of SOA in isoprene-NO2 irradiations are oligomers formed from the gas phase. SOA formation from isoprene-NO2 irradiations is controlled by stable Criegee intermediates (SCIs) that are greatly influenced by water. As a result, high RH can obstruct the oligomerization reaction of SCIs to form SOA.

  5. Strong influence of deposition and vertical mixing on secondary organic aerosol concentrations in CMAQ and CAMx

    Science.gov (United States)

    Shu, Qian; Koo, Bonyoung; Yarwood, Greg; Henderson, Barron H.

    2017-12-01

    Differences between two air quality modeling systems reveal important uncertainties in model representations of secondary organic aerosol (SOA) fate. Two commonly applied models (CMAQ: Community Multiscale Air Quality; CAMx: Comprehensive Air Quality Model with extensions) predict very different OA concentrations over the eastern U.S., even when using the same source data for emissions and meteorology and the same SOA modeling approach. Both models include an option to output a detailed accounting of how each model process (e.g., chemistry, deposition, etc.) alters the mass of each modeled species, referred to as process analysis. We therefore perform a detailed diagnostic evaluation to quantify simulated tendencies (Gg/hr) of each modeled process affecting both the total model burden (Gg) of semi-volatile organic compounds (SVOC) in the gas (g) and aerosol (a) phases and the vertical structures to identify causes of concentration differences between the two models. Large differences in deposition (CMAQ: 69.2 Gg/d; CAMx: 46.5 Gg/d) contribute to significant OA bias in CMAQ relative to daily averaged ambient concentration measurements. CMAQ's larger deposition results from faster daily average deposition velocities (VD) for both SVOC (g) (VD,cmaq = 2.15 × VD,camx) and aerosols (VD,cmaq = 4.43 × Vd,camx). Higher aerosol deposition velocity would be expected to cause similar biases for inert compounds like elemental carbon (EC), but this was not seen. Daytime low-biases in EC were also simulated in CMAQ as expected but were offset by nighttime high-biases. Nighttime high-biases were a result of overly shallow mixing in CMAQ leading to a higher fraction of EC total atmospheric mass in the first layer (CAMx: 5.1-6.4%; CMAQ: 5.6-6.9%). Because of the opposing daytime and nighttime biases, the apparent daily average bias for EC is reduced. For OA, there are two effects of reduced vertical mixing: SOA and SVOC are concentrated near the surface, but SOA yields are reduced

  6. Secondary Organic Aerosol Production from Gasoline Vehicle Exhaust: Effects of Engine Technology, Cold Start, and Emission Certification Standard.

    Science.gov (United States)

    Zhao, Yunliang; Lambe, Andrew T; Saleh, Rawad; Saliba, Georges; Robinson, Allen L

    2018-02-06

    Secondary organic aerosol (SOA) formation from dilute exhaust from 16 gasoline vehicles was investigated using a potential aerosol mass (PAM) oxidation flow reactor during chassis dynamometer testing using the cold-start unified cycle (UC). Ten vehicles were equipped with gasoline direct injection engines (GDI vehicles) and six with port fuel injection engines (PFI vehicles) certified to a wide range of emissions standards. We measured similar SOA production from GDI and PFI vehicles certified to the same emissions standard; less SOA production from vehicles certified to stricter emissions standards; and, after accounting for differences in gas-particle partitioning, similar effective SOA yields across different engine technologies and certification standards. Therefore the ongoing, dramatic shift from PFI to GDI vehicles in the United States should not alter the contribution of gasoline vehicles to ambient SOA and the natural replacement of older vehicles with newer ones certified to stricter emissions standards should reduce atmospheric SOA levels. Compared to hot operations, cold-start exhaust had lower effective SOA yields, but still contributed more SOA overall because of substantially higher organic gas emissions. We demonstrate that the PAM reactor can be used as a screening tool for vehicle SOA production by carefully accounting for the effects of the large variations in emission rates.

  7. Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model – Part 2: Assessing the influence of vapor wall losses

    OpenAIRE

    Cappa, Christopher D.; Jathar, Shantanu H.; Kleeman, Michael J.; Docherty, Kenneth S.; Jimenez, Jose L.; Seinfeld, John H.; Wexler, Anthony S.

    2016-01-01

    The influence of losses of organic vapors to chamber walls during secondary organic aerosol (SOA) formation experiments has recently been established. Here, the influence of such losses on simulated ambient SOA concentrations and properties is assessed in the UCD/CIT regional air quality model using the statistical oxidation model (SOM) for SOA. The SOM was fit to laboratory chamber data both with and without accounting for vapor wall losses following the approa...

  8. Characterization of polar organic compounds and source analysis of fine organic aerosols in Hong Kong

    Science.gov (United States)

    Li, Yunchun

    compounds in aerosol chemistry and physics. By reference to tracers for the major organic aerosol sources, it is deduced that the oxygenated compounds are mainly of secondary origin and direct/indirect contribution from biomass burning could also be important. The chemical composition of these oxygenated species in PM2.5 samples in Hong Kong provide useful information to further ambient and model study in the aspects of chemical formation pathways and speciated organic mass distribution. (2) Source apportionment of PM2.5 organic aerosols in Hong Kong were carried out in two studies. In the first study, chemical characterization and source analysis involved samples collected on high particulate matter (PM) days (avg. PM 2.5 >84 mug m-3) at six general stations and one roadside station from October to December in 2003. Analysis of synoptic weather conditions identified three types of high PM episodes: local, regional transport (RT) and long-range transport (LRT). Roadside samples were discussed separately. Using chemical mass balance (CMB) model, contributions of major primary sources (vehicle exhaust, cooking, biomass burning, cigarette smoke, vegetative detritus, and coal combustion) were estimated, which indicate that vehicle exhaust was the most important primary source, followed by cooking and biomass burning. All primary sources except vegetative detritus had the highest contributions at roadside station, in line with its site characteristics. Primary sources dominated roadside and local samples (>64% of fine OC), while un-apportioned OC (i.e., the difference between measured OC and apportioned primary OC) dominated RT and LRT episodes (>60% of fine OC) and un-apportioned OC had characteristics of secondary OC. In the second study, cold front episodes during winter 2004 and 2005 were targeted to investigate the effect of cold front-related LRT on chemical characteristics and organic aerosol sources of PM2.5 in Hong Kong. In comparison with days under influences of

  9. Real time in situ detection of organic nitrates in atmospheric aerosols.

    Science.gov (United States)

    Rollins, Andrew W; Smith, Jared D; Wilson, Kevin R; Cohen, Ronald C

    2010-07-15

    A novel instrument is described that quantifies total particle-phase organic nitrates in real time with a detection limit of 0.11 microg m(-3) min(-1), 45 ppt min(-1) (-ONO(2)). Aerosol nitrates are separated from gas-phase nitrates with a short residence time activated carbon denuder. Detection of organic molecules containing -ONO(2) subunits is accomplished using thermal dissociation coupled to laser induced fluorescence detection of NO(2). This instrument is capable of high time resolution (seconds) measurements of particle-phase organic nitrates, without interference from inorganic nitrate. Here we use it to quantify organic nitrates in secondary organic aerosol generated from high-NO(x) photooxidation of limonene, alpha-pinene, Delta-3-carene, and tridecane. In these experiments the organic nitrate moiety is observed to be 6-15% of the total SOA mass.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-05-10

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

  11. Black carbon aerosol mixing state, organic aerosols and aerosol optical properties over the UK

    Science.gov (United States)

    McMeeking, G. R.; Morgan, W. T.; Flynn, M.; Highwood, E. J.; Turnbull, K.; Haywood, J.; Coe, H.

    2011-05-01

    Black carbon (BC) aerosols absorb sunlight thereby leading to a positive radiative forcing and a warming of climate and can also impact human health through their impact on the respiratory system. The state of mixing of BC with other aerosol species, particularly the degree of internal/external mixing, has been highlighted as a major uncertainty in assessing its radiative forcing and hence its climate impact, but few in situ observations of mixing state exist. We present airborne single particle soot photometer (SP2) measurements of refractory BC (rBC) mass concentrations and mixing state coupled with aerosol composition and optical properties measured in urban plumes and regional pollution over the UK. All data were obtained using instrumentation flown on the UK's BAe-146-301 large Atmospheric Research Aircraft (ARA) operated by the Facility for Airborne Atmospheric Measurements (FAAM). We measured sub-micron aerosol composition using an aerosol mass spectrometer (AMS) and used positive matrix factorization to separate hydrocarbon-like (HOA) and oxygenated organic aerosols (OOA). We found a higher number fraction of thickly coated rBC particles in air masses with large OOA relative to HOA, higher ozone-to-nitrogen oxides (NOx) ratios and large concentrations of total sub-micron aerosol mass relative to rBC mass concentrations. The more ozone- and OOA-rich air masses were associated with transport from continental Europe, while plumes from UK cities had higher HOA and NOx and fewer thickly coated rBC particles. We did not observe any significant change in the rBC mass absorption efficiency calculated from rBC mass and light absorption coefficients measured by a particle soot absorption photometer despite observing significant changes in aerosol composition and rBC mixing state. The contributions of light scattering and absorption to total extinction (quantified by the single scattering albedo; SSA) did change for different air masses, with lower SSA observed in

  12. Evolution of organic aerosol mass spectra upon heating: implications for OA phase and partitioning behavior

    Energy Technology Data Exchange (ETDEWEB)

    UC Davis; Cappa, Christopher D.; Wilson, Kevin R.

    2010-10-28

    Vacuum Ultraviolet (VUV) photoionization mass spectrometry has been used to measure the evolution of chemical composition for two distinct organic aerosol types as they are passed through a thermodenuder at different temperatures. The two organic aerosol types considered are primary lubricating oil (LO) aerosol and secondary aerosol from the alpha-pinene + O3 reaction (alphaP). The evolution of the VUV mass spectra for the two aerosol types with temperature are observed to differ dramatically. For LO particles, the spectra exhibit distinct changes with temperature in which the lower m/z peaks, corresponding to compounds with higher vapor pressures, disappear more rapidly than the high m/z peaks. In contrast, the alphaP aerosol spectrum is essentially unchanged by temperature even though the particles experience significant mass loss due to evaporation. The variations in the LO spectra are found to be quantitatively in agreement with expectations from absorptive partitioning theory whereas the alphaP spectra suggest that the evaporation of alphaP derived aerosol appears to not be governed by partitioning theory. We postulate that this difference arises from the alphaP particles existing as in a glassy state instead of having the expected liquid-like behavior. To reconcile these observations with decades of aerosol growth measurements, which indicate that OA formation is described by equilibrium partitioning, we present a conceptual model wherein the secondary OA is formed and then rapidly converted from an absorbing form to a non-absorbing form. The results suggest that although OA growth may be describable by equilibrium partitioning theory, the properties of organic aerosol once formed may differ significantly from the properties determined in the equilibrium framework.

  13. Impacts of Siberian biomass burning on organic aerosols over the North Pacific Ocean and the Arctic: primary and secondary organic tracers.

    Science.gov (United States)

    Ding, Xiang; Wang, Xinming; Xie, Zhouqing; Zhang, Zhou; Sun, Liguang

    2013-04-02

    During the 2003 Chinese Arctic Research Expedition (CHINARE2003) from the Bohai Sea to the high Arctic (37°N-80°N), filter-based particle samples were collected and analyzed for tracers of primary and secondary organic aerosols (SOA) as well as water-soluble organic carbon (WSOC). Biomass burning (BB) tracer levoglucosan had comparatively much higher summertime average levels (476 ± 367 pg/m(3)) during our cruise due to the influence of intense forest fires then in Siberia. On the basis of 5-day back trajectories, samples with air masses passing through Siberia had organic tracers 1.3-4.4 times of those with air masses transporting only over the oceans, suggesting substantial contribution of continental emissions to organic aerosols in the marine atmosphere. SOA tracers from anthropogenic aromatics were negligible or not detected, while those from biogenic terpenenoids were ubiquitously observed with the sum of SOA tracers from isoprene (623 ± 414 pg/m(3)) 1 order of magnitude higher than that from monoterpenes (63 ± 49 pg/m(3)). 2-Methylglyceric acid as a product of isoprene oxidation under high-NOx conditions was dominant among SOA tracers, implying that these BSOA tracers were not formed over the oceans but mainly transported from the adjacent Siberia where a high-NOx environment could be induced by intense forest fires. The carbon fractions shared by biogenic SOA tracers and levoglucosan in WSOC in our ocean samples were 1-2 orders of magnitude lower than those previously reported in continental samples, BB emissions or chamber simulation samples, largely due to the chemical evolution of organic tracers during transport. As a result of the much faster decline in levels of organic tracers than that of WSOC during transport, the trace-based approach, which could well reconstruct WSOC using biogenic SOA and BB tracers for continental samples, only explained ∼4% of measured WSOC during our expedition if the same tracer-WSOC or tracer-SOC relationships were

  14. Glyoxal contribution to aerosols over Los Angeles

    Science.gov (United States)

    Balcerak, Ernie

    2012-01-01

    Laboratory and field studies have indicated that glyoxal (chemical formula OCHCHO), an atmospheric oxidation product of isoprene and aromatic compounds, may contribute to secondary organic aerosols in the atmosphere, which can block sunlight and affect atmospheric chemistry. Some aerosols are primary aerosols, emitted directly into the atmosphere, while others are secondary, formed through chemical reactions in the atmosphere. Washenfelder et al. describe in situ glyoxal measurements from Pasadena, Calif., near Los Angeles, made during summer 2010. They used three different methods to calculate the contribution of glyoxal to secondary atmospheric aerosol and found that it is responsible for 0-0.2 microgram per cubic meter, or 0-4%, of the secondary organic aerosol mass. The researchers also compared their results to those of a previous study that calculated the glyoxal contribution to aerosol for Mexico City. Mexico City had higher levels of organic aerosol mass from glyoxal. They suggest that the lower contribution of glyoxal to aerosol concentrations for Los Angeles may be due to differences in the composition or water content of the aerosols above the two cities. (Journal of Geophysical Research-Atmospheres, doi:10.1029/2011JD016314, 2011)

  15. Secondary organic aerosol formation from ambient air in an oxidation flow reactor in central Amazonia

    Science.gov (United States)

    Palm, Brett B.; de Sá, Suzane S.; Day, Douglas A.; Campuzano-Jost, Pedro; Hu, Weiwei; Seco, Roger; Sjostedt, Steven J.; Park, Jeong-Hoo; Guenther, Alex B.; Kim, Saewung; Brito, Joel; Wurm, Florian; Artaxo, Paulo; Thalman, Ryan; Wang, Jian; Yee, Lindsay D.; Wernis, Rebecca; Isaacman-VanWertz, Gabriel; Goldstein, Allen H.; Liu, Yingjun; Springston, Stephen R.; Souza, Rodrigo; Newburn, Matt K.; Lizabeth Alexander, M.; Martin, Scot T.; Jimenez, Jose L.

    2018-01-01

    Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O3, over ranges from hours to days (O3) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to as much as 10 µg m-3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C ˜ 1.0, and then decreased as O : C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O3, they could only explain 10-50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C = C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign

  16. Primary and secondary contributions to aerosol light scattering and absorption in Mexico City during the MILAGRO 2006 campaign

    Directory of Open Access Journals (Sweden)

    G. Paredes-Miranda

    2009-06-01

    Full Text Available A photoacoustic spectrometer, a nephelometer, an aethalometer, and an aerosol mass spectrometer were used to measure at ground level real-time aerosol light absorption, scattering, and chemistry at an urban site located in North East Mexico City (Instituto Mexicano del Petroleo, Mexican Petroleum Institute, denoted by IMP, as part of the Megacity Impact on Regional and Global Environments field experiment, MILAGRO, in March 2006. Photoacoustic and reciprocal nephelometer measurements at 532 nm accomplished with a single instrument compare favorably with conventional measurements made with an aethalometer and a TSI nephelometer. The diurnally averaged single scattering albedo at 532 nm was found to vary from 0.60 to 0.85 with the peak value at midday and the minimum value at 07:00 a.m. local time, indicating that the Mexico City plume is likely to have a net warming effect on local climate. The peak value is associated with strong photochemical generation of secondary aerosol. It is estimated that the photochemical production of secondary aerosol (inorganic and organic is approximately 75% of the aerosol mass concentration and light scattering in association with the peak single scattering albedo. A strong correlation of aerosol scattering at 532 nm and total aerosol mass concentration was found, and an average mass scattering efficiency factor of 3.8 m2/g was determined. Comparisons of photoacoustic and aethalometer light absorption with oxygenated organic aerosol concentration (OOA indicate a very small systematic bias of the filter based measurement associated with OOA and the peak aerosol single scattering albedo.

  17. Primary and secondary contributions to aerosol light scattering and absorption in Mexico City during the MILAGRO 2006 campaign

    Science.gov (United States)

    Paredes-Miranda, G.; Arnott, W. P.; Jimenez, J. L.; Aiken, A. C.; Gaffney, J. S.; Marley, N. A.

    2009-06-01

    A photoacoustic spectrometer, a nephelometer, an aethalometer, and an aerosol mass spectrometer were used to measure at ground level real-time aerosol light absorption, scattering, and chemistry at an urban site located in North East Mexico City (Instituto Mexicano del Petroleo, Mexican Petroleum Institute, denoted by IMP), as part of the Megacity Impact on Regional and Global Environments field experiment, MILAGRO, in March 2006. Photoacoustic and reciprocal nephelometer measurements at 532 nm accomplished with a single instrument compare favorably with conventional measurements made with an aethalometer and a TSI nephelometer. The diurnally averaged single scattering albedo at 532 nm was found to vary from 0.60 to 0.85 with the peak value at midday and the minimum value at 07:00 a.m. local time, indicating that the Mexico City plume is likely to have a net warming effect on local climate. The peak value is associated with strong photochemical generation of secondary aerosol. It is estimated that the photochemical production of secondary aerosol (inorganic and organic) is approximately 75% of the aerosol mass concentration and light scattering in association with the peak single scattering albedo. A strong correlation of aerosol scattering at 532 nm and total aerosol mass concentration was found, and an average mass scattering efficiency factor of 3.8 m2/g was determined. Comparisons of photoacoustic and aethalometer light absorption with oxygenated organic aerosol concentration (OOA) indicate a very small systematic bias of the filter based measurement associated with OOA and the peak aerosol single scattering albedo.

  18. Anthropogenic Influence on Secondary Aerosol Formation and Total Water-Soluble Carbon on Atmospheric Particles

    Science.gov (United States)

    Gioda, Adriana; Mateus, Vinicius; Monteiro, Isabela; Taira, Fabio; Esteves, Veronica; Saint'Pierre, Tatiana

    2013-04-01

    On a global scale, the atmosphere is an important source of nutrients, as well as pollutants, because of its interfaces with soil and water. Important compounds in the gaseous phase are in both organic and inorganic forms, such as organic acids, nitrogen, sulfur and chloride. In spite of the species in gas form, a huge number of process, anthropogenic and natural, are able to form aerosols, which may be transported over long distances. Sulfates e nitrates are responsible for rain acidity; they may also increase the solubility of organic compounds and metals making them more bioavailable, and also can act as cloud condensation nuclei (CCN). Aerosol samples (PM2.5) were collected in a rural and industrial area in Rio de Janeiro, Brazil, in order to quantify chemical species and evaluate anthropogenic influences in secondary aerosol formation and organic compounds. Samples were collected during 24 h every six days using a high-volume sampler from August 2010 to July 2011. The aerosol mass was determined by Gravimetry. The water-soluble ionic composition (WSIC) was obtained by Ion Chromatography in order to determine the major anions (NO3-, SO4= and Cl-); total water-soluble carbon (TWSC) was determined by a TOC analyzer. The average aerosol (PM2.5) concentrations ranged from 1 to 43 ug/m3 in the industrial site and from 4 to 35 ug/m3 in the rural area. Regarding anions, the highest concentrations were measured for SO42- (10.6 μg/m3-12.6 μg/m3); where the lowest value was found in the rural site and the highest in the industrial. The concentrations for NO3- and Cl- ranged from 4.2 μg/m3 to 9.3 μg/m3 and 3.1 μg/m3 to 6.4 μg /m3, respectively. Sulfate was the major species and, like nitrate, it is related to photooxidation in the atmosphere. Interestingly sulfate concentrations were higher during the dry period and could be related to photochemistry activity. The correlations between nitrate and non-sea-salt sulfate were weak, suggesting different sources for these

  19. Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ben H.; Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurtén, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D' Ambro, Emma L.; Thornton, Joel A.

    2016-01-25

    Organic nitrates (ON = RONO2 + RO2NO2) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NOx=NO+NO2). ON formed from isoprene oxidation alone are responsible for the export of 8 to 30% of anthropogenic NOx out of the U.S. continental boundary layer [Horowitz et al., 1998; Liang et al., 1998]. Regional NOx budgets and tropospheric ozone (O3) production, are therefore particularly sensitive to uncertainties in the yields and fates of ON [Beaver et al., 2012; Browne et al., 2013]. The yields implemented in modeling studies are determined from laboratory experiments in which only a few of the first generation gaseous ON or the total gas and particle-phase ON have been quantified [Perring et al., 2013 and references therein], while production of highly functionalized ON capable of strongly partitioning to the particle-phase have been inferred [Farmer et al., 2010; Ng et al., 2007; Nguyen et al., 2011; Perraud et al., 2012; Rollins et al., 2012], or directly measured [Ehn et al., 2014]. Addition of a nitrate (–ONO2) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5 to 3 orders of magnitude [e.g. Capouet and Muller, 2006]. Thus, organic nitrate formation can potentially enhance particle-phase partitioning of hydrocarbons in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) formation [Ng et al., 2007]. There has, however, been no high time-resolved measurements of speciated ON in the particle-phase. We utilize a newly developed high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adduct ionization [B H Lee et al., 2014a] with a filter inlet for gases and aerosols (FIGAERO) [Lopez-Hilfiker et al., 2014] that allows alternating in situ measurement of the molecular composition of gas and particle phases. We present observations of speciated ON in the particle-phase obtained during the 2013 Southern Oxidant

  20. Kinetically controlled glass transition measurement of organic aerosol thin films using broadband dielectric spectroscopy

    Directory of Open Access Journals (Sweden)

    Y. Zhang

    2018-06-01

    Full Text Available Glass transitions from liquid to semi-solid and solid phase states have important implications for reactivity, growth, and cloud-forming (cloud condensation nuclei and ice nucleation capabilities of secondary organic aerosols (SOAs. The small size and relatively low mass concentration of SOAs in the atmosphere make it difficult to measure atmospheric SOA glass transitions using conventional methods. To circumvent these difficulties, we have adapted a new technique for measuring glass-forming properties of atmospherically relevant organic aerosols. Aerosol particles to be studied are deposited in the form of a thin film onto an interdigitated electrode (IDE using electrostatic precipitation. Dielectric spectroscopy provides dipole relaxation rates for organic aerosols as a function of temperature (373 to 233 K that are used to calculate the glass transition temperatures for several cooling or heating rates. IDE-enabled broadband dielectric spectroscopy (BDS was successfully used to measure the kinetically controlled glass transition temperatures of aerosols consisting of glycerol and four other compounds with selected cooling and heating rates. The glass transition results agree well with available literature data for these five compounds. The results indicate that the IDE-BDS method can provide accurate glass transition data for organic aerosols under atmospheric conditions. The BDS data obtained with the IDE-BDS technique can be used to characterize glass transitions for both simulated and ambient organic aerosols and to model their climate effects.

  1. Final Report, The Influence of Organic-Aerosol Emissions and Aging on Regional and Global Aerosol Size Distributions and the CCN Number Budget

    Energy Technology Data Exchange (ETDEWEB)

    Donahue, Neil M. [Carnegie Mellon Univ., Pittsburgh, PA (United States)

    2015-12-23

    We conducted laboratory experiments and analyzed data on aging of organic aerosol and analysis of field data on volatility and CCN activity. With supplemental ASR funding we participated in the FLAME-IV campaign in Missoula MT in the Fall of 2012, deploying a two-chamber photochemical aging system to enable experimental exploration of photochemical aging of biomass burning emissions. Results from that campaign will lead to numerous publications, including demonstration of photochemical production of Brown Carbon (BrC) from secondary organic aerosol associated with biomass burning emissions as well as extensive characterization of the effect of photochemical aging on the overall concentrations of biomass burning organic aerosol. Excluding publications arising from the FLAME-IV campaign, project research resulted in 8 papers: [11, 5, 3, 10, 12, 4, 8, 7], including on in Nature Geoscience addressing the role of organic compounds in nanoparticle growth [11

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

    Science.gov (United States)

    Shiraiwa, Manabu; Yee, Lindsay D.; Schilling, Katherine A.; Loza, Christine L.; Craven, Jill S.; Zuend, Andreas; Ziemann, Paul J.; Seinfeld, John H.

    2013-01-01

    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 aerosols (SOAs). 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 multigeneration 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 midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

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

    Science.gov (United States)

    Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

    2013-07-16

    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 aerosols (SOAs). 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 multigeneration 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 midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

  4. Secondary Organic Aerosol Production over Seoul, South Korea, during KORUS-AQ

    Science.gov (United States)

    Nault, B.; Campuzano Jost, P.; Day, D. A.; Schroder, J. C.; Blake, D. R.; Brune, W. H.; Choi, Y.; DiGangi, J. P.; Fried, A.; Huey, L. G.; Knote, C. J.; Montzka, D. D.; Weinheimer, A. J.; Jimenez, J. L.; Armin, W.

    2017-12-01

    Secondary organic aerosol (SOA) is rapidly produced over and downwind of urban areas, causing important effects on health, visibility, and climate. However, multiple studies over different cities have shown that the production of SOA over urban areas cannot be accounted for when only using traditional volatile compounds (e.g., aromatics). Non-traditional anthropogenic volatile compounds—semi- and intermediate-volatile organic compounds (S/IVOC) are needed to account the observed urban SOA production. At this time, only a few megacities have been well characterized for urban SOA production; however, urban SOA production has not been well characterized in a megacity embedded in a region of rapid economic growth and energy consumption. In this study, we utilize observations from the NASA DC-8 over Seoul, South Korea, during the NASA/NIER 2016 KORean United States-Air Quality (KORUS-AQ) study to investigate the influence of transported OA and SOA precursors to Seoul versus the influence of local emissions of SOA precursors on the observed SOA production. We utilize the ambient gas-phase and OA observations over Seoul and the Western Sea along with Oxidation Flow Reactor (OFR) observations and FLEXPART tracer analysis to investigate the influence of transport versus local emissions. We find that the contribution of transported OA and SOA precursors to Seoul, during the campaign, was minor and had a small impact on the observed SOA production. Using the observed traditional volatile compounds, along with estimates of S/IVOC, brought near closure for the observed SOA production. We found that greater than 90% of the SOA production can be accounted for by reactive organic compounds with OH lifetimes less than 1 day, consistent with several previous megacity studies, further suggesting that local SOA precursor emissions are dominant. Our study highlights the need to further investigate and account for speciated S/IVOC measurements, as these represented an estimated 60

  5. Black carbon aerosol mixing state, organic aerosols and aerosol optical properties over the United Kingdom

    Science.gov (United States)

    McMeeking, G. R.; Morgan, W. T.; Flynn, M.; Highwood, E. J.; Turnbull, K.; Haywood, J.; Coe, H.

    2011-09-01

    Black carbon (BC) aerosols absorb sunlight thereby leading to a positive radiative forcing and a warming of climate and can also impact human health through their impact on the respiratory system. The state of mixing of BC with other aerosol species, particularly the degree of internal/external mixing, has been highlighted as a major uncertainty in assessing its radiative forcing and hence its climate impact, but few in situ observations of mixing state exist. We present airborne single particle soot photometer (SP2) measurements of refractory BC (rBC) mass concentrations and mixing state coupled with aerosol composition and optical properties measured in urban plumes and regional pollution over the United Kingdom. All data were obtained using instrumentation flown on the UK's BAe-146-301 large Atmospheric Research Aircraft (ARA) operated by the Facility for Airborne Atmospheric Measurements (FAAM). We measured sub-micron aerosol composition using an aerosol mass spectrometer (AMS) and used positive matrix factorization to separate hydrocarbon-like (HOA) and oxygenated organic aerosols (OOA). We found a higher number fraction of thickly coated rBC particles in air masses with large OOA relative to HOA, higher ozone-to-nitrogen oxides (NOx) ratios and large concentrations of total sub-micron aerosol mass relative to rBC mass concentrations. The more ozone- and OOA-rich air masses were associated with transport from continental Europe, while plumes from UK cities had higher HOA and NOx and fewer thickly coated rBC particles. We did not observe any significant change in the rBC mass absorption efficiency calculated from rBC mass and light absorption coefficients measured by a particle soot absorption photometer despite observing significant changes in aerosol composition and rBC mixing state. The contributions of light scattering and absorption to total extinction (quantified by the single scattering albedo; SSA) did change for different air masses, with lower SSA

  6. Black carbon aerosol mixing state, organic aerosols and aerosol optical properties over the United Kingdom

    Directory of Open Access Journals (Sweden)

    G. R. McMeeking

    2011-09-01

    Full Text Available Black carbon (BC aerosols absorb sunlight thereby leading to a positive radiative forcing and a warming of climate and can also impact human health through their impact on the respiratory system. The state of mixing of BC with other aerosol species, particularly the degree of internal/external mixing, has been highlighted as a major uncertainty in assessing its radiative forcing and hence its climate impact, but few in situ observations of mixing state exist. We present airborne single particle soot photometer (SP2 measurements of refractory BC (rBC mass concentrations and mixing state coupled with aerosol composition and optical properties measured in urban plumes and regional pollution over the United Kingdom. All data were obtained using instrumentation flown on the UK's BAe-146-301 large Atmospheric Research Aircraft (ARA operated by the Facility for Airborne Atmospheric Measurements (FAAM. We measured sub-micron aerosol composition using an aerosol mass spectrometer (AMS and used positive matrix factorization to separate hydrocarbon-like (HOA and oxygenated organic aerosols (OOA. We found a higher number fraction of thickly coated rBC particles in air masses with large OOA relative to HOA, higher ozone-to-nitrogen oxides (NOx ratios and large concentrations of total sub-micron aerosol mass relative to rBC mass concentrations. The more ozone- and OOA-rich air masses were associated with transport from continental Europe, while plumes from UK cities had higher HOA and NOx and fewer thickly coated rBC particles. We did not observe any significant change in the rBC mass absorption efficiency calculated from rBC mass and light absorption coefficients measured by a particle soot absorption photometer despite observing significant changes in aerosol composition and rBC mixing state. The contributions of light scattering and absorption to total extinction (quantified by the single scattering albedo; SSA did change for

  7. Factor analysis of combined organic and inorganic aerosol mass spectra from high resolution aerosol mass spectrometer measurements

    Directory of Open Access Journals (Sweden)

    Y. L. Sun

    2012-09-01

    Full Text Available Positive matrix factorization (PMF was applied to the merged high resolution mass spectra of organic and inorganic aerosols from aerosol mass spectrometer (AMS measurements to investigate the sources and evolution processes of submicron aerosols in New York City in summer 2009. This new approach is able to study the distribution of organic and inorganic species in different types of aerosols, the acidity of organic aerosol (OA factors, and the fragment ion patterns related to photochemical processing. In this study, PMF analysis of the unified AMS spectral matrix resolved 8 factors. The hydrocarbon-like OA (HOA and cooking OA (COA factors contain negligible amounts of inorganic species. The two factors that are primarily ammonium sulfate (SO4-OA and ammonium nitrate (NO3-OA, respectively, are overall neutralized. Among all OA factors the organic fraction of SO4-OA shows the highest degree of oxidation (O/C = 0.69. Two semi-volatile oxygenated OA (OOA factors, i.e., a less oxidized (LO-OOA and a more oxidized (MO-OOA, were also identified. MO-OOA represents local photochemical products with a diurnal profile exhibiting a pronounced noon peak, consistent with those of formaldehyde (HCHO and Ox(= O3 + NO2. The NO+/NO2+ ion ratio in MO-OOA is much higher than that in NO3-OA and in pure ammonium nitrate, indicating the formation of organic nitrates. The nitrogen-enriched OA (NOA factor contains ~25% of acidic inorganic salts, suggesting the formation of secondary OA via acid-base reactions of amines. The size distributions of OA factors derived from the size-resolved mass spectra show distinct diurnal evolving behaviors but overall a progressing evolution from smaller to larger particle mode as the oxidation degree of OA increases. Our results demonstrate that PMF analysis of the unified aerosol mass spectral matrix which contains both

  8. Phase, composition, and growth mechanism for secondary organic aerosol from the ozonolysis of α-cedrene

    Directory of Open Access Journals (Sweden)

    Y. Zhao

    2016-03-01

    Full Text Available Sesquiterpenes are an important class of biogenic volatile organic compounds (BVOCs and have a high secondary organic aerosol (SOA forming potential. However, SOA formation from sesquiterpene oxidation has received less attention compared to other BVOCs such as monoterpenes, and the underlying mechanisms remain poorly understood. In this work, we present a comprehensive experimental investigation of the ozonolysis of α-cedrene both in a glass flow reactor (27–44 s reaction times and in static Teflon chambers (30–60 min reaction times. The SOA was collected by impaction or filters, followed by analysis using attenuated total reflectance Fourier transform infrared (ATR-FTIR spectroscopy and electrospray ionization mass spectrometry (ESI-MS, or measured online using direct analysis in real-time mass spectrometry (DART-MS and aerosol mass spectrometry (AMS. The slow evaporation of 2-ethylhexyl nitrate that was incorporated into the SOA during its formation and growth gives an estimated diffusion coefficient of 3  ×  10−15 cm2 s−1 and shows that SOA is a highly viscous semisolid. Possible structures of four newly observed low molecular weight (MW  ≤  300 Da reaction products with higher oxygen content than those previously reported were identified. High molecular weight (HMW products formed in the early stages of the oxidation have structures consistent with aldol condensation products, peroxyhemiacetals, and esters. The size-dependent distributions of HMW products in the SOA, as well as the effects of stabilized Criegee intermediate (SCI scavengers on HMW products and particle formation, confirm that HMW products and reactions of SCI play a crucial role in early stages of particle formation. Our studies provide new insights into mechanisms of SOA formation and growth in α-cedrene ozonolysis and the important role of sesquiterpenes in new particle formation as suggested by field measurements.

  9. Gas-particle partitioning of semivolatile organic compounds (SOCs) on mixtures of aerosols in a smog chamber.

    Science.gov (United States)

    Chandramouli, Bharadwaj; Jang, Myoseon; Kamens, Richard M

    2003-09-15

    The partitioning behavior of a set of diverse SOCs on two and three component mixtures of aerosols from different sources was studied using smog chamber experimental data. A set of SOCs of different compound types was introduced into a system containing a mixture of aerosols from two or more sources. Gas and particle samples were taken using a filter-filter-denuder sampling system, and a partitioning coefficient Kp was estimated using Kp = Cp/(CgTSP). Particle size distributions were measured using a differential mobility analyzer and a light scattering detector. Gas and particle samples were analyzed using GCMS. The aerosol composition in the chamber was tracked chemically using a combination of signature compounds and the organic matter mass fraction (f(om)) of the individual aerosol sources. The physical nature of the aerosol mixture in the chamber was determined using particle size distributions, and an aggregate Kp was estimated from theoretically calculated Kp on the individual sources. Model fits for Kp showed that when the mixture involved primary sources of aerosol, the aggregate Kp of the mixture could be successfully modeled as an external mixture of the Kp on the individual aerosols. There were significant differences observed for some SOCs between modeling the system as an external and as an internal mixture. However, when one of the aerosol sources was secondary, the aggregate model Kp required incorporation of the secondary aerosol products on the preexisting aerosol for adequate model fits. Modeling such a system as an external mixture grossly overpredicted the Kp of alkanes in the mixture. Indirect evidence of heterogeneous, acid-catalyzed reactions in the particle phase was also seen, leading to a significant increase in the polarity of the resulting aerosol mix and a resulting decrease in the observed Kp of alkanes in the chamber. The model was partly consistent with this decrease but could not completely explain the reduction in Kp because of

  10. SMOG CHAMBER STUDIES OF SECONDARY ORGANIC AEROSOLS FROM IRRADIATED HYDROCARBONS UNDER AMBIENT CONDITIONS

    Science.gov (United States)

    Understanding the physics and chemistry of aerosols is fundamental to evaluating health risks and developing and evaluating atmospheric models. However, as noted in a recent NRC report only about 10% of the organics in PM2.5 have been identified. A significant portion of the un...

  11. Water-soluble Organic Components in Aerosols Associated with Savanna Fires in Southern Africa: Identification, Evolution and Distribution

    Science.gov (United States)

    Gao, Song; Hegg, Dean A.; Hobbs, Peter V.; Kirchstetter, Thomas W.; Magi, Brian I.; Sadilek, Martin

    2003-01-01

    During the SAFARI 2000 field campaign, both smoke aerosols from savanna fires and haze aerosols in the boundary layer and in the free troposphere were collected from an aircraft in southern Africa. These aerosol samples were analyzed for their water-soluble chemical components, particularly the organic species. A novel technique, electrospray ionization-ion trap mass spectrometry, was used concurrently with an ion chromatography system to analyze for carbohydrate species. Seven carbohydrates, seven organic acids, five metallic elements, and three inorganic anions were identified and quantified. On the average, these 22 species comprised 36% and 27% of the total aerosol mass in haze and smoke aerosols, respectively. For the smoke aerosols, levoglucosan was the most abundant carbohydrate species, while gluconic acid was tentatively identified as the most abundant organic acid. The mass abundance and possible source of each class of identified species are discussed, along with their possible formation pathways. The combustion phase of a fire had an impact on the chemical composition of the emitted aerosols. Secondary formation of sulfate, nitrate, levoglucosan, and several organic acids occurred during the initial aging of smoke aerosols. It is likely that under certain conditions, some carbohydrate species in smoke aerosols, such as levoglucosan, were converted to organic acids during upward transport.

  12. Global-scale combustion sources of organic aerosols: sensitivity to formation and removal mechanisms

    Science.gov (United States)

    Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Pandis, Spyros N.; Lelieveld, Jos

    2017-06-01

    Organic compounds from combustion sources such as biomass burning and fossil fuel use are major contributors to the global atmospheric load of aerosols. We analyzed the sensitivity of model-predicted global-scale organic aerosols (OA) to parameters that control primary emissions, photochemical aging, and the scavenging efficiency of organic vapors. We used a computationally efficient module for the description of OA composition and evolution in the atmosphere (ORACLE) of the global chemistry-climate model EMAC (ECHAM/MESSy Atmospheric Chemistry). A global dataset of aerosol mass spectrometer (AMS) measurements was used to evaluate simulated primary (POA) and secondary (SOA) OA concentrations. Model results are sensitive to the emission rates of intermediate-volatility organic compounds (IVOCs) and POA. Assuming enhanced reactivity of semi-volatile organic compounds (SVOCs) and IVOCs with OH substantially improved the model performance for SOA. The use of a hybrid approach for the parameterization of the aging of IVOCs had a small effect on predicted SOA levels. The model performance improved by assuming that freshly emitted organic compounds are relatively hydrophobic and become increasingly hygroscopic due to oxidation.

  13. Physical parameters effect on ozone-initiated formation of indoor secondary organic aerosols with emissions from cleaning products.

    Science.gov (United States)

    Huang, Yu; Ho, Kin Fai; Ho, Steven Sai Hang; Lee, Shun Cheng; Yau, P S; Cheng, Yan

    2011-09-15

    The effect of air exchange rate (ACH), temperature (T), and relative humidity (RH) on the formation of indoor secondary organic aerosols (SOAs) through ozonolysis of biogenic organic compounds (BVOCs) emitted from floor cleaner was investigated in this study. The total particle count (with D(p) of 6-225 nm) was up to 1.2 × 10(3)#cm(-3) with ACH of 1.08 h(-1), and it became much more significant with ACH of 0.36 h(-1) (1.1 × 10(4)#cm(-3)). This suggests that a higher ventilation rate can effectively dilute indoor BVOCs, resulting in a less ultrafine particle formation. The total particle count increased when temperature changed from 15 to 23 °C but it decreased when the temperature further increased to 30 °C. It could be explained that high temperature restrained the condensation of formed semi-volatile compounds resulting in low yields of SOAs. When the RH was at 50% and 80%, SOA formation (1.1-1.2 × 10(4)#cm(-3)) was the more efficient compared with that at RH of 30% (5.9 × 10(3)#cm(-3)), suggesting higher RH facilitating the initial nucleation processes. Oxidation generated secondary carbonyl compounds were also quantified. Acetone was the most abundant carbonyl compound. The formation mechanisms of formaldehyde and acetone were proposed. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Primary aerosol and secondary inorganic aerosol budget over the Mediterranean Basin during 2012 and 2013

    Science.gov (United States)

    Guth, Jonathan; Marécal, Virginie; Josse, Béatrice; Arteta, Joaquim; Hamer, Paul

    2018-04-01

    In the frame of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx), we analyse the budget of primary aerosols and secondary inorganic aerosols over the Mediterranean Basin during the years 2012 and 2013. To do this, we use two year-long numerical simulations with the chemistry-transport model MOCAGE validated against satellite- and ground-based measurements. The budget is presented on an annual and a monthly basis on a domain covering 29 to 47° N latitude and 10° W to 38° E longitude. The years 2012 and 2013 show similar seasonal variations. The desert dust is the main contributor to the annual aerosol burden in the Mediterranean region with a peak in spring, and sea salt being the second most important contributor. The secondary inorganic aerosols, taken as a whole, contribute a similar level to sea salt. The results show that all of the considered aerosol types, except for sea salt aerosols, experience net export out of our Mediterranean Basin model domain, and thus this area should be considered as a source region for aerosols globally. Our study showed that 11 % of the desert dust, 22.8 to 39.5 % of the carbonaceous aerosols, 35 % of the sulfate and 9 % of the ammonium emitted or produced into the study domain are exported. The main sources of variability for aerosols between 2012 and 2013 are weather-related variations, acting on emissions processes, and the episodic import of aerosols from North American fires. In order to assess the importance of the anthropogenic emissions of the marine and the coastal areas which are central for the economy of the Mediterranean Basin, we made a sensitivity test simulation. This simulation is similar to the reference simulation but with the removal of the international shipping emissions and the anthropogenic emissions over a 50 km wide band inland along the coast. We showed that around 30 % of the emissions of carbonaceous aerosols and 35 to 60 % of the exported carbonaceous aerosols originates from the marine and

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

    Science.gov (United States)

    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.

  16. Source apportionment of size and time resolved trace elements and organic aerosols from an urban courtyard site in Switzerland

    Directory of Open Access Journals (Sweden)

    A. Richard

    2011-09-01

    Full Text Available Time and size resolved data of trace elements were obtained from measurements with a rotating drum impactor (RDI and subsequent X-ray fluorescence spectrometry. Trace elements can act as indicators for the identification of sources of particulate matter <10 μm (PM10 in ambient air. Receptor modeling was performed with positive matrix factorization (PMF for trace element data from an urban background site in Zürich, Switzerland. Eight different sources were identified for the three examined size ranges (PM1−0.1, PM2.5−1 and PM10−2.5: secondary sulfate, wood combustion, fire works, road traffic, mineral dust, de-icing salt, industrial and local anthropogenic activities. The major component was secondary sulfate for the smallest size range; the road traffic factor was found in all three size ranges. This trace element analysis is complemented with data from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS, assessing the PM1 fraction of organic aerosols. A separate PMF analysis revealed three factors related to three of the sources found with the RDI: oxygenated organic aerosol (OOA, related to inorganic secondary sulfate, hydrocarbon-like organic aerosol (HOA, related to road traffic and biomass burning organic aerosol (BBOA, explaining 60 %, 22 % and 17 % of total measured organics, respectively. Since different compounds are used for the source classification, a higher percentage of the ambient PM10 mass concentration can be apportioned to sources by the combination of both methods.

  17. Secondary organic aerosol formation from ambient air in an oxidation flow reactor in central Amazonia

    Directory of Open Access Journals (Sweden)

    B. B. Palm

    2018-01-01

    Full Text Available Secondary organic aerosol (SOA formation from ambient air was studied using an oxidation flow reactor (OFR coupled to an aerosol mass spectrometer (AMS during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5 field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O3, over ranges from hours to days (O3 or weeks (OH of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to as much as 10 µg m−3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C ∼ 1.0, and then decreased as O : C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O3, they could only explain 10–50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C = C bonds are present in ambient air and can explain such additional SOA formation. To investigate the sources of the

  18. Organic molecular composition of marine aerosols over the Arctic Ocean in summer: contributions of primary emission and secondary aerosol formation

    OpenAIRE

    P. Q. Fu; K. Kawamura; J. Chen; B. Charrière; R. Sempéré

    2013-01-01

    Organic molecular composition of marine aerosol samples collected during the MALINA cruise in the Arctic Ocean was investigated by gas chromatography/mass spectrometry. More than 110 individual organic compounds were determined in the samples and were grouped into different compound classes based on the functionality and sources. The concentrations of total quantified organics ranged from 7.3 to 185 ng m−3 (mean 47.6 ng m−3), accounting ...

  19. Secondary organic aerosol from ozone-initiated reactions with terpene-rich household products

    Energy Technology Data Exchange (ETDEWEB)

    Coleman, Beverly; Coleman, Beverly K.; Lunden, Melissa M.; Destaillats, Hugo; Nazaroff, William W.

    2008-01-01

    We analyzed secondary organic aerosol (SOA) data from a series of small-chamber experiments in which terpene-rich vapors from household products were combined with ozone under conditions analogous to product use indoors. Reagents were introduced into a continuously ventilated 198 L chamber at steady rates. Consistently, at the time of ozone introduction, nucleation occurred exhibiting behavior similar to atmospheric events. The initial nucleation burst and growth was followed by a period in which approximately stable particle levels were established reflecting a balance between new particle formation, condensational growth, and removal by ventilation. Airborne particles were measured with a scanning mobility particle sizer (SMPS, 10 to 400 nm) in every experiment and with an optical particle counter (OPC, 0.1 to 2.0 ?m) in a subset. Parameters for a three-mode lognormal fit to the size distribution at steady state were determined for each experiment. Increasing the supply ozone level increased the steady-state mass concentration and yield of SOA from each product tested. Decreasing the air-exchange rate increased the yield. The steady-state fine-particle mass concentration (PM1.1) ranged from 10 to> 300 mu g m-3 and yields ranged from 5percent to 37percent. Steady-state nucleation rates and SOA mass formation rates were on the order of 10 cm-3 s-1 and 10 mu g m-3 min-1, respectively.

  20. Effect of relative humidity on the composition of secondary organic aerosol from the oxidation of toluene

    Directory of Open Access Journals (Sweden)

    M. L. Hinks

    2018-02-01

    Full Text Available The effect of relative humidity (RH on the chemical composition of secondary organic aerosol (SOA formed from low-NOx toluene oxidation in the absence of seed particles was investigated. SOA samples were prepared in an aerosol smog chamber at < 2 % RH and 75 % RH, collected on Teflon filters, and analyzed with nanospray desorption electrospray ionization high-resolution mass spectrometry (nano-DESI–HRMS. Measurements revealed a significant reduction in the fraction of oligomers present in the SOA generated at 75 % RH compared to SOA generated under dry conditions. In a separate set of experiments, the particle mass concentrations were measured with a scanning mobility particle sizer (SMPS at RHs ranging from < 2 to 90 %. It was found that the particle mass loading decreased by nearly an order of magnitude when RH increased from < 2 to 75–90 % for low-NOx toluene SOA. The volatility distributions of the SOA compounds, estimated from the distribution of molecular formulas using the molecular corridor approach, confirmed that low-NOx toluene SOA became more volatile on average under high-RH conditions. In contrast, the effect of RH on SOA mass loading was found to be much smaller for high-NOx toluene SOA. The observed increase in the oligomer fraction and particle mass loading under dry conditions were attributed to the enhancement of condensation reactions, which produce water and oligomers from smaller compounds in low-NOx toluene SOA. The reduction in the fraction of oligomeric compounds under humid conditions is predicted to partly counteract the previously observed enhancement in the toluene SOA yield driven by the aerosol liquid water chemistry in deliquesced inorganic seed particles.

  1. Evaluation of the volatility basis-set approach for the simulation of organic aerosol formation in the Mexico City metropolitan area

    Directory of Open Access Journals (Sweden)

    A. P. Tsimpidi

    2010-01-01

    Full Text Available New primary and secondary organic aerosol modules have been added to PMCAMx, a three dimensional chemical transport model (CTM, for use with the SAPRC99 chemistry mechanism based on recent smog chamber studies. The new modelling framework is based on the volatility basis-set approach: both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. This new framework with the use of the new volatility basis parameters for low-NOx and high-NOx conditions tends to predict 4–6 times higher anthropogenic SOA concentrations than those predicted with the older generation of models. The resulting PMCAMx-2008 was applied in Mexico City Metropolitan Area (MCMA for approximately a week during April 2003 during a period of very low regional biomass burning impact. The emission inventory, which uses as a starting point the MCMA 2004 official inventory, is modified and the primary organic aerosol (POA emissions are distributed by volatility based on dilution experiments. The predicted organic aerosol (OA concentrations peak in the center of Mexico City, reaching values above 40 μg m−3. The model predictions are compared with the results of the Positive Matrix Factorization (PMF analysis of the Aerosol Mass Spectrometry (AMS observations. The model reproduces both Hydrocarbon-like Organic Aerosol (HOA and Oxygenated Organic Aerosol (OOA concentrations and diurnal profiles. The small OA underprediction during the rush-hour periods and overprediction in the afternoon suggest potential improvements to the description of fresh primary organic emissions and the formation of the oxygenated organic aerosols, respectively, although they may also be due to errors in the simulation of dispersion and vertical mixing. However, the AMS OOA data are not specific enough to prove that the model reproduces the organic aerosol

  2. Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Nga Lee; Brown, Steven S.; Archibald, Alexander T.; Atlas, Elliot; Cohen, Ronald C.; Crowley, John N.; Day, Douglas A.; Donahue, Neil M.; Fry, Juliane L.; Fuchs, Hendrik; Griffin, Robert J.; Guzman, Marcelo I.; Herrmann, Hartmut; Hodzic, Alma; Iinuma, Yoshiteru; Jimenez, José L.; Kiendler-Scharr, Astrid; Lee, Ben H.; Luecken, Deborah J.; Mao, Jingqiu; McLaren, Robert; Mutzel, Anke; Osthoff, Hans D.; Ouyang, Bin; Picquet-Varrault, Benedicte; Platt, Ulrich; Pye, Havala O. T.; Rudich, Yinon; Schwantes, Rebecca H.; Shiraiwa, Manabu; Stutz, Jochen; Thornton, Joel A.; Tilgner, Andreas; Williams, Brent J.; Zaveri, Rahul A.

    2017-01-01

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models.

    This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

  3. Secondary organic aerosols from ozone-initiated reactions with emissions from wood-based materials and a ‘‘green’’ paint

    DEFF Research Database (Denmark)

    Toftum, Jørn; Freund, Sarah; Salthammer, Tunga

    2008-01-01

    This study examined the formation and growth of secondary organic aerosols (SOA) generated when ozone was added to a 1 m3 glass chamber that contained either pine shelving, oriented strand board (OSB), beech boards, or beach boards painted with an ‘‘eco’’ paint. The experiments were conducted...... dramatically; the mass concentration reached w15 mgm3 at w20 ppb O3, and w95 mgm3 at w40 ppb O3. The OSB emitted primarily limonene and a-pinene. Although the particle counts increased when O3 was introduced, the increase was not as large as anticipated based on the terpene concentrations. The beech boards...

  4. Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry

    Science.gov (United States)

    Faxon, Cameron; Hammes, Julia; Le Breton, Michael; Kant Pathak, Ravi; Hallquist, Mattias

    2018-04-01

    The gas-phase nitrate radical (NO3⚫) initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA) formation and organic nitrates may serve as a NOx reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO3⚫ with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO). Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM) limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C10H15NO6, C10H17NO6, C8H11NO6, C10H17NO7, and C9H13NO7) that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO3⚫ produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.

  5. Characterization of organic nitrate constituents of secondary organic aerosol (SOA from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    C. Faxon

    2018-04-01

    Full Text Available The gas-phase nitrate radical (NO3⚫ initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA formation and organic nitrates may serve as a NOx reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO3⚫ with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS combined with a Filter Inlet for Gases and AEROsols (FIGAERO. Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C10H15NO6, C10H17NO6, C8H11NO6, C10H17NO7, and C9H13NO7 that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO3⚫ produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.

  6. Laboratory and field measurements of organic aerosols with the photoionization aerosol mass spectrometer

    Science.gov (United States)

    Dreyfus, Matthew A.

    . The high-time resolution data shows that rapid concentration changes of a common individual species can be lost with traditional bulk sampling, and a time resolution of 30 minutes is suggested to accurately represent these changes. Using the mass spectra collected from the extended sampling campaign, source apportionment was performed with positive matrix factorization (PMF). The resulting model features six factors either correlated to specific sources (meat cooking, car emissions/road dust, diesel exhaust) or types of compounds (phthalates, alkanes/alkanoic acids, PAHs). The high-time resolution data allowed for the observation of specific trends in each factor's behavior as a function of time and wind direction relative to the receptor site. Elemental carbon/organic carbon (EC/OC) data is used to calculate the percentages of primary and secondary organic aerosol. Primary organic aerosol (POA) constituted the vast majority of the total carbon at 91% (an average of 2.8 +/- 1.1mug/m 3); 30% of which came from combustion, and 70% from non-combustion sources. These results can be explained by the PIAMS data: the diesel factor contributes to the combustion-related POA; the car/road dust, meat cooking, and alkane/alkanoic acid factors contribute the majority of non-combustion POA. The remaining factors represent products from the ozonolysis of various monoterpenes. The product ion peaks observed indicates that both the stabilized Criegee intermediate pathway and the hydroperoxide channel are both active pathways in yielding dimers and high-order oligomer.

  7. Ozonolysis and Subsequent Photolysis of unsaturated organic molecules: Model Systems for Photochemical Aging of Organic Aerosol Particles

    Science.gov (United States)

    Park, J.; Gomez, A. L.; Walser, M. L.; Lin, A.; Nizkorodov, S. A.

    2005-12-01

    Chemical and photochemical aging of organic species adsorbed on aerosol particle surfaces is believed to have a significant effect on cloud condensation properties of atmospheric aerosols. Ozone initiated oxidation reactions of thin films of undecylenic acid and alkene-terminated self assembled monolayers (SAMs) on SiO2 surface were investigated using a combination of spectroscopic and mass spectrometric techniques. Photolysis of the oxidized film in the tropospheric actinic region (λ>290 nm) readily produces formaldehyde and formic acid as gas-phase products. Photodissociation action spectra of the oxidized film suggest that organic peroxides are responsible for the enhanced photochemical activity. The presence of peroxides in the oxidized sample was confirmed by mass-spectrometric analysis and by an iodometric test. Significant polymerization resulting from secondary reactions of Criegee radicals during ozonolysis of the film is also observed. The reaction mechanism and its implications for photochemical aging of atmospheric aerosol particles will be discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

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

    Directory of Open Access Journals (Sweden)

    W. Hu

    2016-09-01

    Full Text Available 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

  10. The impact of biogenic, anthropogenic, and biomass burning volatile organic compound emissions on regional and seasonal variations in secondary organic aerosol

    Science.gov (United States)

    Kelly, Jamie M.; Doherty, Ruth M.; O'Connor, Fiona M.; Mann, Graham W.

    2018-05-01

    The global secondary organic aerosol (SOA) budget is highly uncertain, with global annual SOA production rates, estimated from global models, ranging over an order of magnitude and simulated SOA concentrations underestimated compared to observations. In this study, we use a global composition-climate model (UKCA) with interactive chemistry and aerosol microphysics to provide an in-depth analysis of the impact of each VOC source on the global SOA budget and its seasonality. We further quantify the role of each source on SOA spatial distributions, and evaluate simulated seasonal SOA concentrations against a comprehensive set of observations. The annual global SOA production rates from monoterpene, isoprene, biomass burning, and anthropogenic precursor sources is 19.9, 19.6, 9.5, and 24.6 Tg (SOA) a-1, respectively. When all sources are included, the SOA production rate from all sources is 73.6 Tg (SOA) a-1, which lies within the range of estimates from previous modelling studies. SOA production rates and SOA burdens from biogenic and biomass burning SOA sources peak during Northern Hemisphere (NH) summer. In contrast, the anthropogenic SOA production rate is fairly constant all year round. However, the global anthropogenic SOA burden does have a seasonal cycle which is lowest during NH summer, which is probably due to enhanced wet removal. Inclusion of the new SOA sources also accelerates the ageing by condensation of primary organic aerosol (POA), making it more hydrophilic, leading to a reduction in the POA lifetime. With monoterpene as the only source of SOA, simulated SOA and total organic aerosol (OA) concentrations are underestimated by the model when compared to surface and aircraft measurements. Model agreement with observations improves with all new sources added, primarily due to the inclusion of the anthropogenic source of SOA, although a negative bias remains. A further sensitivity simulation was performed with an increased anthropogenic SOA reaction

  11. Relating cloud condensation nuclei activity and oxidation level of alpha-pinene secondary organic aerosols

    DEFF Research Database (Denmark)

    Foverskov, Mia Frosch Mogensbæk; Bilde, M.; DeCarlo, P. F.

    2011-01-01

    During a series of smog chamber experiments, the effects of chemical and photochemical aging on the ability of organic aerosols generated from ozonolysis of alpha-pinene to act as cloud condensation nuclei (CCN) were investigated. In particular, the study focused on the relation between oxygenation...

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

    Science.gov (United States)

    Pan, Xiang

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

  13. Methods of analysis for complex organic aerosol mixtures from urban emission sources of particulate carbon

    International Nuclear Information System (INIS)

    Mazurek, M.A.; Hildemann, L.M.; Simoneit, B.R.T.

    1990-10-01

    Organic aerosols comprise approximately 30% by mass of the total fine particulate matter present in urban atmospheres. The chemical composition of such aerosols is complex and reflects input from multiple sources of primary emissions to the atmosphere, as well as from secondary production of carbonaceous aerosol species via photochemical reactions. To identify discrete sources of fine carbonaceous particles in urban atmospheres, analytical methods must reconcile both bulk chemical and molecular properties of the total carbonaceous aerosol fraction. This paper presents an overview of the analytical protocol developed and used in a study of the major sources of fine carbon particles emitted to an urban atmosphere. 23 refs., 1 fig., 2 tabs

  14. Potential of select intermediate-volatility organic compounds and consumer products for secondary organic aerosol and ozone formation under relevant urban conditions

    Science.gov (United States)

    Li, Weihua; Li, Lijie; Chen, Chia-li; Kacarab, Mary; Peng, Weihan; Price, Derek; Xu, Jin; Cocker, David R.

    2018-04-01

    Emissions of certain low vapor pressure-volatile organic compounds (LVP-VOCs) are considered exempt to volatile organic compounds (VOC) regulations due to their low evaporation rates. However, these compounds may still play a role in ambient secondary organic aerosol (SOA) and ozone formation. The LVP-VOCs selected for this work are categorized as intermediate-volatility organic compounds (IVOCs) according to their vapor pressures and molecular formulas. In this study, the evaporation rates of 14 select IVOCs are investigated with half of them losing more than 95% of their mass in less than one month. Further, SOA and ozone formation are presented from 11 select IVOCs and 5 IVOC-containing generic consumer products under atmospherically relevant conditions using varying radical sources (NOx and/or H2O2) and a surrogate reactive organic gas (ROG) mixture. Benzyl alcohol (0.41), n-heptadecane (0.38), and diethylene glycol monobutyl ether (0.16) are determined to have SOA yields greater than 0.1 in the presence of NOx and a surrogate urban hydrocarbon mixture. IVOCs also influence ozone formation from the surrogate urban mixture by impacting radical levels and NOx availability. The addition of lab created generic consumer products has a weak influence on ozone formation from the surrogate mixture but strongly affects SOA formation. The overall SOA and ozone formation of the generic consumer products could not be explained solely by the results of the pure IVOC experiments.

  15. Ozonolysis of α-phellandrene - Part 2: Compositional analysis of secondary organic aerosol highlights the role of stabilised Criegee intermediates

    Science.gov (United States)

    Mackenzie-Rae, Felix A.; Wallis, Helen J.; Rickard, Andrew R.; Pereira, Kelly L.; Saunders, Sandra M.; Wang, Xinming; Hamilton, Jacqueline F.

    2018-04-01

    The molecular composition of the water-soluble fraction of secondary organic aerosol (SOA) generated from the ozonolysis of α-phellandrene is investigated for the first time using high-pressure liquid chromatography coupled to high-resolution quadrupole-Orbitrap tandem mass spectrometry. In total, 21 prominent products or isomeric product groups were identified using both positive and negative ionisation modes, with potential formation mechanisms discussed. The aerosol was found to be composed primarily of polyfunctional first- and second-generation species containing one or more carbonyl, acid, alcohol and hydroperoxide functionalities, with the products significantly more complex than those proposed from basic gas-phase chemistry in the companion paper (Mackenzie-Rae et al., 2017). Mass spectra show a large number of dimeric products are also formed. Both direct scavenging evidence using formic acid and indirect evidence from double bond equivalency factors suggest the dominant oligomerisation mechanism is the bimolecular reaction of stabilised Criegee intermediates (SCIs) with non-radical ozonolysis products. Saturation vapour concentration estimates suggest monomeric species cannot explain the rapid nucleation burst of fresh aerosol observed in chamber experiments; hence, dimeric species are believed to be responsible for new particle formation, with detected first- and second-generation products driving further particle growth in the system. Ultimately, identification of the major constituents and formation pathways of α-phellandrene SOA leads to a greater understanding of the atmospheric processes and implications of monoterpene emissions and SCIs, especially around eucalypt forests where α-phellandrene is primarily emitted.

  16. Gas-phase products and secondary organic aerosol formation from the ozonolysis and photooxidation of myrcene

    Science.gov (United States)

    Böge, Olaf; Mutzel, Anke; Iinuma, Yoshiteru; Yli-Pirilä, Pasi; Kahnt, Ariane; Joutsensaari, Jorma; Herrmann, Hartmut

    2013-11-01

    In this study, the ozone and OH-radical reactions of myrcene were investigated in an aerosol chamber (at 292-295 K and 50% relative humidity) to examine the gas-phase oxidation products and secondary organic aerosol (SOA) formation. The ozone reaction studies were performed in the presence and absence of CO, which serves as an OH radical scavenger. In the photooxidation experiments OH radicals were generated by photolysis of methyl nitrite. The ozonolysis of myrcene in the presence of CO resulted in a substantial yield of 4-vinyl-4-pentenal (55.3%), measured as m/z 111 plus m/z 93 using proton transfer reaction-mass spectrometry (PTR-MS) and confirmed unambiguously as C7H10O by denuder measurements and HPLC/ESI-TOFMS analysis of its 2,4-dinitrophenylhydrazine (DNPH) derivative. Additionally, the formation of two different organic dicarbonyls with m/z 113 and a molecular formula of C6H8O2 were observed (2.1%). The yields of these dicarbonyls were higher in the ozonolysis experiments without an OH scavenger (5.4%) and even higher (13.8%) in the myrcene OH radical reaction. The formation of hydroxyacetone as a direct product of the myrcene reaction with ozone with a molar yield of 17.6% was also observed. The particle size distribution and volume concentrations were monitored and facilitated the calculation of SOA yields, which ranged from 0 to 0.01 (ozonolysis in the presence of CO) to 0.39 (myrcene OH radical reaction). Terpenylic acid was found in the SOA samples collected from the ozonolysis of myrcene in the absence of an OH scavenger and the OH radical-initiated reaction of myrcene but not in samples collected from the ozonolysis in the presence of CO as an OH radical scavenger, suggesting that terpenylic acid formation involves the reaction of myrcene with an OH radical. A reaction mechanism describing the formation of terpenylic acid is proposed.

  17. Submicrometer aerosol in rural and urban backgrounds in southern Poland: primary and secondary components of PM1.

    Science.gov (United States)

    Rogula-Kozłowska, Wioletta; Klejnowski, Krzysztof

    2013-01-01

    Diurnal samples of PM(1) (submicrometer particles, having aerodynamic diameters not greater than 1 μm) were collected at an urban background site in Zabrze (from 01.08. to 31.12.2009) and a rural background site in Racibórz (from 01.08. to 31.12.2010). The samples were analyzed for carbon (organic and elemental), water soluble ions (Na(+), NH(4) (+), K(+), Mg(2+), Ca(2+), Cl(-), NO(3)(-), SO(4)(2-)) and concentrations of 21 elements by using, respectively, a Sunset Laboratory carbon analyzer, a Herisau Metrohm AG ion chromatograph, a PANalitycal Epsilon 5 spectrometer. To perform the monthly mass closure calculations for PM(1), the chemical components were categorized into organic matter (OM), elemental carbon (EC), secondary inorganic aerosol (SIA), crustal matter (CM), marine components (MC), other elements (OE) and unidentified matter (UM). The mass contributions of secondary (SOM) and primary (POM) organic matter to PM(1) were also estimated. In average, 50 % of PM(1) in Zabrze and 40 % in Racibórz were secondary aerosol coming from the transformations of its gaseous precursors. High concentrations and mass contributions of EC and OM to PM, and probable PM acidic nature in Zabrze, indicate particularly high hazard from the ambient submicrometer particles to the inhabitants of southern Poland.

  18. Secondary organic aerosol formation from semi- and intermediate-volatility organic compounds and glyoxal: Relevance of O/C as a tracer for aqueous multiphase chemistry

    Science.gov (United States)

    Waxman, Eleanor M.; Dzepina, Katja; Ervens, Barbara; Lee-Taylor, Julia; Aumont, Bernard; Jimenez, Jose L.; Madronich, Sasha; Volkamer, Rainer

    2013-03-01

    The role of aqueous multiphase chemistry in the formation of secondary organic aerosol (SOA) remains difficult to quantify. We investigate it here by testing the rapid formation of moderate oxygen-to-carbon (O/C) SOA during a case study in Mexico City. A novel laboratory-based glyoxal-SOA mechanism is applied to the field data, and explains why less gas-phase glyoxal mass is observed than predicted. Furthermore, we compare an explicit gas-phase chemical mechanism for SOA formation from semi- and intermediate-volatility organic compounds (S/IVOCs) with empirical parameterizations of S/IVOC aging. The mechanism representing our current understanding of chemical kinetics of S/IVOC oxidation combined with traditional SOA sources and mixing of background SOA underestimates the observed O/C by a factor of two at noon. Inclusion of glyoxal-SOA with O/C of 1.5 brings O/C predictions within measurement uncertainty, suggesting that field observations can be reconciled on reasonable time scales using laboratory-based empirical relationships for aqueous chemistry.

  19. Impact of fog processing on water soluble organic aerosols.

    Science.gov (United States)

    Tripathi, S. N.; Chakraborty, A.; Gupta, T.

    2017-12-01

    Fog is a natural meteorological phenomenon that occurs all around the world, and contains a substantial quantity of liquid water. Fog is generally seen as a natural cleansing agent but can also form secondary organic aerosols (SOA) via aqueous processing of ambient organics. Few field studies have reported elevated O/C ratio and SOA mass during or after fog events. However, mechanism behind aqueous SOA formation and its contribution to total organic aerosols (OA) still remains unclear. In this study we have tried to explore the impact of fog/aqueous processing on the characteristics of water soluble organic aerosols (WSOC), which to our knowledge has not been studied before. To assess this, both online (using HR-ToF-AMS) and offline (using a medium volume PM2.5 sampler and quartz filter) aerosol sampling were carried out at Kanpur, India from 15 December 2014 - 10 February 2015. Further, offline analysis of the aqueous extracts of the collected filters were carried out by AMS to characterize the water soluble OA (WSOA). Several (17) fog events occurred during the campaign and high concentrations of OA (151 ± 68 µg/m3) and WSOA (47 ± 19 µg/m3) were observed. WSOA/OA ratios were similar during fog (0.36 ± 0.14) and nofog (0.34 ± 0.15) periods. WSOA concentrations were also similar (slightly higher) during foggy (49 ± 18 µg/m3) and non-foggy periods (46 ± 20 µg/m3), in spite of fog scavenging. However, WSOA was more oxidized during foggy period (average O/C = 0.81) than non foggy periods (average O/C = 0.70). Like WSOA, OA was also more oxidized during foggy periods (average O/C = 0.64) than non foggy periods (average O/C = 0.53). During fog, WSOA to WIOA (water insoluble OA) ratios were higher (0.65 ± 0.16) compared to non foggy periods (0.56 ± 0.15). These observations clearly showed that WSOA become more dominant and processed during fog events, possibly due to the presence of fog droplets. This study highlights that fog processing of soluble organics

  20. Aged organic aerosol in the Eastern Mediterranean: the Finokalia Aerosol Measurement Experiment – 2008

    Directory of Open Access Journals (Sweden)

    L. Hildebrandt

    2010-05-01

    Full Text Available Aged organic aerosol (OA was measured at a remote coastal site on the island of Crete, Greece during the Finokalia Aerosol Measurement Experiment-2008 (FAME-2008, which was part of the EUCAARI intensive campaign of May 2008. The site at Finokalia is influenced by air masses from different source regions, including long-range transport of pollution from continental Europe. A quadrupole aerosol mass spectrometer (Q-AMS was employed to measure the size-resolved chemical composition of non-refractory submicron aerosol (NR-PM1, and to estimate the extent of oxidation of the organic aerosol. Factor analysis was used to gain insights into the processes and sources affecting the OA composition. The particles were internally mixed and liquid. The largest fraction of the dry NR-PM1 sampled was ammonium sulfate and ammonium bisulfate, followed by organics and a small amount of nitrate. The variability in OA composition could be explained with two factors of oxygenated organic aerosol (OOA with differing extents of oxidation but similar volatility. Hydrocarbon-like organic aerosol (HOA was not detected. There was no statistically significant diurnal variation in the bulk composition of NR-PM1 such as total sulfate or total organic aerosol concentrations. However, the OA composition exhibited statistically significant diurnal variation with more oxidized OA in the afternoon. The organic aerosol was highly oxidized, regardless of the source region. Total OA concentrations also varied little with source region, suggesting that local sources had only a small effect on OA concentrations measured at Finokalia. The aerosol was transported for about one day before arriving at the site, corresponding to an OH exposure of approximately 4×1011 molecules cm−3 s. The constant extent of oxidation suggests that atmospheric aging results in a highly oxidized OA at these OH exposures, regardless of the aerosol source.

  1. Wintertime aerosol chemical composition and source apportionment of the organic fraction in the metropolitan area of Paris

    Directory of Open Access Journals (Sweden)

    M. Crippa

    2013-01-01

    Full Text Available The effect of a post-industrial megacity on local and regional air quality was assessed via a month-long field measurement campaign in the Paris metropolitan area during winter 2010. Here we present source apportionment results from three aerosol mass spectrometers and two aethalometers deployed at three measurement stations within the Paris region. Submicron aerosol composition is dominated by the organic fraction (30–36% and nitrate (28–29%, with lower contributions from sulfate (14–16%, ammonium (12–14% and black carbon (7–13%.

    Organic source apportionment was performed using positive matrix factorization, resulting in a set of organic factors corresponding both to primary emission sources and secondary production. The dominant primary sources are traffic (11–15% of organic mass, biomass burning (13–15% and cooking (up to 35% during meal hours. Secondary organic aerosol contributes more than 50% to the total organic mass and includes a highly oxidized factor from indeterminate and/or diverse sources and a less oxidized factor related to wood burning emissions. Black carbon was apportioned to traffic and wood burning sources using a model based on wavelength-dependent light absorption of these two combustion sources. The time series of organic and black carbon factors from related sources were strongly correlated. The similarities in aerosol composition, total mass and temporal variation between the three sites suggest that particulate pollution in Paris is dominated by regional factors, and that the emissions from Paris itself have a relatively low impact on its surroundings.

  2. Atmospheric hydrogen peroxide and organic hydroperoxides during PRIDE-PRD'06, China: their concentration, formation mechanism and contribution to secondary aerosols

    Science.gov (United States)

    Hua, W.; Chen, Z. M.; Jie, C. Y.; Kondo, Y.; Hofzumahaus, A.; Takegawa, N.; Chang, C. C.; Lu, K. D.; Miyazaki, Y.; Kita, K.; Wang, H. L.; Zhang, Y. H.; Hu, M.

    2008-11-01

    in samples of rainwater collected in a heavy shower on 25 July when a typhoon passed through, indicating that a considerable mixing ratio of hydroperoxides, particularly MHP, resided above the boundary layer, which might be transported on a regional scale and further influence the redistribution of HOx and ROx radicals. It was found that hydroperoxides, in particular H2O2, play an important role in the formation of secondary sulfate in the aerosol phase, where the heterogeneous reaction might contribute substantially. A negative correlation between hydroperoxides and water-soluble organic compounds (WSOC), a considerable fraction of the secondary organic aerosol (SOA), was observed, possibly providing field evidence for the importance of hydroperoxides in the formation of SOA found in previous laboratory studies. We suggest that hydroperoxides act as an important link between sulfate and organic aerosols, which needs further study and should be considered in current atmospheric models.

  3. Global distribution and climate forcing of marine organic aerosol: 1. Model improvements and evaluation

    Directory of Open Access Journals (Sweden)

    N. Meskhidze

    2011-11-01

    Full Text Available Marine organic aerosol emissions have been implemented and evaluated within the National Center of Atmospheric Research (NCAR's Community Atmosphere Model (CAM5 with the Pacific Northwest National Laboratory's 7-mode Modal Aerosol Module (MAM-7. Emissions of marine primary organic aerosols (POA, phytoplankton-produced isoprene- and monoterpenes-derived secondary organic aerosols (SOA and methane sulfonate (MS are shown to affect surface concentrations of organic aerosols in remote marine regions. Global emissions of submicron marine POA is estimated to be 7.9 and 9.4 Tg yr−1, for the Gantt et al. (2011 and Vignati et al. (2010 emission parameterizations, respectively. Marine sources of SOA and particulate MS (containing both sulfur and carbon atoms contribute an additional 0.2 and 5.1 Tg yr−1, respectively. Widespread areas over productive waters of the Northern Atlantic, Northern Pacific, and the Southern Ocean show marine-source submicron organic aerosol surface concentrations of 100 ng m−3, with values up to 400 ng m−3 over biologically productive areas. Comparison of long-term surface observations of water insoluble organic matter (WIOM with POA concentrations from the two emission parameterizations shows that despite revealed discrepancies (often more than a factor of 2, both Gantt et al. (2011 and Vignati et al. (2010 formulations are able to capture the magnitude of marine organic aerosol concentrations, with the Gantt et al. (2011 parameterization attaining better seasonality. Model simulations show that the mixing state of the marine POA can impact the surface number concentration of cloud condensation nuclei (CCN. The largest increases (up to 20% in CCN (at a supersaturation (S of 0.2% number concentration are obtained over biologically productive ocean waters when marine organic aerosol is assumed to be externally mixed with sea-salt. Assuming

  4. Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

    Directory of Open Access Journals (Sweden)

    E. A. Marais

    2016-02-01

    Full Text Available Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA, but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS and ground-based (SOAS observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx  ≡  NO + NO2 over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2 react significantly with both NO (high-NOx pathway and HO2 (low-NOx pathway, leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA and formaldehyde (a product of isoprene oxidation. Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA from the low-NOx pathway and glyoxal (28 % from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation, but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume. The US Environmental Protection Agency (EPA projects 2013–2025 decreases in

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

    Directory of Open Access Journals (Sweden)

    X. Pan

    2009-06-01

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

  6. Studying volatility from composition, dilution, and heating measurements of secondary organic aerosols formed during α-pinene ozonolysis

    Science.gov (United States)

    Sato, Kei; Fujitani, Yuji; Inomata, Satoshi; Morino, Yu; Tanabe, Kiyoshi; Ramasamy, Sathiyamurthi; Hikida, Toshihide; Shimono, Akio; Takami, Akinori; Fushimi, Akihiro; Kondo, Yoshinori; Imamura, Takashi; Tanimoto, Hiroshi; Sugata, Seiji

    2018-04-01

    Traditional yield curve analysis shows that semi-volatile organic compounds are a major component of secondary organic aerosols (SOAs). We investigated the volatility distribution of SOAs from α-pinene ozonolysis using positive electrospray ionization mass analysis and dilution- and heat-induced evaporation measurements. Laboratory chamber experiments were conducted on α-pinene ozonolysis, in the presence and absence of OH scavengers. Among these, we identified not only semi-volatile products, but also less volatile highly oxygenated molecules (HOMs) and dimers. Ozonolysis products were further exposed to OH radicals to check the effects of photochemical aging. HOMs were also formed during OH-initiated photochemical aging. Most HOMs that formed from ozonolysis and photochemical aging had 10 or fewer carbons. SOA particle evaporation after instantaneous dilution was measured at fraction remaining of SOAs decreased with time and the equilibration timescale was determined to be 24-46 min for SOA evaporation. The experimental results of the equilibration timescale can be explained when the mass accommodation coefficient is assumed to be 0.1, suggesting that the existence of low-volatility materials in SOAs, kinetic inhibition, or some combined effect may affect the equilibration timescale measured in this study.

  7. Droplet activation properties of organic aerosols observed at an urban site during CalNex-LA

    Energy Technology Data Exchange (ETDEWEB)

    Mei, Fan [Brookhaven National Laboratory, Upton New York USA; Pacific Northwest National Laboratory, Richland Washington USA; Hayes, Patrick L. [Cooperative Institute for Research in Environmental Sciences, Boulder Colorado USA; Department of Chemistry and Biochemistry, University of Colorado, Boulder Colorado USA; Ortega, Amber [Cooperative Institute for Research in Environmental Sciences, Boulder Colorado USA; Department of Chemistry and Biochemistry, University of Colorado, Boulder Colorado USA; Taylor, Jonathan W. [School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Manchester UK; Allan, James D. [School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Manchester UK; National Centre for Atmospheric Science, University of Manchester, Manchester UK; Gilman, Jessica [NOAA Earth System Research Laboratory, Boulder Colorado USA; Kuster, William [NOAA Earth System Research Laboratory, Boulder Colorado USA; de Gouw, Joost [NOAA Earth System Research Laboratory, Boulder Colorado USA; Jimenez, Jose L. [Cooperative Institute for Research in Environmental Sciences, Boulder Colorado USA; Department of Chemistry and Biochemistry, University of Colorado, Boulder Colorado USA; Wang, Jian [Brookhaven National Laboratory, Upton New York USA

    2013-04-11

    Size-resolved cloud condensation nuclei (CCN) spectra and aerosol chemical composition were characterized at an urban supersite in Pasadena, California, from 15 May to 4 June 2010, during the CalNex campaign. The derived hygroscopicity (κCCN) of CCN-active particles with diameter between 97 and 165 nm ranged from 0.05 to 0.4. Diurnal variation showed a slight decrease of κCCN from 8:00 to 16:00 (from 0.24 to 0.20), which is attributed to increasing organics volume fraction resulted from secondary organic aerosol (SOA) formation. The derived hygroscopicity distribution and maximum activated fraction of the size selected particles were examined as functions of photochemical age. The result indicates that condensation of secondary species (e.g., SOA and sulfate) quickly converted hydrophobic particles to hydrophilic ones, and during daytime, nearly every particle became a CCN at ~0.4% in just a few hours. Based on κCCN and aerosol chemical composition, the organic hygroscopicity (κorg) was derived, and ranged from 0.05 to 0.23 with an average value of 0.13, consistent with the results from earlier studies. The derived κorg generally increased with the organic oxidation level, and most of the variation in κorg could be explained by the variation of the organic O : C atomic ratio alone. The least squares fit of the data yielded κorg = (0.83 ± 0.06) × (O:C) + (-0.19 ± 0.02). Compared to previous results based on CCN measurements of laboratory generated aerosols, κorg derived from measurements during the CalNex campaign exhibited stronger increase with O : C atomic ratio and therefore substantially higher values for organics with average O : C greater than 0.5.

  8. Secondary aerosol formation from stress-induced biogenic emissions and possible climate feedbacks

    Directory of Open Access Journals (Sweden)

    Th. F. Mentel

    2013-09-01

    Full Text Available Atmospheric aerosols impact climate by scattering and absorbing solar radiation and by acting as ice and cloud condensation nuclei. Biogenic secondary organic aerosols (BSOAs comprise an important component of atmospheric aerosols. Biogenic volatile organic compounds (BVOCs emitted by vegetation are the source of BSOAs. Pathogens and insect attacks, heat waves and droughts can induce stress to plants that may impact their BVOC emissions, and hence the yield and type of formed BSOAs, and possibly their climatic effects. This raises questions of whether stress-induced changes in BSOA formation may attenuate or amplify effects of climate change. In this study we assess the potential impact of stress-induced BVOC emissions on BSOA formation for tree species typical for mixed deciduous and Boreal Eurasian forests. We studied the photochemical BSOA formation for plants infested by aphids in a laboratory setup under well-controlled conditions and applied in addition heat and drought stress. The results indicate that stress conditions substantially modify BSOA formation and yield. Stress-induced emissions of sesquiterpenes, methyl salicylate, and C17-BVOCs increase BSOA yields. Mixtures including these compounds exhibit BSOA yields between 17 and 33%, significantly higher than mixtures containing mainly monoterpenes (4–6% yield. Green leaf volatiles suppress SOA formation, presumably by scavenging OH, similar to isoprene. By classifying emission types, stressors and BSOA formation potential, we discuss possible climatic feedbacks regarding aerosol effects. We conclude that stress situations for plants due to climate change should be considered in climate–vegetation feedback mechanisms.

  9. Seasonal and spatial variability of the organic matter-to-organic carbon mass ratios in Chinese urban organic aerosols and a first report of high correlations between aerosol oxalic acid and zinc

    Science.gov (United States)

    Xing, L.; Fu, T.-M.; Cao, J. J.; Lee, S. C.; Wang, G. H.; Ho, K. F.; Cheng, M.-C.; You, C.-F.; Wang, T. J.

    2013-01-01

    We calculated the organic matter to organic carbon mass ratios (OM/OC mass ratios) in PM2.5 collected from 14 Chinese cities during summer and winter of 2003 and analyzed the causes for their seasonal and spatial variability. The OM/OC mass ratios were calculated two ways. Using a mass balance method, the calculated OM/OC mass ratios averaged 1.92 ± 0.39 yr-round, with no significant seasonal or spatial variation. The second calculation was based on chemical species analyses of the organic compounds extracted from the PM2.5 samples using dichloromethane/methanol and water. The calculated OM/OC mass ratio in summer was relatively high (1.75 ± 0.13) and spatially-invariant, due to vigorous photochemistry and secondary OA production throughout the country. The calculated OM/OC mass ratio in winter (1.59 ± 0.18) was significantly lower than that in summer, with lower values in northern cities (1.51 ± 0.07) than in southern cities (1.65 ± 0.15). This likely reflects the wider usage of coal for heating purposes in northern China in winter, in contrast to the larger contributions from biofuel and biomass burning in southern China in winter. On average, organic matters constituted 36% and 34% of Chinese urban PM2.5 mass in summer and winter, respectively. We reported, for the first time, high correlations between Zn and oxalic acid in Chinese urban aerosols in summer. This is consistent with the formation of stable Zn oxalate complex in the aerosol phase previously proposed by Furukawa and Takahashi (2011). We found that many other dicarboxylic acids were also highly correlated with Zn in the summer Chinese urban aerosol samples, suggesting that they may also form stable organic complexes with Zn. Such formation may have profound implications for the atmospheric abundance and hygroscopic property of aerosol dicarboxylic acids.

  10. MATRIX-VBS (v1.0): Implementing an Evolving Organic Aerosol Volatility in an Aerosol Microphysics Model

    Science.gov (United States)

    Gao, Chloe Y.; Tsigaridis, Kostas; Bauer, Susanne E.

    2017-01-01

    The gas-particle partitioning and chemical aging of semi-volatile organic aerosol are presented in a newly developed box model scheme, where its effect on the growth, composition, and mixing state of particles is examined. The volatility-basis set (VBS) framework is implemented into the aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state), which resolves mass and number aerosol concentrations and in multiple mixing-state classes. The new scheme, MATRIX-VBS, has the potential to significantly advance the representation of organic aerosols in Earth system models by improving upon the conventional representation as non-volatile particulate organic matter, often also with an assumed fixed size distribution. We present results from idealized cases representing Beijing, Mexico City, a Finnish forest, and a southeastern US forest, and investigate the evolution of mass concentrations and volatility distributions for organic species across the gas and particle phases, as well as assessing their mixing state among aerosol populations. Emitted semi-volatile primary organic aerosols evaporate almost completely in the intermediate-volatility range, while they remain in the particle phase in the low-volatility range. Their volatility distribution at any point in time depends on the applied emission factors, oxidation by OH radicals, and temperature. We also compare against parallel simulations with the original scheme, which represented only the particulate and non-volatile component of the organic aerosol, examining how differently the condensed-phase organic matter is distributed across the mixing states in the model. The results demonstrate the importance of representing organic aerosol as a semi-volatile aerosol, and explicitly calculating the partitioning of organic species between the gas and particulate phases.

  11. Org Areo Boreal Forest Sources, compositions and properties of newly formed and regional organic aerosol in a boreal forest during the Biogenic Aerosol: Effects on Clouds and Climate Campaign

    Energy Technology Data Exchange (ETDEWEB)

    Thornton, Joel A [Univ. of Washington, Seattle, WA (United States)

    2017-12-01

    The major goals of this project were to make unique measurements, as part of the DOE sponsored Biogenic Aerosol Effects on Clouds and Climate (BAECC) campaign, of the volatility and molecular composition of organic aerosol, as well as gas-phase concentrations of oxygenated organic compounds that interact and affect organic aerosol. In addition, we aimed to conduct a similar set of measurements as part of a collaborative set of environmental simulation chamber experiments at PNNL, the aim of which was to simulate the atmospheric oxidation of key biogenic volatile organic compounds (BVOC) and study the associated formation and evolution of secondary organic aerosol (SOA). The target BVOC were a set of monoterpenes, isoprene, and related intermediates such as IEPOX. The ultimate goal of such measurements are to develop a more detailed mechanistic understanding of the sensitivity of SOA mass formation and lifetime to precursor and environmental conditions. Molecular composition and direct volatility measurements provide robust tracers of chemical processing and properties. As such, meeting these goals will allow for stronger constraints on the types of processes and their fundamental descriptions needed to simulate aerosol particle number and size, and cloud nucleating ability in regional and global earth system models.

  12. Can Condensing Organic Aerosols Lead to Less Cloud Particles?

    Science.gov (United States)

    Gao, C. Y.; Tsigaridis, K.; Bauer, S.

    2017-12-01

    We examined the impact of condensing organic aerosols on activated cloud number concentration in a new aerosol microphysics box model, MATRIX-VBS. The model includes the volatility-basis set (VBS) framework in an aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state) that resolves aerosol mass and number concentrations and aerosol mixing state. Preliminary results show that by including the condensation of organic aerosols, the new model (MATRIX-VBS) has less activated particles compared to the original model (MATRIX), which treats organic aerosols as non-volatile. Parameters such as aerosol chemical composition, mass and number concentrations, and particle sizes which affect activated cloud number concentration are thoroughly evaluated via a suite of Monte-Carlo simulations. The Monte-Carlo simulations also provide information on which climate-relevant parameters play a critical role in the aerosol evolution in the atmosphere. This study also helps simplifying the newly developed box model which will soon be implemented in the global model GISS ModelE as a module.

  13. Effects of diesel engine exhaust origin secondary organic aerosols on novel object recognition ability and maternal behavior in BALB/c mice.

    Science.gov (United States)

    Win-Shwe, Tin-Tin; Fujitani, Yuji; Kyi-Tha-Thu, Chaw; Furuyama, Akiko; Michikawa, Takehiro; Tsukahara, Shinji; Nitta, Hiroshi; Hirano, Seishiro

    2014-10-30

    Epidemiological studies have reported an increased risk of cardiopulmonary and lung cancer mortality associated with increasing exposure to air pollution. Ambient particulate matter consists of primary particles emitted directly from diesel engine vehicles and secondary organic aerosols (SOAs) are formed by oxidative reaction of the ultrafine particle components of diesel exhaust (DE) in the atmosphere. However, little is known about the relationship between exposure to SOA and central nervous system functions. Recently, we have reported that an acute single intranasal instillation of SOA may induce inflammatory response in lung, but not in brain of adult mice. To clarify the whole body exposure effects of SOA on central nervous system functions, we first created inhalation chambers for diesel exhaust origin secondary organic aerosols (DE-SOAs) produced by oxidation of diesel exhaust particles caused by adding ozone. Male BALB/c mice were exposed to clean air (control), DE and DE-SOA in inhalation chambers for one or three months (5 h/day, 5 days/week) and were examined for memory function using a novel object recognition test and for memory function-related gene expressions in the hippocampus by real-time RT-PCR. Moreover, female mice exposed to DE-SOA for one month were mated and maternal behaviors and the related gene expressions in the hypothalamus examined. Novel object recognition ability and N-methyl-D-aspartate (NMDA) receptor expression in the hippocampus were affected in male mice exposed to DE-SOA. Furthermore, a tendency to decrease maternal performance and significantly decreased expression levels of estrogen receptor (ER)-α, and oxytocin receptor were found in DE-SOA exposed dams compared with the control. This is the first study of this type and our results suggest that the constituents of DE-SOA may be associated with memory function and maternal performance based on the impaired gene expressions in the hippocampus and hypothalamus, respectively.

  14. Effects of Diesel Engine Exhaust Origin Secondary Organic Aerosols on Novel Object Recognition Ability and Maternal Behavior in BALB/C Mice

    Directory of Open Access Journals (Sweden)

    Tin-Tin Win-Shwe

    2014-10-01

    Full Text Available Epidemiological studies have reported an increased risk of cardiopulmonary and lung cancer mortality associated with increasing exposure to air pollution. Ambient particulate matter consists of primary particles emitted directly from diesel engine vehicles and secondary organic aerosols (SOAs are formed by oxidative reaction of the ultrafine particle components of diesel exhaust (DE in the atmosphere. However, little is known about the relationship between exposure to SOA and central nervous system functions. Recently, we have reported that an acute single intranasal instillation of SOA may induce inflammatory response in lung, but not in brain of adult mice. To clarify the whole body exposure effects of SOA on central nervous system functions, we first created inhalation chambers for diesel exhaust origin secondary organic aerosols (DE-SOAs produced by oxidation of diesel exhaust particles caused by adding ozone. Male BALB/c mice were exposed to clean air (control, DE and DE-SOA in inhalation chambers for one or three months (5 h/day, 5 days/week and were examined for memory function using a novel object recognition test and for memory function-related gene expressions in the hippocampus by real-time RT-PCR. Moreover, female mice exposed to DE-SOA for one month were mated and maternal behaviors and the related gene expressions in the hypothalamus examined. Novel object recognition ability and N-methyl-D-aspartate (NMDA receptor expression in the hippocampus were affected in male mice exposed to DE-SOA. Furthermore, a tendency to decrease maternal performance and significantly decreased expression levels of estrogen receptor (ER-a, and oxytocin receptor were found in DE-SOA exposed dams compared with the control. This is the first study of this type and our results suggest that the constituents of DE-SOA may be associated with memory function and maternal performance based on the impaired gene expressions in the hippocampus and hypothalamus

  15. Functional group composition of ambient and source organic aerosols determined by tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Dron, J.; El Haddad, I.; Temime-Roussel, B.; Wortham, H.; Marchand, N. [Univ Aix Marseille, CNRS, Lab Chim Provence, Equipe Instrumentat and React Atmospher, UMR 6264, F-13331 Marseille 3 (France); Jaffrezo, J.L. [Univ Grenoble 1, CNRS, UMR 5183, Lab Glaciol and Geophys Environm, F-38402 St Martin Dheres (France)

    2010-07-01

    The functional group composition of various organic aerosols (OA) is investigated using a recently developed analytical approach based on atmospheric pressure chemical ionisation-tandem mass spectrometry (APCIMS/MS). The determinations of three functional groups contents are performed quantitatively by neutral loss (carboxylic and carbonyl groups, R-COOH and R-CO-R' respectively) and precursor ion (nitro groups, R-NO{sub 2}) scanning modes of a tandem mass spectrometer. Major organic aerosol sources are studied: vehicular emission and wood combustion for primary aerosol sources; and a secondary organic aerosol (SOA) produced through photooxidation of o-xylene. The results reveal significant differences in the functional group contents of these source aerosols. The laboratory generated SOA is dominated by carbonyls while carboxylics are preponderate in the wood combustion particles. On the other hand, vehicular emissions are characterised by a strong nitro content. The total amount of the three functional groups accounts for 1.7% (vehicular) to 13.5% (o-xylene photooxidation) of the organic carbon. Diagnostic functional group ratios are then used to tentatively discriminate sources of particles collected in an urban background environment located in an Alpine valley (Chamonix, France) during a strong winter pollution event. The three functional groups under study account for a total functionalization rate of 2.2 to 3.8% of the organic carbon in this ambient aerosol, which is also dominated by carboxylic moieties. In this particular case study of a deep alpine valley during winter, we show that the nitro- and carbonyl-to-carboxylic diagnostic ratios can be a useful tool to discriminate sources. In these conditions, the total OA concentrations are highly dominated by wood combustion OA. This result is confirmed by an organic markers source apportionment approach which assess a wood burning organic carbon contribution of about 60%. Finally, examples of functional

  16. Functional group composition of ambient and source organic aerosols determined by tandem mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. Dron

    2010-08-01

    Full Text Available The functional group composition of various organic aerosols (OA is investigated using a recently developed analytical approach based on atmospheric pressure chemical ionisation-tandem mass spectrometry (APCI-MS/MS. The determinations of three functional groups contents are performed quantitatively by neutral loss (carboxylic and carbonyl groups, R-COOH and R-CO-R´ respectively and precursor ion (nitro groups, R-NO2 scanning modes of a tandem mass spectrometer. Major organic aerosol sources are studied: vehicular emission and wood combustion for primary aerosol sources; and a secondary organic aerosol (SOA produced through photooxidation of o-xylene. The results reveal significant differences in the functional group contents of these source aerosols. The laboratory generated SOA is dominated by carbonyls while carboxylics are preponderate in the wood combustion particles. On the other hand, vehicular emissions are characterised by a strong nitro content. The total amount of the three functional groups accounts for 1.7% (vehicular to 13.5% (o-xylene photooxidation of the organic carbon. Diagnostic functional group ratios are then used to tentatively discriminate sources of particles collected in an urban background environment located in an Alpine valley (Chamonix, France during a strong winter pollution event. The three functional groups under study account for a total functionalisation rate of 2.2 to 3.8% of the organic carbon in this ambient aerosol, which is also dominated by carboxylic moieties. In this particular case study of a deep alpine valley during winter, we show that the nitro- and carbonyl-to-carboxylic diagnostic ratios can be a useful tool to discriminate sources. In these conditions, the total OA concentrations are highly dominated by wood combustion OA. This result is confirmed by an organic markers source apportionment approach which assess a wood burning organic carbon contribution of about 60

  17. Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston

    Directory of Open Access Journals (Sweden)

    E. C. Wood

    2010-09-01

    Full Text Available 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 better understood, we investigate the correlation of odd-oxygen ([Ox]≡[O3]+[NO2] and the oxygenated component of organic aerosol (OOA, which is interpreted as a surrogate for SOA. OOA and Ox measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 μg m−3/ppm (STP in Houston during time periods affected by large petrochemical plant emissions to as high as 160 μg m−3/ppm in Mexico City, where typical values were near 120 μg m−3/ppm. On several days in Mexico City, the [OOA]/[Ox] ratio decreased by a factor of ~2 between 08:00 and 13:00 local time. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the Ox production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[Ox] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed

  18. Temperature effect on physical and chemical properties of secondary organic aerosol from m-xylene photooxidation

    Directory of Open Access Journals (Sweden)

    D. R. Cocker III

    2010-04-01

    Full Text Available The chemical and physical differences of secondary organic aerosol (SOA formed at select isothermal temperatures (278 K, 300 K, and 313 K are explored with respect to density, particle volatility, particle hygroscopicity, and elemental chemical composition. A transition point in SOA density, volatility, hygroscopicity and elemental composition is observed near 290–292 K as SOA within an environmental chamber is heated from 278 K to 313 K, indicating the presence of a thermally labile compound. No such transition points are observed for SOA produced at 313 K or 300 K and subsequently cooled to 278 K. The SOA formed at the lowest temperatures (278 K is more than double the SOA formed at 313 K. SOA formed at 278 K is less hydrophilic and oxygenated while more volatile and dense than SOA formed at 300 K or 313 K. The properties of SOA formed at 300 K and 313 K when reduced to 278 K did not match the properties of SOA initially formed at 278 K. This study demonstrates that it is insufficient to utilize the enthalpy of vaporization when predicting SOA temperature dependence.

  19. Simulation of the interannual variations of biogenic emissions of volatile organic compounds in China: Impacts on tropospheric ozone and secondary organic aerosol

    Science.gov (United States)

    Fu, Y.; Liao, H.

    2012-12-01

    We use the MEGAN (Model of emissions of Gases and Aerosols from Nature) module embedded within the global three-dimensional Goddard Earth Observing System chemical transport model (GEOS-Chem) to simulate the interannual variations in biogenic volatile organic compound (BVOC) emissions and concentrations of ozone and secondary organic aerosols (SOA) in China over years 2001-2006. To have better representation of biogenic emissions, we have updated in the model the land cover and leaf area index in China using Moderate Resolution Imaging Spectroradiometer (MODIS) satellite measurements, and we have developed a new classification of vegetation with 21 plant functional types. Estimated annual BVOC emission in China averaged over 2001-2006 is 18.85 Tg C yr-1, in which emissions of isoprene, monoterpenes, and other reactive volatile organic compounds account for 50.9%, 15.0%, and 34.1%, respectively. The simulated BVOC emissions in China have large interannual variations. The values of regionally averaged absolute percent departure from the mean (APDM) of isoprene emissions are in the range of 21-42% in January and 15-28% in July. The APDM values of monoterpene emissions are 14-32% in January and 10-21% in July, which are generally smaller than those of isoprene emissions. Model results indicate that the interannual variations in isoprene emissions are more dependent on variations in meteorological fields, whereas the interannual variations in monoterpene emissions are more sensitive to changes in vegetation parameters. With fixed anthropogenic emissions, as a result of the variations in both meteorological parameters and vegetation, simulated O3 concentrations show interannual variations of 0.8-5 ppbv (or largest APDM values of 4-15%), and simulated SOA shows APDM values of 5-15% in southwestern China in January as well as 10-25% in southeastern and 20-35% in northeastern China in July. On a regional mean basis, the interannual variations in BVOCs alone can lead to 2

  20. Elemental analysis of chamber organic aerosol using an aerodyne high-resolution aerosol mass spectrometer

    Directory of Open Access Journals (Sweden)

    P. S. Chhabra

    2010-05-01

    Full Text Available The elemental composition of laboratory chamber secondary organic aerosol (SOA from glyoxal uptake, α-pinene ozonolysis, isoprene photooxidation, single-ring aromatic photooxidation, and naphthalene photooxidation is evaluated using Aerodyne high-resolution time-of-flight mass spectrometer data. SOA O/C ratios range from 1.13 for glyoxal uptake experiments to 0.30–0.43 for α-pinene ozonolysis. The elemental composition of α-pinene and naphthalene SOA is also confirmed by offline mass spectrometry. The fraction of organic signal at m/z 44 is generally a good measure of SOA oxygenation for α-pinene/O3, isoprene/high-NOx, and naphthalene SOA systems. The agreement between measured and estimated O/C ratios tends to get closer as the fraction of organic signal at m/z 44 increases. This is in contrast to the glyoxal uptake system, in which m/z 44 substantially underpredicts O/C. Although chamber SOA has generally been considered less oxygenated than ambient SOA, single-ring aromatic- and naphthalene-derived SOA can reach O/C ratios upward of 0.7, well within the range of ambient PMF component OOA, though still not as high as some ambient measurements. The spectra of aromatic and isoprene-high-NOx SOA resemble that of OOA, but the spectrum of glyoxal uptake does not resemble that of any ambient organic aerosol PMF component.

  1. Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols.

    Science.gov (United States)

    McNeill, V Faye

    2015-02-03

    Over the past decade, it has become clear that aqueous chemical processes occurring in cloud droplets and wet atmospheric particles are an important source of organic atmospheric particulate matter. Reactions of water-soluble volatile (or semivolatile) organic gases (VOCs or SVOCs) in these aqueous media lead to the formation of highly oxidized organic particulate matter (secondary organic aerosol; SOA) and key tracer species, such as organosulfates. These processes are often driven by a combination of anthropogenic and biogenic emissions, and therefore their accurate representation in models is important for effective air quality management. Despite considerable progress, mechanistic understanding of some key aqueous processes is still lacking, and these pathways are incompletely represented in 3D atmospheric chemistry and air quality models. In this article, the concepts, historical context, and current state of the science of aqueous pathways of SOA formation are discussed.

  2. Gas phase emissions from cooking processes and their secondary aerosol production potential

    Science.gov (United States)

    Klein, Felix; Platt, Stephen; Bruns, Emily; Termime-roussel, Brice; Detournay, Anais; Mohr, Claudia; Crippa, Monica; Slowik, Jay; Marchand, Nicolas; Baltensperger, Urs; Prevot, Andre; El Haddad, Imad

    2014-05-01

    Long before the industrial evolution and the era of fossil fuels, high concentrations of aerosol particles were alluded to in heavily populated areas, including ancient Rome and medieval London. Recent radiocarbon measurements (14C) conducted in modern megacities came as a surprise: carbonaceous aerosol (mainly organic aerosol, OA), a predominant fraction of particulate matter (PM), remains overwhelmingly non-fossil despite extensive fossil fuel combustion. Such particles are directly emitted (primary OA, POA) or formed in-situ in the atmosphere (secondary OA, SOA) via photochemical reactions of volatile organic compounds (VOCs). Urban levels of non-fossil OA greatly exceed the levels measured in pristine environments strongly impacted by biogenic emissions, suggesting a contribution from unidentified anthropogenic non-fossil sources to urban OA. Positive matrix factorization (PMF) techniques applied to ambient aerosol mass spectrometer (AMS, Aerodyne) data identify primary cooking emissions (COA) as one of the main sources of primary non-fossil OA in major cities like London (Allan et al., 2010), New York (Sun et al., 2011) and Beijing (Huang et al., 2010). Cooking processes can also emit VOCs that can act as SOA precursors, potentially explaining in part the high levels of oxygenated OA (OOA) identified by the AMS in urban areas. However, at present, the chemical nature of these VOCs and their secondary aerosol production potential (SAPP) remain virtually unknown. The approach adopted here involves laboratory quantification of PM and VOC emission factors from the main primary COA emitting processes and their SAPP. Primary emissions from deep-fat frying, vegetable boiling, vegetable frying and meat cooking for different oils, meats and vegetables were analysed under controlled conditions after ~100 times dilution. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a high resolution proton transfer time-of-flight mass spectrometer (PTR

  3. Elemental composition and oxidation of chamber organic aerosol

    Directory of Open Access Journals (Sweden)

    P. S. Chhabra

    2011-09-01

    Full Text Available Recently, graphical representations of aerosol mass spectrometer (AMS spectra and elemental composition have been developed to explain the oxidative and aging processes of secondary organic aerosol (SOA. It has been shown previously that oxygenated organic aerosol (OOA components from ambient and laboratory data fall within a triangular region in the f44 vs. f43 space, where f44 and f43 are the ratios of the organic signal at m/z 44 and 43 to the total organic signal in AMS spectra, respectively; we refer to this graphical representation as the "triangle plot." Alternatively, the Van Krevelen diagram has been used to describe the evolution of functional groups in SOA. In this study we investigate the variability of SOA formed in chamber experiments from twelve different precursors in both "triangle plot" and Van Krevelen domains. Spectral and elemental data from the high-resolution Aerodyne aerosol mass spectrometer are compared to offline species identification analysis and FTIR filter analysis to better understand the changes in functional and elemental composition inherent in SOA formation and aging. We find that SOA formed under high- and low-NOx conditions occupy similar areas in the "triangle plot" and Van Krevelen diagram and that SOA generated from already oxidized precursors allows for the exploration of areas higher on the "triangle plot" not easily accessible with non-oxidized precursors. As SOA ages, it migrates toward the top of the triangle along a path largely dependent on the precursor identity, which suggests increasing organic acid content and decreasing mass spectral variability. The most oxidized SOA come from the photooxidation of methoxyphenol precursors which yielded SOA O/C ratios near unity. α-pinene ozonolysis and naphthalene photooxidation SOA systems have had the highest degree of mass closure in previous chemical characterization studies and also show the

  4. Modelling organic particles in the atmosphere

    International Nuclear Information System (INIS)

    Couvidat, Florian

    2012-01-01

    Organic aerosol formation in the atmosphere is investigated via the development of a new model named H 2 O (Hydrophilic/Hydrophobic Organics). First, a parameterization is developed to take into account secondary organic aerosol formation from isoprene oxidation. It takes into account the effect of nitrogen oxides on organic aerosol formation and the hydrophilic properties of the aerosols. This parameterization is then implemented in H 2 O along with some other developments and the results of the model are compared to organic carbon measurements over Europe. Model performance is greatly improved by taking into account emissions of primary semi-volatile compounds, which can form secondary organic aerosols after oxidation or can condense when temperature decreases. If those emissions are not taken into account, a significant underestimation of organic aerosol concentrations occurs in winter. The formation of organic aerosols over an urban area was also studied by simulating organic aerosols concentration over the Paris area during the summer campaign of Megapoli (July 2009). H 2 O gives satisfactory results over the Paris area, although a peak of organic aerosol concentrations from traffic, which does not appear in the measurements, appears in the model simulation during rush hours. It could be due to an underestimation of the volatility of organic aerosols. It is also possible that primary and secondary organic compounds do not mix well together and that primary semi volatile compounds do not condense on an organic aerosol that is mostly secondary and highly oxidized. Finally, the impact of aqueous-phase chemistry was studied. The mechanism for the formation of secondary organic aerosol includes in-cloud oxidation of glyoxal, methylglyoxal, methacrolein and methylvinylketone, formation of methyltetrols in the aqueous phase of particles and cloud droplets, and the in-cloud aging of organic aerosols. The impact of wet deposition is also studied to better estimate the

  5. Inflammatory responses to secondary organic aerosols (SOA generated from biogenic and anthropogenic precursors

    Directory of Open Access Journals (Sweden)

    W. Y. Tuet

    2017-09-01

    Full Text Available Cardiopulmonary health implications resulting from exposure to secondary organic aerosols (SOA, which comprise a significant fraction of ambient particulate matter (PM, have received increasing interest in recent years. In this study, alveolar macrophages were exposed to SOA generated from the photooxidation of biogenic and anthropogenic precursors (isoprene, α-pinene, β-caryophyllene, pentadecane, m-xylene, and naphthalene under different formation conditions (RO2 + HO2 vs. RO2 + NO dominant, dry vs. humid. Various cellular responses were measured, including reactive oxygen and nitrogen species (ROS/RNS production and secreted levels of cytokines, tumor necrosis factor-α (TNF-α and interleukin-6 (IL-6. SOA precursor identity and formation condition affected all measured responses in a hydrocarbon-specific manner. With the exception of naphthalene SOA, cellular responses followed a trend where TNF-α levels reached a plateau with increasing IL-6 levels. ROS/RNS levels were consistent with relative levels of TNF-α and IL-6, due to their respective inflammatory and anti-inflammatory effects. Exposure to naphthalene SOA, whose aromatic-ring-containing products may trigger different cellular pathways, induced higher levels of TNF-α and ROS/RNS than suggested by the trend. Distinct cellular response patterns were identified for hydrocarbons whose photooxidation products shared similar chemical functionalities and structures, which suggests that the chemical structure (carbon chain length and functionalities of photooxidation products may be important for determining cellular effects. A positive nonlinear correlation was also detected between ROS/RNS levels and previously measured DTT (dithiothreitol activities for SOA samples. In the context of ambient samples collected during summer and winter in the greater Atlanta area, all laboratory-generated SOA produced similar or higher levels of ROS/RNS and DTT activities. These results

  6. Structural signatures of water-soluble organic aerosols in contrasting environments in South America and Western Europe.

    Science.gov (United States)

    Duarte, Regina M B O; Matos, João T V; Paula, Andreia S; Lopes, Sónia P; Pereira, Guilherme; Vasconcellos, Pérola; Gioda, Adriana; Carreira, Renato; Silva, Artur M S; Duarte, Armando C; Smichowski, Patricia; Rojas, Nestor; Sanchez-Ccoyllo, Odon

    2017-08-01

    This study describes and compares the key structural units present in water-soluble organic carbon (WSOC) fraction of atmospheric aerosols collected in different South American (Colombia - Medellín and Bogotá, Peru - Lima, Argentina - Buenos Aires, and Brazil - Rio de Janeiro, São Paulo, and Porto Velho, during moderate (MBB) and intense (IBB) biomass burning) and Western European (Portugal - Aveiro and Lisbon) locations. Proton nuclear magnetic resonance ( 1 H NMR) spectroscopy was employed to assess the relative distribution of non-exchangeable proton functional groups in aerosol WSOC of diverse origin, for the first time to the authors' knowledge in South America. The relative contribution of the proton functional groups was in the order H-C > H-C-C= > H-C-O > Ar-H, except in Porto Velho during MBB, Medellín, Bogotá, and Buenos Aires, for which the relative contribution of H-C-O was higher than that of H-C-C=. The 1 H NMR source attribution confirmed differences in aging processes or regional sources between the two geographic regions, allowing the differentiation between urban combustion-related aerosol and biological particles. The aerosol WSOC in Aveiro, Lisbon, and Rio de Janeiro during summer are more oxidized than those from the remaining locations, indicating the predominance of secondary organic aerosols. Fresh emissions, namely of smoke particles, becomes important during winter in Aveiro and São Paulo, and in Porto Velho during IBB. The biosphere is an important source altering the chemical composition of aerosol WSOC in South America locations. The source attribution in Medellín, Bogotá, Buenos Aires, and Lima confirmed the mixed contributions of biological material, secondary formation, as well as urban and biomass burning emissions. Overall, the information and knowledge acquired in this study provide important diagnostic tools for future studies aiming at understanding the water-soluble organic aerosol problem, their sources and

  7. Volatility of Organic Aerosol: Evaporation of Ammonium Sulfate/Succinic Acid Aqueous Solution Droplets

    Science.gov (United States)

    2013-01-01

    Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol. PMID:24107221

  8. Processing of Unsaturated Organic Acid Aerosols by Ozone

    Science.gov (United States)

    Aloisio, S.; Donaldson, D. J.; Eliason, T. L.; Cziczo, D.; Vaida, V.

    2002-05-01

    We present results of in-situ studies of the oxidative "processing" of organic aerosols composed of unsaturated organic compounds. Aerosol samples of 2-octenoic acid and undecylenic acid were exposed to approx. 10 mbar ozone in a room temperature, atmospheric pressure flow tube reactor. In-situ spectroscopic probing of the reaction mixture, as well as GC-MS analysis of the flow tube effluent, shows evidence of efficient oxidation of double bonds in the organic species, with production of gas-phase and aerosol phase ozonolysis products.

  9. Global combustion sources of organic aerosols: model comparison with 84 AMS factor-analysis data sets

    Science.gov (United States)

    Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Pandis, Spyros N.; Lelieveld, Jos

    2016-07-01

    Emissions of organic compounds from biomass, biofuel, and fossil fuel combustion strongly influence the global atmospheric aerosol load. Some of the organics are directly released as primary organic aerosol (POA). Most are emitted in the gas phase and undergo chemical transformations (i.e., oxidation by hydroxyl radical) and form secondary organic aerosol (SOA). In this work we use the global chemistry climate model ECHAM/MESSy Atmospheric Chemistry (EMAC) with a computationally efficient module for the description of organic aerosol (OA) composition and evolution in the atmosphere (ORACLE). The tropospheric burden of open biomass and anthropogenic (fossil and biofuel) combustion particles is estimated to be 0.59 and 0.63 Tg, respectively, accounting for about 30 and 32 % of the total tropospheric OA load. About 30 % of the open biomass burning and 10 % of the anthropogenic combustion aerosols originate from direct particle emissions, whereas the rest is formed in the atmosphere. A comprehensive data set of aerosol mass spectrometer (AMS) measurements along with factor-analysis results from 84 field campaigns across the Northern Hemisphere are used to evaluate the model results. Both the AMS observations and the model results suggest that over urban areas both POA (25-40 %) and SOA (60-75 %) contribute substantially to the overall OA mass, whereas further downwind and in rural areas the POA concentrations decrease substantially and SOA dominates (80-85 %). EMAC does a reasonable job in reproducing POA and SOA levels during most of the year. However, it tends to underpredict POA and SOA concentrations during winter indicating that the model misses wintertime sources of OA (e.g., residential biofuel use) and SOA formation pathways (e.g., multiphase oxidation).

  10. Diffusivity measurements of volatile organics in levitated viscous aerosol particles

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    S. Bastelberger

    2017-07-01

    Full Text Available Field measurements indicating that atmospheric secondary organic aerosol (SOA particles can be present in a highly viscous, glassy state have spurred numerous studies addressing low diffusivities of water in glassy aerosols. The focus of these studies is on kinetic limitations of hygroscopic growth and the plasticizing effect of water. In contrast, much less is known about diffusion limitations of organic molecules and oxidants in viscous matrices. These may affect atmospheric chemistry and gas–particle partitioning of complex mixtures with constituents of different volatility. In this study, we quantify the diffusivity of a volatile organic in a viscous matrix. Evaporation of single particles generated from an aqueous solution of sucrose and small amounts of volatile tetraethylene glycol (PEG-4 is investigated in an electrodynamic balance at controlled relative humidity (RH and temperature. The evaporative loss of PEG-4 as determined by Mie resonance spectroscopy is used in conjunction with a radially resolved diffusion model to retrieve translational diffusion coefficients of PEG-4. Comparison of the experimentally derived diffusivities with viscosity estimates for the ternary system reveals a breakdown of the Stokes–Einstein relationship, which has often been invoked to infer diffusivity from viscosity. The evaporation of PEG-4 shows pronounced RH and temperature dependencies and is severely depressed for RH ≲ 30 %, corresponding to diffusivities < 10−14 cm2 s−1 at temperatures < 15 °C. The temperature dependence is strong, suggesting a diffusion activation energy of about 300 kJ mol−1. We conclude that atmospheric volatile organic compounds can be subject to severe diffusion limitations in viscous organic aerosol particles. This may enable an important long-range transport mechanism for organic material, including pollutant molecules such as polycyclic aromatic hydrocarbons (PAHs.

  11. Evaluation of factors controlling global secondary organic aerosol production from cloud processes

    Directory of Open Access Journals (Sweden)

    C. He

    2013-02-01

    Full Text Available Secondary organic aerosols (SOA exert a significant influence on ambient air quality and regional climate. Recent field, laboratorial and modeling studies have confirmed that in-cloud processes contribute to a large fraction of SOA production with large space-time heterogeneity. This study evaluates the key factors that govern the production of cloud-process SOA (SOAcld on a global scale based on the GFDL coupled chemistry-climate model AM3 in which full cloud chemistry is employed. The association between SOAcld production rate and six factors (i.e., liquid water content (LWC, total carbon chemical loss rate (TCloss, temperature, VOC/NOx, OH, and O3 is examined. We find that LWC alone determines the spatial pattern of SOAcld production, particularly over the tropical, subtropical and temperate forest regions, and is strongly correlated with SOAcld production. TCloss ranks the second and mainly represents the seasonal variability of vegetation growth. Other individual factors are essentially uncorrelated spatiotemporally to SOAcld production. We find that the rate of SOAcld production is simultaneously determined by both LWC and TCloss, but responds linearly to LWC and nonlinearly (or concavely to TCloss. A parameterization based on LWC and TCloss can capture well the spatial and temporal variability of the process-based SOAcld formation (R2 = 0.5 and can be easily applied to global three dimensional models to represent the SOA production from cloud processes.

  12. Dissolved organic matter in sea spray: a transfer study from marine surface water to aerosols

    Science.gov (United States)

    Schmitt-Kopplin, P.; Liger-Belair, G.; Koch, B. P.; Flerus, R.; Kattner, G.; Harir, M.; Kanawati, B.; Lucio, M.; Tziotis, D.; Hertkorn, N.; Gebefügi, I.

    2012-04-01

    Atmospheric aerosols impose direct and indirect effects on the climate system, for example, by absorption of radiation in relation to cloud droplets size, on chemical and organic composition and cloud dynamics. The first step in the formation of Organic primary aerosols, i.e. the transfer of dissolved organic matter from the marine surface into the atmosphere, was studied. We present a molecular level description of this phenomenon using the high resolution analytical tools of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and nuclear magnetic resonance spectroscopy (NMR). Our experiments confirm the chemoselective transfer of natural organic molecules, especially of aliphatic compounds from the surface water into the atmosphere via bubble bursting processes. Transfer from marine surface water to the atmosphere involves a chemical gradient governed by the physicochemical properties of the involved molecules when comparing elemental compositions and differentiating CHO, CHNO, CHOS and CHNOS bearing compounds. Typical chemical fingerprints of compounds enriched in the aerosol phase were CHO and CHOS molecular series, smaller molecules of higher aliphaticity and lower oxygen content, and typical surfactants. A non-targeted metabolomics analysis demonstrated that many of these molecules corresponded to homologous series of oxo-, hydroxy-, methoxy-, branched fatty acids and mono-, di- and tricarboxylic acids as well as monoterpenes and sugars. These surface active biomolecules were preferentially transferred from surface water into the atmosphere via bubble bursting processes to form a significant fraction of primary organic aerosols. This way of sea spray production leaves a selective biological signature of the surface water in the corresponding aerosol that may be transported into higher altitudes up to the lower atmosphere, thus contributing to the formation of secondary organic aerosol on a global scale or transported laterally with

  13. Functional characterization of the water-soluble organic carbon of size-fractionated aerosol in the southern Mississippi Valley

    Science.gov (United States)

    Chalbot, M.-C. G.; Brown, J.; Chitranshi, P.; Gamboa da Costa, G.; Pollock, E. D.; Kavouras, I. G.

    2014-06-01

    The chemical content of water-soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for periods when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5% of particle mass for particles with dp > 0.96 μm and 10% of particle mass for particles with dp magnetic resonance (1H-NMR). The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m-3 for particles with 1.5 fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosols and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from -26.81 ± 0.18‰ for the smallest particles to -25.93 ± 0.31‰ for the largest particles and the relative distribution of the functional groups as compared to those previously observed for marine, biomass burning and secondary organic aerosol. The latter also allowed for the differentiation of urban combustion-related aerosol and biological particles. The five types of organic hydrogen accounted for the majority of WSOC for particles with dp > 3.0 μm and dp < 0.96 μm.

  14. Functional characterization of the water-soluble organic carbon of size fractionated aerosol in the Southern Mississippi Valley

    Science.gov (United States)

    Chalbot, M.-C. G.; Brown, J.; Chitranshi, P.; Gamboa da Costa, G.; Pollock, E. D.; Kavouras, I. G.

    2014-02-01

    The chemical content of the water soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to: (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for the period when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5% of particle mass for particles with dp > 0.96 μm and 10% of particle mass for particles with dp magnetic resonance. The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m-3 for particles with 0.96 fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosol and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from -26.81 ± 0.18‰ for the smallest particles to -25.93 ± 0.31‰ for the largest particles and the relative distribution of the functional groups as compared to those previously observed for marine, biomass burning and secondary organic aerosol. The latter also allowed for the differentiation of urban combustion-related aerosol and biological particles. The five types of organic hydrogen accounted for the majority of WSOC for particles with dp > 3.0 μm and dp < 0.96 μm.

  15. Organic Aerosol Component (OACOMP) Value-Added Product

    Energy Technology Data Exchange (ETDEWEB)

    Fast, J [Pacific Northwest National Laboratory; Zhang, Q; tilp, A [Brookhaven National Laboratory; Shippert, T [Pacific Northwest National Laboratory; Parworth, C; Mei, F [Pacific Northwest National Laboratory

    2013-08-23

    Organic aerosol (OA, i.e., the organic fraction of particles) accounts for 10–90% of the fine aerosol mass globally and is a key determinant of aerosol radiative forcing. But atmospheric OA is poorly characterized and its life cycle insufficiently represented in models. As a result, current models are unable to simulate OA concentrations and properties accurately. This deficiency represents a large source of uncertainty in quantification of aerosol effects and prediction of future climate change. Evaluation and development of aerosol models require data products generated from field observations. Real-time, quantitative data acquired with aerosol mass spectrometers (AMS) (Canagaratna et al. 2007) are critical to this need. The AMS determines size-resolved concentrations of non-refractory (NR) species in submicrometer particles (PM1) with fast time resolution suitable for both ground-based and aircraft deployments. The high-resolution AMS (HR-AMS), which is equipped with a high mass resolution time-of-flight mass spectrometer, can be used to determine the elemental composition and oxidation degrees of OA (DeCarlo et al. 2006).

  16. Effects of NOx and SO2 on the secondary organic aerosol formation from photooxidation of α-pinene and limonene

    Directory of Open Access Journals (Sweden)

    D. Zhao

    2018-02-01

    Full Text Available Anthropogenic emissions such as NOx and SO2 influence the biogenic secondary organic aerosol (SOA formation, but detailed mechanisms and effects are still elusive. We studied the effects of NOx and SO2 on the SOA formation from the photooxidation of α-pinene and limonene at ambient relevant NOx and SO2 concentrations (NOx: < 1to 20 ppb, SO2: < 0.05 to 15 ppb. In these experiments, monoterpene oxidation was dominated by OH oxidation. We found that SO2 induced nucleation and enhanced SOA mass formation. NOx strongly suppressed not only new particle formation but also SOA mass yield. However, in the presence of SO2 which induced a high number concentration of particles after oxidation to H2SO4, the suppression of the mass yield of SOA by NOx was completely or partly compensated for. This indicates that the suppression of SOA yield by NOx was largely due to the suppressed new particle formation, leading to a lack of particle surface for the organics to condense on and thus a significant influence of vapor wall loss on SOA mass yield. By compensating for the suppressing effect on nucleation of NOx, SO2 also compensated for the suppressing effect on SOA yield. Aerosol mass spectrometer data show that increasing NOx enhanced nitrate formation. The majority of the nitrate was organic nitrate (57–77 %, even in low-NOx conditions (<  ∼  1 ppb. Organic nitrate contributed 7–26 % of total organics assuming a molecular weight of 200 g mol−1. SOA from α-pinene photooxidation at high NOx had a generally lower hydrogen to carbon ratio (H ∕ C, compared to low NOx. The NOx dependence of the chemical composition can be attributed to the NOx dependence of the branching ratio of the RO2 loss reactions, leading to a lower fraction of organic hydroperoxides and higher fractions of organic nitrates at high NOx. While NOx suppressed new particle formation and SOA mass formation, SO2 can compensate for such effects, and the

  17. Organic composition of carbonaceous aerosols in an aged prescribed fire plume

    Directory of Open Access Journals (Sweden)

    B. Yan

    2008-11-01

    Full Text Available Aged smoke from a prescribed fire (dominated by conifers impacted Atlanta, GA on 28 February 2007 and dramatically increased hourly ambient concentrations of PM2.5 and organic carbon (OC up to 140 and 72 μg m−3, respectively. It was estimated that over 1 million residents were exposed to the smoky air lasting from the late afternoon to midnight. To better understand the processes impacting the aging of fire plumes, a detailed chemical speciation of carbonaceous aerosols was conducted by gas chromatography/mass spectrometry (GC/MS analysis. Ambient concentrations of many organic species (levoglucosan, resin acids, retene, n-alkanes and n-alkanoic acids associated with wood burning emission were significantly elevated on the event day. Levoglucosan increased by a factor of 10, while hopanes, steranes, cholesterol and major polycyclic aromatic hydrocarbons (PAHs did not show obvious increases. Strong odd over even carbon number predominance was found for n-alkanes versus even over odd predominance for n-alkanoic acids. Alteration of resin acids during transport from burning sites to monitors is suggested by the observations. Our study also suggests that large quantities of biogenic volatile organic compounds (VOCs and semivolatile organic compounds (SVOCs were released both as products of combustion and unburned vegetation heated by the fire. Higher leaf temperature can stimulate biogenic VOC and SVOC emissions, which enhanced formation of secondary organic aerosols (SOA in the atmosphere. This is supported by elevated ambient concentrations of secondary organic tracers (dicarboxylic acids, 2-methyltetrols, pinonic acid and pinic acid. An approximate source profile was built for the aged fire plume to help better understand evolution of wood smoke emission and for use in source impact assessment.

  18. Impacts of Biomass Burning on Organic Aerosols over the Northwestern Pacific Ocean

    Science.gov (United States)

    Guo, T.; Guo, Z.

    2017-12-01

    During the cruise from East China Sea to Northwestern Pacific in March-April 2014, total suspended particle samples were collected and analyzed for tracers of primary and secondary organic aerosols (SOA) as well as OC and EC. In the study, the sum of all tracers during the sampling period ranged from 3.60 to 181.58 ng/m3, with a mean being 59.87±62.70 ng/m3. Among these tracers, glucose was the dominant compound (average: 17.73±20.60 ng/m3), followed by levoglucosan (12.82±14.37 ng/m3) and fructose (10.47±13.28 ng/m3). LEVO in samples affected by long range transport of biomass burning aerosol (17.38±21.32ng/m3) was about 1 order magnitude higher than the other (1.76±0.92ng/m3, pBTs. Thus organic aerosols over NWPO were deeply influenced by forest fires taking place in Siberia and North China as a result of long-range transport of both directly emitted OA and secondarily formed OA under high-NOx conditions during fire events.

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

    Directory of Open Access Journals (Sweden)

    A. Mahmud

    2013-07-01

    Full Text Available The secondary organic aerosol (SOA module in the Model for Ozone and Related Chemical Tracers, version 4 (MOZART-4 was updated by replacing existing two-product (2p parameters with those obtained from two-product volatility basis set (2p-VBS fits (MZ4-C1, and by treating SOA formation from the following additional volatile organic compounds (VOCs: isoprene, propene and lumped alkenes (MZ4-C2. Strong seasonal and spatial variations in global SOA distributions were demonstrated, with significant differences in the predicted concentrations between the base case and updated model simulations. Updates to the model resulted in significant increases in annual average SOA mass concentrations, particularly for the MZ4-C2 simulation in which the additional SOA precursor VOCs were treated. Annual average SOA concentrations predicted by the MZ4-C2 simulation were 1.00 ± 1.04 μg m−3 in South America, 1.57 ± 1.88 μg m−3 in Indonesia, 0.37 ± 0.27 μg m−3 in the USA, and 0.47 ± 0.29 μg m−3 in Europe with corresponding increases of 178, 406, 311 and 292% over the base-case simulation, respectively, primarily due to inclusion of isoprene. The increases in predicted SOA mass concentrations resulted in corresponding increases in SOA contributions to annual average total aerosol optical depth (AOD by ~ 1–6%. Estimated global SOA production was 5.8, 6.6 and 19.1 Tg yr−1 with corresponding burdens of 0.22, 0.24 and 0.59 Tg for the base-case, MZ4-C1 and MZ4-C2 simulations, respectively. The predicted SOA budgets fell well within reported ranges for comparable modeling studies, 6.7 to 96 Tg yr−1, but were lower than recently reported observationally constrained values, 50 to 380 Tg yr−1. For MZ4-C2, simulated SOA concentrations at the surface also were in reasonable agreement with comparable modeling studies and observations. Total organic aerosol (OA mass concentrations at the surface, however, were slightly over-predicted in Europe, Amazonian

  20. Mitigating secondary aerosol generation potentials from biofuel use in the energy sector.

    Science.gov (United States)

    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.

  1. Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3

    Directory of Open Access Journals (Sweden)

    M. E. Jenkin

    2004-01-01

    Full Text Available The formation and detailed composition of secondary organic aerosol (SOA from the gas phase ozonolysis of α- and β-pinene has been simulated using the Master Chemical Mechanism version 3 (MCM v3, coupled with a representation of gas-to-aerosol transfer of semivolatile and involatile oxygenated products. A kinetics representation, based on equilibrium absorptive partitioning of ca. 200 semivolatile products, was found to provide an acceptable description of the final mass concentrations observed in a number of reported laboratory and chamber experiments, provided partitioning coefficients were increased by about two orders of magnitude over those defined on the basis of estimated vapour pressures. This adjustment is believed to be due, at least partially, to the effect of condensed phase association reactions of the partitioning products. Even with this adjustment, the simulated initial formation of SOA was delayed relative to that observed, implying the requirement for the formation of species of much lower volatility to initiate SOA formation. The inclusion of a simplified representation of the formation and gas-to-aerosol transfer of involatile dimers of 22 bi- and multifunctional carboxylic acids (in addition to the absorptive partitioning mechanism allowed a much improved description of SOA formation for a wide range of conditions. The simulated SOA composition recreates certain features of the product distributions observed in a number of experimental studies, but implies an important role for multifunctional products containing hydroperoxy groups (i.e. hydroperoxides. This is particularly the case for experiments in which 2-butanol is used to scavenge OH radicals, because [HO2]/[RO2] ratios are elevated in such systems. The optimized mechanism is used to calculate SOA yields from α- and β-pinene ozonolysis in the presence and absence of OH scavengers, and as a function of temperature.

  2. Photochemical age of air pollutants, ozone, and secondary organic aerosol in transboundary air observed on Fukue Island, Nagasaki, Japan

    Science.gov (United States)

    Irei, Satoshi; Takami, Akinori; Sadanaga, Yasuhiro; Nozoe, Susumu; Yonemura, Seiichiro; Bandow, Hiroshi; Yokouchi, Yoko

    2016-04-01

    To better understand the secondary air pollution in transboundary air over westernmost Japan, ground-based field measurements of the chemical composition of fine particulate matter ( ≤ 1 µm), mixing ratios of trace gas species (CO, O3, NOx, NOy, i-pentane, toluene, and ethyne), and meteorological elements were conducted with a suite of instrumentation. The CO mixing ratio dependence on wind direction showed that there was no significant influence from primary emission sources near the monitoring site, indicating long- and/or mid-range transport of the measured chemical species. Despite the considerably different atmospheric lifetimes of NOy and CO, these mixing ratios were correlated (r2 = 0.67). The photochemical age of the pollutants, t[OH] (the reaction time × the mean concentration of OH radical during the atmospheric transport), was calculated from both the NOx / NOy concentration ratio (NOx / NOy clock) and the toluene / ethyne concentration ratio (hydrocarbon clock). It was found that the toluene / ethyne concentration ratio was significantly influenced by dilution with background air containing 0.16 ppbv of ethyne, causing significant bias in the estimation of t[OH]. In contrast, the influence of the reaction of NOx with O3, a potentially biasing reaction channel on [NOx] / [NOy], was small. The t[OH] values obtained with the NOx / NOy clock ranged from 2.9 × 105 to 1.3 × 108 h molecule cm-3 and were compared with the fractional contribution of the m/z 44 signal to the total signal in the organic aerosol mass spectra (f44, a quantitative oxidation indicator of carboxylic acids) and O3 mixing ratio. The comparison of t[OH] with f44 showed evidence for a systematic increase of f44 as t[OH] increased, an indication of secondary organic aerosol (SOA) formation. To a first approximation, the f44 increase rate was (1.05 ± 0.03) × 10-9 × [OH] h-1, which is comparable to the background-corrected increase rate observed during the New England Air Quality

  3. Characterizing source fingerprints and ageing processes in laboratory-generated secondary organic aerosols using proton-nuclear magnetic resonance (1H-NMR) analysis and HPLC HULIS determination

    Science.gov (United States)

    Zanca, Nicola; Lambe, Andrew T.; Massoli, Paola; Paglione, Marco; Croasdale, David R.; Parmar, Yatish; Tagliavini, Emilio; Gilardoni, Stefania; Decesari, Stefano

    2017-09-01

    The study of secondary organic aerosol (SOA) in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM) oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescales that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization - proton nuclear magnetic resonance (1H-NMR) spectroscopy and HPLC determination of humic-like substances (HULIS). Results were compared with previous Aerodyne aerosol mass spectrometer (AMS) measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1 × 1012 molec OH cm-3 × s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC), providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.

  4. Carbonaceous PM(2.5) and secondary organic aerosol across the Veneto region (NE Italy).

    Science.gov (United States)

    Khan, Md Badiuzzaman; Masiol, Mauro; Formenton, Gianni; Di Gilio, Alessia; de Gennaro, Gianluigi; Agostinelli, Claudio; Pavoni, Bruno

    2016-01-15

    Organic and elemental carbon (OC-EC) were measured in 360 PM2.5 samples collected from April 2012 to February 2013 at six provinces in the Veneto region, to determine the factors affecting the carbonaceous aerosol variations. The 60 daily samples have been collected simultaneously in all sites during 10 consecutive days for 6 months (April, June, August, October, December and February). OC ranged from 0.98 to 22.34 μg/m(3), while the mean value was 5.5 μg/m(3), contributing 79% of total carbon. EC concentrations fluctuated from 0.19 to 11.90 μg/m(3) with an annual mean value of 1.31 μg/m(3) (19% of the total carbon). The monthly OC concentration gradually increased from April to December. The EC did not vary in accordance with OC. However the highest values for both parameters were recorded in the cold period. The mean OC/EC ratio is 4.54, which is higher than the values observed in most of the other European cities. The secondary organic carbon (SOC) contributed for 69% of the total OC and this was confirmed by both the approaches OC/EC minimum ratio and regression. The results show that OC, EC and SOC exhibited higher concentration during winter months in all measurement sites, suggesting that the stable atmosphere and lower mixing play important role for the accumulation of air pollutant and hasten the condensation or adsorption of volatile organic compounds over the Veneto region. Significant meteorological factors controlling OC and EC were investigated by fitting linear models and using a robust procedure based on weighted likelihood, suggesting that low wind speed and temperature favour accumulation of emissions from local sources. Conditional probability function and conditional bivariate probability function plots indicate that both biomass burning and vehicular traffic are probably the main local sources for carbonaceous particulate matter emissions in two selected cities. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Secondary aerosol formation from photochemical aging of aircraft exhaust in a smog chamber

    Directory of Open Access Journals (Sweden)

    M. A. Miracolo

    2011-05-01

    Full Text Available Field experiments were performed to investigate the effects of photo-oxidation on fine particle emissions from an in-use CFM56-2B gas turbine engine mounted on a KC-135 Stratotanker airframe. Emissions were sampled into a portable smog chamber from a rake inlet installed one-meter downstream of the engine exit plane of a parked and chocked aircraft. The chamber was then exposed to sunlight and/or UV lights to initiate photo-oxidation. Separate tests were performed at different engine loads (4, 7, 30, 85 %. Photo-oxidation created substantial secondary particulate matter (PM, greatly exceeding the direct PM emissions at each engine load after an hour or less of aging at typical summertime conditions. After several hours of photo-oxidation, the ratio of secondary-to-primary PM mass was on average 35 ± 4.1, 17 ± 2.5, 60 ± 2.2, and 2.7 ± 1.1 for the 4, 7, 30, and 85 % load experiments, respectively. The composition of secondary PM formed strongly depended on load. At 4 % load, secondary PM was dominated by secondary organic aerosol (SOA. At higher loads, the secondary PM was mainly secondary sulfate. A traditional SOA model that accounts for SOA formation from single-ring aromatics and other volatile organic compounds underpredicts the measured SOA formation by ~60 % at 4 % load and ~40 % at 85 % load. Large amounts of lower-volatiliy organic vapors were measured in the exhaust; they represent a significant pool of SOA precursors that are not included in traditional SOA models. These results underscore the importance of accounting for atmospheric processing when assessing the influence of aircraft emissions on ambient PM levels. Models that do not account for this processing will likely underpredict the contribution of aircraft emissions to local and regional air pollution.

  6. Time-resolved molecular characterization of organic aerosols by PILS + UPLC/ESI-Q-TOFMS

    Science.gov (United States)

    Zhang, X.; Dalleska, N. F.; Huang, D. D.; Bates, K. H.; Sorooshian, A.; Flagan, R. C.; Seinfeld, J. H.

    2016-04-01

    Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS + UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ∼0.7. The PILS + UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.

  7. Quantifying the Relationship between Organic Aerosol Composition and Hygroscopicity/CCN Activity

    Energy Technology Data Exchange (ETDEWEB)

    Ziemann, Paul J. [Univ. of California, Riverside, CA (United States); Kreidenweis, Sonia M. [Colorado State Univ., Fort Collins, CO (United States); Petters, Markus D. [North Carolina State Univ., Raleigh, NC (United States)

    2013-06-30

    The overall objective for this project was to provide the data and underlying process level understanding necessary to facilitate the dynamic treatment of organic aerosol CCN activity in future climate models. The specific objectives were as follows: (1) employ novel approaches to link organic aerosol composition and CCN activity, (2) evaluate the effects of temperature and relative humidity on organic aerosol CCN activity, and (3) develop parameterizations to link organic aerosol composition and CCN activity.

  8. Aerosol Mass Scattering Efficiency: Generalized Treatment of the Organic Fraction

    Science.gov (United States)

    Garland, R. M.; Ravishankara, A. R.; Lovejoy, E. R.; Tolbert, M. A.; Baynard, T.

    2005-12-01

    Atmospheric aerosols are complex mixtures of organic and inorganic compounds. Current efforts to provide a simplified parameterization to describe the RH dependence of water uptake and associated optical properties lack the capability to include any dependence on the composition of the organic fraction. Using laboratory generated aerosol we have investigated the validity of such simplified treatment of organic fraction and estimated potential biases. In this study, we use cavity ring-down aerosol extinction photometry (CRD-AEP) to study the relative humidity (RH) dependence of the light extinction of aerosols, σep, simultaneously considering the influence of particle size, chemical composition, and mixing state (internal and external mixtures). We have produced internally mixed aerosol systems including; ammonium sulfate, ammonium nitrate, sodium chloride, dicarboxylic acids, sugars, amino acids and humic acid. These aerosols are produced with an atomizer and size-selected with a Differential Mobility Analyzer (DMA). The particles then enter into a CRD-AEP to measure dry extinction, σep(Dry), after which they travel into a RH conditioner and another CRD-AEP to measure the humidified aerosol extinction, fσ(ep)RH. The ratio of the humidified extinction to the dry extinction is fσ(ep)RH. Representative organic compounds were found to have fσ(ep)RH values that are much smaller than pure salts; though the fσ(ep)RH values vary little within the organic compounds studied. In addition, we have found that treating the inorganic/organic aerosols as external mixtures is generally correct to within ~10%, indicating appropriate simplified treatment of the RH dependence of atmospheric aerosol according to inorganic/organic fraction. In this presentation, we include recommendations for the generalized treatment of the organic fraction, exceptions to this generalized behavior, and estimates of the potential bias caused by generalized treatment.

  9. Ozonolysis of α-phellandrene – Part 2: Compositional analysis of secondary organic aerosol highlights the role of stabilised Criegee intermediates

    Directory of Open Access Journals (Sweden)

    F. A. Mackenzie-Rae

    2018-04-01

    Full Text Available The molecular composition of the water-soluble fraction of secondary organic aerosol (SOA generated from the ozonolysis of α-phellandrene is investigated for the first time using high-pressure liquid chromatography coupled to high-resolution quadrupole–Orbitrap tandem mass spectrometry. In total, 21 prominent products or isomeric product groups were identified using both positive and negative ionisation modes, with potential formation mechanisms discussed. The aerosol was found to be composed primarily of polyfunctional first- and second-generation species containing one or more carbonyl, acid, alcohol and hydroperoxide functionalities, with the products significantly more complex than those proposed from basic gas-phase chemistry in the companion paper (Mackenzie-Rae et al., 2017. Mass spectra show a large number of dimeric products are also formed. Both direct scavenging evidence using formic acid and indirect evidence from double bond equivalency factors suggest the dominant oligomerisation mechanism is the bimolecular reaction of stabilised Criegee intermediates (SCIs with non-radical ozonolysis products. Saturation vapour concentration estimates suggest monomeric species cannot explain the rapid nucleation burst of fresh aerosol observed in chamber experiments; hence, dimeric species are believed to be responsible for new particle formation, with detected first- and second-generation products driving further particle growth in the system. Ultimately, identification of the major constituents and formation pathways of α-phellandrene SOA leads to a greater understanding of the atmospheric processes and implications of monoterpene emissions and SCIs, especially around eucalypt forests where α-phellandrene is primarily emitted.

  10. Fractionation of Stable Isotopes in Atmospheric Aerosol Reactions

    DEFF Research Database (Denmark)

    Meusinger, Carl

    -independent) fractionation processes of stable isotopes of C, N, O and S in order to investigate three different systems related to aerosols: 1. Post-depositional processes of nitrate in snow that obscure nitrate ice core records 2. Formation and aging of secondary organic aerosol generated by ozonolysis of X...... reactions and undergo complex chemical and physical changes during their lifetimes. In order to assess processes that form and alter aerosols, information provided by stable isotopes can be used to help constrain estimates on the strength of aerosol sources and sinks. This thesis studies (mass...... as required. The kndings provide important results for the studies' respective felds, including a description of the isotopic fractionation and quantum yield of nitrate photolysis in snow, equilibrium fractionation in secondary organic aerosol and fractionation constants of different oxidation pathways of SO2....

  11. Secondary inorganic aerosols in Europe: sources and the significant influence of biogenic VOC emissions, especially on ammonium nitrate

    Science.gov (United States)

    Aksoyoglu, Sebnem; Ciarelli, Giancarlo; El-Haddad, Imad; Baltensperger, Urs; Prévôt, André S. H.

    2017-06-01

    Contributions of various anthropogenic sources to the secondary inorganic aerosol (SIA) in Europe as well as the role of biogenic emissions on SIA formation were investigated using the three-dimensional regional model CAMx (comprehensive air quality model with extensions). Simulations were carried out for two periods of EMEP field campaigns, February-March 2009 and June 2006, which are representative of cold and warm seasons, respectively. Biogenic volatile organic compounds (BVOCs) are known mainly as precursors of ozone and secondary organic aerosol (SOA), but their role on inorganic aerosol formation has not attracted much attention so far. In this study, we showed the importance of the chemical reactions of BVOCs and how they affect the oxidant concentrations, leading to significant changes, especially in the formation of ammonium nitrate. A sensitivity test with doubled BVOC emissions in Europe during the warm season showed a large increase in secondary organic aerosol (SOA) concentrations (by about a factor of two), while particulate inorganic nitrate concentrations decreased by up to 35 %, leading to a better agreement between the model results and measurements. Sulfate concentrations decreased as well; the change, however, was smaller. The changes in inorganic nitrate and sulfate concentrations occurred at different locations in Europe, indicating the importance of precursor gases and biogenic emission types for the negative correlation between BVOCs and SIA. Further analysis of the data suggested that reactions of the additional terpenes with nitrate radicals at night were responsible for the decline in inorganic nitrate formation, whereas oxidation of BVOCs with OH radicals led to a decrease in sulfate. Source apportionment results suggest that the main anthropogenic source of precursors leading to formation of particulate inorganic nitrate is road transport (SNAP7; see Table 1 for a description of the categories), whereas combustion in energy and

  12. Gas-particle partitioning of semi-volatile organics on organic aerosols using a predictive activity coefficient model: analysis of the effects of parameter choices on model performance

    Science.gov (United States)

    Chandramouli, Bharadwaj; Jang, Myoseon; Kamens, Richard M.

    The partitioning of a diverse set of semivolatile organic compounds (SOCs) on a variety of organic aerosols was studied using smog chamber experimental data. Existing data on the partitioning of SOCs on aerosols from wood combustion, diesel combustion, and the α-pinene-O 3 reaction was augmented by carrying out smog chamber partitioning experiments on aerosols from meat cooking, and catalyzed and uncatalyzed gasoline engine exhaust. Model compositions for aerosols from meat cooking and gasoline combustion emissions were used to calculate activity coefficients for the SOCs in the organic aerosols and the Pankow absorptive gas/particle partitioning model was used to calculate the partitioning coefficient Kp and quantitate the predictive improvements of using the activity coefficient. The slope of the log K p vs. log p L0 correlation for partitioning on aerosols from meat cooking improved from -0.81 to -0.94 after incorporation of activity coefficients iγ om. A stepwise regression analysis of the partitioning model revealed that for the data set used in this study, partitioning predictions on α-pinene-O 3 secondary aerosol and wood combustion aerosol showed statistically significant improvement after incorporation of iγ om, which can be attributed to their overall polarity. The partitioning model was sensitive to changes in aerosol composition when updated compositions for α-pinene-O 3 aerosol and wood combustion aerosol were used. The octanol-air partitioning coefficient's ( KOA) effectiveness as a partitioning correlator over a variety of aerosol types was evaluated. The slope of the log K p- log K OA correlation was not constant over the aerosol types and SOCs used in the study and the use of KOA for partitioning correlations can potentially lead to significant deviations, especially for polar aerosols.

  13. Temperature Dependency of the Correlation between Secondary Organic Aerosol and Monoterpenes Concentrations at a Boreal Forest Site in Finland

    Science.gov (United States)

    Zhou, Y.; Zhang, W.; Rinne, J.

    2016-12-01

    Climate feedbacks represent the large uncertainty in the climate projection partly due to the difficulties to quantify the feedback mechanisms in the biosphere-atmosphere interaction. Recently, a negative climate feedback mechanism whereby higher temperatures and CO2-levels boost continental biomass production, leading to increased biogenic secondary organic aerosol (SOA) and cloud condensation nuclei concentrations, tending to cause cooling, has been attached much attention. To quantify the relationship between biogenic organic compounds (BVOCs) and SOA, a five-year data set (2008, 2010-2011,2013-2014) for SOA and monoterpenes concentrations (the dominant fraction of BVOCs) measured at the SMEAR II station in Hyytiälä, Finland, is analyzed. Our results show that there is a moderate linear correlation between SOA and monoterpenes concentration with the correlation coefficient (R) as 0.66. To rule out the influence of anthropogenic aerosols, the dataset is further filtered by selecting the data at the wind direction of cleaner air mass, leading to an improved R as 0.68. As temperature is a critical factor for vegetation growth, BVOC emissions, and condensation rate, the correlation between SOA and monoterpenes concentration at different temperature windows are studied. The result shows a higher R and slope of linear regression as temperature increases. To identify the dominant oxidant responsible for the BVOC-SOA conversion, the correlations between SOA concentration and the monoterpenes oxidation rates by O3 and OH are compared, suggesting more SOA is contributed by O3 oxidation process. Finally, the possible processes and factors such as the atmospheric boundary layer depth, limiting factor in the monoterpenes oxidation process, as well as temperature sensitivity in the condensation process contributing to the temperature dependence of correlation between BVOA and SOA are investigated.

  14. Modeling organic aerosol from the oxidation of α-pinene in a Potential Aerosol Mass (PAM chamber

    Directory of Open Access Journals (Sweden)

    S. Chen

    2013-05-01

    Full Text Available A model has been developed to simulate the formation and evolution of secondary organic aerosol (SOA and was tested against data produced in a Potential Aerosol Mass (PAM flow reactor and a large environmental chamber. The model framework is based on the two-dimensional volatility basis set approach (2D-VBS, in which SOA oxidation products in the model are distributed on the 2-D space of effective saturation concentration (Ci* and oxygen-to-carbon ratio (O : C. The modeled organic aerosol mass concentrations (COA and O : C agree with laboratory measurements within estimated uncertainties. However, while both measured and modeled O : C increase with increasing OH exposure as expected, the increase of modeled O : C is rapid at low OH exposure and then slows as OH exposure increases while the increase of measured O : C is initially slow and then accelerates as OH exposure increases. A global sensitivity analysis indicates that modeled COA values are most sensitive to the assumed values for the number of Ci* bins, the heterogeneous OH reaction rate coefficient, and the yield of first-generation products. Modeled SOA O : C values are most sensitive to the assumed O : C of first-generation oxidation products, the number of Ci* bins, the heterogeneous OH reaction rate coefficient, and the number of O : C bins. All these sensitivities vary as a function of OH exposure. The sensitivity analysis indicates that the 2D-VBS model framework may require modifications to resolve discrepancies between modeled and measured O : C as a function of OH exposure.

  15. Modelling organic aerosol concentrations and properties during ChArMEx summer campaigns of 2012 and 2013 in the western Mediterranean region

    Directory of Open Access Journals (Sweden)

    M. Chrit

    2017-10-01

    Full Text Available In the framework of the Chemistry-Aerosol Mediterranean Experiment, a measurement site was set up at a remote site (Ersa on Corsica Island in the northwestern Mediterranean Sea. Measurement campaigns performed during the summers of 2012 and 2013 showed high organic aerosol concentrations, mostly from biogenic origin. This work aims to represent the organic aerosol concentrations and properties (oxidation state and hydrophilicity using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA formation. Biogenic precursors are isoprene, monoterpenes and sesquiterpenes. In this work, the following model oxidation products of monoterpenes are added: (i a carboxylic acid (MBTCA to represent multi-generation oxidation products in the low-NOx regime, (ii organic nitrate chemistry and (iii extremely low-volatility organic compounds (ELVOCs formed by ozonolysis. The model shows good agreement of measurements of organic concentrations for both 2012 and 2013 summer campaigns. The modelled oxidation property and hydrophilic organic carbon properties of the organic aerosols also agree reasonably well with the measurements. The influence of the different chemical processes added to the model on the oxidation level of organics is studied. Measured and simulated water-soluble organic carbon (WSOC concentrations show that even at a remote site next to the sea, about 64 % of the organic carbon is soluble. The concentrations of WSOC vary with the origins of the air masses and the composition of organic aerosols. The marine organic emissions only contribute to a few percent of the organic mass in PM1, with maxima above the sea.

  16. Modelling organic aerosol concentrations and properties during ChArMEx summer campaigns of 2012 and 2013 in the western Mediterranean region

    Science.gov (United States)

    Chrit, Mounir; Sartelet, Karine; Sciare, Jean; Pey, Jorge; Marchand, Nicolas; Couvidat, Florian; Sellegri, Karine; Beekmann, Matthias

    2017-10-01

    In the framework of the Chemistry-Aerosol Mediterranean Experiment, a measurement site was set up at a remote site (Ersa) on Corsica Island in the northwestern Mediterranean Sea. Measurement campaigns performed during the summers of 2012 and 2013 showed high organic aerosol concentrations, mostly from biogenic origin. This work aims to represent the organic aerosol concentrations and properties (oxidation state and hydrophilicity) using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA) formation. Biogenic precursors are isoprene, monoterpenes and sesquiterpenes. In this work, the following model oxidation products of monoterpenes are added: (i) a carboxylic acid (MBTCA) to represent multi-generation oxidation products in the low-NOx regime, (ii) organic nitrate chemistry and (iii) extremely low-volatility organic compounds (ELVOCs) formed by ozonolysis. The model shows good agreement of measurements of organic concentrations for both 2012 and 2013 summer campaigns. The modelled oxidation property and hydrophilic organic carbon properties of the organic aerosols also agree reasonably well with the measurements. The influence of the different chemical processes added to the model on the oxidation level of organics is studied. Measured and simulated water-soluble organic carbon (WSOC) concentrations show that even at a remote site next to the sea, about 64 % of the organic carbon is soluble. The concentrations of WSOC vary with the origins of the air masses and the composition of organic aerosols. The marine organic emissions only contribute to a few percent of the organic mass in PM1, with maxima above the sea.

  17. Estimate of biogenic VOC emissions in Japan and their effects on photochemical formation of ambient ozone and secondary organic aerosol

    Science.gov (United States)

    Chatani, Satoru; Matsunaga, Sou N.; Nakatsuka, Seiji

    2015-11-01

    A new gridded database has been developed to estimate the amount of isoprene, monoterpene, and sesquiterpene emitted from all the broadleaf and coniferous trees in Japan with the Model of Emissions of Gases and Aerosols from Nature (MEGAN). This database reflects the vegetation specific to Japan more accurately than existing ones. It estimates much lower isoprene emitted from other vegetation than trees, and higher sesquiterpene emissions mainly emitted from Cryptomeria japonica, which is the most abundant plant type in Japan. Changes in biogenic emissions result in the decrease in ambient ozone and increase in organic aerosol simulated by the air quality simulation over the Tokyo Metropolitan Area in Japan. Although newly estimated biogenic emissions contribute to a better model performance on overestimated ozone and underestimated organic aerosol, they are not a single solution to solve problems associated with the air quality simulation.

  18. Emission and chemistry of organic carbon in the gas and aerosol phase at a sub-urban site near Mexico City in March 2006 during the MILAGRO study

    Directory of Open Access Journals (Sweden)

    J. A. de Gouw

    2009-05-01

    Full Text Available Volatile organic compounds (VOCs and carbonaceous aerosol were measured at a sub-urban site near Mexico City in March of 2006 during the MILAGRO study (Megacity Initiative: Local and Global Research Objectives. Diurnal variations of hydrocarbons, elemental carbon (EC and hydrocarbon-like organic aerosol (HOA were dominated by a high peak in the early morning when local emissions accumulated in a shallow boundary layer, and a minimum in the afternoon when the emissions were diluted in a significantly expanded boundary layer and, in case of the reactive gases, removed by OH. In comparison, diurnal variations of species with secondary sources such as the aldehydes, ketones, oxygenated organic aerosol (OOA and water-soluble organic carbon (WSOC stayed relatively high in the afternoon indicating strong photochemical formation. Emission ratios of many hydrocarbon species relative to CO were higher in Mexico City than in the U.S., but we found similar emission ratios for most oxygenated VOCs and organic aerosol. Secondary formation of acetone may be more efficient in Mexico City than in the U.S., due to higher emissions of alkane precursors from the use of liquefied petroleum gas. Secondary formation of organic aerosol was similar between Mexico City and the U.S. Combining the data for all measured gas and aerosol species, we describe the budget of total observed organic carbon (TOOC, and find that the enhancement ratio of TOOC relative to CO is conserved between the early morning and mid afternoon despite large compositional changes. Finally, the influence of biomass burning is investigated using the measurements of acetonitrile, which was found to correlate with levoglucosan in the particle phase. Diurnal variations of acetonitrile indicate a contribution from local burning sources. Scatter plots of acetonitrile versus CO suggest that the contribution of biomass burning to the enhancement of most gas and aerosol species was not dominant and perhaps

  19. Emission and Chemistry of Organic Carbon in the Gas and Aerosol Phase at a Sub-Urban Site Near Mexico City in March 2006 During the MILAGRO Study

    Energy Technology Data Exchange (ETDEWEB)

    de Gouw, Joost A.; Welsh-Bon, Daniel; Warneke, Carsten; Kuster, W. C.; Alexander, M. L.; Baker, Angela K.; Beyersdorf, Andreas J.; Blake, D. R.; Canagaratna, Manjula R.; Celada, A. T.; Huey, L. G.; Junkermann, W.; Onasch, Timothy B.; Salcido, A.; Sjostedt, S. J.; Sullivan, Amy; Tanner, David J.; Vargas-Ortiz, Leroy; Weber, R. J.; Worsnop, Douglas R.; Yu, Xiao-Ying; Zaveri, Rahul A.

    2009-05-28

    Volatile organic compounds (VOCs) and carbonaceous aerosol were measured at a sub-urban site near Mexico City in March of 2006 during the MILAGRO study (Megacity Initiative: Local and Global Research Objectives). Diurnal variations of hydrocarbons, elemental carbon (EC) and hydrocarbon-like organic aerosol (HOA) were dominated by a high peak in the early morning when local emissions accumulated in a shallow boundary layer, and a minimum in the afternoon when the emissions were diluted in a significantly expanded boundary layer and, in case of the reactive gases, removed by OH. In comparison, diurnal variations of species with secondary sources such as the aldehydes, ketones, oxygenated organic aerosol (OOA) and water-soluble organic carbon (WSOC) stayed relatively high in the afternoon indicating strong photochemical formation. Emission ratios of many hydrocarbon species relative to CO were higher in Mexico City than in the U.S., but we found similar emission ratios for most oxygenated VOCs and organic aerosol. Secondary formation of acetone may be more efficient in Mexico City than in the U.S., due to higher emissions of alkane precursors from the use of liquefied petroleum gas. Secondary formation of organic aerosol was similar between Mexico City and the U.S. Combining the data for all measured gas and aerosol species, we describe the budget of total observed organic carbon (TOOC), and find that the enhancement ratio of TOOC relative to CO is conserved between the early morning and mid afternoon despite large compositional changes. Finally, the influence of biomass burning is investigated using the measurements of acetonitrile, which was found to correlate with levoglucosan in the particle phase. Diurnal variations of acetonitrile indicate a contribution from local burning sources. Scatter plots of acetonitrile versus CO suggest that the contribution of biomass burning to the enhancement of most gas and aerosol species was not dominant and perhaps not dissimilar

  20. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    Science.gov (United States)

    Heringa, M. F.; Decarlo, P. F.; Chirico, R.; Tritscher, T.; Clairotte, M.; Mohr, C.; Crippa, M.; Slowik, J. G.; Pfaffenberger, L.; Dommen, J.; Weingartner, E.; Prévôt, A. S. H.; Baltensperger, U.

    2012-02-01

    Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from α-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA) observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25-0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions. The HR data of the four sources could be clustered and separated using principal component analysis (PCA). The model showed a significant separation of the four SOA types and clustering of the duplicate experiments on the first two principal components (PCs), which explained 79% of the total variance. Projection of ambient SV-OOA spectra resolved by positive matrix factorization (PMF) showed that this approach could be useful to identify large contributions of the tested SOA sources to SV-OOA. The first results from this

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

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset contains data presented in the figures of the paper "On the implications of aerosol liquid water and phase separation for organic aerosol mass"...

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

    Science.gov (United States)

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

    2015-09-28

    Atmospheric brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365 nm = 0.78 m(2) g(-1)) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene atmosphere.

  3. Effects of Relative Humidity on Ozone and Secondary Organic Aerosol Formation from the Photooxidation of Benzene and Ethylbenzene

    Science.gov (United States)

    Jia, L.; Xu, Y.

    2012-12-01

    The formation of ozone and secondary organic aerosol from benzene-NOx and ethylbenzene-NOx irradiations was investigated under different levels of relative humidity (RH) in a smog chamber. The results show that the increase in RH can greatly reduce the maximum O3 by the transformation of -NO2 and -ONO2-containing products into the particle phase. In benzene irradiations, the SOA number concentration increases over 26 times as RH rises from ethylbenzene irradiations, ethylglyoxal favors the formation of monohydrate, which limits the RH effects. During evaporating processes, the lost substances have similar structures for both benzene and ethylbenzene. This demonstrates that ethyl-containing substances are very stable and difficult to evaporate. For benzene some of glyoxal hydrates are left to form C-O-C and C=O-containing species like hemiacetal and acetal after evaporation, whereas for ethylbenzene, glyoxal favors cross reactions with ethylglyoxal during the evaporating process. It is concluded that the increase in RH can irreversibly enhance the yields of SOA from both benzene and ethylbenzene.

  4. Impacts of springtime biomass burning in the northern Southeast Asia on marine organic aerosols over the Gulf of Tonkin, China.

    Science.gov (United States)

    Zheng, Lishan; Yang, Xiaoyang; Lai, Senchao; Ren, Hong; Yue, Siyao; Zhang, Yingyi; Huang, Xin; Gao, Yuanguan; Sun, Yele; Wang, Zifa; Fu, Pingqing

    2018-06-01

    Fine particles (PM 2.5 ) samples, collected at Weizhou Island over the Gulf of Tonkin on a daytime and nighttime basis in the spring of 2015, were analyzed for primary and secondary organic tracers, together with organic carbon (OC), elemental carbon (EC), and stable carbon isotopic composition (δ 13 C) of total carbon (TC). Five organic compound classes, including saccharides, lignin/resin products, fatty acids, biogenic SOA tracers and phthalic acids, were quantified by gas chromatography/mass spectrometry (GC/MS). Levoglucosan was the most abundant organic species, indicating that the sampling site was under strong influence of biomass burning. Based on the tracer-based methods, the biomass-burning-derived fraction was estimated to be the dominant contributor to aerosol OC, accounting for 15.7% ± 11.1% and 22.2% ± 17.4% of OC in daytime and nighttime samples, respectively. In two episodes E1 and E2, organic aerosols characterized by elevated concentrations of levoglucosan as well as its isomers, sugar compounds, lignin products, high molecular weight (HMW) fatty acids and β-caryophyllinic acid, were attributed to the influence of intensive biomass burning in the northern Southeast Asia (SEA). However, the discrepancies in the ratios of levoglucosan to mannosan (L/M) and OC (L/OC) as well as the δ 13 C values suggest the type of biomass burning and the sources of organic aerosols in E1 and E2 were different. Hardwood and/or C 4 plants were the major burning materials in E1, while burning of softwood and/or C 3 plants played important role in E2. Furthermore, more complex sources and enhanced secondary contribution were found to play a part in organic aerosols in E2. This study highlights the significant influence of springtime biomass burning in the northern SEA to the organic molecular compositions of marine aerosols over the Gulf of Tonkin. Copyright © 2018 Elsevier Ltd. All rights reserved.

  5. Atmospheric hydrogen peroxide and organic hydroperoxides during PRIDE-PRD'06, China: their concentration, formation mechanism and contribution to secondary aerosols

    Directory of Open Access Journals (Sweden)

    W. Hua

    2008-11-01

    detected in this region can account for the production of hydroperoxides, while the moderate level of NOx suppressed the formation of hydroperoxides. High concentrations of hydroperoxides were detected in samples of rainwater collected in a heavy shower on 25 July when a typhoon passed through, indicating that a considerable mixing ratio of hydroperoxides, particularly MHP, resided above the boundary layer, which might be transported on a regional scale and further influence the redistribution of HOx and ROx radicals. It was found that hydroperoxides, in particular H2O2, play an important role in the formation of secondary sulfate in the aerosol phase, where the heterogeneous reaction might contribute substantially. A negative correlation between hydroperoxides and water-soluble organic compounds (WSOC, a considerable fraction of the secondary organic aerosol (SOA, was observed, possibly providing field evidence for the importance of hydroperoxides in the formation of SOA found in previous laboratory studies. We suggest that hydroperoxides act as an important link between sulfate and organic aerosols, which needs further study and should be considered in current atmospheric models.

  6. Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

    Energy Technology Data Exchange (ETDEWEB)

    D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D.; Schobesberger, Siegfried; Liu, Jiumeng; Shilling, John E.; Lee, Ben Hwan; Kjaergaard, Henrik G.; Thornton, Joel A.

    2017-04-11

    We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.

  7. Characterizing source fingerprints and ageing processes in laboratory-generated secondary organic aerosols using proton-nuclear magnetic resonance (1H-NMR analysis and HPLC HULIS determination

    Directory of Open Access Journals (Sweden)

    N. Zanca

    2017-09-01

    Full Text Available The study of secondary organic aerosol (SOA in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescales that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization – proton nuclear magnetic resonance (1H-NMR spectroscopy and HPLC determination of humic-like substances (HULIS. Results were compared with previous Aerodyne aerosol mass spectrometer (AMS measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1  ×  1012 molec OH cm−3  ×  s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC, providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.

  8. The impact of bark beetle infestations on monoterpene emissions and secondary organic aerosol formation in western North America

    Directory of Open Access Journals (Sweden)

    A. R. Berg

    2013-03-01

    Full Text Available Over the last decade, extensive beetle outbreaks in western North America have destroyed over 100 000 km2 of forest throughout British Columbia and the western United States. Beetle infestations impact monoterpene emissions through both decreased emissions as trees are killed (mortality effect and increased emissions in trees under attack (attack effect. We use 14 yr of beetle-induced tree mortality data together with beetle-induced monoterpene emission data in the National Center for Atmospheric Research (NCAR Community Earth System Model (CESM to investigate the impact of beetle-induced tree mortality and attack on monoterpene emissions and secondary organic aerosol (SOA formation in western North America. Regionally, beetle infestations may have a significant impact on monoterpene emissions and SOA concentrations, with up to a 4-fold increase in monoterpene emissions and up to a 40% increase in SOA concentrations in some years (in a scenario where the attack effect is based on observed lodgepole pine response. Responses to beetle attack depend on the extent of previous mortality and the number of trees under attack in a given year, which can vary greatly over space and time. Simulated enhancements peak in 2004 (British Columbia and 2008 (US. Responses to beetle attack are shown to be substantially larger (up to a 3-fold localized increase in summertime SOA concentrations in a scenario based on bark-beetle attack in spruce trees. Placed in the context of observations from the IMPROVE network, the changes in SOA concentrations due to beetle attack are in most cases small compared to the large annual and interannual variability in total organic aerosol which is driven by wildfire activity in western North America. This indicates that most beetle-induced SOA changes are not likely detectable in current observation networks; however, these changes may impede efforts to achieve natural visibility conditions in the national parks and wilderness

  9. Ice nucleation in sulfuric acid/organic aerosols: implications for cirrus cloud formation

    Directory of Open Access Journals (Sweden)

    M. R. Beaver

    2006-01-01

    Full Text Available Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C3 to C10 and ketones (C3 and C9 on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point were found to play a dominant role in determining the inferred mode of nucleation (homogenous or heterogeneous and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C4-C7, (of intermediate solubility and melting temperatures nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.

  10. Characterization of primary organic aerosol emissions from meat cooking, trash burning, and motor vehicles with high-resolution aerosol mass spectrometry and comparison with ambient and chamber observations.

    Science.gov (United States)

    Mohr, Claudia; Huffman, Alex; Cubison, Michael J; Aiken, Allison C; Docherty, Kenneth S; Kimmel, Joel R; Ulbrich, Ingrid M; Hannigan, Michael; Jimenez, Jose L

    2009-04-01

    Organic aerosol (OA) emissions from motor vehicles, meat-cooking and trash burning are analyzed here using a high-resolution aerosol mass spectrometer (AMS). High resolution data show that aerosols emitted by combustion engines and plastic burning are dominated by hydrocarbon-like organic compounds. Meat cooking and especially paper burning emissions contain significant fractions of oxygenated organic compounds; however, their unit-resolution mass spectral signatures are very similar to those from ambient hydrocarbon-like OA, and very different from the mass spectra of ambient secondary or oxygenated OA (OOA). Thus, primary OA from these sources is unlikelyto be a significant direct source of ambient OOA. There are significant differences in high-resolution tracer m/zs that may be useful for differentiating some of these sources. Unlike in most ambient spectra, all of these sources have low total m/z 44 and this signal is not dominated by the CO2+ ion. All sources have high m/z 57, which is low during high OOA ambient periods. Spectra from paper burning are similar to some types of biomass burning OA, with elevated m/z 60. Meat cooking aerosols also have slightly elevated m/z 60, whereas motor vehicle emissions have very low signal at this m/z.

  11. Organic compounds in aerosols from selected European sites - Biogenic versus anthropogenic sources

    Science.gov (United States)

    Alves, Célia; Vicente, Ana; Pio, Casimiro; Kiss, Gyula; Hoffer, Andras; Decesari, Stefano; Prevôt, André S. H.; Minguillón, María Cruz; Querol, Xavier; Hillamo, Risto; Spindler, Gerald; Swietlicki, Erik

    2012-11-01

    Atmospheric aerosol samples from a boreal forest (Hyytiälä, April 2007), a rural site in Hungary (K-puszta, summer 2008), a polluted rural area in Italy (San Pietro Capofiume, Po Valley, April 2008), a moderately polluted rural site in Germany located on a meadow (Melpitz, May 2008), a natural park in Spain (Montseny, March 2009) and two urban background locations (Zurich, December 2008, and Barcelona, February/March 2009) were collected. Aliphatics, polycyclic aromatic hydrocarbons, carbonyls, sterols, n-alkanols, acids, phenolic compounds and anhydrosugars in aerosols were chemically characterised by gas chromatography-mass spectrometry, along with source attribution based on the carbon preference index (CPI), the ratios between the unresolved and the chromatographically resolved aliphatics, the contribution of wax n-alkanes, n-alkanols and n-alkanoic acids from plants, diagnostic ratios of individual target compounds and source-specific markers to organic carbon ratios. In spite of transboundary pollution episodes, Hyytiälä registered the lowest levels among all locations. CPI values close to 1 for the aliphatic fraction of the Montseny aerosol suggest that the anthropogenic input may be associated with the transport of aged air masses from the surrounding industrial/urban areas, which superimpose the locally originated hydrocarbons with biogenic origin. Aliphatic and aromatic hydrocarbons in samples from San Pietro Capofiume reveal that fossil fuel combustion is a major source influencing the diel pattern of concentrations. This source contributed to 25-45% of the ambient organic carbon (OC) at the Po Valley site. Aerosols from the German meadow presented variable contributions from both biogenic and anthropogenic sources. The highest levels of vegetation wax components and biogenic secondary organic aerosol (SOA) products were observed at K-puszta, while anthropogenic SOA compounds predominated in Barcelona. The primary vehicular emissions in the Spanish

  12. An advanced technique for speciation of organic nitrogen in atmospheric aerosols

    Science.gov (United States)

    Samy, S.; Robinson, J.; Hays, M. D.

    2011-12-01

    The chemical composition of organic nitrogen (ON) in the environment is a research topic of broad significance. The topic intersects the branches of atmospheric, aquatic, and ecological science; thus, a variety of instrumentation, analytical methods, and data interpretation tools have evolved for determination of ON. Recent studies that focus on atmospheric particulate nitrogen (N) suggest a significant fraction (20-80%) of total N is bound in organic compounds. The sources, bioavailability and transport mechanisms of these N-containing compounds can differ, producing a variety of environmental consequences. Amino acids (AA) are a key class of atmospheric ON compounds that can contribute to secondary organic aerosol (SOA) formation and potentially influence water cycles, air pollutant scavenging, and the radiation balance. AA are water-soluble organic compounds (WSOC) that can significantly alter the acid-base chemistry of aerosols, and may explain the buffering capacity that impacts heterogeneous atmospheric chemistry. The chemical transformations that N-containing organic compounds (including AA) undergo can increase the light-absorbing capacity of atmospheric carbon via formation of 'brown carbon'. Suggested sources of atmospheric AA include: marine surface layer transport from bursting sea bubbles, the suspension of bacteria, fungi, algae, pollen, spores, or biomass burning. Methodology for detection of native (underivatized) amino acids (AA) in atmospheric aerosols has been developed and validated (Samy et al., 2011). This presentation describes the use of LC-MS (Q-TOF) and microwave-assisted gas phase hydrolysis for detection of free and combined amino acids in aerosols collected in a Southeastern U.S. forest environment. Accurate mass detection and the addition of isotopically labeled surrogates prior to sample preparation allows for sensitive quantitation of target AA in a complex aerosol matrix. A total of 16 native AA were detected above the reporting

  13. Connecting Organic Aerosol Climate-Relevant Properties to Chemical Mechanisms of Sources and Processing

    Energy Technology Data Exchange (ETDEWEB)

    Thornton, Joel [Univ. of Washington, Seattle, WA (United States)

    2015-01-26

    The research conducted on this project aimed to improve our understanding of secondary organic aerosol (SOA) formation in the atmosphere, and how the properties of the SOA impact climate through its size, phase state, and optical properties. The goal of this project was to demonstrate that the use of molecular composition information to mechanistically connect source apportionment and climate properties can improve the physical basis for simulation of SOA formation and properties in climate models. The research involved developing and improving methods to provide online measurements of the molecular composition of SOA under atmospherically relevant conditions and to apply this technology to controlled simulation chamber experiments and field measurements. The science we have completed with the methodology will impact the simulation of aerosol particles in climate models.

  14. Diffusivity measurements of volatile organics in levitated viscous aerosol particles

    Science.gov (United States)

    Bastelberger, Sandra; Krieger, Ulrich K.; Luo, Beiping; Peter, Thomas

    2017-07-01

    Field measurements indicating that atmospheric secondary organic aerosol (SOA) particles can be present in a highly viscous, glassy state have spurred numerous studies addressing low diffusivities of water in glassy aerosols. The focus of these studies is on kinetic limitations of hygroscopic growth and the plasticizing effect of water. In contrast, much less is known about diffusion limitations of organic molecules and oxidants in viscous matrices. These may affect atmospheric chemistry and gas-particle partitioning of complex mixtures with constituents of different volatility. In this study, we quantify the diffusivity of a volatile organic in a viscous matrix. Evaporation of single particles generated from an aqueous solution of sucrose and small amounts of volatile tetraethylene glycol (PEG-4) is investigated in an electrodynamic balance at controlled relative humidity (RH) and temperature. The evaporative loss of PEG-4 as determined by Mie resonance spectroscopy is used in conjunction with a radially resolved diffusion model to retrieve translational diffusion coefficients of PEG-4. Comparison of the experimentally derived diffusivities with viscosity estimates for the ternary system reveals a breakdown of the Stokes-Einstein relationship, which has often been invoked to infer diffusivity from viscosity. The evaporation of PEG-4 shows pronounced RH and temperature dependencies and is severely depressed for RH ≲ 30 %, corresponding to diffusivities pollutant molecules such as polycyclic aromatic hydrocarbons (PAHs).

  15. Submicron organic aerosol in Tijuana, Mexico, from local and Southern California sources during the CalMex campaign

    Science.gov (United States)

    Takahama, S.; Johnson, A.; Guzman Morales, J.; Russell, L. M.; Duran, R.; Rodriguez, G.; Zheng, J.; Zhang, R.; Toom-Sauntry, D.; Leaitch, W. R.

    2013-05-01

    The CalMex campaign was conducted from May 15 to June 30 of 2010 to study the properties and sources of air pollution in Tijuana, Mexico. In this study, submicron organic aerosol mass (OM) composition measured by Fourier Transform Infrared Spectroscopy (FTIR), Aerosol Chemical Speciation Monitor (ACSM), and X-ray spectromicroscopy are combined with statistical analysis and measurements of other atmospheric constituents. The average (±one standard deviation) OM concentration was 3.3 ± 1.7 μg m-3. A large source of submicron aerosol mass at this location was determined to be vehicular sources, which contributed approximately 40% to the submicron OM; largely during weekday mornings. The O/C ratio estimated from ACSM measurements was 0.64 ± 0.19; diurnal variations in this value and the more oxygenated fraction of OM as determined from Positive Matrix Factorization and classification analyses suggest the high degree of oxygenation originates from aged OM, rather than locally-produced secondary organic aerosol. A large contribution of this oxygenated aerosol to Tijuana from various source classes was observed; some fraction of this aerosol mass may be associated with non-refractory components, such as dust or BC. Backtrajectory simulations using the HYSPLIT model suggest that the mean wind vector consistently originated from the northwest region, over the Pacific Ocean and near the Southern California coast, which suggests that the origin of much of the oxygenated organic aerosol observed in Tijuana (as much as 60% of OM) may have been the Southern California Air Basin. The marine aerosol contribution to OM during the period was on average 23 ± 24%, though its contribution varied over synoptic rather than diurnal timescales. BB aerosol contributed 20 ± 20% of the OM during the campaign period, with notable BB events occurring during several weekend evenings.

  16. Indoor secondary organic aerosols formation from ozonolysis of monoterpene: An example of d-limonene with ammonia and potential impacts on pulmonary inflammations.

    Science.gov (United States)

    Niu, Xinyi; Ho, Steven Sai Hang; Ho, Kin Fai; Huang, Yu; Cao, Junji; Shen, Zhenxing; Sun, Jian; Wang, Xiumei; Wang, Yu; Lee, Shuncheng; Huang, Rujin

    2017-02-01

    Monoterpene is one class of biogenic volatile organic compounds (BVOCs) which widely presents in household cleaning products and air fresheners. It plays reactive role in secondary organic aerosols (SOAs) formation with ozone (O 3 ) in indoor environments. Such ozonolysis can be influenced by the presence of gaseous pollutants such as ammonia (NH 3 ). This study focuses on investigations of ozone-initiated formation of indoor SOAs with d-limonene, one of the most abundant indoor monoterpenes, in a large environmental chamber. The maximum total particle number concentration from the ozonolysis in the presence of NH 3 was 60% higher than that in the absence of NH 3 . Both of the nuclei coagulation and condensation involve in the SOAs growth. The potential risks of pulmonary injury for the exposure to the secondary particles formed were presented with the indexes of tumor necrosis factor-α (TNF-α), interleukin-6 (IL-6) and interleukin-10 (IL-10) expression levels in bronchoalveolar lavage fluid (BALF) upon intratracheal instillation in mice lung for 6 and 12h. The results indicated that there was 22-39% stronger pulmonary inflammatory effect on the particles generated with NH 3 . This is a pilot study which demonstrates the toxicities of the indoor SOAs formed from the ozonolysis of a monoterpene. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

    Science.gov (United States)

    Pindado, Oscar; Pérez, Rosa M. a.; García, Susana; Sánchez, Miguel; Galán, Pilar; Fernández, Marta

    The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σ n-alkane and ΣPAHs ranged from 3 to 81 ng m -3 and 0.1 to 6 ng m -3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m -3 and 39 to 733 ng m -3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.

  18. Hydrolysis of glyoxal in water-restricted environments: formation of organic aerosol precursors through formic acid catalysis.

    Science.gov (United States)

    Hazra, Montu K; Francisco, Joseph S; Sinha, Amitabha

    2014-06-12

    The hydrolysis of glyoxal involving one to three water molecules and also in the presence of a water molecule and formic acid has been investigated. Our results show that glyoxal-diol is the major product of the hydrolysis and that formic acid, through its ability to facilitate intermolecular hydrogen atom transfer, is considerably more efficient than water as a catalyst in the hydrolysis process. Additionally, once the glyoxal-diol is formed, the barrier for further hydrolysis to form the glyoxal-tetrol is effectively reduced to zero in the presence of a single water and formic acid molecule. There are two important implications arising from these findings. First, the results suggest that under the catalytic influence of formic acid, glyoxal hydrolysis can impact the growth of atmospheric aerosols. As a result of enhanced hydrogen bonding, mediated through their polar OH functional groups, the diol and tetrol products are expected to have significantly lower vapor pressure than the parent glyoxal molecule; hence they can more readily partition into the particle phase and contribute to the growth of secondary organic aerosols. In addition, our findings provide insight into how glyoxal-diol and glyoxal-tetrol might be formed under atmospheric conditions associated with water-restricted environments and strongly suggest that the formation of these precursors for secondary organic aerosol growth is not likely restricted solely to the bulk aqueous phase as is currently assumed.

  19. Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

    Science.gov (United States)

    Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

    2015-04-21

    Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

  20. Diurnal variations of organic molecular tracers and stable carbon isotopic compositions in atmospheric aerosols over Mt. Tai in North China Plain: an influence of biomass burning

    Science.gov (United States)

    Fu, P. Q.; Kawamura, K.; Chen, J.; Li, J.; Sun, Y. L.; Liu, Y.; Tachibana, E.; Aggarwal, S. G.; Okuzawa, K.; Tanimoto, H.; Kanaya, Y.; Wang, Z. F.

    2012-04-01

    Organic tracer compounds of tropospheric aerosols, as well as organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and stable carbon isotope ratios (δ13C) of total carbon (TC) have been investigated for aerosol samples collected during early and late periods of Mount Tai eXperiment 2006 (MTX2006) field campaign in North China Plain. Total solvent extracts were investigated by gas chromatography/mass spectrometry. More than 130 organic compounds were detected in the aerosol samples. They were grouped into twelve organic compound classes, including biomass burning tracers, biogenic primary sugars, biogenic secondary organic aerosol (SOA) tracers, and anthropogenic tracers such as phthalates, hopanes and polycyclic aromatic hydrocarbons (PAHs). In early June when the field burning activities of wheat straws in North China Plain were very active, the total identified organics (2090 ± 1170 ng m-3) were double those in late June (926 ± 574 ng m-3). All the compound classes were more abundant in early June than in late June, except phthalate esters, which were higher in late June. Levoglucosan (88-1210 ng m-3, 403 ng m-3) was found as the most abundant single compound in early June, while diisobutyl phthalate was the predominant species in late June. During the biomass-burning period in early June, the diurnal trends of most of the primary and secondary organic aerosol tracers were characterized by the concentration peaks observed at mid-night or in early morning, while in late June most of the organic species peaked in late afternoon. This suggests that smoke plumes from biomass burning can uplift the aerosol particulate matter to a certain altitude and then transported to and encountered the summit of Mt. Tai during nighttime. On the basis of the tracer-based method for the estimation of biomass-burning OC, fungal-spore OC and biogenic secondary organic carbon (SOC), we estimate that an average of 24% (up to 64%) of the OC in the Mt. Tai

  1. Modeling reactive ammonia uptake by secondary organic aerosol in CMAQ: application to the continental US

    Directory of Open Access Journals (Sweden)

    S. Zhu

    2018-03-01

    Full Text Available Ammonium salts such as ammonium nitrate and ammonium sulfate constitute an important fraction of the total fine particulate matter (PM2.5 mass. While the conversion of inorganic gases into particulate-phase sulfate, nitrate, and ammonium is now well understood, there is considerable uncertainty over interactions between gas-phase ammonia and secondary organic aerosols (SOAs. Observations have confirmed that ammonia can react with carbonyl compounds in SOA, forming nitrogen-containing organic compounds (NOCs. This chemistry consumes gas-phase NH3 and may therefore affect the amount of ammonium nitrate and ammonium sulfate in particulate matter (PM as well as particle acidity. In order to investigate the importance of such reactions, a first-order loss rate for ammonia onto SOA was implemented into the Community Multiscale Air Quality (CMAQ model based on the ammonia uptake coefficients reported in the literature. Simulations over the continental US were performed for the winter and summer of 2011 with a range of uptake coefficients (10−3–10−5. Simulation results indicate that a significant reduction in gas-phase ammonia may be possible due to its uptake onto SOA; domain-averaged ammonia concentrations decrease by 31.3 % in the winter and 67.0 % in the summer with the highest uptake coefficient (10−3. As a result, the concentration of particulate matter is also significantly affected, with a distinct spatial pattern over different seasons. PM concentrations decreased during the winter, largely due to the reduction in ammonium nitrate concentrations. On the other hand, PM concentrations increased during the summer due to increased biogenic SOA (BIOSOA production resulting from enhanced acid-catalyzed uptake of isoprene-derived epoxides. Since ammonia emissions are expected to increase in the future, it is important to include NH3 + SOA chemistry in air quality models.

  2. Modeling reactive ammonia uptake by secondary organic aerosol in CMAQ: application to the continental US

    Science.gov (United States)

    Zhu, Shupeng; Horne, Jeremy R.; Montoya-Aguilera, Julia; Hinks, Mallory L.; Nizkorodov, Sergey A.; Dabdub, Donald

    2018-03-01

    Ammonium salts such as ammonium nitrate and ammonium sulfate constitute an important fraction of the total fine particulate matter (PM2.5) mass. While the conversion of inorganic gases into particulate-phase sulfate, nitrate, and ammonium is now well understood, there is considerable uncertainty over interactions between gas-phase ammonia and secondary organic aerosols (SOAs). Observations have confirmed that ammonia can react with carbonyl compounds in SOA, forming nitrogen-containing organic compounds (NOCs). This chemistry consumes gas-phase NH3 and may therefore affect the amount of ammonium nitrate and ammonium sulfate in particulate matter (PM) as well as particle acidity. In order to investigate the importance of such reactions, a first-order loss rate for ammonia onto SOA was implemented into the Community Multiscale Air Quality (CMAQ) model based on the ammonia uptake coefficients reported in the literature. Simulations over the continental US were performed for the winter and summer of 2011 with a range of uptake coefficients (10-3-10-5). Simulation results indicate that a significant reduction in gas-phase ammonia may be possible due to its uptake onto SOA; domain-averaged ammonia concentrations decrease by 31.3 % in the winter and 67.0 % in the summer with the highest uptake coefficient (10-3). As a result, the concentration of particulate matter is also significantly affected, with a distinct spatial pattern over different seasons. PM concentrations decreased during the winter, largely due to the reduction in ammonium nitrate concentrations. On the other hand, PM concentrations increased during the summer due to increased biogenic SOA (BIOSOA) production resulting from enhanced acid-catalyzed uptake of isoprene-derived epoxides. Since ammonia emissions are expected to increase in the future, it is important to include NH3 + SOA chemistry in air quality models.

  3. Sources and atmospheric processing of organic aerosol in the Mediterranean: insights from aerosol mass spectrometer factor analysis

    Directory of Open Access Journals (Sweden)

    L. Hildebrandt

    2011-12-01

    Full Text Available Atmospheric particles were measured in the late winter (25 February–26 March 2009 at a remote coastal site on the island of Crete, Greece during the Finokalia Aerosol Measurement Experiment-2009. A quadrupole aerosol mass spectrometer (Q-AMS was employed to quantify the size-resolved chemical composition of non-refractory submicron aerosol, and a thermodenuder was used to analyze the organic aerosol (OA volatility. Complementary measurements included particle size distributions from a scanning mobility particle sizer, inorganic and organic particle composition from filter analysis, air ion concentrations, O3, NOx and NOy concentrations, and meteorological measurements. Factor analysis was performed on the OA mass spectra, and the variability in OA composition could best be explained with three OA components. The oxygenated organic aerosol (OOA was similar in composition and volatility to the summertime OA previously measured at this site and may represent an effective endpoint in particle-phase oxidation of organics. The two other OA components, one associated with amines (Amine-OA and the other probably associated with the burning of olive branches (OB-OA, had very low volatility but were less oxygenated. Hydrocarbon-like organic aerosol (HOA was not detected. The absence of OB-OA and Amine-OA in the summer data may be due to lower emissions and/or photochemical conversion of these components to OOA.

  4. Development and first application of an Aerosol Collection Module (ACM) for quasi online compound specific aerosol measurements

    Science.gov (United States)

    Hohaus, Thorsten; Kiendler-Scharr, Astrid; Trimborn, Dagmar; Jayne, John; Wahner, Andreas; Worsnop, Doug

    2010-05-01

    Atmospheric aerosols influence climate and human health on regional and global scales (IPCC, 2007). In many environments organics are a major fraction of the aerosol influencing its properties. Due to the huge variety of organic compounds present in atmospheric aerosol current measurement techniques are far from providing a full speciation of organic aerosol (Hallquist et al., 2009). The development of new techniques for compound specific measurements with high time resolution is a timely issue in organic aerosol research. Here we present first laboratory characterisations of an aerosol collection module (ACM) which was developed to allow for the sampling and transfer of atmospheric PM1 aerosol. The system consists of an aerodynamic lens system focussing particles on a beam. This beam is directed to a 3.4 mm in diameter surface which is cooled to -30 °C with liquid nitrogen. After collection the aerosol sample can be evaporated from the surface by heating it to up to 270 °C. The sample is transferred through a 60cm long line with a carrier gas. In order to test the ACM for linearity and sensitivity we combined it with a GC-MS system. The tests were performed with octadecane aerosol. The octadecane mass as measured with the ACM-GC-MS was compared versus the mass as calculated from SMPS derived total volume. The data correlate well (R2 0.99, slope of linear fit 1.1) indicating 100 % collection efficiency. From 150 °C to 270 °C no effect of desorption temperature on transfer efficiency could be observed. The ACM-GC-MS system was proven to be linear over the mass range 2-100 ng and has a detection limit of ~ 2 ng. First experiments applying the ACM-GC-MS system were conducted at the Jülich Aerosol Chamber. Secondary organic aerosol (SOA) was formed from ozonolysis of 600 ppbv of b-pinene. The major oxidation product nopinone was detected in the aerosol and could be shown to decrease from 2 % of the total aerosol to 0.5 % of the aerosol over the 48 hours of

  5. Characterizing Organic Aerosol Processes and Climatically Relevant Properties via Advanced and Integrated Analyses of Aerosol Mass Spectrometry Datasets from DOE Campaigns and ACRF Measurements. Final report for DE-SC0007178

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Qi [Univ. of California, Davis, CA (United States)

    2017-05-21

    Organic aerosols (OA) are an important but poorly characterized component of the earth’s climate system. Enormous complexities commonly associated with OA composition and life cycle processes have significantly complicated the simulation and quantification of aerosol effects. To unravel these complexities and improve understanding of the properties, sources, formation, evolution processes, and radiative properties of atmospheric OA, we propose to perform advanced and integrated analyses of multiple DOE aerosol mass spectrometry datasets, including two high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) datasets from intensive field campaigns on the aerosol life cycle and the Aerosol Chemical Speciation Monitor (ACSM) datasets from long-term routine measurement programs at ACRF sites. In this project, we will focus on 1) characterizing the chemical (i.e., composition, organic elemental ratios), physical (i.e., size distribution and volatility), and radiative (i.e., sub- and super-saturated growth) properties of organic aerosols, 2) examining the correlations of these properties with different source and process regimes (e.g., primary, secondary, urban, biogenic, biomass burning, marine, or mixtures), 3) quantifying the evolutions of these properties as a function of photochemical processing, 4) identifying and characterizing special cases for important processes such as SOA formation and new particle formation and growth, and 5) correlating size-resolved aerosol chemistry with measurements of radiative properties of aerosols to determine the climatically relevant properties of OA and characterize the relationship between these properties and processes of atmospheric aerosol organics. Our primary goal is to improve a process-level understanding of the life cycle of organic aerosols in the Earth’s atmosphere. We will also aim at bridging between observations and models via synthesizing and translating the results and insights generated from this

  6. Local source impacts on primary and secondary aerosols in the Midwestern United States

    Science.gov (United States)

    Jayarathne, Thilina; Rathnayake, Chathurika M.; Stone, Elizabeth A.

    2016-04-01

    Atmospheric particulate matter (PM) exhibits heterogeneity in composition across urban areas, leading to poor representation of outdoor air pollutants in human exposure assessments. To examine heterogeneity in PM composition and sources across an urban area, fine particulate matter samples (PM2.5) were chemically profiled in Iowa City, IA from 25 August to 10 November 2011 at two monitoring stations. The urban site is the federal reference monitoring (FRM) station in the city center and the peri-urban site is located 8.0 km to the west on the city edge. Measurements of PM2.5 carbonaceous aerosol, inorganic ions, molecular markers for primary sources, and secondary organic aerosol (SOA) tracers were used to assess statistical differences in composition and sources across the two sites. PM2.5 mass ranged from 3 to 26 μg m-3 during this period, averaging 11.2 ± 4.9 μg m-3 (n = 71). Major components of PM2.5 at the urban site included organic carbon (OC; 22%), ammonium (14%), sulfate (13%), nitrate (7%), calcium (2.9%), and elemental carbon (EC; 2.2%). Periods of elevated PM were driven by increases in ammonium, sulfate, and SOA tracers that coincided with hot and dry conditions and southerly winds. Chemical mass balance (CMB) modeling was used to apportion OC to primary sources; biomass burning, vegetative detritus, diesel engines, and gasoline engines accounted for 28% of OC at the urban site and 24% of OC at the peri-urban site. Secondary organic carbon from isoprene and monoterpene SOA accounted for an additional 13% and 6% of OC at the urban and peri-urban sites, respectively. Differences in biogenic SOA across the two sites were associated with enhanced combustion activities in the urban area and higher aerosol acidity at the urban site. Major PM constituents (e.g., OC, ammonium, sulfate) were generally well-represented by a single monitoring station, indicating a regional source influence. Meanwhile, nitrate, biomass burning, food cooking, suspended dust, and

  7. Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study

    Directory of Open Access Journals (Sweden)

    W. Rattanavaraha

    2016-04-01

    Full Text Available In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA that contributes to fine particulate matter (PM2.5. Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2, oxides of nitrogen (NOx, and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter samples were collected at the Birmingham, Alabama (BHM, ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS. Sample extracts were analyzed by gas chromatography–electron ionization-mass spectrometry (GC/EI-MS with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM ( ∼  7 to  ∼  20 %. Isoprene-derived SOA tracers correlated with sulfate (SO42− (r2 = 0.34, n = 117 but not with NOx. Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML-derived SOA tracers with nitrate radical production (P[NO3] (r2 = 0.57, n = 40 were observed during nighttime, suggesting a

  8. Measurements of organic gases during aerosol formation events in the boreal forest atmosphere during QUEST

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    K. Sellegri

    2005-01-01

    Full Text Available Biogenic VOCs are important in the growth and possibly also in the early stages of formation of atmospheric aerosol particles. In this work, we present 10 min-time resolution measurements of organic trace gases at Hyytiälä, Finland during March 2002. The measurements were part of the project QUEST (Quantification of Aerosol Nucleation in the European Boundary Layer and took place during a two-week period when nucleation events occurred with various intensities nearly every day. Using a ground-based Chemical Ionization Mass Spectrometer (CIMS instrument, the following trace gases were detected: acetone, TMA, DMA, mass 68amu (candidate=isoprene, monoterpenes, methyl vinyl ketone (MVK and methacrolein (MaCR and monoterpene oxidation products (MTOP. For all of them except for the amines, we present daily variations during different classes of nucleation events, and non-event days. BVOC oxidation products (MVK, MaCR and MTOP show a higher ratio to the CS on event days compared to non-event days, indicating that their abundance relative to the surface of aerosol available is higher on nucleation days. Moreover, BVOC oxidation products are found to show significant correlations with the condensational sink (CS on nucleation event days, which indicates that they are representative of less volatile organic compounds that contribute to the growth of the nucleated particles and generally secondary organic aerosol formation. Behaviors of BVOC on event and non event days are compared to the behavior of CO.

  9. Organic Aerosol Component (OACOMP) Value-Added Product Report

    Energy Technology Data Exchange (ETDEWEB)

    Fast, J; Zhang, Q; Tilp, A; Shippert, T; Parworth, C; Mei, F

    2013-08-23

    Significantly improved returns in their aerosol chemistry data can be achieved via the development of a value-added product (VAP) of deriving OA components, called Organic Aerosol Components (OACOMP). OACOMP is primarily based on multivariate analysis of the measured organic mass spectral matrix. The key outputs of OACOMP are the concentration time series and the mass spectra of OA factors that are associated with distinct sources, formation and evolution processes, and physicochemical properties.

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

    Directory of Open Access Journals (Sweden)

    N. Sareen

    2016-11-01

    Full Text Available 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

  11. Characterization of water-soluble organic aerosol in coastal New England: Implications of variations in size distribution

    Science.gov (United States)

    Ziemba, L. D.; Griffin, R. J.; Whitlow, S.; Talbot, R. W.

    2011-12-01

    Size distributions up to 10-micron aerosol diameter ( DP) of organic carbon (OC) and water-soluble organic carbon (WSOC) were measured at two sites in coastal New England, slightly inland at Thompson Farm (TF) and offshore at Isles of Shoals (IOS). Significant OC concentrations were measured across the full size distribution at TF and IOS, respectively. The WSOC fraction (WSOC/OC) was largest in the accumulation mode with values of 0.86 and 0.93 and smallest in the coarse mode with values of 0.61 and 0.79 at TF and IOS, respectively. Dicarboxylic acids containing up to five carbon atoms (C 5) were concentrated in droplet and accumulation mode aerosol with only minor contributions in the coarse mode. C 1-C 3 monocarboxylic acids were generally near or below detection limits. Results from proton nuclear magnetic resonance (H +-NMR) spectroscopy analyses showed that the organic functional group characterized by protons in the alpha position to an unsaturated carbon atoms ([H-C-C dbnd ]) was the dominant WSOC functionality at both TF and IOS, constituting 34 and 43% of carbon-weighted H +-NMR signal, respectively. Size distributions of each H +-NMR-resolved organic functionality are presented. Source apportionment using H +-NMR fingerprints is also presented, and results indicate that nearly all of the WSOC at TF and IOS spectroscopically resembled secondary organic aerosol, regardless of DP.

  12. Long-term chemical analysis and organic aerosol source apportionment at nine sites in central Europe: source identification and uncertainty assessment

    Science.gov (United States)

    Daellenbach, Kaspar R.; Stefenelli, Giulia; Bozzetti, Carlo; Vlachou, Athanasia; Fermo, Paola; Gonzalez, Raquel; Piazzalunga, Andrea; Colombi, Cristina; Canonaco, Francesco; Hueglin, Christoph; Kasper-Giebl, Anne; Jaffrezo, Jean-Luc; Bianchi, Federico; Slowik, Jay G.; Baltensperger, Urs; El-Haddad, Imad; Prévôt, André S. H.

    2017-11-01

    Long-term monitoring of organic aerosol is important for epidemiological studies, validation of atmospheric models, and air quality management. In this study, we apply a recently developed filter-based offline methodology using an aerosol mass spectrometer (AMS) to investigate the regional and seasonal differences of contributing organic aerosol sources. We present offline AMS measurements for particulate matter smaller than 10 µm at nine stations in central Europe with different exposure characteristics for the entire year of 2013 (819 samples). The focus of this study is a detailed source apportionment analysis (using positive matrix factorization, PMF) including in-depth assessment of the related uncertainties. Primary organic aerosol (POA) is separated in three components: hydrocarbon-like OA related to traffic emissions (HOA), cooking OA (COA), and biomass burning OA (BBOA). We observe enhanced production of secondary organic aerosol (SOA) in summer, following the increase in biogenic emissions with temperature (summer oxygenated OA, SOOA). In addition, a SOA component was extracted that correlated with an anthropogenic secondary inorganic species that is dominant in winter (winter oxygenated OA, WOOA). A factor (sulfur-containing organic, SC-OA) explaining sulfur-containing fragments (CH3SO2+), which has an event-driven temporal behaviour, was also identified. The relative yearly average factor contributions range from 4 to 14 % for HOA, from 3 to 11 % for COA, from 11 to 59 % for BBOA, from 5 to 23 % for SC-OA, from 14 to 27 % for WOOA, and from 15 to 38 % for SOOA. The uncertainty of the relative average factor contribution lies between 2 and 12 % of OA. At the sites north of the alpine crest, the sum of HOA, COA, and BBOA (POA) contributes less to OA (POA / OA = 0.3) than at the southern alpine valley sites (0.6). BBOA is the main contributor to POA with 87 % in alpine valleys and 42 % north of the alpine crest. Furthermore, the influence of primary

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

    Science.gov (United States)

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

    2011-03-01

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

  14. Persistence of urban organic aerosols composition: Decoding their structural complexity and seasonal variability.

    Science.gov (United States)

    Matos, João T V; Duarte, Regina M B O; Lopes, Sónia P; Silva, Artur M S; Duarte, Armando C

    2017-12-01

    Organic Aerosols (OAs) are typically defined as highly complex matrices whose composition changes in time and space. Focusing on time vector, this work uses two-dimensional nuclear magnetic resonance (2D NMR) techniques to examine the structural features of water-soluble (WSOM) and alkaline-soluble organic matter (ASOM) sequentially extracted from fine atmospheric aerosols collected in an urban setting during cold and warm seasons. This study reveals molecular signatures not previously decoded in NMR-related studies of OAs as meaningful source markers. Although the ASOM is less hydrophilic and structurally diverse than its WSOM counterpart, both fractions feature a core with heteroatom-rich branched aliphatics from both primary (natural and anthropogenic) and secondary origin, aromatic secondary organics originated from anthropogenic aromatic precursors, as well as primary saccharides and amino sugar derivatives from biogenic emissions. These common structures represent those 2D NMR spectral signatures that are present in both seasons and can thus be seen as an "annual background" profile of the structural composition of OAs at the urban location. Lignin-derived structures, nitroaromatics, disaccharides, and anhydrosaccharides signatures were also identified in the WSOM samples only from periods identified as smoke impacted, which reflects the influence of biomass-burning sources. The NMR dataset on the H-C molecules backbone was also used to propose a semi-quantitative structural model of urban WSOM, which will aid efforts for more realistic studies relating the chemical properties of OAs with their atmospheric behavior. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Photochemical age of air pollutants, ozone, and secondary organic aerosol in transboundary air observed on Fukue Island, Nagasaki, Japan

    Directory of Open Access Journals (Sweden)

    S. Irei

    2016-04-01

    Full Text Available To better understand the secondary air pollution in transboundary air over westernmost Japan, ground-based field measurements of the chemical composition of fine particulate matter ( ≤  1 µm, mixing ratios of trace gas species (CO, O3, NOx, NOy, i-pentane, toluene, and ethyne, and meteorological elements were conducted with a suite of instrumentation. The CO mixing ratio dependence on wind direction showed that there was no significant influence from primary emission sources near the monitoring site, indicating long- and/or mid-range transport of the measured chemical species. Despite the considerably different atmospheric lifetimes of NOy and CO, these mixing ratios were correlated (r2 = 0.67. The photochemical age of the pollutants, t[OH] (the reaction time  ×  the mean concentration of OH radical during the atmospheric transport, was calculated from both the NOx ∕ NOy concentration ratio (NOx ∕ NOy clock and the toluene ∕ ethyne concentration ratio (hydrocarbon clock. It was found that the toluene / ethyne concentration ratio was significantly influenced by dilution with background air containing 0.16 ppbv of ethyne, causing significant bias in the estimation of t[OH]. In contrast, the influence of the reaction of NOx with O3, a potentially biasing reaction channel on [NOx] / [NOy], was small. The t[OH] values obtained with the NOx ∕ NOy clock ranged from 2.9  ×  105 to 1.3  ×  108 h molecule cm−3 and were compared with the fractional contribution of the m∕z 44 signal to the total signal in the organic aerosol mass spectra (f44, a quantitative oxidation indicator of carboxylic acids and O3 mixing ratio. The comparison of t[OH] with f44 showed evidence for a systematic increase of f44 as t[OH] increased, an indication of secondary organic aerosol (SOA formation. To a first approximation, the f44 increase rate was (1.05 ± 0.03  ×  10−9

  16. High summertime aerosol organic functional group concentrations from marine and seabird sources at Ross Island, Antarctica, during AWARE

    Directory of Open Access Journals (Sweden)

    J. Liu

    2018-06-01

    Full Text Available Observations of the organic components of the natural aerosol are scarce in Antarctica, which limits our understanding of natural aerosols and their connection to seasonal and spatial patterns of cloud albedo in the region. From November 2015 to December 2016, the ARM West Antarctic Radiation Experiment (AWARE measured submicron aerosol properties near McMurdo Station at the southern tip of Ross Island. Submicron organic mass (OM, particle number, and cloud condensation nuclei concentrations were higher in summer than other seasons. The measurements included a range of compositions and concentrations that likely reflected both local anthropogenic emissions and natural background sources. We isolated the natural organic components by separating a natural factor and a local combustion factor. The natural OM was 150 times higher in summer than in winter. The local anthropogenic emissions were not hygroscopic and had little contribution to the CCN concentrations. Natural sources that included marine sea spray and seabird emissions contributed 56 % OM in summer but only 3 % in winter. The natural OM had high hydroxyl group fraction (55 %, 6 % alkane, and 6 % amine group mass, consistent with marine organic composition. In addition, the Fourier transform infrared (FTIR spectra showed the natural sources of organic aerosol were characterized by amide group absorption, which may be from seabird populations. Carboxylic acid group contributions were high in summer and associated with natural sources, likely forming by secondary reactions.

  17. Influence of intense secondary aerosol formation and long-range transport on aerosol chemistry and properties in the Seoul Metropolitan Area during spring time: results from KORUS-AQ

    Science.gov (United States)

    Kim, Hwajin; Zhang, Qi; Heo, Jongbae

    2018-05-01

    Non-refractory submicrometer particulate matter (NR-PM1) was measured in the Seoul Metropolitan Area (SMA), Korea, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) from 14 April to 15 June 2016, as a part of the Korea-US Air Quality Study (KORUS-AQ) campaign. This was the first highly time-resolved, real-time measurement study of springtime aerosol in SMA and the results reveal valuable insights into the sources and atmospheric processes that contribute to PM pollution in this region. The average concentration of submicrometer aerosol (PM1 = NR-PM1 + black carbon (BC)) was 22.1 µg m-3, which was composed of 44 % organics, 20 % sulfate, 17 % nitrate, 12 % ammonium, and 7 % BC. Organics had an average atomic oxygen-to-carbon (O / C) ratio of 0.49 and an average organic mass-to-carbon (OM/OC) ratio of 1.82. Four distinct sources of OA were identified via positive matrix factorization (PMF) analysis of the HR-ToF-AMS data: vehicle emissions represented by a hydrocarbon-like OA factor (HOA; O / C = 0.15; 17 % of OA mass), food cooking activities represented by a cooking-influenced OA factor (COA; O / C = 0.19; 22 % of OA mass), and secondary organic aerosol (SOA) represented by a semi-volatile oxygenated OA factor (SV-OOA; O / C = 0.44; 27 % of OA mass) and a low-volatility oxygenated OA factor (LV-OOA; O / C = 0.91; 34 % of OA mass). Our results indicate that air quality in SMA during KORUS-AQ was influenced strongly by secondary aerosol formation, with sulfate, nitrate, ammonium, SV-OOA, and LV-OOA together accounting for 76 % of the PM1 mass. In particular, the formation of LV-OOA and sulfate was mainly promoted by elevated ozone concentrations and photochemical reactions during daytime, whereas SV-OOA and nitrate formation was contributed by both nocturnal processing of VOC and nitrogen oxides, respectively, and daytime photochemical reactions. In addition, lower nighttime temperature promoted gas-to-particle partitioning of

  18. Investigation of a Particle into Liquid Sampler to Study the Formation & Ageing of Secondary Organic Aerosol

    Science.gov (United States)

    Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Munoz, A.; Vazquez, M.; Rodenas, M.; Vera, T.; Borrás, E.

    2012-12-01

    The atmospheric oxidation of Volatile Organic Compounds (VOCs) in the presence of NOx results in the formation of tropospheric ozone and Secondary Organic Aerosol (SOA) [Hallquist et al., 2009]. Whilst SOA is known to affect both climate and human health, the VOC oxidation pathways leading to SOA formation are poorly understood [Solomon et al., 2007]. This is in part due to the vast number and the low concentration of SOA species present in the ambient atmosphere. It has been estimated as many as 10,000 to 100,000 VOCs have been detected in the atmosphere, all of which can undergo photo-chemical oxidation and contribute to SOA formation [Goldstein and Galbally, 2007]. Atmospheric simulation chambers such as the EUropean PHOtoREactor (EUPHORE) in Valencia, Spain, are often used to study SOA formation from a single VOC precursor under controlled conditions. SOA composition and formation can be studied using online techniques such as Aerosol Mass Spectrometry (AMS), which provide high time resolution but limited structural information [Zhang et al., 2007]. Offline techniques, such as collection onto filters, extraction and subsequent analysis, provide detailed SOA composition but only usually one or two samples per experiment. In this work we report time resolved SOA composition analysis using a Particle into Liquid Sampler (PILS) followed by Liquid Chromatography Ion-Trap Mass Spectrometry (LC-IT-MS/MS) and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS/MS). Experiments were performed at EUPHORE investigating the formation and composition of Methyl Chavicol SOA. Methyl Chavicol (also known as Estragole) was identified as the highest floral emission from an oil palm plantation in Malaysian Borneo and has also been observed in US pine forests [Bouvier-Brown et al., 2009; Misztal et al., 2010]. Previous studies indicate a high SOA yield from Methyl Chavicol at around 40 % [Lee et al., 2006], however currently there have been very few literature

  19. Modeling regional air quality and climate: improving organic aerosol and aerosol activation processes in WRF/Chem version 3.7.1

    Science.gov (United States)

    Yahya, Khairunnisa; Glotfelty, Timothy; Wang, Kai; Zhang, Yang; Nenes, Athanasios

    2017-06-01

    Air quality and climate influence each other through the uncertain processes of aerosol formation and cloud droplet activation. In this study, both processes are improved in the Weather, Research and Forecasting model with Chemistry (WRF/Chem) version 3.7.1. The existing Volatility Basis Set (VBS) treatments for organic aerosol (OA) formation in WRF/Chem are improved by considering the following: the secondary OA (SOA) formation from semi-volatile primary organic aerosol (POA), a semi-empirical formulation for the enthalpy of vaporization of SOA, and functionalization and fragmentation reactions for multiple generations of products from the oxidation of VOCs. Over the continental US, 2-month-long simulations (May to June 2010) are conducted and results are evaluated against surface and aircraft observations during the Nexus of Air Quality and Climate Change (CalNex) campaign. Among all the configurations considered, the best performance is found for the simulation with the 2005 Carbon Bond mechanism (CB05) and the VBS SOA module with semivolatile POA treatment, 25 % fragmentation, and the emissions of semi-volatile and intermediate volatile organic compounds being 3 times the original POA emissions. Among the three gas-phase mechanisms (CB05, CB6, and SAPRC07) used, CB05 gives the best performance for surface ozone and PM2. 5 concentrations. Differences in SOA predictions are larger for the simulations with different VBS treatments (e.g., nonvolatile POA versus semivolatile POA) compared to the simulations with different gas-phase mechanisms. Compared to the simulation with CB05 and the default SOA module, the simulations with the VBS treatment improve cloud droplet number concentration (CDNC) predictions (normalized mean biases from -40.8 % to a range of -34.6 to -27.7 %), with large differences between CB05-CB6 and SAPRC07 due to large differences in their OH and HO2 predictions. An advanced aerosol activation parameterization based on the Fountoukis and Nenes

  20. Simulation of fine organic aerosols in the western Mediterranean area during the ChArMEx 2013 summer campaign

    Science.gov (United States)

    Cholakian, Arineh; Beekmann, Matthias; Colette, Augustin; Coll, Isabelle; Siour, Guillaume; Sciare, Jean; Marchand, Nicolas; Couvidat, Florian; Pey, Jorge; Gros, Valerie; Sauvage, Stéphane; Michoud, Vincent; Sellegri, Karine; Colomb, Aurélie; Sartelet, Karine; Langley DeWitt, Helen; Elser, Miriam; Prévot, André S. H.; Szidat, Sonke; Dulac, François

    2018-05-01

    The simulation of fine organic aerosols with CTMs (chemistry-transport models) in the western Mediterranean basin has not been studied until recently. The ChArMEx (the Chemistry-Aerosol Mediterranean Experiment) SOP 1b (Special Observation Period 1b) intensive field campaign in summer of 2013 gathered a large and comprehensive data set of observations, allowing the study of different aspects of the Mediterranean atmosphere including the formation of organic aerosols (OAs) in 3-D models. In this study, we used the CHIMERE CTM to perform simulations for the duration of the SAFMED (Secondary Aerosol Formation in the MEDiterranean) period (July to August 2013) of this campaign. In particular, we evaluated four schemes for the simulation of OA, including the CHIMERE standard scheme, the VBS (volatility basis set) standard scheme with two parameterizations including aging of biogenic secondary OA, and a modified version of the VBS scheme which includes fragmentation and formation of nonvolatile OA. The results from these four schemes are compared to observations at two stations in the western Mediterranean basin, located on Ersa, Cap Corse (Corsica, France), and at Cap Es Pinar (Mallorca, Spain). These observations include OA mass concentration, PMF (positive matrix factorization) results of different OA fractions, and 14C observations showing the fossil or nonfossil origins of carbonaceous particles. Because of the complex orography of the Ersa site, an original method for calculating an orographic representativeness error (ORE) has been developed. It is concluded that the modified VBS scheme is close to observations in all three aspects mentioned above; the standard VBS scheme without BSOA (biogenic secondary organic aerosol) aging also has a satisfactory performance in simulating the mass concentration of OA, but not for the source origin analysis comparisons. In addition, the OA sources over the western Mediterranean basin are explored. OA shows a major biogenic

  1. Diurnal variations of organic molecular tracers and stable carbon isotopic composition in atmospheric aerosols over Mt. Tai in the North China Plain: an influence of biomass burning

    Science.gov (United States)

    Fu, P. Q.; Kawamura, K.; Chen, J.; Li, J.; Sun, Y. L.; Liu, Y.; Tachibana, E.; Aggarwal, S. G.; Okuzawa, K.; Tanimoto, H.; Kanaya, Y.; Wang, Z. F.

    2012-09-01

    Organic tracer compounds, as well as organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and stable carbon isotope ratios (δ13C) of total carbon (TC) have been investigated in aerosol samples collected during early and late periods of the Mount Tai eXperiment 2006 (MTX2006) field campaign in the North China Plain. Total solvent-extractable fractions were investigated by gas chromatography/mass spectrometry. More than 130 organic compounds were detected in the aerosol samples. They were grouped into twelve organic compound classes, including biomass burning tracers, biogenic primary sugars, biogenic secondary organic aerosol (SOA) tracers, and anthropogenic tracers such as phthalates, hopanes and polycyclic aromatic hydrocarbons (PAHs). In early June when the field burning activities of wheat straws in the North China Plain were very active, the total identified organics (2090 ± 1170 ng m-3) were double those in late June (926 ± 574 ng m-3). All the compound classes were more abundant in early June than in late June, except phthalate esters, which were higher in late June. Levoglucosan (88-1210 ng m-3, mean 403 ng m-3) was found as the most abundant single compound in early June, while diisobutyl phthalate was the predominant species in late June. During the biomass-burning period in early June, the diurnal trends of most of the primary and secondary organic aerosol tracers were characterized by the concentration peaks observed at mid-night or in early morning, while in late June most of the organic species peaked in late afternoon. This suggests that smoke plumes from biomass burning can uplift the aerosol particulate matter to a certain altitude, which could be further transported to and encountered the summit of Mt. Tai during nighttime. On the basis of the tracer-based method for the estimation of biomass-burning OC, fungal-spore OC and biogenic secondary organic carbon (SOC), we estimate that an average of 24% (up to 64%) of the

  2. COBRA: A Computational Brewing Application for Predicting the Molecular Composition of Organic Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Fooshee, David R.; Nguyen, Tran B.; Nizkorodov, Sergey A.; Laskin, Julia; Laskin, Alexander; Baldi, Pierre

    2012-05-08

    Atmospheric organic aerosols (OA) represent a significant fraction of airborne particulate matter and can impact climate, visibility, and human health. These mixtures are difficult to characterize experimentally due to the enormous complexity and dynamic nature of their chemical composition. We introduce a novel Computational Brewing Application (COBRA) and apply it to modeling oligomerization chemistry stemming from condensation and addition reactions of monomers pertinent to secondary organic aerosol (SOA) formed by photooxidation of isoprene. COBRA uses two lists as input: a list of chemical structures comprising the molecular starting pool, and a list of rules defining potential reactions between molecules. Reactions are performed iteratively, with products of all previous iterations serving as reactants for the next one. The simulation generated thousands of molecular structures in the mass range of 120-500 Da, and correctly predicted ~70% of the individual SOA constituents observed by high-resolution mass spectrometry (HR-MS). Selected predicted structures were confirmed with tandem mass spectrometry. Esterification and hemiacetal formation reactions were shown to play the most significant role in oligomer formation, whereas aldol condensation was shown to be insignificant. COBRA is not limited to atmospheric aerosol chemistry, but is broadly applicable to the prediction of reaction products in other complex mixtures for which reasonable reaction mechanisms and seed molecules can be supplied by experimental or theoretical methods.

  3. A global perspective on aerosol from low-volatility organic compounds

    Directory of Open Access Journals (Sweden)

    H. O. T. Pye

    2010-05-01

    Full Text Available Global production of organic aerosol from primary emissions of semivolatile (SVOCs and intermediate (IVOCs volatility organic compounds is estimated using the global chemical transport model, GEOS-Chem. SVOC oxidation is predicted to be a larger global source of net aerosol production than oxidation of traditional parent hydrocarbons (terpenes, isoprene, and aromatics. Using a prescribed rate constant and reduction in volatility for atmospheric oxidation, the yield of aerosol from SVOCs is predicted to be about 75% on a global, annually-averaged basis. For IVOCs, the use of a naphthalene-like surrogate with different high-NOx and low-NOx parameterizations produces a global aerosol yield of about 30%, or roughly 5 Tg/yr of aerosol. Estimates of the total global organic aerosol source presented here range between 60 and 100 Tg/yr. This range reflects uncertainty in the parameters for SVOC volatility, SVOC oxidation, SVOC emissions, and IVOC emissions, as well as wet deposition. The highest estimates result if SVOC emissions are significantly underestimated (by more than a factor of 2 or if wet deposition of the gas-phase semivolatile species is less effective than previous estimates. A significant increase in SVOC emissions, a reduction of the volatility of the SVOC emissions, or an increase in the enthalpy of vaporization of the organic aerosol all lead to an appreciable reduction of prediction/measurement discrepancy. In addition, if current primary organic aerosol (POA inventories capture only about one-half of the SVOC emission and the Henrys Law coefficient for oxidized semivolatiles is on the order of 103 M/atm, a global estimate of OA production is not inconsistent with the top-down estimate of 140 Tg/yr by (Goldstein and Galbally, 2007. Additional information is needed to constrain the emissions and treatment of SVOCs and IVOCs, which have traditionally not been included in models.

  4. Effects of continental anthropogenic sources on organic aerosols in the coastal atmosphere of East China

    International Nuclear Information System (INIS)

    Shang, Dongjie; Hu, Min; Guo, Qingfeng; Zou, Qi; Zheng, Jing; Guo, Song

    2017-01-01

    Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM 2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM 2.5 samples from the marine and Changdao Island atmospheres were 5.5 ± 3.1 μgC/m 3 and 6.9 ± 2.4 μgC/m 3 , respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM 2.5 samples was 17.0 ± 20.2 ng/m 3 , indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the “North China” marine atmospheric samples. The “Northeast China” marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM 2.5 without considering high spatial resolution

  5. Characterization of organic nitrogen in aerosols at a forest site in the southern Appalachian Mountains

    Science.gov (United States)

    Chen, Xi; Xie, Mingjie; Hays, Michael D.; Edgerton, Eric; Schwede, Donna; Walker, John T.

    2018-05-01

    This study investigates the composition of organic particulate matter in PM2.5 in a remote montane forest in the southeastern US, focusing on the role of organic nitrogen (N) in sulfur-containing secondary organic aerosol (nitrooxy-organosulfates) and aerosols associated with biomass burning (nitro-aromatics). Bulk water-soluble organic N (WSON) represented ˜ 14 % w/w of water-soluble total N (WSTN) in PM2.5 on average across seasonal measurement campaigns conducted in the spring, summer, and fall of 2015. The largest contributions of WSON to WSTN were observed in spring ( ˜ 18 % w/w) and the lowest in the fall ( ˜ 10 % w/w). On average, identified nitro-aromatic and nitrooxy-organosulfate compounds accounted for a small fraction of WSON, ranging from ˜ 1 % in spring to ˜ 4 % in fall, though were observed to contribute as much as 28 % w/w of WSON in individual samples that were impacted by local biomass burning. The highest concentrations of oxidized organic N species occurred during summer (average of 0.65 ng N m-3) along with a greater relative abundance of higher-generation oxygenated terpenoic acids, indicating an association with more aged aerosol. The highest concentrations of nitro-aromatics (e.g., nitrocatechol and methyl-nitrocatechol), levoglucosan, and aged SOA tracers were observed during fall, associated with aged biomass burning plumes. Nighttime nitrate radical chemistry is the most likely formation pathway for nitrooxy-organosulfates observed at this low NOx site (generally chemistry and deposition of reactive N.

  6. A Role for 2-Methyl Pyrrole in the Browning of 4-Oxopentanal and Limonene Secondary Organic Aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Aiona, Paige K. [Department; Lee, Hyun Ji [Department; Lin, Peng [Department; Heller, Forrest [Environmental; Laskin, Alexander [Department; Laskin, Julia [Department; Nizkorodov, Sergey A. [Department

    2017-09-15

    “Brown Carbon” (BrC) is a type of organic particulate matter that absorbs visible and near ultraviolet radiation. Reactions of carbonyls in secondary organic aerosol (SOA) produced from limonene with ammonia (NH3) or ammonium sulfate (AS) are known to produce BrC with a distinctive absorption band at 500 nm. Although the general mechanism for this process has been proposed in previous studies, the specific molecular structures of the light-absorbing species remain unclear. This study examined the browning processes occurring in aqueous solutions of AS and 4-oxopentanal (4-OPA), which has a 1,4-dicarbonyl structural motif present in many limonene SOA compounds. The reaction of 4-OPA with AS in a bulk aqueous solution produces a 2-methyl pyrrole (2-MP) intermediate, which is not a strong light absorber by itself, but can react further with carbonyl compounds leading to the eventual formation of BrC chromophores. The direct involvement of 2-MP in the browning process was demonstrated by reacting 2-MP with 4-OPA and with limonene SOA, both of which produced BrC chromophores with distinctive absorption bands at visible wavelengths. The formation of BrC in reaction of 4-OPA with AS and ammonium nitrate (AN) was found to be accelerated by evaporation of the solution suggesting an important role of the dehydration processes in BrC formation from 1,4- dicarbonyls. 4-OPA was also found to produce BrC in aqueous reactions with a broad spectrum of amino acids and amines. The results suggest that 4-OPA may be the smallest atmospherically relevant compound capable of browning by the same mechanism as limonene SOA.

  7. Effect of phytoplackton-derived organic matter on the behavior of marine aerosols

    Science.gov (United States)

    Fuentes, E.; Coe, H.; McFiggans, G.; Green, D.

    2009-04-01

    The presence of significant concentrations of organic material in marine aerosols has been appreciated for several decades; however, only recently has significant progress been made towards demonstrating that this organic content is biogenically formed. Biogenic organics of placktonic life origin are incorporated in marine aerosol composition as a result of bubble bursting/breaking waves mechanisms that occur at the ocean surface. The presence of organic surfactants in the marine aerosol composition might have a significant impact on the properties of the generated aerosols by affecting the particles surface tension and solution balance properties. Nevertheless, it remains uncertain the role of such organics on the physical-chemical behavior of marine aerosols. In this work an experimental study was performed in order to determine the influence of biogenic marine organic compounds on the size distribution, hygroscopicity and cloud-nucleating properties of marine aerosols. For the experimental study a laboratory water recirculation system (bubble tank), designed for the simulation of bubble-burst aerosol formation, was used as marine aerosol generator. The bubble spectra produced by such system was characterized by means of an optical bubble measuring device (BMS) and it was found to be consistent with oceanic bubble spectra properties. Seawater proxy solutions were prepared from laboratory biologically-synthesized exudates produced by oceanic representative algal species and introduced in the tank for the generation of marine aerosol by bubble bursting. Two experimental methods were employed for seawater proxies preparation: the formation of surface monolayers from the biogenic surfactants extracted by a solid phase extraction technique (monolayer method) and the mixing of the exudates in the sea salt water bulk (bulk mixing method). Particle size distribution, hygroscopicity and cloud condensation nuclei experiments for different monolayers, and exudate mixtures

  8. Annual cycle of size-resolved organic aerosol characterization in an urbanized desert environment

    Science.gov (United States)

    Cahill, Thomas M.

    2013-06-01

    Studies of size-resolved organic speciation of aerosols are still relatively rare and are generally only conducted over short durations. However, size-resolved organic data can both suggest possible sources of the aerosols and identify the human exposure to the chemicals since different aerosol sizes have different lung capture efficiencies. The objective of this study was to conduct size-resolved organic aerosol speciation for a calendar year in Phoenix, Arizona to determine the seasonal variations in both chemical concentrations and size profiles. The results showed large seasonal differences in combustion pollutants where the highest concentrations were observed in winter. Summertime aerosols have a greater proportion of biological compounds (e.g. sugars and fatty acids) and the biological compounds represent the largest fraction of the organic compounds detected. These results suggest that standard organic carbon (OC) measurements might be heavily influenced by primary biological compounds particularly if the samples are PM10 and TSP samples. Several large dust storms did not significantly alter the organic aerosol profile since Phoenix resides in a dusty desert environment, so the soil and plant tracer of trehalose was almost always present. The aerosol size profiles showed that PAHs were generally most abundant in the smallest aerosol size fractions, which are most likely to be captured by the lung, while the biological compounds were almost exclusively found in the coarse size fraction.

  9. Organic Aerosols as Cloud Condensation Nuclei

    Science.gov (United States)

    Hudson, J. G.

    2002-05-01

    The large organic component of the atmospheric aerosol contributes to both natural and anthropogenic cloud condensation nuclei (CCN). Moreover, some organic substances may reduce droplet surface tension (Facchini et al. 1999), while others may be partially soluble (Laaksonen et al. 1998), and others may inhibit water condensation. The interaction of organics with water need to be understood in order to better understand the indirect aerosol effect. Therefore, laboratory CCN spectral measurements of organic aerosols are presented. These are measurements of the critical supersaturation (Sc), the supersaturation needed to produce an activated cloud droplet, as a function of the size of the organic particles. Substances include sodium lauryl (dodecyl) sulfate, oxalic, adipic, pinonic, hexadecanedioic, glutaric, stearic, succinic, phthalic, and benzoic acids. These size-Sc relationships are compared with theoretical and measured size-Sc relationships of common inorganic compounds (e.g., NaCl, KI, ammonium and calcium sulfate). Unlike most inorganics some organics display variations in solubility per unit mass as a function of particle size. Those showing relatively greater solubility at smaller sizes may be attributable to surface tension reduction, which is greater for less water dilution, as is the case for smaller particles, which are less diluted at the critical sizes. This was the case for sodium dodecyl sulfate, which does reduce surface tension. Relatively greater solubility for larger particles may be caused by greater dissolution at the higher dilutions that occur with larger particles; this is partial solubility. Measurements are also presented of internal mixtures of various organic and inorganic substances. These measurements were done with two CCN spectrometers (Hudson 1989) operating simultaneously. These two instruments usually displayed similar results in spite of the fact that they have different flow rates and supersaturation profiles. The degree of

  10. Assessing the influence of NOx concentrations and relative humidity on secondary organic aerosol yields from α-pinene photo-oxidation through smog chamber experiments and modelling calculations

    Science.gov (United States)

    Stirnweis, Lisa; Marcolli, Claudia; Dommen, Josef; Barmet, Peter; Frege, Carla; Platt, Stephen M.; Bruns, Emily A.; Krapf, Manuel; Slowik, Jay G.; Wolf, Robert; Prévôt, Andre S. H.; Baltensperger, Urs; El-Haddad, Imad

    2017-04-01

    Secondary organic aerosol (SOA) yields from the photo-oxidation of α-pinene were investigated in smog chamber (SC) experiments at low (23-29 %) and high (60-69 %) relative humidity (RH), various NOx / VOC ratios (0.04-3.8) and with different aerosol seed chemical compositions (acidic to neutralized sulfate-containing or hydrophobic organic). A combination of a scanning mobility particle sizer and an Aerodyne high-resolution time-of-flight aerosol mass spectrometer was used to determine SOA mass concentration and chemical composition. We used a Monte Carlo approach to parameterize smog chamber SOA yields as a function of the condensed phase absorptive mass, which includes the sum of OA and the corresponding bound liquid water content. High RH increased SOA yields by up to 6 times (1.5-6.4) compared to low RH. The yields at low NOx / VOC ratios were in general higher compared to yields at high NOx / VOC ratios. This NOx dependence follows the same trend as seen in previous studies for α-pinene SOA. A novel approach of data evaluation using volatility distributions derived from experimental data served as the basis for thermodynamic phase partitioning calculations of model mixtures in this study. These calculations predict liquid-liquid phase separation into organic-rich and electrolyte phases. At low NOx conditions, equilibrium partitioning between the gas and liquid phases can explain most of the increase in SOA yields observed at high RH, when in addition to the α-pinene photo-oxidation products described in the literature, fragmentation products are added to the model mixtures. This increase is driven by both the increase in the absorptive mass and the solution non-ideality described by the compounds' activity coefficients. In contrast, at high NOx, equilibrium partitioning alone could not explain the strong increase in the yields with RH. This suggests that other processes, e.g. reactive uptake of semi-volatile species into the liquid phase, may occur and be

  11. Effects of continental anthropogenic sources on organic aerosols in the coastal atmosphere of East China.

    Science.gov (United States)

    Shang, Dongjie; Hu, Min; Guo, Qingfeng; Zou, Qi; Zheng, Jing; Guo, Song

    2017-10-01

    Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM 2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM 2.5 samples from the marine and Changdao Island atmospheres were 5.5 ± 3.1 μgC/m 3 and 6.9 ± 2.4 μgC/m 3 , respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM 2.5 samples was 17.0 ± 20.2 ng/m 3 , indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the "North China" marine atmospheric samples. The "Northeast China" marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM 2.5 without considering high spatial resolution source

  12. Observations of gas- and aerosol-phase organic nitrates at BEACHON-RoMBAS 2011

    Directory of Open Access Journals (Sweden)

    J. L. Fry

    2013-09-01

    Full Text Available At the Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS field campaign in the Colorado front range, July–August 2011, measurements of gas- and aerosol-phase organic nitrates enabled a study of the role of NOx (NOx = NO + NO2 in oxidation of forest-emitted volatile organic compounds (VOCs and subsequent aerosol formation. Substantial formation of peroxy- and alkyl-nitrates is observed every morning, with an apparent 2.9% yield of alkyl nitrates from daytime RO2 + NO reactions. Aerosol-phase organic nitrates, however, peak in concentration during the night, with concentrations up to 140 ppt as measured by both optical spectroscopic and mass spectrometric instruments. The diurnal cycle in aerosol fraction of organic nitrates shows an equilibrium-like response to the diurnal temperature cycle, suggesting some reversible absorptive partitioning, but the full dynamic range cannot be reproduced by thermodynamic repartitioning alone. Nighttime aerosol organic nitrate is observed to be positively correlated with [NO2] × [O3] but not with [O3]. These observations support the role of nighttime NO3-initiated oxidation of monoterpenes as a significant source of nighttime aerosol. Nighttime production of organic nitrates is comparable in magnitude to daytime photochemical production at this site, which we postulate to be representative of the Colorado front range forests.

  13. On the contribution of organics to the North East Atlantic aerosol number concentration

    International Nuclear Information System (INIS)

    Bialek, Jakub; Dall’Osto, Manuel; Monahan, Ciaran; O’Dowd, Colin; Beddows, David

    2012-01-01

    k-means statistical-cluster analysis of submicron aerosol size distributions is combined with coincident humidity tandem differential mobility analyser data, leading to five unique aerosol categories for hygroscopic growth factors (HGFs): low sea-salt background marine, high sea-salt background marine, coastal nucleation, open ocean nucleation and anthropogenically influenced scenarios. When considering only marine conditions, and generic aerosol species associated with this environment (e.g. non-sea-salt sulfate, sea-salt, partly soluble organic matter and water insoluble organic matter), the two-year annual average contribution to aerosol number concentration from the different generic species was made up as follows: 46% (30–54%) of partially modified ammonium sulfate particles; 23% (11–40%) of partially modified sea-salt; and the remaining 31% (25–35%) contribution attributed to two distinct organic species as evidenced by different, but low, HGFs. The analysis reveals that on annual timescales, ∼30% of the submicron marine aerosol number concentration is sourced from predominantly organic aerosol while 60% of the anthropogenic aerosol number is predominantly organic. Coastal nucleation events show the highest contribution of the lowest HGF mode (1.19), although this contribution is more likely to be influenced by inorganic iodine oxides. While organic mass internally mixed with inorganic salts will lower the activation potential of these mixed aerosol types, thereby potentially reducing the concentration of cloud condensation nuclei (CCN), pure organic water soluble particles are still likely to be activated into cloud droplets, thereby increasing the concentration of CCN. A combination of dynamics and aerosol concentrations will determine which effect will prevail under given conditions. (letter)

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

    Science.gov (United States)

    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.

  15. Primary gas- and particle-phase emissions and secondary organic aerosol production from gasoline and diesel off-road engines.

    Science.gov (United States)

    Gordon, Timothy D; Tkacik, Daniel S; Presto, Albert A; Zhang, Mang; Jathar, Shantanu H; Nguyen, Ngoc T; Massetti, John; Truong, Tin; Cicero-Fernandez, Pablo; Maddox, Christine; Rieger, Paul; Chattopadhyay, Sulekha; Maldonado, Hector; Maricq, M Matti; Robinson, Allen L

    2013-12-17

    Dilution and smog chamber experiments were performed to characterize the primary emissions and secondary organic aerosol (SOA) formation from gasoline and diesel small off-road engines (SOREs). These engines are high emitters of primary gas- and particle-phase pollutants relative to their fuel consumption. Two- and 4-stroke gasoline SOREs emit much more (up to 3 orders of magnitude more) nonmethane organic gases (NMOGs), primary PM and organic carbon than newer on-road gasoline vehicles (per kg of fuel burned). The primary emissions from a diesel transportation refrigeration unit were similar to those of older, uncontrolled diesel engines used in on-road vehicles (e.g., premodel year 2007 heavy-duty diesel trucks). Two-strokes emitted the largest fractional (and absolute) amount of SOA precursors compared to diesel and 4-stroke gasoline SOREs; however, 35-80% of the NMOG emissions from the engines could not be speciated using traditional gas chromatography or high-performance liquid chromatography. After 3 h of photo-oxidation in a smog chamber, dilute emissions from both 2- and 4-stroke gasoline SOREs produced large amounts of semivolatile SOA. The effective SOA yield (defined as the ratio of SOA mass to estimated mass of reacted precursors) was 2-4% for 2- and 4-stroke SOREs, which is comparable to yields from dilute exhaust from older passenger cars and unburned gasoline. This suggests that much of the SOA production was due to unburned fuel and/or lubrication oil. The total PM contribution of different mobile source categories to the ambient PM burden was calculated by combining primary emission, SOA production and fuel consumption data. Relative to their fuel consumption, SOREs are disproportionately high total PM sources; however, the vastly greater fuel consumption of on-road vehicles renders them (on-road vehicles) the dominant mobile source of ambient PM in the Los Angeles area.

  16. Lipid organics in background aerosols, cloudwater, and snow and implication for organic scavenging

    International Nuclear Information System (INIS)

    Groellert, C.

    1998-01-01

    During three years free tropospheric snow, aerosol, and cloudwater samples were collected at Mount Sonnblick, Austria, at an elevation of 3106 m a.s.l. The samples were analyzed for their lipid organic trace components using extraction with n-hexane as sample pretreatment and gas chromatography-mass spectrometry-flame ionization detection for identification and quantification of the substances. The main components identified in all the samples were the phthalic acid esters which are of anthropogenic origin. Of further interest were aliphatic alcohols (not detected in aerosols) and phenols. They are of biogenic origin. The concentrations were found to be higher in spring than in the fall season. To compare the concentrations of aerosol, cloudwater and snow samples scavenging ratios (aerosol to snow), scavenging efficiencies (aerosol to cloud) and cloud to snow ratios were calculated for the first time for organic compounds. Scavenging ratios were 10 to 100 times lower, scavenging efficiencies 2 to 10 times lower than sulfate. This can result from the poor watersolubility of the compounds or from gas phase sorptions on the filter surface (overestimation of aerosol concentrations). The cloud to snow ratios were generally higher than for sulfate. However, a few components exhibited very low cloud to snow ratios which might be due to additional sources in snow for these substances (alcohols). (author)

  17. Secondary organic aerosol formation from in situ OH, O3, and NO3 oxidation of ambient forest air in an oxidation flow reactor

    Science.gov (United States)

    Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.; Ortega, Amber M.; Fry, Juliane L.; Brown, Steven S.; Zarzana, Kyle J.; Dube, William; Wagner, Nicholas L.; Draper, Danielle C.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Gutiérrez-Montes, Cándido; Jimenez, Jose L.

    2017-04-01

    Ambient pine forest air was oxidized by OH, O3, or NO3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O3 and NO3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20-30 min, in order to determine how the availability of SOA precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O3 or NO3 oxidation. This is likely because O3 and NO3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O3 and NO3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O3 and NO3 oxidation produced SOA with elemental O : C and H : C

  18. Causes and consequences of decreasing atmospheric organic aerosol in the United States

    Science.gov (United States)

    Ridley, D. A.; Heald, C. L.; Ridley, K. J.; Kroll, J. H.

    2018-01-01

    Exposure to atmospheric particulate matter (PM) exacerbates respiratory and cardiovascular conditions and is a leading source of premature mortality globally. Organic aerosol contributes a significant fraction of PM in the United States. Here, using surface observations between 1990 and 2012, we show that organic carbon has declined dramatically across the entire United States by 25–50%; accounting for more than 30% of the US-wide decline in PM. The decline is in contrast with the increasing organic aerosol due to wildfires and no clear trend in biogenic emissions. By developing a carbonaceous emissions database for the United States, we show that at least two-thirds of the decline in organic aerosol can be explained by changes in anthropogenic emissions, primarily from vehicle emissions and residential fuel burning. We estimate that the decrease in anthropogenic organic aerosol is responsible for averting 180,000 (117,000–389,000) premature deaths between 1990 and 2012. The unexpected decrease in organic aerosol, likely a consequence of the implementation of Clean Air Act Amendments, results in 84,000 (30,000–164,000) more lives saved than anticipated by the EPA between 2000 and 2010.

  19. Diurnal variations of organic molecular tracers and stable carbon isotopic composition in atmospheric aerosols over Mt. Tai in the North China Plain: an influence of biomass burning

    Directory of Open Access Journals (Sweden)

    P. Q. Fu

    2012-09-01

    Full Text Available Organic tracer compounds, as well as organic carbon (OC, elemental carbon (EC, water-soluble organic carbon (WSOC, and stable carbon isotope ratios (δ13C of total carbon (TC have been investigated in aerosol samples collected during early and late periods of the Mount Tai eXperiment 2006 (MTX2006 field campaign in the North China Plain. Total solvent-extractable fractions were investigated by gas chromatography/mass spectrometry. More than 130 organic compounds were detected in the aerosol samples. They were grouped into twelve organic compound classes, including biomass burning tracers, biogenic primary sugars, biogenic secondary organic aerosol (SOA tracers, and anthropogenic tracers such as phthalates, hopanes and polycyclic aromatic hydrocarbons (PAHs. In early June when the field burning activities of wheat straws in the North China Plain were very active, the total identified organics (2090 ± 1170 ng m−3 were double those in late June (926 ± 574 ng m−3. All the compound classes were more abundant in early June than in late June, except phthalate esters, which were higher in late June. Levoglucosan (88–1210 ng m−3, mean 403 ng m−3 was found as the most abundant single compound in early June, while diisobutyl phthalate was the predominant species in late June. During the biomass-burning period in early June, the diurnal trends of most of the primary and secondary organic aerosol tracers were characterized by the concentration peaks observed at mid-night or in early morning, while in late June most of the organic species peaked in late afternoon. This suggests that smoke plumes from biomass burning can uplift the aerosol particulate matter to a certain altitude, which could be further transported to and encountered the summit of Mt. Tai during nighttime. On the basis of the tracer-based method for the estimation of biomass-burning OC, fungal-spore OC and biogenic secondary

  20. A new physically-based quantification of marine isoprene and primary organic aerosol emissions

    Directory of Open Access Journals (Sweden)

    N. Meskhidze

    2009-07-01

    Full Text Available The global marine sources of organic carbon (OC are estimated here using a physically-based parameterization for the emission of marine isoprene and primary organic matter. The marine isoprene emission model incorporates new physical parameters such as light sensitivity of phytoplankton isoprene production and dynamic euphotic depth to simulate hourly marine isoprene emissions totaling 0.92 Tg C yr−1. Sensitivity studies using different schemes for the euphotic zone depth and ocean phytoplankton speciation produce the upper and the lower range of marine-isoprene emissions of 0.31 to 1.09 Tg C yr−1, respectively. Established relationships between sea spray fractionation of water-insoluble organic carbon (WIOC and chlorophyll-a concentration are used to estimate the total primary sources of marine sub- and super-micron OC of 2.9 and 19.4 Tg C yr−1, respectively. The consistent spatial and temporal resolution of the two emission types allow us, for the first time, to explore the relative contributions of sub- and super-micron organic matter and marine isoprene-derived secondary organic aerosol (SOA to the total OC fraction of marine aerosol. Using a fixed 3% mass yield for the conversion of isoprene to SOA, our emission simulations show minor (<0.2% contribution of marine isoprene to the total marine source of OC on a global scale. However, our model calculations also indicate that over the tropical oceanic regions (30° S to 30° N, marine isoprene SOA may contribute over 30% of the total monthly-averaged sub-micron OC fraction of marine aerosol. The estimated contribution of marine isoprene SOA to hourly-averaged sub-micron marine OC emission is even higher, approaching 50% over the vast regions of the oceans during the midday hours when isoprene emissions are highest. As it is widely believed that sub-micron OC has the potential to influence the cloud droplet activation of marine aerosols, our

  1. Evaluating the mutagenic potential of aerosol organic compounds using informatics-based screening

    Science.gov (United States)

    Decesari, Stefano; Kovarich, Simona; Pavan, Manuela; Bassan, Arianna; Ciacci, Andrea; Topping, David

    2018-02-01

    Whilst general policy objectives to reduce airborne particulate matter (PM) health effects are to reduce exposure to PM as a whole, emerging evidence suggests that more detailed metrics associating impacts with different aerosol components might be needed. Since it is impossible to conduct toxicological screening on all possible molecular species expected to occur in aerosol, in this study we perform a proof-of-concept evaluation on the information retrieved from in silico toxicological predictions, in which a subset (N = 104) of secondary organic aerosol (SOA) compounds were screened for their mutagenicity potential. An extensive database search showed that experimental data are available for 13 % of the compounds, while reliable predictions were obtained for 82 %. A multivariate statistical analysis of the compounds based on their physico-chemical, structural, and mechanistic properties showed that 80 % of the compounds predicted as mutagenic were grouped into six clusters, three of which (five-membered lactones from monoterpene oxidation, oxygenated multifunctional compounds from substituted benzene oxidation, and hydroperoxides from several precursors) represent new candidate groups of compounds for future toxicological screenings. These results demonstrate that coupling model-generated compositions to in silico toxicological screening might enable more comprehensive exploration of the mutagenic potential of specific SOA components.

  2. Evolution of Asian aerosols during transpacific transport in INTEX-B

    Energy Technology Data Exchange (ETDEWEB)

    Dunlea, E. J.; DeCarlo, Peter; Aiken, Allison; Kimmel, Joel; Peltier, R. E.; Weber, R. J.; Tomlinson, Jason M.; Collins, Donald R.; Shinozuka, Yohei; McNaughton, C. S.; Howell, S. G.; Clarke, A. D.; Emmons, L.; Apel, Eric; Pfister, G. G.; van Donkelaar, A.; Martin, R. V.; Millet, D. B.; Heald, C. L.; Jimenez, J. L.

    2009-10-01

    Measurements of aerosol composition were made with an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) on board the NSF/NCAR C-130 aircraft as part of the Intercontinental Chemical Transport Experiment Phase B 5 (INTEX-B) field campaign over the Eastern Pacific Ocean. The HR-ToF-AMS measurements of non-refractory submicron aerosol mass are shown to compare well with other aerosol instrumentation in the INTEX-B field study. Two case studies are described for pollution layers transported across the Pacific from the Asian continent, intercepted 3–4 days and 7–10 days downwind of Asia, respectively. Aerosol chemistry is shown to 10 be a robust tracer for air masses originating in Asia, specifically the presence of sulfate dominated aerosol is a distinguishing feature of Asian pollution layers that have been transported to the Eastern Pacific. We examine the time scales of processing for sulfate and organic aerosol in the atmosphere and show that our observations confirm a conceptual model for transpacific transport from Asia proposed by Brock et al. (2004). 15 Our observations of both sulfate and organic aerosol in aged Asian pollution layers are consistent with fast formation near the Asian continent, followed by washout during lofting and subsequent transformation during transport across the Pacific. Our observations are the first atmospheric measurements to indicate that although secondary organic aerosol (SOA) formation from pollution happens on the timescale of one day, 20 the oxidation of organic aerosol continues at longer timescales in the atmosphere. Comparisons with chemical transport models of data from the entire campaign reveal an under-prediction of SOA mass in the MOZART model, but much smaller discrepancies with the GEOS-Chem model than found in previous studies over the Western Pacific. No evidence is found to support a previous hypothesis for significant secondary 25 organic aerosol formation in the free troposphere.

  3. Aerosol characterization over the southeastern United States using high-resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition and sources with a focus on organic nitrates

    Science.gov (United States)

    Xu, L.; Suresh, S.; Guo, H.; Weber, R. J.; Ng, N. L.

    2015-07-01

    on the HR-ToF-AMS measurements, we estimate that the nitrate functionality from organic nitrates contributes 63-100 % to the total measured nitrates in summer. Furthermore, the contribution of organic nitrates to total OA is estimated to be 5-12 % in summer, suggesting that organic nitrates are important components in the ambient aerosol in the southeastern USA. The spatial distribution of OA is investigated by comparing simultaneous HR-ToF-AMS measurements with ACSM measurements at two different sampling sites. OA is found to be spatially homogeneous in summer due possibly to stagnant air mass and a dominant amount of regional secondary organic aerosol (SOA) in the southeastern USA. The homogeneity is less in winter, which is likely due to spatial variation of primary emissions. We observe that the seasonality of OA concentration shows a clear urban/rural contrast. While OA exhibits weak seasonal variation in the urban sites, its concentration is higher in summer than winter for rural sites. This observation from our year-long measurements is consistent with 14 years of organic carbon (OC) data from the SouthEastern Aerosol Research and Characterization (SEARCH) network. The comparison between short-term measurements with advanced instruments and long-term measurements of basic air quality indicators not only tests the robustness of the short-term measurements but also provides insights in interpreting long-term measurements. We find that OA factors resolved from PMF analysis on HR-ToF-AMS measurements have distinctly different diurnal variations. The compensation of OA factors with different diurnal trends is one possible reason for the repeatedly observed, relatively flat OA diurnal profile in the southeastern USA. In addition, analysis of long-term measurements shows that the correlation between OC and sulfate is substantially stronger in summer than winter. This seasonality could be partly due to the effects of sulfate on isoprene SOA formation as revealed by

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

    Energy Technology Data Exchange (ETDEWEB)

    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

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

    Directory of Open Access Journals (Sweden)

    J. G. Slowik

    2011-03-01

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

  6. Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

    Directory of Open Access Journals (Sweden)

    M. C. Woody

    2016-03-01

    Full Text Available Community Multiscale Air Quality (CMAQ model simulations utilizing the traditional organic aerosol (OA treatment (CMAQ-AE6 and a volatility basis set (VBS treatment for OA (CMAQ-VBS were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN and Interagency Monitoring of Protected Visual Environments (IMPROVE and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex field campaign to examine important sources of OA in southern California. Traditionally, CMAQ treats primary organic aerosol (POA as nonvolatile and uses a two-product framework to represent secondary organic aerosol (SOA formation. CMAQ-VBS instead treats POA as semivolatile and lumps OA using volatility bins spaced an order of magnitude apart. The CMAQ-VBS approach underpredicted organic carbon (OC at IMPROVE and CSN sites to a greater degree than CMAQ-AE6 due to the semivolatile POA treatment. However, comparisons to aerosol mass spectrometer (AMS measurements collected at Pasadena, CA, indicated that CMAQ-VBS better represented the diurnal profile and primary/secondary split of OA. CMAQ-VBS SOA underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate for SOA concentration by a factor of 5.2, representing a considerable improvement to CMAQ-AE6 SOA predictions (factor of 24 lower than AMS. We use two new methods, one based on species ratios (SOA/ΔCO and SOA/Ox and another on a simplified SOA parameterization, to apportion the SOA underprediction for CMAQ-VBS to slow photochemical oxidation (estimated as 1.5 ×  lower than observed at Pasadena using −log(NOx : NOy, low intrinsic SOA formation efficiency (low by 1.6 to 2 ×  for Pasadena, and low emissions or excessive dispersion for the Pasadena site (estimated to be 1.6 to 2.3 ×  too low/excessive. The first and third factors are common to CMAQ-AE6, while the intrinsic SOA formation efficiency

  7. Comparison of secondary organic aerosol formation from toluene on initially wet and dry ammonium sulfate particles at moderate relative humidity

    Science.gov (United States)

    Liu, Tengyu; Huang, Dan Dan; Li, Zijun; Liu, Qianyun; Chan, ManNin; Chan, Chak K.

    2018-04-01

    The formation of secondary organic aerosol (SOA) has been widely studied in the presence of dry seed particles at low relative humidity (RH). At higher RH, initially dry seed particles can exist as wet particles due to water uptake by the seeds as well as the SOA. Here, we investigated the formation of SOA from the photooxidation of toluene using an oxidation flow reactor in the absence of NOx under a range of OH exposures on initially wet or dry ammonium sulfate (AS) seed particles at an RH of 68 %. The ratio of the SOA yield on wet AS seeds to that on dry AS seeds, the relative SOA yield, decreased from 1.31 ± 0.02 at an OH exposure of 4.66 × 1010 molecules cm-3 s to 1.01 ± 0.01 at an OH exposure of 5.28 × 1011 molecules cm-3 s. This decrease may be due to the early deliquescence of initially dry AS seeds after being coated by highly oxidized toluene-derived SOA. SOA formation lowered the deliquescence RH of AS and resulted in the uptake of water by both AS and SOA. Hence the initially dry AS seeds contained aerosol liquid water (ALW) soon after SOA formed, and the SOA yield and ALW approached those of the initially wet AS seeds as OH exposure and ALW increased, especially at high OH exposure. However, a higher oxidation state of the SOA on initially wet AS seeds than that on dry AS seeds was observed at all levels of OH exposure. The difference in mass fractions of m / z 29, 43 and 44 of SOA mass spectra, obtained using an aerosol mass spectrometer (AMS), indicated that SOA formed on initially wet seeds may be enriched in earlier-generation products containing carbonyl functional groups at low OH exposures and later-generation products containing acidic functional groups at high exposures. Our results suggest that inorganic dry seeds become at least partially deliquesced particles during SOA formation and hence that ALW is inevitably involved in the SOA formation at moderate RH. More laboratory experiments conducted with a wide variety of SOA precursors

  8. Primary emissions and secondary aerosol production potential from woodstoves for residential heating: Influence of the stove technology and combustion efficiency

    Science.gov (United States)

    Bertrand, Amelie; Stefenelli, Giulia; Bruns, Emily A.; Pieber, Simone M.; Temime-Roussel, Brice; Slowik, Jay G.; Prévôt, André S. H.; Wortham, Henri; El Haddad, Imad; Marchand, Nicolas

    2017-11-01

    To reduce the influence of biomass burning on air quality, consumers are encouraged to replace their old woodstove with new and cleaner appliances. While their primary emissions have been extensively investigated, the impact of atmospheric aging on these emissions, including secondary organic aerosol (SOA) formation, remains unknown. Here, using an atmospheric smog chamber, we aim at understanding the chemical nature and quantify the emission factors of the primary organic aerosols (POA) from three types of appliances for residential heating, and to assess the influence of aging thereon. Two, old and modern, logwood stoves and one pellet burner were operated under typical conditions. Emissions from an entire burning cycle (past the start-up operation) were injected, including the smoldering and flaming phases, resulting in highly variable emission factors. The stoves emitted a significant fraction of POA (up to 80%) and black carbon. After ageing, the total mass concentration of organic aerosol (OA) increased on average by a factor of 5. For the pellet stove, flaming conditions were maintained throughout the combustion. The aerosol was dominated by black carbon (over 90% of the primary emission) and amounted to the same quantity of primary aerosol emitted by the old logwood stove. However, after ageing, the OA mass was increased by a factor of 1.7 only, thus rendering OA emissions by the pellet stove almost negligible compared to the other two stoves tested. Therefore, the pellet stove was the most reliable and least polluting appliance out of the three stoves tested. The spectral signatures of the POA and aged emissions by a High Resolution - Time of Flight - Aerosol Mass Spectrometer (Electron Ionization (EI) at 70 eV) were also investigated. The m/z 44 (CO2+) and high molecular weight fragments (m/z 115 (C9H7+), 137 (C8H9O2+), 167 (C9H11O3+) and 181 (C9H9O4+, C14H13+)) correlate with the modified combustion efficiency (MCE) allowing us to discriminate further

  9. Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene.

    Science.gov (United States)

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

    2017-08-24

    Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (formation can be explained by the decomposition of organic hydroperoxides, which are a prominent fraction of SOA, through interactions with water and Fenton-like reactions with dissolved transition metal ions. Our findings imply that the chemical reactivity and aging of SOA particles can be enhanced upon interaction with mineral dust in deliquesced particles or cloud/fog droplets. SOA decomposition could be comparably important to the classical Fenton reaction of H 2 O 2 with Fe 2+ and that SOA can be the main source of OH radicals in aqueous droplets at low concentrations of H 2 O 2 and Fe 2+ . In the human respiratory tract, the inhalation and deposition of SOA and mineral dust can also lead to the release of ROS, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols in the Anthropocene.

  10. The effect of organic coating on the heterogeneous ice nucleation efficiency of mineral dust aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Moehler, O; Benz, S; Saathoff, H; Schnaiter, M; Wagner, R [Forschungszentrum Karlsruhe, Institute for Meteorology and Climate Research, 76021 Karlsruhe (Germany); Schneider, J; Walter, S [Max Planck Institute for Chemistry, 55128 Mainz (Germany); Ebert, V; Wagner, S [University of Heidelberg, Institute for Physical Chemistry, 69120 Heidelberg (Germany)], E-mail: Ottmar.Moehler@imk.fzk.de

    2008-04-15

    The effect of organic coating on the heterogeneous ice nucleation (IN) efficiency of dust particles was investigated at simulated cirrus cloud conditions in the AIDA cloud chamber of Forschungszentrum Karlsruhe. Arizona test dust (ATD) and the clay mineral illite were used as surrogates for atmospheric dust aerosols. The dry dust samples were dispersed into a 3.7 m{sup 3} aerosol vessel and either directly transferred into the 84 m{sup 3} cloud simulation chamber or coated before with the semi-volatile products from the reaction of {alpha}-pinene with ozone in order to mimic the coating of atmospheric dust particles with secondary organic aerosol (SOA) substances. The ice-active fraction was measured in AIDA expansion cooling experiments as a function of the relative humidity with respect to ice, RHi, in the temperature range from 205 to 210 K. Almost all uncoated dust particles with diameters between 0.1 and 1.0 {mu}m acted as efficient deposition mode ice nuclei at RHi between 105 and 120%. This high ice nucleation efficiency was markedly suppressed by coating with SOA. About 20% of the ATD particles coated with a SOA mass fraction of 17 wt% were ice-active at RHi between 115 and 130%, and only 10% of the illite particles coated with an SOA mass fraction of 41 wt% were ice-active at RHi between 160 and 170%. Only a minor fraction of pure SOA particles were ice-active at RHi between 150 and 190%. Strong IN activation of SOA particles was observed only at RHi above 200%, which is clearly above water saturation at the given temperature. The IN suppression and the shift of the heterogeneous IN onset to higher RHi seem to depend on the coating thickness or the fractional surface coverage of the mineral particles. The results indicate that the heterogeneous ice nucleation potential of atmospheric mineral particles may also be suppressed if they are coated with secondary organics.

  11. The effect of organic coating on the heterogeneous ice nucleation efficiency of mineral dust aerosols

    International Nuclear Information System (INIS)

    Moehler, O; Benz, S; Saathoff, H; Schnaiter, M; Wagner, R; Schneider, J; Walter, S; Ebert, V; Wagner, S

    2008-01-01

    The effect of organic coating on the heterogeneous ice nucleation (IN) efficiency of dust particles was investigated at simulated cirrus cloud conditions in the AIDA cloud chamber of Forschungszentrum Karlsruhe. Arizona test dust (ATD) and the clay mineral illite were used as surrogates for atmospheric dust aerosols. The dry dust samples were dispersed into a 3.7 m 3 aerosol vessel and either directly transferred into the 84 m 3 cloud simulation chamber or coated before with the semi-volatile products from the reaction of α-pinene with ozone in order to mimic the coating of atmospheric dust particles with secondary organic aerosol (SOA) substances. The ice-active fraction was measured in AIDA expansion cooling experiments as a function of the relative humidity with respect to ice, RHi, in the temperature range from 205 to 210 K. Almost all uncoated dust particles with diameters between 0.1 and 1.0 μm acted as efficient deposition mode ice nuclei at RHi between 105 and 120%. This high ice nucleation efficiency was markedly suppressed by coating with SOA. About 20% of the ATD particles coated with a SOA mass fraction of 17 wt% were ice-active at RHi between 115 and 130%, and only 10% of the illite particles coated with an SOA mass fraction of 41 wt% were ice-active at RHi between 160 and 170%. Only a minor fraction of pure SOA particles were ice-active at RHi between 150 and 190%. Strong IN activation of SOA particles was observed only at RHi above 200%, which is clearly above water saturation at the given temperature. The IN suppression and the shift of the heterogeneous IN onset to higher RHi seem to depend on the coating thickness or the fractional surface coverage of the mineral particles. The results indicate that the heterogeneous ice nucleation potential of atmospheric mineral particles may also be suppressed if they are coated with secondary organics

  12. Effect of secondary organic aerosol coating thickness on the real-time detection and characterization of biomass-burning soot by two particle mass spectrometers

    Directory of Open Access Journals (Sweden)

    A. T. Ahern

    2016-12-01

    Full Text Available Biomass burning is a large source of light-absorbing refractory black carbon (rBC particles with a wide range of morphologies and sizes. The net radiative forcing from these particles is strongly dependent on the amount and composition of non-light-absorbing material internally mixed with the rBC and on the morphology of the mixed particles. Understanding how the mixing state and morphology of biomass-burning aerosol evolves in the atmosphere is critical for constraining the influence of these particles on radiative forcing and climate. We investigated the response of two commercial laser-based particle mass spectrometers, the vacuum ultraviolet (VUV ablation LAAPTOF and the IR vaporization SP-AMS, to monodisperse biomass-burning particles as we sequentially coated the particles with secondary organic aerosol (SOA from α-pinene ozonolysis. We studied three mobility-selected soot core sizes, each with a number of successively thicker coatings of SOA applied. Using IR laser vaporization, the SP-AMS had different changes in sensitivity to rBC compared to potassium as a function of applied SOA coatings. We show that this is due to different effective beam widths for the IR laser vaporization region of potassium versus black carbon. The SP-AMS's sensitivity to black carbon (BC mass was not observed to plateau following successive SOA coatings, despite achieving high OA : BC mass ratios greater than 9. We also measured the ion fragmentation pattern of biomass-burning rBC and found it changed only slightly with increasing SOA mass. The average organic matter ion signal measured by the LAAPTOF demonstrated a positive correlation with the condensed SOA mass on individual particles, despite the inhomogeneity of the particle core compositions. This demonstrates that the LAAPTOF can obtain quantitative mass measurements of aged soot-particle composition from realistic biomass-burning particles with complex morphologies and composition.

  13. Factors influencing the outdoor concentration of carbonaceous aerosols at urban schools in Brisbane, Australia: Implications for children's exposure

    International Nuclear Information System (INIS)

    Crilley, L.R.; Ayoko, G.A.; Mazaheri, M.; Morawska, L.

    2016-01-01

    This comprehensive study aimed to determine the sources and driving factors of organic carbon (OC) and elemental carbon (EC) concentrations in ambient PM 2.5 in urban schools. Sampling was conducted outdoors at 25 schools in the Brisbane Metropolitan Area, Australia. Concentrations of primary and secondary OC were quantified using the EC tracer method, with secondary OC accounting for an average of 60%. Principal component analysis distinguished the contributing sources above the background and identified groups of schools with differing levels of primary and secondary carbonaceous aerosols. Overall, the results showed that vehicle emissions, local weather conditions and secondary organic aerosols (SOA) were the key factors influencing concentrations of carbonaceous component of PM 2.5 at these schools. These results provide insights into children's exposure to vehicle emissions and SOA at such urban schools. - Highlights: • We aimed to find the contributing sources to children's exposure at school. • Measured outdoor organic carbon and elemental carbon at 25 urban schools. • Schools varied in exposure to primary and secondary sources. • Secondary organic carbon the largest component of carbonaceous aerosols. • Vehicle emission levels at schools are primarily dependent on local traffic counts. - Key factors influencing concentrations of carbonaceous component of PM 2.5 at urban schools were found to be vehicle emissions, secondary organic aerosols and local weather conditions.

  14. The sensitivity of secondary organic aerosol (SOA component partitioning to the predictions of component properties – Part 3: Investigation of condensed compounds generated by a near-explicit model of VOC oxidation

    Directory of Open Access Journals (Sweden)

    G. McFiggans

    2011-12-01

    Full Text Available Calculations of the absorptive partitioning of secondary organic aerosol components were carried out using a number of methods to estimate vapour pressure and non-ideality. The sensitivity of predicted condensed component masses, volatility, O:C ratio, molar mass and functionality distribution to the choice of estimation methods was investigated in mixtures of around 2700 compounds generated by a near explicit mechanism of atmospheric VOC degradation. The sensitivities in terms of all metrics were comparable to those previously reported (using 10 000 semi-randomly generated compounds. In addition, the change in predicted aerosol properties and composition with changing VOC emission scenario was investigated showing key dependencies on relative anthropogenic and biogenic contributions. Finally, the contribution of non-ideality to the changing distribution of condensed components was explored in terms of the shift in effective volatility by virtue of component activity coefficients, clearly demonstrating both enhancement and reduction of component masses associated with negative and positive deviations from ideality.

  15. Development of an inorganic and organic aerosol model (CHIMERE 2017β v1.0): seasonal and spatial evaluation over Europe

    Science.gov (United States)

    Couvidat, Florian; Bessagnet, Bertrand; Garcia-Vivanco, Marta; Real, Elsa; Menut, Laurent; Colette, Augustin

    2018-01-01

    A new aerosol module was developed and integrated in the air quality model CHIMERE. Developments include the use of the Model of Emissions and Gases and Aerosols from Nature (MEGAN) 2.1 for biogenic emissions, the implementation of the inorganic thermodynamic model ISORROPIA 2.1, revision of wet deposition processes and of the algorithms of condensation/evaporation and coagulation and the implementation of the secondary organic aerosol (SOA) mechanism H2O and the thermodynamic model SOAP. Concentrations of particles over Europe were simulated by the model for the year 2013. Model concentrations were compared to the European Monitoring and Evaluation Programme (EMEP) observations and other observations available in the EBAS database to evaluate the performance of the model. Performances were determined for several components of particles (sea salt, sulfate, ammonium, nitrate, organic aerosol) with a seasonal and regional analysis of results. The model gives satisfactory performance in general. For sea salt, the model succeeds in reproducing the seasonal evolution of concentrations for western and central Europe. For sulfate, except for an overestimation of sulfate in northern Europe, modeled concentrations are close to observations and the model succeeds in reproducing the seasonal evolution of concentrations. For organic aerosol, the model reproduces with satisfactory results concentrations for stations with strong modeled biogenic SOA concentrations. However, the model strongly overestimates ammonium nitrate concentrations during late autumn (possibly due to problems in the temporal evolution of emissions) and strongly underestimates summer organic aerosol concentrations over most of the stations (especially in the northern half of Europe). This underestimation could be due to a lack of anthropogenic SOA or biogenic emissions in northern Europe. A list of recommended tests and developments to improve the model is also given.

  16. Organics, Meteoritic Material, and other Elements in High Altitude Aerosols

    Science.gov (United States)

    Mahoney, M.; Murphy, D. M.; Thomson, D. S.

    1998-01-01

    Recent in situ measurements of the chemical composition of single aerosol particles at altitudes up to 19 km have revealed a number of surprising features about ambient particles. Upper tropospheric aerosols in the study region often contained more organic material than sulfate.

  17. Impact of NOx and OH on secondary organic aerosol formation from β-pinene photooxidation

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    M. Sarrafzadeh

    2016-09-01

    Full Text Available In this study, the NOx dependence of secondary organic aerosol (SOA formation from photooxidation of the biogenic volatile organic compound (BVOC β-pinene was comprehensively investigated in the Jülich Plant Atmosphere Chamber. Consistent with the results of previous NOx studies we found increases of SOA yields with increasing [NOx] at low-NOx conditions ([NOx]0  <  30 ppb, [BVOC]0 ∕ [NOx]0  >  10 ppbC ppb−1. Furthermore, increasing [NOx] at high-NOx conditions ([NOx]0  >  30 ppb, [BVOC]0 ∕ [NOx]0  ∼  10 to  ∼  2.6 ppbC ppb−1 suppressed the SOA yield. The increase of SOA yield at low-NOx conditions was attributed to an increase of OH concentration, most probably by OH recycling in NO + HO2  →  NO2 + OH reaction. Separate measurements without NOx addition but with different OH primary production rates confirmed the OH dependence of SOA yields. After removing the effect of OH concentration on SOA mass growth by keeping the OH concentration constant, SOA yields only decreased with increasing [NOx]. Measuring the NOx dependence of SOA yields at lower [NO] ∕ [NO2] ratio showed less pronounced increase in both OH concentration and SOA yield. This result was consistent with our assumption of OH recycling by NO and to SOA yields being dependent on OH concentrations. Our results furthermore indicated that NOx dependencies vary for different NOx compositions. A substantial fraction of the NOx-induced decrease of SOA yields at high-NOx conditions was caused by NOx-induced suppression of new particle formation (NPF, which subsequently limits the particle surface where low volatiles condense. This was shown by probing the NOx dependence of SOA formation in the presence of seed particles. After eliminating the effect of NOx-induced suppression of NPF and NOx-induced changes of OH concentrations, the remaining effect of NOx on the SOA yield from

  18. Effect of Heterogeneous Chemical Reactions on the Köhler Activation of Aqueous Organic Aerosols.

    Science.gov (United States)

    Djikaev, Yuri S; Ruckenstein, Eli

    2018-05-03

    We study some thermodynamic aspects of the activation of aqueous organic aerosols into cloud droplets considering the aerosols to consist of liquid solution of water and hydrophilic and hydrophobic organic compounds, taking into account the presence of reactive species in the air. The hydrophobic (surfactant) organic molecules on the surface of such an aerosol can be processed by chemical reactions with some atmospheric species; this affects the hygroscopicity of the aerosol and hence its ability to become a cloud droplet either via nucleation or via Köhler activation. The most probable pathway of such processing involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic organic molecules located on the aerosol surface (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). These two reactions play a crucial role in the enhancement of the Köhler activation of the aerosol and its evolution into a cloud droplet. Taking them and a third reaction (next in the multistep chain of relevant heterogeneous reactions) into account, one can derive an explicit expression for the free energy of formation of a four-component aqueous droplet on a ternary aqueous organic aerosol as a function of four independent variables of state of a droplet. The results of numerical calculations suggest that the formation of cloud droplets on such (aqueous hydrophilic/hydrophobic organic) aerosols is most likely to occur as a Köhler activation-like process rather than via nucleation. The model allows one to determine the threshold parameters of the system necessary for the Köhler activation of such aerosols, which are predicted to be very sensitive to the equilibrium constant of the chain of three heterogeneous reactions involved in the chemical aging of aerosols.

  19. Hygroscopic properties of organic and inorganic aerosols[Dissertation 17260

    Energy Technology Data Exchange (ETDEWEB)

    Sjoegren, N O Staffan

    2007-07-01

    The atmosphere contains gases and particulate matter (aerosol). Organic material is present both in the gas phase and in the aerosol phase. Biogenic sources such as vegetation and anthropogenic sources such as biomass burning, fossil fuel use and various industries contribute to their emissions. The study of organic compounds in aerosol particles is of importance because they affect the water uptake (hygroscopicity) of inorganic aerosol, and hence the radiation budget of the Earth through the direct and indirect aerosol effects. The hygroscopicity of mixed organic/inorganic aerosol particles produced in the laboratory was characterized. This work reports on the following substances, and mixtures of them with ammonium sulfate (AS): adipic acid (AA), citric acid (CA), glutaric acid (GA) and humic acid sodium salt (NaHA). The AA and NaHA mixtures with AS were found to require up to tens of seconds for equilibrium water content to be reached. Therefore, measurements carried out on timescales shorter than a few seconds underestimate the hygroscopic growth factor (GF) with up to 10%, for samples containing a solid phase. Conversely, the GA and CA mixtures with AS were found to take up water readily and were well described by the Zdanovskii-Stokes-Robinson (ZSR) mixing rule. The distinct deliquescence and efflorescence points of AS could be seen to gradually disappear as the CA content was increased. Furthermore mineral dust (standard Arizona test dust) was investigated, as well as the influence of nitric acid (HNO{sub 3}) uptake thereon. Mineral dust is hydrophobic, but after processing with HNO{sub 3} turns slightly hygroscopic. Large amounts of dust are injected to the atmosphere (largely from the Sahara and the Gobi deserts, but also from human land-use). Mineral dust is important as ice nuclei, and due to its larger sizes it can also contribute as cloud condensation nuclei. Mineral dust also offers surface for heterogeneous chemistry, and can play an important role

  20. Investigations of primary and secondary particulate matter of different wood combustion appliances with a high-resolution time-of-flight aerosol mass spectrometer

    Directory of Open Access Journals (Sweden)

    M. F. Heringa

    2011-06-01

    Full Text Available A series of photo-oxidation smog chamber experiments were performed to investigate the primary emissions and secondary aerosol formation from two different log wood burners and a residential pellet burner under different burning conditions: starting and flaming phase. Emissions were sampled from the chimney and injected into the smog chamber leading to primary organic aerosol (POA concentrations comparable to ambient levels. The composition of the aerosol was measured by an Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS and black carbon (BC instrumentation. The primary emissions were then exposed to xenon light to initiate photo-chemistry and subsequent secondary organic aerosol (SOA production. After correcting for wall losses, the average increase in organic matter (OM concentrations by SOA formation for the starting and flaming phase experiments with the two log wood burners was found to be a factor of 4.1±1.4 after five hours of aging. No SOA formation was observed for the stable burning phase of the pellet burner. The startup emissions of the pellet burner showed an increase in OM concentration by a factor of 3.3. Including the measured SOA formation potential, average emission factors of BC+POA+SOA, calculated from CO2 emission, were found to be in the range of 0.04 to 3.9 g/kg wood for the stable burning pellet burner and an old log wood burner during startup respectively. SOA contributed significantly to the ion C2H4O2+ at mass to charge ratio m/z 60, a commonly used marker for primary emissions of wood burning. This contribution at m/z 60 can overcompensate for the degradation of levoglucosan leading to an overestimation of the contribution of wood burning or biomass burning to the total OM. The primary organic emissions from the three different burners showed a wide range in O:C atomic ratio (0.19−0.60 for the starting and flaming

  1. Chemical and physical drivers of the evolution of organic aerosols over forests

    NARCIS (Netherlands)

    Janssen, R.H.H.

    2013-01-01

    Diurnal evolution of organic aerosol over boreal and tropical forests

    The first research question of this thesis is: how do local surface forcings and large-scale meteorological forcings shape the evolution of organic aerosol over the boreal and tropical forest? This

  2. The Effect of Aerosol Hygroscopicity and Volatility on Aerosol Optical Properties During Southern Oxidant and Aerosol Study

    Science.gov (United States)

    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.

  3. Aqueous Photochemistry of Secondary Organic Aerosol of α-Pinene and α-Humulene Oxidized with Ozone, Hydroxyl Radical, and Nitrate Radical

    Energy Technology Data Exchange (ETDEWEB)

    Romonosky, Dian E.; Li, Ying; Shiraiwa, Manabu; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2017-01-18

    Formation of secondary organic aerosols (SOA) from biogenic volatile organic compounds 13 (BVOC) occurs via O3- and OH-initiated reactions during the day and reactions with NO3 during the 14 night. We explored the effect of these three oxidation conditions on the molecular composition and 15 aqueous photochemistry of model SOA prepared from two common BVOC. A common monoterpene, α- 16 pinene, and sesquiterpene, α-humulene, were used to form SOA in a smog chamber via BVOC + O3, 17 BVOC + NO3, and BVOC + OH + NOx oxidation. Samples of SOA were collected, extracted in water, 18 and photolyzed in an aqueous solution in order to simulate the photochemical cloud processing of SOA. 19 The extent of change in the molecular level composition of SOA over 4 hours of photolysis (roughly 20 equivalent to 64 hours of photolysis under ambient conditions) was assessed with high-resolution 21 electrospray ionization mass spectrometry. The analysis revealed significant differences in the molecular 22 composition between monoterpene and sesquiterpene SOA formed by the different oxidation pathways. 23 The composition further evolved during photolysis with the most notable change corresponding to the 24 nearly-complete removal of nitrogen-containing organic compounds. Hydrolysis of SOA compounds also 25 occurred in parallel with photolysis. The preferential loss of larger SOA compounds during photolysis 26 and hydrolysis made the SOA compounds more volatile on average. This study suggests that cloud- and 27 fog-processing may under certain conditions lead to a reduction in the SOA loading as opposed to an 28 increase in SOA loading commonly assumed in the literature.

  4. Characterization of the sources and processes of organic and inorganic aerosols in New York city with a high-resolution time-of-flight aerosol mass apectrometer

    Directory of Open Access Journals (Sweden)

    Y.-L. Sun

    2011-02-01

    Full Text Available Submicron aerosol particles (PM1 were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer during the summer 2009 Field Intensive Study at Queens College in New York, NY. Organic aerosol (OA and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of the total PM1 mass. The average mass-based size distribution of OA presents a small mode peaking at ~150 nm (Dva and an accumulation mode (~550 nm that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of both sulfate and OA peak between 01:00–02:00 p.m. EST due to photochemical production. The average (±σ oxygen-to-carbon (O/C, hydrogen-to-carbon (H/C, and nitrogen-to-carbon (N/C ratios of OA in NYC are 0.36 (±0.09, 1.49 (±0.08, and 0.012 (±0.005, respectively, corresponding to an average organic mass-to-carbon (OM/OC ratio of 1.62 (±0.11. Positive matrix factorization (PMF of the high resolution mass spectra identified two primary OA (POA sources, traffic and cooking, and three secondary OA (SOA components including a highly oxidized, regional low-volatility oxygenated OA (LV-OOA; O/C = 0.63, a less oxidized, semi-volatile SV-OOA (O/C = 0.38 and a unique nitrogen-enriched OA (NOA; N/C = 0.053 characterized with prominent CxH2x + 2N+ peaks likely from amino compounds. Our results indicate that cooking and traffic are two distinct and mass-equivalent POA sources in NYC, together contributing ~30% of the total OA mass during this study. The OA composition is dominated by secondary species, especially during high PM events. SV-OOA and LV-OOA on average account for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC appears to progress with a continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed

  5. Formation of organic aerosol in the Paris region during the MEGAPOLI summer campaign: evaluation of the volatility-basis-set approach within the CHIMERE model

    Directory of Open Access Journals (Sweden)

    Q. J. Zhang

    2013-06-01

    Full Text Available Simulations with the chemistry transport model CHIMERE are compared to measurements performed during the MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation summer campaign in the Greater Paris region in July 2009. The volatility-basis-set approach (VBS is implemented into this model, taking into account the volatility of primary organic aerosol (POA and the chemical aging of semi-volatile organic species. Organic aerosol is the main focus and is simulated with three different configurations with a modified treatment of POA volatility and modified secondary organic aerosol (SOA formation schemes. In addition, two types of emission inventories are used as model input in order to test the uncertainty related to the emissions. Predictions of basic meteorological parameters and primary and secondary pollutant concentrations are evaluated, and four pollution regimes are defined according to the air mass origin. Primary pollutants are generally overestimated, while ozone is consistent with observations. Sulfate is generally overestimated, while ammonium and nitrate levels are well simulated with the refined emission data set. As expected, the simulation with non-volatile POA and a single-step SOA formation mechanism largely overestimates POA and underestimates SOA. Simulation of organic aerosol with the VBS approach taking into account the aging of semi-volatile organic compounds (SVOC shows the best correlation with measurements. High-concentration events observed mostly after long-range transport are well reproduced by the model. Depending on the emission inventory used, simulated POA levels are either reasonable or underestimated, while SOA levels tend to be overestimated. Several uncertainties related to the VBS scheme (POA volatility, SOA yields, the aging parameterization, to emission input data, and to simulated OH levels can be responsible for

  6. Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol: Part 1 – Evidence from measurements

    Directory of Open Access Journals (Sweden)

    H. Wex

    2009-06-01

    Full Text Available Secondary Organic Aerosols (SOA studied in previous laboratory experiments generally showed only slight hygroscopic growth, but a much better activity as a CCN (Cloud Condensation Nucleus than indicated by the hygroscopic growth. This discrepancy was examined at LACIS (Leipzig Aerosol Cloud Interaction Simulator, using a portable generator that produced SOA particles from the ozonolysis of α-pinene, and adding butanol or butanol and water vapor during some of the experiments. The light scattering signal of dry SOA-particles was measured by the LACIS optical particle spectrometer and was used to derive a refractive index for SOA of 1.45. LACIS also measured the hygroscopic growth of SOA particles up to 99.6% relative humidity (RH, and a CCN counter was used to measure the particle activation. SOA-particles were CCN active with critical diameters of e.g. 100 nm and 55 nm at super-saturations of 0.4% and 1.1%, respectively. But only slight hygroscopic growth with hygroscopic growth factors ≤1.05 was observed at RH<98% RH. At RH>98%, the hygroscopic growth increased stronger than would be expected if a constant hygroscopicity parameter for the particle/droplet solution was assumed. An increase of the hygroscopicity parameter by a factor of 4–6 was observed in the RH-range from below 90% to 99.6%, and this increase continued for increasingly diluted particle solutions for activating particles. This explains an observation already made in the past: that the relation between critical super-saturation and dry diameter for activation is steeper than what would be expected for a constant value of the hygroscopicity. Combining measurements of hygroscopic growth and activation, it was found that the surface tension that has to be assumed to interpret the measurements consistently is greater than 55 mN/m, possibly close to that of pure water, depending on the different SOA-types produced, and therefore only in part accounts for the discrepancy

  7. Continuous measurements at the urban roadside in an Asian megacity by Aerosol Chemical Speciation Monitor (ACSM): particulate matter characteristics during fall and winter seasons in Hong Kong

    Science.gov (United States)

    Sun, C.; Lee, B. P.; Huang, D.; Jie Li, Y.; Schurman, M. I.; Louie, P. K. K.; Luk, C.; Chan, C. K.

    2016-02-01

    Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM) in the fall and winter seasons of 2013 on the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA), characterized by application of Positive Matrix Factorization (PMF), and sulfate are found to be dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear mealtime concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during mealtimes, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and the influence of continental air masses.

  8. Continuous measurements at the urban roadside in an Asian megacity by Aerosol Chemical Speciation Monitor (ACSM: particulate matter characteristics during fall and winter seasons in Hong Kong

    Directory of Open Access Journals (Sweden)

    C. Sun

    2016-02-01

    Full Text Available Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM in the fall and winter seasons of 2013 on the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA, characterized by application of Positive Matrix Factorization (PMF, and sulfate are found to be dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear mealtime concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during mealtimes, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and the influence of continental air masses.

  9. Light absorption of organic aerosol from pyrolysis of corn stalk

    Science.gov (United States)

    Li, Xinghua; Chen, Yanju; Bond, Tami C.

    2016-11-01

    Organic aerosol (OA) can absorb solar radiation in the low-visible and ultra-violet wavelengths thereby modifying radiative forcing. Agricultural waste burning emits a large quantity of organic carbon in many developing countries. In this work, we improved the extraction and analysis method developed by Chen and Bond, and extended the spectral range of OC absorption. We examined light absorbing properties of primary OA from pyrolysis of corn stalk, which is a major type of agricultural wastes. Light absorption of bulk liquid extracts of OA was measured using a UV-vis recording spectrophotometer. OA can be extracted by methanol at 95%, close to full extent, and shows polar character. Light absorption of organic aerosol has strong spectral dependence (Absorption Ångström exponent = 7.7) and is not negligible at ultra-violet and low-visible regions. Higher pyrolysis temperature produced OA with higher absorption. Imaginary refractive index of organic aerosol (kOA) is 0.041 at 400 nm wavelength and 0.005 at 550 nm wavelength, respectively.

  10. Secondary organic carbon quantification and source apportionment of PM10 in Kaifeng, China

    Institute of Scientific and Technical Information of China (English)

    WU Lin; FENG Yinchang; WU Jianhui; ZHU Tan; BI Xiaohui; HAN Bo; YANG Weihong; YANG Zhiqiang

    2009-01-01

    During 2005, the filter samples of ambient PM10 from five sites and the source samples of particulate matter were collected in Kaifeng, Henan province of China. Nineteen elements, water-soluble ions, total carbon (TC) and organic carbon (OC) contained in samples were analyzed. Seven contributive source types were identified and their contributions to ambient PM10 were estimated by chemical mass balance (CMB) receptor model. Weak associations between the concentrations of organic carbon and element carbon (EC) were observed during the sampling periods, indicating that there was secondary organic aerosol pollution in the urban atmosphere. An indirect method of "OC/EC minimum ratio" was applied to estimate the concentration of secondary organic carbon (SOC). The results showed that SOC contributed 26.2%, 32.4% and 18.0% of TC in spring, summer-fall and winter respectively, and the annual average SOC concentration was 7.07 μg/m3, accounting for 5.73% of the total mass in ambient PM10. The carbon species concentrations in ambient PM10 were recalculated by subtracting the SOC concentrations from measured concentrations of TC and OC to increase the compatibility of source and receptor measurements for CMB model.

  11. Development of an inorganic and organic aerosol model (CHIMERE 2017β v1.0: seasonal and spatial evaluation over Europe

    Directory of Open Access Journals (Sweden)

    F. Couvidat

    2018-01-01

    Full Text Available A new aerosol module was developed and integrated in the air quality model CHIMERE. Developments include the use of the Model of Emissions and Gases and Aerosols from Nature (MEGAN 2.1 for biogenic emissions, the implementation of the inorganic thermodynamic model ISORROPIA 2.1, revision of wet deposition processes and of the algorithms of condensation/evaporation and coagulation and the implementation of the secondary organic aerosol (SOA mechanism H2O and the thermodynamic model SOAP. Concentrations of particles over Europe were simulated by the model for the year 2013. Model concentrations were compared to the European Monitoring and Evaluation Programme (EMEP observations and other observations available in the EBAS database to evaluate the performance of the model. Performances were determined for several components of particles (sea salt, sulfate, ammonium, nitrate, organic aerosol with a seasonal and regional analysis of results. The model gives satisfactory performance in general. For sea salt, the model succeeds in reproducing the seasonal evolution of concentrations for western and central Europe. For sulfate, except for an overestimation of sulfate in northern Europe, modeled concentrations are close to observations and the model succeeds in reproducing the seasonal evolution of concentrations. For organic aerosol, the model reproduces with satisfactory results concentrations for stations with strong modeled biogenic SOA concentrations. However, the model strongly overestimates ammonium nitrate concentrations during late autumn (possibly due to problems in the temporal evolution of emissions and strongly underestimates summer organic aerosol concentrations over most of the stations (especially in the northern half of Europe. This underestimation could be due to a lack of anthropogenic SOA or biogenic emissions in northern Europe. A list of recommended tests and developments to improve the model is also given.

  12. On Surface Order and Disorder of α-Pinene-Derived Secondary Organic Material

    Energy Technology Data Exchange (ETDEWEB)

    Shrestha, Mona; Zhang, Yue; Upshur, Mary Alice; Liu, Pengfei; Blair, Sandra L.; Wang, Hongfei; Nizkorodov, Sergey; Thomson, Regan; Martin, Scot T.; Geiger, Franz M.

    2015-05-14

    The surfaces of secondary organic aerosol particles are notoriously difficult to access experimentally, even though they are the key location where exchange between the aerosol particle phase and its gas phase occurs. Here, we overcome this difficulty by applying standard and sub 1-cm-1 resolution vibrational sum frequency generation (SFG) spectroscopy to detect C–H oscillators at the surfaces of secondary organic material (SOM) prepared from the ozonolysis of α-pinene at Harvard University and at the University of California, Irvine that were subsequently collected on Teflon filters as well as CaF2 windows using electrostatic deposition. We find both samples yield comparable SFG spectra featuring an intense peak at 2940 cm-1 that are independent of spectral resolution and location or method of preparation. We hypothesize that the SFG spectra are due to surface-active C–H oscillators associated with the four-membered ring motif of α-pinene, which produces an unresolvable spectral continuum of approximately 50 cm-1 width reminiscent of the similar, albeit much broader, O–H stretching continuum observed in the SFG spectra of aqueous surfaces. Upon subjecting the SOM samples to cycles in relative humidity (RH) between <2% RH and 95% RH, we observe reversible changes in the SFG signal intensity across the entire spectral range surveyed for a polarization combination probing components of the vibrational transition dipole moments that are oriented parallel to the plane of incidence, but no signal intensity changes for any other polarization combination investigated. These results support the notion that the C–H oscillators at the surfaces of α-pinene-derived SOM deposited on CaF2 windows shift back and forth between two different molecular orientation distributions as the RH is lowered (more ordered) or raised (less ordered). The findings thus point towards the presence of a reversible surface switch for hindering (more ordered, <2%RH) and promoting (less

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

    Science.gov (United States)

    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

  14. Sea Spray Aerosols

    DEFF Research Database (Denmark)

    Butcher, Andrew Charles

    emissions produced directly from bubble bursting as the result of air entrainment from breaking waves and particles generated from secondary emissions of volatile organic compounds. In the first paper, we study the chemical properties of particles produced from several sea water proxies with the use...... of a cloud condensation nuclei ounter. Proxy solutions with high inorganic salt concentrations and some organics produce sea spray aerosol particles with little change in cloud condensation activity relative to pure salts. Comparison is made between a frit based method for bubble production and a plunging...... a relationship between plunging jet particle ux, oceanic particle ux, and energy dissipation rate in both systems. Previous sea spray aerosol studies dissipate an order of magnitude more energy for the same particle ux production as the open ocean. A scaling factor related to the energy expended in air...

  15. Climate implications of carbonaceous aerosols: An aerosol microphysical study using the GISS/MATRIX climate model

    International Nuclear Information System (INIS)

    Bauer, Susanne E.; Menon, Surabi; Koch, Dorothy; Bond, Tami; Tsigaridis, Kostas

    2010-01-01

    Recently, attention has been drawn towards black carbon aerosols as a likely short-term climate warming mitigation candidate. However the global and regional impacts of the direct, cloud-indirect and semi-direct forcing effects are highly uncertain, due to the complex nature of aerosol evolution and its climate interactions. Black carbon is directly released as particle into the atmosphere, but then interacts with other gases and particles through condensation and coagulation processes leading to further aerosol growth, aging and internal mixing. A detailed aerosol microphysical scheme, MATRIX, embedded within the global GISS modelE includes the above processes that determine the lifecycle and climate impact of aerosols. This study presents a quantitative assessment of the impact of microphysical processes involving black carbon, such as emission size distributions and optical properties on aerosol cloud activation and radiative forcing. Our best estimate for net direct and indirect aerosol radiative forcing change is -0.56 W/m 2 between 1750 and 2000. However, the direct and indirect aerosol effects are very sensitive to the black and organic carbon size distribution and consequential mixing state. The net radiative forcing change can vary between -0.32 to -0.75 W/m 2 depending on these carbonaceous particle properties. Assuming that sulfates, nitrates and secondary organics form a coating shell around a black carbon core, rather than forming a uniformly mixed particles, changes the overall net radiative forcing from a negative to a positive number. Black carbon mitigation scenarios showed generally a benefit when mainly black carbon sources such as diesel emissions are reduced, reducing organic and black carbon sources such as bio-fuels, does not lead to reduced warming.

  16. Comparison of secondary organic aerosol formation from toluene on initially wet and dry ammonium sulfate particles at moderate relative humidity

    Directory of Open Access Journals (Sweden)

    T. Liu

    2018-04-01

    Full Text Available The formation of secondary organic aerosol (SOA has been widely studied in the presence of dry seed particles at low relative humidity (RH. At higher RH, initially dry seed particles can exist as wet particles due to water uptake by the seeds as well as the SOA. Here, we investigated the formation of SOA from the photooxidation of toluene using an oxidation flow reactor in the absence of NOx under a range of OH exposures on initially wet or dry ammonium sulfate (AS seed particles at an RH of 68 %. The ratio of the SOA yield on wet AS seeds to that on dry AS seeds, the relative SOA yield, decreased from 1.31 ± 0.02 at an OH exposure of 4.66 × 1010 molecules cm−3 s to 1.01 ± 0.01 at an OH exposure of 5.28 × 1011 molecules cm−3 s. This decrease may be due to the early deliquescence of initially dry AS seeds after being coated by highly oxidized toluene-derived SOA. SOA formation lowered the deliquescence RH of AS and resulted in the uptake of water by both AS and SOA. Hence the initially dry AS seeds contained aerosol liquid water (ALW soon after SOA formed, and the SOA yield and ALW approached those of the initially wet AS seeds as OH exposure and ALW increased, especially at high OH exposure. However, a higher oxidation state of the SOA on initially wet AS seeds than that on dry AS seeds was observed at all levels of OH exposure. The difference in mass fractions of m ∕ z 29, 43 and 44 of SOA mass spectra, obtained using an aerosol mass spectrometer (AMS, indicated that SOA formed on initially wet seeds may be enriched in earlier-generation products containing carbonyl functional groups at low OH exposures and later-generation products containing acidic functional groups at high exposures. Our results suggest that inorganic dry seeds become at least partially deliquesced particles during SOA formation and hence that ALW is inevitably involved in the SOA formation at moderate RH. More laboratory

  17. Aerosol studies during the ESCOMPTE experiment: an overview

    Science.gov (United States)

    Cachier, Hélène; Aulagnier, Fabien; Sarda, Roland; Gautier, François; Masclet, Pierre; Besombes, Jean-Luc; Marchand, Nicolas; Despiau, Serge; Croci, Delphine; Mallet, Marc; Laj, Paolo; Marinoni, Angela; Deveau, Pierre-Alexandre; Roger, Jean-Claude; Putaud, Jean-Philippe; Van Dingenen, Rita; Dell'Acqua, Alessandro; Viidanoja, Jyrkki; Martins-Dos Santos, Sebastiao; Liousse, Cathy; Cousin, Frédéric; Rosset, Robert; Gardrat, Eric; Galy-Lacaux, Corinne

    2005-03-01

    The "Expérience sur Site pour COntraindre les Modèles de Pollution atmosphérique et de Transport d'Emissions" (ESCOMPTE) experiment took place in the Southern part of France in the Marseilles/Fos-Berre region during 6 weeks in June and July 2001. One task was to document the regional sources of atmospheric particles and to gain some insight into the aerosol transformations in the atmosphere. For this purpose, seven sites were chosen and equipped with the same basic instrumentation to obtain the chemical closure of the bulk aerosol phase and size-segregated samples. Some specific additional experiments were conducted for the speciation of the organic matter and the aerosol size distribution in number. Finally, four multiwavelength sun-photometers were also deployed during the experiment. Interestingly, in this region, three intense aerosol sources (urban, industrial and biogenic) are very active, and data show consistent results, enlightening an important background of particles over the whole ESCOMPTE domain. Notable is the overwhelming importance of the carbonaceous fraction (comprising primary and secondary particles), which is always more abundant than sulphates. Particle size studies show that, on average, more than 90% of the mean regional aerosol number is found on a size range smaller than 300 nm in diameter. The most original result is the evidence of the rapid formation of secondary aerosols occurring in the whole ESCOMPTE domain. This formation is much more important than that usually observed at these latitudes since two thirds of the particulate mass collected off source zones is estimated to be generated during atmospheric transport. On the other hand, the marine source has poor influence in the region, especially during the overlapping pollution events of Intensive Observation Periods (IOP). Preliminary results from the 0D and 3D versions of the MesoNH-aerosol model show that, with optimised gas and particle sources, the model accounts

  18. Impacts of land use and land cover changes on biogenic emissions of volatile organic compounds in China from the late 1980s to the mid-2000s: implications for tropospheric ozone and secondary organic aerosol

    Directory of Open Access Journals (Sweden)

    Yu Fu

    2014-11-01

    Full Text Available Based on the MEGAN (Model of Emissions of Gases and Aerosols from Nature module embedded within the global chemical transport model (GEOS-Chem, we estimate the changes in emissions of biogenic volatile organic compounds (BVOCs and their impacts on surface-layer O3 and secondary organic aerosols (SOA in China between the late 1980s and the mid-2000s by using the land cover dataset derived from remote sensing images and land use survey. The land cover change in China from the late 1980s to the mid-2000s can be characterised by an expansion of urban areas (the total urban area in the mid-2000s was four times that in the late 1980s and a reduction in total vegetation coverage by 4%. Regionally, the fractions of land covered by forests exhibited increases in southeastern and northeastern China by 10–30 and 5–15%, respectively, those covered by cropland decreased in most regions except that the farming–pastoral zone in northern China increased by 5–20%, and the factions of grassland in northern China showed a large reduction of 5–30%. With changes in both land cover and meteorological fields, annual BVOC emission in China is estimated to increase by 11.4% in the mid-2000s relative to the late 1980s. With anthropogenic emissions of O3 precursors, aerosol precursors and aerosols fixed at year 2005 levels, the changes in land cover and meteorological parameters from the late 1980s to the mid-2000s are simulated to change the seasonal mean surface-layer O3 concentrations by −4 to +6 ppbv (−10 to +20% and to change the seasonal mean surface-layer SOA concentrations by −0.4 to +0.6 µg m−3 (−20 to +30% over China. We find that the decadal changes in meteorological parameters had larger collective effects on BVOC emissions and surface-layer concentrations of O3 and SOA than those in land cover and land use alone. We also perform a sensitivity simulation to compare the impacts of changes in anthropogenic emissions on concentrations of O3

  19. Evaluation of New and Proposed Organic Aerosol Sources and Mechanisms using the Aerosol Modeling Testbed. MILAGRO, CARES, CalNex, BEACHON, and GVAX

    Energy Technology Data Exchange (ETDEWEB)

    Hodzic, Alma [National Center for Atmospheric Research (NCAR), Boulder, CO (United States); Jimenez, Jose L. [Univ. of Colorado, Boulder, CO (United States)

    2015-04-09

    This work investigated the formation and evolution of organic aerosols (OA) arising from anthropogenic and biogenic sources in a framework that combined state-of-the-science process and regional modeling, and their evaluation against advanced and emerging field measurements. Although OA are the dominant constituents of submicron particles, our understanding of their atmospheric lifecycle is limited, and current models fail to describe the observed amounts and properties of chemically formed secondary organic aerosols (SOA), leaving large uncertainties on the effects of SOA on climate. Our work has provided novel modeling constraints on sources, formation, aging and removal of SOA by investigating in particular (i) the contribution of trash burning emissions to OA levels in a megacity, (ii) the contribution of glyoxal to SOA formation in aqueous particles in California during CARES/CalNex and over the continental U.S., (iii) SOA formation and regional growth over a pine forest in Colorado and its sensitivity to anthropogenic NOx levels during BEACHON, and the sensitivity of SOA to (iv) the sunlight exposure during its atmospheric lifetime, and to (v) changes in solubility and removal of organic vapors in the urban plume (MILAGRO, Mexico City), and over the continental U.S.. We have also developed a parameterization of water solubility for condensable organic gases produced from major anthropogenic and biogenic precursors based on explicit chemical modeling, and made it available to the wider community. This work used for the first time constraints from the explicit model GECKO-A to improve SOA representation in 3D regional models such as WRF-Chem.

  20. Effect of Terrestrial and Marine Organic Aerosol on Regional and Global Climate: Model Development, Application, and Verification with Satellite Data

    Energy Technology Data Exchange (ETDEWEB)

    Meskhidze, Nicholas; Zhang, Yang; Kamykowski, Daniel

    2012-03-28

    In this DOE project the improvements to parameterization of marine primary organic matter (POM) emissions, hygroscopic properties of marine POM, marine isoprene derived secondary organic aerosol (SOA) emissions, surfactant effects, new cloud droplet activation parameterization have been implemented into Community Atmosphere Model (CAM 5.0), with a seven mode aerosol module from the Pacific Northwest National Laboratory (PNNL)'s Modal Aerosol Model (MAM7). The effects of marine aerosols derived from sea spray and ocean emitted biogenic volatile organic compounds (BVOCs) on microphysical properties of clouds were explored by conducting 10 year CAM5.0-MAM7 model simulations at a grid resolution 1.9° by 2.5° with 30 vertical layers. Model-predicted relationship between ocean physical and biological systems and the abundance of CCN in remote marine atmosphere was compared to data from the A-Train satellites (MODIS, CALIPSO, AMSR-E). Model simulations show that on average, primary and secondary organic aerosol emissions from the ocean can yield up to 20% increase in Cloud Condensation Nuclei (CCN) at 0.2% Supersaturation, and up to 5% increases in droplet number concentration of global maritime shallow clouds. Marine organics were treated as internally or externally mixed with sea salt. Changes associated with cloud properties reduced (absolute value) the model-predicted short wave cloud forcing from -1.35 Wm-2 to -0.25 Wm-2. By using different emission scenarios, and droplet activation parameterizations, this study suggests that addition of marine primary aerosols and biologically generated reactive gases makes an important difference in radiative forcing assessments. All baseline and sensitivity simulations for 2001 and 2050 using global-through-urban WRF/Chem (GU-WRF) were completed. The main objective of these simulations was to evaluate the capability of GU-WRF for an accurate representation of the global atmosphere by exploring the most accurate

  1. Herbivory by an Outbreaking Moth Increases Emissions of Biogenic Volatiles and Leads to Enhanced Secondary Organic Aerosol Formation Capacity.

    Science.gov (United States)

    Yli-Pirilä, Pasi; Copolovici, Lucian; Kännaste, Astrid; Noe, Steffen; Blande, James D; Mikkonen, Santtu; Klemola, Tero; Pulkkinen, Juha; Virtanen, Annele; Laaksonen, Ari; Joutsensaari, Jorma; Niinemets, Ülo; Holopainen, Jarmo K

    2016-11-01

    In addition to climate warming, greater herbivore pressure is anticipated to enhance the emissions of climate-relevant biogenic volatile organic compounds (VOCs) from boreal and subarctic forests and promote the formation of secondary aerosols (SOA) in the atmosphere. We evaluated the effects of Epirrita autumnata, an outbreaking geometrid moth, feeding and larval density on herbivore-induced VOC emissions from mountain birch in laboratory experiments and assessed the impact of these emissions on SOA formation via ozonolysis in chamber experiments. The results show that herbivore-induced VOC emissions were strongly dependent on larval density. Compared to controls without larval feeding, clear new particle formation by nucleation in the reaction chamber was observed, and the SOA mass loadings in the insect-infested samples were significantly higher (up to 150-fold). To our knowledge, this study provides the first controlled documentation of SOA formation from direct VOC emission of deciduous trees damaged by known defoliating herbivores and suggests that chewing damage on mountain birch foliage could significantly increase reactive VOC emissions that can importantly contribute to SOA formation in subarctic forests. Additional feeding experiments on related silver birch confirmed the SOA results. Thus, herbivory-driven volatiles are likely to play a major role in future biosphere-vegetation feedbacks such as sun-screening under daily 24 h sunshine in the subarctic.

  2. The Optical Properties of Limonene Secondary Organic Aerosols: The Role of NO3, OH, and O3 in the Oxidation Processes

    Science.gov (United States)

    Peng, Chao; Wang, Weigang; Li, Kun; Li, Junling; Zhou, Li; Wang, Lingshu; Ge, Maofa

    2018-03-01

    Limonene, a typical proxy of monoterpenes emitted from biogenic sources, plays an important role in secondary organic aerosol (SOA) formation. However, the optical properties of SOA generated from limonene under various oxidation pathways remain poorly understood. In this study, we investigate the refractive index (RI) of limonene SOA produced from four oxidation conditions with cavity ring-down spectrometer (CRDS) and photoacoustic extinctiometer operated at 532 and 375 nm. Our results show that there is a significant difference in RI values of SOA produced from NO3 oxidation compared to other oxidation pathways. The mean values of RI of SOA produced from NO3 oxidation, NOx oxidation, OH oxidation with NOx-free, and O3 oxidation experiments are 1.578, 1.469, 1.495, and 1.494 at 532 nm; and 1.591, 1.527, 1.513, and 1.537 at 375 nm, respectively, while no detectable absorption is found in all oxidation conditions. We attribute the high RI values of SOA by NO3 oxidation to two factors: a large proportion of organic nitrates and high-molecular-weight dimers/oligomers in the SOA. Our study results indicate that the nighttime chemistry may significantly influence the optical properties of limonene oxidation products. The RI values of limonene SOA generated under various oxidation conditions at different wavelengths retrieved in our laboratory experiments could help improve the model predictions for evaluating the effect of biogenic SOA on the global radiative forcing as well as climate change.

  3. ACTRIS ACSM intercomparison - Part 2: Intercomparison of ME-2 organic source apportionment results from 15 individual, co-located aerosol mass spectrometers

    Science.gov (United States)

    Fröhlich, R.; Crenn, V.; Setyan, A.; Belis, C. A.; Canonaco, F.; Favez, O.; Riffault, V.; Slowik, J. G.; Aas, W.; Aijälä, M.; Alastuey, A.; Artiñano, B.; Bonnaire, N.; Bozzetti, C.; Bressi, M.; Carbone, C.; Coz, E.; Croteau, P. L.; Cubison, M. J.; Esser-Gietl, J. K.; Green, D. C.; Gros, V.; Heikkinen, L.; Herrmann, H.; Jayne, J. T.; Lunder, C. R.; Minguillón, M. C.; Močnik, G.; O'Dowd, C. D.; Ovadnevaite, J.; Petralia, E.; Poulain, L.; Priestman, M.; Ripoll, A.; Sarda-Estève, R.; Wiedensohler, A.; Baltensperger, U.; Sciare, J.; Prévôt, A. S. H.

    2015-06-01

    Chemically resolved atmospheric aerosol data sets from the largest intercomparison of the Aerodyne aerosol chemical speciation monitors (ACSMs) performed to date were collected at the French atmospheric supersite SIRTA. In total 13 quadrupole ACSMs (Q-ACSM) from the European ACTRIS ACSM network, one time-of-flight ACSM (ToF-ACSM), and one high-resolution ToF aerosol mass spectrometer (AMS) were operated in parallel for about 3 weeks in November and December~2013. Part 1 of this study reports on the accuracy and precision of the instruments for all the measured species. In this work we report on the intercomparison of organic components and the results from factor analysis source apportionment by positive matrix factorisation (PMF) utilising the multilinear engine 2 (ME-2). Except for the organic contribution of mass-to-charge ratio m/z 44 to the total organics (f44), which varied by factors between 0.6 and 1.3 compared to the mean, the peaks in the organic mass spectra were similar among instruments. The m/z 44 differences in the spectra resulted in a variable f44 in the source profiles extracted by ME-2, but had only a minor influence on the extracted mass contributions of the sources. The presented source apportionment yielded four factors for all 15 instruments: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA), biomass burning-related organic aerosol (BBOA) and secondary oxygenated organic aerosol (OOA). ME-2 boundary conditions (profile constraints) were optimised individually by means of correlation to external data in order to achieve equivalent / comparable solutions for all ACSM instruments and the results are discussed together with the investigation of the influence of alternative anchors (reference profiles). A comparison of the ME-2 source apportionment output of all 15 instruments resulted in relative standard deviations (SD) from the mean between 13.7 and 22.7 % of the source's average mass contribution depending on the

  4. Importance of relative humidity in the oxidative ageing of organic aerosols: case study of the ozonolysis of maleic acid aerosol

    Directory of Open Access Journals (Sweden)

    P. J. Gallimore

    2011-12-01

    Full Text Available Many important atmospheric aerosol processes depend on the chemical composition of the aerosol, e.g. water uptake and particle cloud interactions. Atmospheric ageing processes, such as oxidation reactions, significantly and continuously change the chemical composition of aerosol particles throughout their lifetime. These ageing processes are often poorly understood. In this study we utilize an aerosol flow tube set up and an ultra-high resolution mass spectrometer to explore the effect of relative humidity (RH in the range of <5–90% on the ozonolysis of maleic acid aerosol which is employed as model organic aerosol system. Due to the slow reaction kinetics relatively high ozone concentrations of 160–200 ppm were used to achieve an appreciable degree of oxidation of maleic acid. The effect of oxidative ageing on the hygroscopicity of maleic acid particles is also investigated using an electrodynamic balance and thermodynamic modelling. RH has a profound effect on the oxidation of maleic acid particles. Very little oxidation is observed at RH < 50% and the only observed reaction products are glyoxylic acid and formic acid. In comparison, when RH > 50% there are about 15 oxidation products identified. This increased oxidation was observed even when the particles were exposed to high humidities long after a low RH ozonolysis reaction. This result might have negative implications for the use of water as an extraction solvent for the analysis of oxidized organic aerosols. These humidity-dependent differences in the composition of the ozonolyzed aerosol demonstrate that water is both a key reactant in the oxidation scheme and a determinant of particle phase and hence diffusivity. The measured chemical composition of the processed aerosol is used to model the hygroscopic growth, which compares favourably with water uptake results from the electrodynamic balance measurements. A reaction mechanism is presented which takes into account the RH dependent

  5. Organic condensation: A vital link connecting aerosol formation to climate forcing (Invited)

    Science.gov (United States)

    Riipinen, I.; Pierce, J. R.; Yli-Juuti, T.; Nieminen, T.; Häkkinen, S.; Ehn, M.; Junninen, H.; Lehtipalo, K.; Petdjd, T. T.; Slowik, J. G.; Chang, R. Y.; Shantz, N. C.; Abbatt, J.; Leaitch, W. R.; Kerminen, V.; Worsnop, D. R.; Pandis, S. N.; Donahue, N. M.; Kulmala, M. T.

    2010-12-01

    Aerosol-cloud interactions represent the largest uncertainty in calculations of Earth’s radiative forcing. Number concentrations of atmospheric aerosol particles are in the core of this uncertainty, as they govern the numbers of cloud condensation nuclei (CCN) and influence the albedo and lifetime of clouds. Aerosols also impair air quality through their adverse effects on atmospheric visibility and human health. The ultrafine fraction ( 100 nm) and enhance the loss of ultrafine particles. Primary organic aerosol (POA) contributes to the large end of the aerosol size distribution, enhancing the scavenging of the ultrafine particles.

  6. Real-time analysis of ambient organic aerosols using aerosol flowing atmospheric-pressure afterglow mass spectrometry (AeroFAPA-MS)

    Science.gov (United States)

    Brüggemann, Martin; Karu, Einar; Stelzer, Torsten; Hoffmann, Thorsten

    2015-04-01

    Organic aerosol accounts for a major fraction of atmospheric aerosols and has implications on the earth's climate and human health. However, due to the chemical complexity its measurement remains a major challenge for analytical instrumentation.1 Here, we present the development, characterization and application of a new soft ionization technique that allows mass spectrometric real-time detection of organic compounds in ambient aerosols. The aerosol flowing atmospheric-pressure afterglow (AeroFAPA) ion source utilizes a helium glow discharge plasma to produce excited helium species and primary reagent ions. Ionization of the analytes occurs in the afterglow region after thermal desorption and results mainly in intact molecular ions, facilitating the interpretation of the acquired mass spectra. In the past, similar approaches were used to detect pesticides, explosives or illicit drugs on a variety of surfaces.2,3 In contrast, the AeroFAPA source operates 'online' and allows the detection of organic compounds in aerosols without a prior precipitation or sampling step. To our knowledge, this is the first application of an atmospheric-pressure glow discharge ionization technique to ambient aerosol samples. We illustrate that changes in aerosol composition and concentration are detected on the time scale of seconds and in the ng-m-3 range. Additionally, the successful application of AeroFAPA-MS during a field study in a mixed forest region in Central Europe is presented. Several oxidation products of monoterpenes were clearly identified using the possibility to perform tandem MS experiments. The acquired data are in agreement with previous studies and demonstrate that AeroFAPA-MS is a suitable tool for organic aerosol analysis. Furthermore, these results reveal the potential of this technique to enable new insights into aerosol formation, growth and transformation in the atmosphere. References: 1) IPCC, 2013: Summary for Policymakers. In: Climate Change 2013: The

  7. Modelled radiative forcing of the direct aerosol effect with multi-observation evaluation

    Directory of Open Access Journals (Sweden)

    G. Myhre

    2009-02-01

    Full Text Available A high-resolution global aerosol model (Oslo CTM2 driven by meteorological data and allowing a comparison with a variety of aerosol observations is used to simulate radiative forcing (RF of the direct aerosol effect. The model simulates all main aerosol components, including several secondary components such as nitrate and secondary organic carbon. The model reproduces the main chemical composition and size features observed during large aerosol campaigns. Although the chemical composition compares best with ground-based measurement over land for modelled sulphate, no systematic differences are found for other compounds. The modelled aerosol optical depth (AOD is compared to remote sensed data from AERONET ground and MODIS and MISR satellite retrievals. To gain confidence in the aerosol modelling, we have tested its ability to reproduce daily variability in the aerosol content, and this is performing well in many regions; however, we also identified some locations where model improvements are needed. The annual mean regional pattern of AOD from the aerosol model is broadly similar to the AERONET and the satellite retrievals (mostly within 10–20%. We notice a significant improvement from MODIS Collection 4 to Collection 5 compared to AERONET data. Satellite derived estimates of aerosol radiative effect over ocean for clear sky conditions differs significantly on regional scales (almost up to a factor two, but also in the global mean. The Oslo CTM2 has an aerosol radiative effect close to the mean of the satellite derived estimates. We derive a radiative forcing (RF of the direct aerosol effect of −0.35 Wm−2 in our base case. Implementation of a simple approach to consider internal black carbon (BC mixture results in a total RF of −0.28 Wm−2. Our results highlight the importance of carbonaceous particles, producing stronger individual RF than considered in the recent IPCC estimate; however, net RF is less different

  8. Modeling the Current and Future Roles of Particulate Organic Nitrates in the Southeastern United States.

    Science.gov (United States)

    Pye, Havala O T; Luecken, Deborah J; Xu, Lu; Boyd, Christopher M; Ng, Nga L; Baker, Kirk R; Ayres, Benjamin R; Bash, Jesse O; Baumann, Karsten; Carter, William P L; Edgerton, Eric; Fry, Juliane L; Hutzell, William T; Schwede, Donna B; Shepson, Paul B

    2015-12-15

    Organic nitrates are an important aerosol constituent in locations where biogenic hydrocarbon emissions mix with anthropogenic NOx sources. While regional and global chemical transport models may include a representation of organic aerosol from monoterpene reactions with nitrate radicals (the primary source of particle-phase organic nitrates in the Southeast United States), secondary organic aerosol (SOA) models can underestimate yields. Furthermore, SOA parametrizations do not explicitly take into account organic nitrate compounds produced in the gas phase. In this work, we developed a coupled gas and aerosol system to describe the formation and subsequent aerosol-phase partitioning of organic nitrates from isoprene and monoterpenes with a focus on the Southeast United States. The concentrations of organic aerosol and gas-phase organic nitrates were improved when particulate organic nitrates were assumed to undergo rapid (τ = 3 h) pseudohydrolysis resulting in nitric acid and nonvolatile secondary organic aerosol. In addition, up to 60% of less oxidized-oxygenated organic aerosol (LO-OOA) could be accounted for via organic nitrate mediated chemistry during the Southern Oxidants and Aerosol Study (SOAS). A 25% reduction in nitrogen oxide (NO + NO2) emissions was predicted to cause a 9% reduction in organic aerosol for June 2013 SOAS conditions at Centreville, Alabama.

  9. Modeling regional air quality and climate: improving organic aerosol and aerosol activation processes in WRF/Chem version 3.7.1

    Directory of Open Access Journals (Sweden)

    K. Yahya

    2017-06-01

    Full Text Available Air quality and climate influence each other through the uncertain processes of aerosol formation and cloud droplet activation. In this study, both processes are improved in the Weather, Research and Forecasting model with Chemistry (WRF/Chem version 3.7.1. The existing Volatility Basis Set (VBS treatments for organic aerosol (OA formation in WRF/Chem are improved by considering the following: the secondary OA (SOA formation from semi-volatile primary organic aerosol (POA, a semi-empirical formulation for the enthalpy of vaporization of SOA, and functionalization and fragmentation reactions for multiple generations of products from the oxidation of VOCs. Over the continental US, 2-month-long simulations (May to June 2010 are conducted and results are evaluated against surface and aircraft observations during the Nexus of Air Quality and Climate Change (CalNex campaign. Among all the configurations considered, the best performance is found for the simulation with the 2005 Carbon Bond mechanism (CB05 and the VBS SOA module with semivolatile POA treatment, 25 % fragmentation, and the emissions of semi-volatile and intermediate volatile organic compounds being 3 times the original POA emissions. Among the three gas-phase mechanisms (CB05, CB6, and SAPRC07 used, CB05 gives the best performance for surface ozone and PM2. 5 concentrations. Differences in SOA predictions are larger for the simulations with different VBS treatments (e.g., nonvolatile POA versus semivolatile POA compared to the simulations with different gas-phase mechanisms. Compared to the simulation with CB05 and the default SOA module, the simulations with the VBS treatment improve cloud droplet number concentration (CDNC predictions (normalized mean biases from −40.8 % to a range of −34.6 to −27.7 %, with large differences between CB05–CB6 and SAPRC07 due to large differences in their OH and HO2 predictions. An advanced aerosol activation

  10. Chemical, microphysical and optical properties of the aerosols during foggy and nonfoggy day over a typical location in Indo-Gangetic Plain

    Science.gov (United States)

    Kaul, D. S.; Tripathi, S. N.; Gupta, T.

    2012-04-01

    An extensive experimental measurement was carried out from January 16, 2010 to February 20, 2010 at Kanpur to study the chemical, microphysical and optical properties of the aerosols. A Micro-Pulse Lidar Network (MPLNET), a part of National Aeronautic Space Administration (NASA), was used for identification of fog duration. PM1 samples and fogwater were collected to examine the organic and inorganic species of aerosol and fogwater. Organic Carbon (OC), Elemental Carbon (EC) and water soluble organic carbon analysis were carried out by an EC-OC analyzer and a TOC analyzer, respectively. Trace gases and solar flux measurement were carried out by gas analyzers and a pyranometer (a part of NASA Aeronet), respectively, to identify the photo-chemical activity. Meteorological data were measured by atmospheric weather station. The microphysical properties such as aerosol size distribution were measured using a scanning mobility particle sizer (SMPS). Optical properties were measured by a photo-acoustic soot spectrometer (PASS). Organic and inorganic species are processed by fog droplets such as production of secondary organic aerosol through aqueous mechanism (Kaul et al., 2011) and scavenging of various water soluble species. The concentrations of almost all the ionic species and organic carbon were higher in aerosols during foggy day. Presence of numerous ionic species and organic carbon in the fogwater indicates their wet scavenging and removal from the atmosphere by the fog droplets. Most of the aerosol is composed of inorganic component, ~80% during foggy day and ~85.5 % during clear day. Biomass burning contribution to PM1 mass concentration was considerably higher during clear days and lower during foggy days; lower concentration during foggy day could be due to wet scavenging of biomass generated aerosols. The study average higher number concentration of aerosol during foggy day during late evening and overnight was due to lower boundary layer height and subsequent

  11. Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

    Science.gov (United States)

    Ortega, Amber M.; Hayes, Patrick L.; Peng, Zhe; Palm, Brett B.; Hu, Weiwei; Day, Douglas A.; Li, Rui; Cubison, Michael J.; Brune, William H.; Graus, Martin; Warneke, Carsten; Gilman, Jessica B.; Kuster, William C.; de Gouw, Joost; Gutiérrez-Montes, Cándido; Jimenez, Jose L.

    2016-06-01

    Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days-6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8-6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and Ox, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive (τOH ˜ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ˜ -0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OSC ˜ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to

  12. Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

    Directory of Open Access Journals (Sweden)

    A. M. Ortega

    2016-06-01

    Full Text Available Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS and a scanning mobility particle sizer (SMPS alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and Ox, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive (τOH  ∼  0.3 day SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope  ∼  −0.65. Oxidation state of carbon (OSc in reactor SOA increased steeply with age and remained elevated (OSC  ∼  2 at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background vs. photochemical age is similar to

  13. Characterization of secondary organic aerosol from photo-oxidation of gasoline exhaust and specific sources of major components.

    Science.gov (United States)

    Ma, Pengkun; Zhang, Peng; Shu, Jinian; Yang, Bo; Zhang, Haixu

    2018-01-01

    To further explore the composition and distribution of secondary organic aerosol (SOA) components from the photo-oxidation of light aromatic precursors (toluene, m-xylene, and 1,3,5-trimethylbenzene (1,3,5-TMB)) and idling gasoline exhaust, a vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) was employed. Peaks of the molecular ions of the SOA components with minimum molecular fragmentation were clearly observed from the mass spectra of SOA, through the application of soft ionization methods in VUV-PIMS. The experiments comparing the exhaust-SOA and light aromatic mixture-SOA showed that the observed distributions of almost all the predominant cluster ions in the exhaust-SOA were similar to that of the mixture-SOA. Based on the characterization experiments of SOA formed from individual light aromatic precursors, the SOA components with molecular weights of 98 and 110 amu observed in the exhaust-SOA resulted from the photo-oxidation of toluene and m-xylene; the components with a molecular weight of 124 amu were derived mainly from m-xylene; and the components with molecular weights of 100, 112, 128, 138, and 156 amu were mainly derived from 1,3,5-TMB. These results suggest that C 7 -C 9 light aromatic hydrocarbons are significant SOA precursors and that major SOA components originate from gasoline exhaust. Additionally, some new light aromatic hydrocarbon-SOA components were observed for the first time using VUV-PIMS. The corresponding reaction mechanisms were also proposed in this study to enrich the knowledge base of the formation mechanisms of light aromatic hydrocarbon-SOA compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Aerosol composition, oxidation properties, and sources in Beijing: results from the 2014 Asia-Pacific Economic Cooperation summit study

    Science.gov (United States)

    Xu, W. Q.; Sun, Y. L.; Chen, C.; Du, W.; Han, T. T.; Wang, Q. Q.; Fu, P. Q.; Wang, Z. F.; Zhao, X. J.; Zhou, L. B.; Ji, D. S.; Wang, P. C.; Worsnop, D. R.

    2015-12-01

    The mitigation of air pollution in megacities remains a great challenge because of the complex sources and formation mechanisms of aerosol particles. The 2014 Asia-Pacific Economic Cooperation (APEC) summit in Beijing serves as a unique experiment to study the impacts of emission controls on aerosol composition, size distributions, and oxidation properties. Herein, a high-resolution time-of-flight aerosol mass spectrometer was deployed in urban Beijing for real-time measurements of size-resolved non-refractory submicron aerosol (NR-PM1) species from 14 October to 12 November 2014, along with a range of collocated measurements. The average (±σ) PM1 was 41.6 (±38.9) μg m-3 during APEC, which was decreased by 53 % compared with that before APEC. The aerosol composition showed substantial changes owing to emission controls during APEC. Secondary inorganic aerosol (SIA: sulfate + nitrate + ammonium) showed significant reductions of 62-69 %, whereas organics presented much smaller decreases (35 %). The results from the positive matrix factorization of organic aerosol (OA) indicated that highly oxidized secondary organic aerosol (SOA) showed decreases similar to those of SIA during APEC. However, primary organic aerosol (POA) from cooking, traffic, and biomass-burning sources were comparable to those before APEC, indicating the presence of strong local source emissions. The oxidation properties showed corresponding changes in response to OA composition. The average oxygen-to-carbon level during APEC was 0.36 (±0.10), which is lower than the 0.43 (±0.13) measured before APEC, demonstrating a decrease in the OA oxidation degree. The changes in size distributions of primary and secondary species varied during APEC. SIA and SOA showed significant reductions in large accumulation modes with peak diameters shifting from ~ 650 to 400 nm during APEC, whereas those of POA remained relatively unchanged. The changes in aerosol composition, size distributions, and oxidation

  15. Seasonal characterization of submicron aerosol chemical composition and organic aerosol sources in the southeastern United States: Atlanta, Georgia,and Look Rock, Tennessee

    Directory of Open Access Journals (Sweden)

    S. H. Budisulistiorini

    2016-04-01

    -derived secondary organic aerosol (SOA. The contribution of 91Fac to the total OA mass was significant (on average 22 % of OA mass at the rural site only during warmer months. Comparison of 91Fac OA time series with SOA tracers measured from filter samples collected at Look Rock suggests that isoprene oxidation through a pathway other than IEPOX SOA chemistry may contribute to its formation. Other biogenic sources could also contribute to 91Fac, but there remains a need to resolve the exact source of this factor based on its significant contribution to rural OA mass.

  16. Formation kinetics and abundance of organic nitrates in α-pinene ozonolysis

    Science.gov (United States)

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

    2016-04-01

    Formation of organic nitrates affects the total atmospheric budget of oxidized nitrogen (NOy) and alters the total aerosol mass yield from secondary sources. We investigated the formation of organic nitrate species during ozonolysis of α-pinene and subsequent formation of secondary organic aerosols (SOA) using the short-lived radioactive tracer 13N inside an aerosol flow reactor (Ammann et al., 2001). The results represent direct measurements of the organic nitrate content of α-pinene secondary aerosol and give insight into the kinetics of organic nitrate formation. Organic nitrates constituted up to 40 % of aerosol mass with a pronounced influence during the initial period of particle growth. Kinetic modelling, as well as additional experiments using OH scavengers and UV irradiation, suggests that organic peroxy radicals (RO2) from the reaction of α-pinene with secondarily produced OH are important intermediates in the organic nitrate formation process. Direct oxidation of α-pinene by NO3 was found to be a less efficient pathway for formation of particle phase nitrate. The organic nitrate content decreased very slightly with an increase of relative humidity on the experimental time scale. The experiments show a tight correlation between organic nitrate content and SOA number concentrations, implying that organic nitrates play an important role in nucleation and growth of nanoparticles. Since present in large amounts in organic aerosol, organic nitrates deposited in the lung might have implications for human health as they release nitric acid upon hydrolysis, especially in regions influenced by urban pollution and large sources of monoterpene SOA precursors. References Ammann et al. (2001) Radiochimica Acta 89, 831.

  17. Characterization of polar organosulfates in secondary organic aerosol from the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal

    Directory of Open Access Journals (Sweden)

    M. S. Shalamzari

    2016-06-01

    Full Text Available We show in the present study that the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal are biogenic volatile organic compound (BVOC precursors for polar organosulfates with molecular weights (MWs 230 and 214, which are also present in ambient fine aerosol from a forested site, i.e., K-puszta, Hungary. These results complement those obtained in a previous study showing that the green leaf aldehyde 3-Z-hexenal serves as a precursor for MW 226 organosulfates. Thus, in addition to isoprene, the green leaf volatiles (GLVs 2-E-hexenal and 3-Z-hexenal, emitted due to plant stress (mechanical wounding or insect attack, and 2-E-pentenal, a photolysis product of 3-Z-hexenal, should be taken into account for secondary organic aerosol and organosulfate formation. Polar organosulfates are of climatic relevance because of their hydrophilic properties and cloud effects. Extensive use was made of organic mass spectrometry (MS and detailed interpretation of MS data (i.e., ion trap MS and accurate mass measurements to elucidate the chemical structures of the MW 230, 214 and 170 organosulfates formed from 2-E-pentenal and indirectly from 2-E-hexenal and 3-Z-hexenal. In addition, quantum chemical calculations were performed to explain the different mass spectral behavior of 2,3-dihydroxypentanoic acid sulfate derivatives, where only the isomer with the sulfate group at C-3 results in the loss of SO3. The MW 214 organosulfates formed from 2-E-pentenal are explained by epoxidation of the double bond in the gas phase and sulfation of the epoxy group with sulfuric acid in the particle phase through the same pathway as that proposed for 3-sulfooxy-2-hydroxy-2-methylpropanoic acid from the isoprene-related α,β-unsaturated aldehyde methacrolein in previous work (Lin et al., 2013. The MW 230 organosulfates formed from 2-E-pentenal are tentatively explained by a novel pathway, which bears features of the latter pathway but introduces an additional hydroxyl

  18. Aerosol Indirect effect on Stratocumulus Organization

    Science.gov (United States)

    Zhou, X.; Heus, T.; Kollias, P.

    2015-12-01

    Large-eddy simulations are used to investigate the role of aerosol loading on organized Stratocumulus. We prescribed the cloud droplet number concentration (Nc) and considered it as the proxy for different aerosol loading. While the presence of drizzle amplifies the mesoscale variability as is in Savic-Jovcic and Stevens (JAS, 2008), two noticeable findings are discussed here: First, the scale of marine boundary layer circulation appears to be independent of aerosol loading, suggesting a major role of the turbulence. The precise role of the turbulence in stratocumulus organization is studied by modifying the large scale fluctuations from the LES domain. Second, while it is commonly thought that the whole circulation needs to be represented for robust cloud development, we find that stratocumulus dynamics, including variables like w'w' and w'w'w', are remarkably robust even if large scales are ignored by simply reducing the domain sizes. The only variable that is sensitive to the change of the scale is the amount of cloudiness. Despite their smaller cloud thickness and inhomogeneous macroscopic structure for low Nc, individual drizzling clouds have sizes that are commensurate with circulation scale. We observe an Nc threshold below which stratocumulus is thin enough so that a little decrease of Nc would lead to great change of cloud fraction. The simulated cloud albedo is more sensitive to in-cloud liquid water content than to the amount of cloudiness since the former decreases at least three times faster than the latter due to drizzle. The main impact of drizzle evaporation is observed to keep the sub-cloud layer moist and as a result to extend the lifetime of stratocumulus by a couple of hours.

  19. ACTRIS ACSM intercomparison – Part 2: Intercomparison of ME-2 organic source apportionment results from 15 individual, co-located aerosol mass spectrometers

    Directory of Open Access Journals (Sweden)

    R. Fröhlich

    2015-06-01

    Full Text Available Chemically resolved atmospheric aerosol data sets from the largest intercomparison of the Aerodyne aerosol chemical speciation monitors (ACSMs performed to date were collected at the French atmospheric supersite SIRTA. In total 13 quadrupole ACSMs (Q-ACSM from the European ACTRIS ACSM network, one time-of-flight ACSM (ToF-ACSM, and one high-resolution ToF aerosol mass spectrometer (AMS were operated in parallel for about 3 weeks in November and December~2013. Part 1 of this study reports on the accuracy and precision of the instruments for all the measured species. In this work we report on the intercomparison of organic components and the results from factor analysis source apportionment by positive matrix factorisation (PMF utilising the multilinear engine 2 (ME-2. Except for the organic contribution of mass-to-charge ratio m/z 44 to the total organics (f44, which varied by factors between 0.6 and 1.3 compared to the mean, the peaks in the organic mass spectra were similar among instruments. The m/z 44 differences in the spectra resulted in a variable f44 in the source profiles extracted by ME-2, but had only a minor influence on the extracted mass contributions of the sources. The presented source apportionment yielded four factors for all 15 instruments: hydrocarbon-like organic aerosol (HOA, cooking-related organic aerosol (COA, biomass burning-related organic aerosol (BBOA and secondary oxygenated organic aerosol (OOA. ME-2 boundary conditions (profile constraints were optimised individually by means of correlation to external data in order to achieve equivalent / comparable solutions for all ACSM instruments and the results are discussed together with the investigation of the influence of alternative anchors (reference profiles. A comparison of the ME-2 source apportionment output of all 15 instruments resulted in relative standard deviations (SD from the mean between 13.7 and 22.7 % of the source's average mass contribution depending on

  20. Evolution of Multispectral Aerosol Absorption Properties in a Biogenically-Influenced Urban Environment during the CARES Campaign

    Energy Technology Data Exchange (ETDEWEB)

    Gyawali, Madhu; Arnott, W.; Zaveri, Rahul; Song, Chen; Flowers, Bradley; Dubey, Manvendra; Setyan, Ari; Zhang, Qi; China, Swarup; Mazzoleni, Claudio; Gorkowski, Kyle; Subramanian, R.; Moosmüller, Hans

    2017-11-01

    We present the evolution of multispectral optical properties as urban aerosols aged and interacted with biogenic emissions resulting in stronger short wavelength absorption and formation of moderately brown secondary organic aerosols. Ground-based aerosol measurements were made during June 2010 within the Sacramento urban area (site T0) and at a 40-km downwind location (site T1) in the forested Sierra Nevada foothills area. Data on black carbon and non-refractory aerosol mass and composition were collected at both sites. In addition, photoacoustic (PA) instruments with integrating nephelometers were used to measure spectral absorption and scattering coefficients for wavelengths ranging from 355 to 870 nm. The daytime absorption Ångström exponent (AAE) indicated a modest wavelength-dependent enhancement of absorption at both sites throughout the study. From the 22nd to the 28th of June, secondary organic aerosol mass increased significantly at both sites due to increased biogenic emissions coupled with intense photochemical activity and air mass recirculation in the area. During this period, the median BC mass-normalized absorption cross-section (MAC) values for 405 nm and 532 nm at T1 increased by ~23% and ~35%, respectively, compared to the relatively less aged urban emissions at the T0 site. In contrast, the average MAC values for the 870 nm wavelength were similar for both sites. These results suggest formation of moderately brown secondary organic aerosols in biogenically-influenced urban air.

  1. OH-initiated Aging of Biomass Burning Aerosol during FIREX

    Science.gov (United States)

    Lim, C. Y.; Hagan, D. H.; Cappa, C. D.; Kroll, J. H.; Coggon, M.; Koss, A.; Sekimoto, K.; De Gouw, J. A.; Warneke, C.

    2017-12-01

    Biomass burning emissions represent a major source of fine particulate matter to the atmosphere, and this source will likely become increasingly important in the future due to changes in the Earth's climate. Understanding the effects that increased fire emissions have on both air quality and climate requires understanding the composition of the particles emitted, since chemical and physical composition directly impact important particle properties such as absorptivity, toxicity, and cloud condensation nuclei activity. However, the composition of biomass burning particles in the atmosphere is dynamic, as the particles are subject to the condensation of low-volatility vapors and reaction with oxidants such as the hydroxyl radical (OH) during transport. Here we present a series of laboratory chamber experiments on the OH-initiated aging of biomass burning aerosol performed at the Fire Sciences Laboratory in Missoula, MT as part of the Fire Influences on Regional and Global Environments Experiment (FIREX) campaign. We describe the evolution of biomass burning aerosol produced from a variety of fuels operating the chamber in both particle-only and gas + particle mode, focusing on changes to the organic composition. In particle-only mode, gas-phase biomass burning emissions are removed before oxidation to focus on heterogeneous oxidation, while gas + particle mode includes both heterogeneous oxidation and condensation of oxidized volatile organic compounds onto the particles (secondary organic aerosol formation). Variability in fuels and burning conditions lead to differences in aerosol loading and secondary aerosol production, but in all cases aging results in a significant and rapid increases in the carbon oxidation state of the particles.

  2. Organic condensation - a vital link connecting aerosol formation to climate forcing

    Science.gov (United States)

    Riipinen, I.; Pierce, J. R.; Yli-Juuti, T.; Nieminen, T.; Häkkinen, S.; Ehn, M.; Junninen, H.; Lehtipalo, K.; Petäjä, T.; Slowik, J.; Chang, R.; Shantz, N. C.; Abbatt, J.; Leaitch, W. R.; Kerminen, V.-M.; Worsnop, D. R.; Pandis, S. N.; Donahue, N. M.; Kulmala, M.

    2011-01-01

    Atmospheric aerosol particles influence global climate as well as impair air quality through their effects on atmospheric visibility and human health. Ultrafine (<100 nm) particles often dominate aerosol numbers, and nucleation of atmospheric vapors is an important source of these particles. To have climatic relevance, however, the freshly-nucleated particles need to grow in size. We combine observations from two continental sites (Egbert, Canada and Hyytiälä, Finland) to show that condensation of organic vapors is a crucial factor governing the lifetimes and climatic importance of the smallest atmospheric particles. We demonstrate that state-of-the-science organic gas-particle partitioning models fail to reproduce the observations, and propose a modeling approach that is consistent with the measurements. We demonstrate the large sensitivity of climatic forcing of atmospheric aerosols to these interactions between organic vapors and the smallest atmospheric nanoparticles - highlighting the need for representing this process in global climate models.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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. - Highlights: • Biomass fuels (wood and dung cake) were studied for brown carbon direct radiative effects. • Model calculations predicted positive contribution of Brown carbon aerosols to organic carbon direct radiative effect. • Average direct radiative values for brown carbon from dung cake were higher compare to wood. • The visible light absorption played major role in brown carbon contribution (67–90 %) to total direct radiative effect.

  4. Nano-Sized Secondary Organic Aerosol of Diesel Engine Exhaust Origin Impairs Olfactory-Based Spatial Learning Performance in Preweaning Mice

    Directory of Open Access Journals (Sweden)

    Tin-Tin Win-Shwe

    2015-06-01

    Full Text Available The aims of our present study were to establish a novel olfactory-based spatial learning test and to examine the effects of exposure to nano-sized diesel exhaust-origin secondary organic aerosol (SOA, a model environmental pollutant, on the learning performance in preweaning mice. Pregnant BALB/c mice were exposed to clean air, diesel exhaust (DE, or DE-origin SOA (DE-SOA from gestational day 14 to postnatal day (PND 10 in exposure chambers. On PND 11, the preweaning mice were examined by the olfactory-based spatial learning test. After completion of the spatial learning test, the hippocampus from each mouse was removed and examined for the expressions of neurological and immunological markers using real-time RT-PCR. In the test phase of the study, the mice exposed to DE or DE-SOA took a longer time to reach the target as compared to the control mice. The expression levels of neurological markers such as the N-methyl-d-aspartate (NMDA receptor subunits NR1 and NR2B, and of immunological markers such as TNF-α, COX2, and Iba1 were significantly increased in the hippocampi of the DE-SOA-exposed preweaning mice as compared to the control mice. Our results indicate that DE-SOA exposure in utero and in the neonatal period may affect the olfactory-based spatial learning behavior in preweaning mice by modulating the expressions of memory function–related pathway genes and inflammatory markers in the hippocampus.

  5. Physico-Chemical Evolution of Organic Aerosol from Wildfire Emissions

    Science.gov (United States)

    Croteau, P.; Jathar, S.; Akherati, A.; Galang, A.; Tarun, S.; Onasch, T. B.; Lewane, L.; Herndon, S. C.; Roscioli, J. R.; Yacovitch, T. I.; Fortner, E.; Xu, W.; Daube, C.; Knighton, W. B.; Werden, B.; Wood, E.

    2017-12-01

    Wildfires are the largest combustion-related source of carbonaceous emissions to the atmosphere; these include direct emissions of black carbon (BC), primary organic aerosol (POA) and semi-volatile, intermediate-volatility, and volatile organic compounds (SVOCs, IVOCs, and VOCs). However, there are large uncertainties surrounding the evolution of these carbonaceous emissions as they are physically and chemically transformed in the atmosphere. To understand these transformations, we performed sixteen experiments using an environmental chamber to simulate day- and night-time chemistry of gas- and aerosol-phase emissions from 6 different fuels at the Fire Laboratory in Missoula, MT. Across the test matrix, the experiments simulated 2 to 8 hours of equivalent day-time aging (with the hydroxyl radical and ozone) or several hours of night-time aging (with the nitrate radical). Aging resulted in an average organic aerosol (OA) mass enhancement of 28% although the full range of OA mass enhancements varied between -10% and 254%. These enhancement findings were consistent with chamber and flow reactor experiments performed at the Fire Laboratory in 2010 and 2012 but, similar to previous studies, offered no evidence to link the OA mass enhancement to fuel type or oxidant exposure. Experiments simulating night-time aging resulted in an average OA mass enhancement of 10% and subsequent day-time aging resulted in a decrease in OA mass of 8%. While small, for the first time, these experiments highlighted the continuous nature of the OA evolution as the wildfire smoke cycled through night- and day-time processes. Ongoing work is focussed on (i) quantifying bulk compositional changes in OA, (ii) comparing the near-field aging simulated in this work with far-field aging simulated during the same campaign (via a mini chamber and flow tube) and (iii) integrating wildfire smoke aging datasets over the past decade to examine the relationship between OA mass enhancement ratios, modified

  6. Development and Characterization of a Thermodenuder for Aerosol Volatility Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Timothy Onasch

    2009-09-09

    This SBIR Phase I project addressed the critical need for improved characterization of carbonaceous aerosol species in the atmosphere. The proposed work focused on the development of a thermodenuder (TD) system capable of systematically measuring volatility profiles of primary and secondary organic aerosol species and providing insight into the effects of absorbing and nonabsorbing organic coatings on particle absorption properties. This work provided the fundamental framework for the generation of essential information needed for improved predictions of ambient aerosol loadings and radiative properties by atmospheric chemistry models. As part of this work, Aerodyne Research, Inc. (ARI) continued to develop and test, with the final objective of commercialization, an improved thermodenuder system that can be used in series with any aerosol instrument or suite of instruments (e.g., aerosol mass spectrometers-AMS, scanning mobility particle sizers-SMPS, photoacoustic absorption spectrometers-PAS, etc.) to obtain aerosol chemical, physical, and optical properties as a function of particle volatility. In particular, we provided the proof of concept for the direct coupling of our improved TD design with a full microphysical model to obtain volatility profiles for different organic aerosol components and to allow for meaningful comparisons between different TD-derived aerosol measurements. In a TD, particles are passed through a heated zone and a denuding (activated charcoal) zone to remove semi-volatile material. Changes in particle size, number concentration, optical absorption, and chemical composition are subsequently detected with aerosol instrumentation. The aerosol volatility profiles provided by the TD will strengthen organic aerosol emission inventories, provide further insight into secondary aerosol formation mechanisms, and provide an important measure of particle absorption (including brown carbon contributions and identification, and absorption enhancements

  7. Hygroscopic properties of smoke-generated organic aerosol particles emitted in the marine atmosphere

    Directory of Open Access Journals (Sweden)

    A. Wonaschütz

    2013-10-01

    Full Text Available During the Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE, a plume of organic aerosol was produced by a smoke generator and emitted into the marine atmosphere from aboard the R/V Point Sur. In this study, the hygroscopic properties and the chemical composition of the plume were studied at plume ages between 0 and 4 h in different meteorological conditions. In sunny conditions, the plume particles had very low hygroscopic growth factors (GFs: between 1.05 and 1.09 for 30 nm and between 1.02 and 1.1 for 150 nm dry size at a relative humidity (RH of 92%, contrasted by an average marine background GF of 1.6. New particles were produced in large quantities (several 10 000 cm−3, which lead to substantially increased cloud condensation nuclei (CCN concentrations at supersaturations between 0.07 and 0.88%. Ratios of oxygen to carbon (O : C and water-soluble organic mass (WSOM increased with plume age: from −3, respectively, while organic mass fractions decreased slightly (~ 0.97 to ~ 0.94. High-resolution aerosol mass spectrometer (AMS spectra show that the organic fragment m/z 43 was dominated by C2H3O+ in the small, new particle mode and by C3H7+ in the large particle mode. In the marine background aerosol, GFs for 150 nm particles at 40% RH were found to be enhanced at higher organic mass fractions: an average GF of 1.06 was observed for aerosols with an organic mass fraction of 0.53, and a GF of 1.04 for an organic mass fraction of 0.35.

  8. Advanced source apportionment of carbonaceous aerosols by coupling offline AMS and radiocarbon size-segregated measurements over a nearly 2-year period

    OpenAIRE

    Vlachou, Athanasia; Daellenbach, Kaspar R.; Bozzetti, Carlo; Chazeau, Benjamin; Salazar Quintero, Gary Abdiel; Szidat, Sönke; Jaffrezo, Jean-Luc; Hueglin, Christoph; Baltensperger, Urs; Haddad, Imad El; Prévôt, André S. H.

    2018-01-01

    Carbonaceous aerosols are related to adverse human health effects. Therefore, identification of their sources and analysis of their chemical composition is important. The offline AMS (aerosol mass spectrometer) technique offers quantitative separation of organic aerosol (OA) factors which can be related to major OA sources, either primary or secondary. While primary OA can be more clearly separated into sources, secondary (SOA) source apportionment is more challenging because different source...

  9. Advanced source apportionment of carbonaceous aerosols by coupling offline AMS and radiocarbon size-segregated measurements over a nearly 2-year period

    OpenAIRE

    A. Vlachou; K. R. Daellenbach; C. Bozzetti; B. Chazeau; G. A. Salazar; S. Szidat; J.-L. Jaffrezo; C. Hueglin; U. Baltensperger; I. E. Haddad; A. S. H. Prévôt

    2018-01-01

    Carbonaceous aerosols are related to adverse human health effects. Therefore, identification of their sources and analysis of their chemical composition is important. The offline AMS (aerosol mass spectrometer) technique offers quantitative separation of organic aerosol (OA) factors which can be related to major OA sources, either primary or secondary. While primary OA can be more clearly separated into sources, secondary (SOA) source apportionment is more challenging because d...

  10. Ambient Aerosol in Southeast Asia: High Resolution Aerosol Mass Spectrometer Measurements Over Oil Palm (Elaeis guineensis)

    Science.gov (United States)

    Phillips, G.; Dimarco, C.; Misztal, P.; Nemitz, E.; Farmer, D.; Kimmel, J.; Jimenez, J.

    2008-12-01

    The emission of organic compounds in the troposphere is important factor in the formation of secondary organic aerosol (SOA). A very large proportion of organic material emitted globally is estimated to arise from biogenic sources, with almost half coming from tropical and sub-tropical forests. Preliminary analyses of leave cuvette emission studies suggest that oil palm (Elaeis guineensis) is a significantly larger source of isoprene than tropical forest. Much larger sources of isoprene over oil palm allied with a larger anthropogenic component of local emissions contrast greatly with the remote tropical forest environment and therefore the character of SOA formed may differ significantly. These issues, allied with the high price of palm oil on international markets leading to increased use of land for oil palm production, could give rise to rapidly changing chemical and aerosol regimes in the tropics. It is therefore important to understand the current emissions and composition of organic aerosol over all important land-uses in the tropical environment. This in turn will lead to a greater understanding of the present, and to an improvement in predictive capacity for the future system. To help address these issues, a high resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) was deployed in the Sabahmas (PPB OIL) oil palm plantation near Lahad Datu, in Eastern Sabah, as part of the field component of the Aerosol Coupling in the Earth System (ACES) project, part of the UK NERC APPRAISE program. This project was allied closely with measurements made of similar chemical species and aerosol components at a forest site in the Danum Valley as part of the UK Oxidant and Particle Photochemical Processes above a Southeast Asian tropical rainforest (OP3) project. Measurements of submicron non- refractory aerosol composition are presented along with some preliminary analysis of chemically resolved aerosol fluxes made with a new eddy covariance system, based on the

  11. The hygroscopicity parameter (κ) of ambient organic aerosol at a field site subject to biogenic and anthropogenic influences: relationship to degree of aerosol oxidation

    Science.gov (United States)

    Chang, R. Y.-W.; Slowik, J. G.; Shantz, N. C.; Vlasenko, A.; Liggio, J.; Sjostedt, S. J.; Leaitch, W. R.; Abbatt, J. P. D.

    2010-06-01

    Cloud condensation nuclei (CCN) concentrations were measured at Egbert, a rural site in Ontario, Canada during the spring of 2007. The CCN concentrations were compared to values predicted from the aerosol chemical composition and size distribution using κ-Köhler theory, with the specific goal of this work being to determine the hygroscopic parameter (κ) of the oxygenated organic component of the aerosol, assuming that oxygenation drives the hygroscopicity for the entire organic fraction of the aerosol. The hygroscopicity of the oxygenated fraction of the organic component, as determined by an Aerodyne aerosol mass spectrometer (AMS), was characterised by two methods. First, positive matrix factorization (PMF) was used to separate oxygenated and unoxygenated organic aerosol factors. By assuming that the unoxygenated factor is completely non-hygroscopic and by varying κ of the oxygenated factor so that the predicted and measured CCN concentrations are internally consistent and in good agreement, κ of the oxygenated organic factor was found to be 0.22±0.04 for the suite of measurements made during this five-week campaign. In a second, equivalent approach, we continue to assume that the unoxygenated component of the aerosol, with a mole ratio of atomic oxygen to atomic carbon (O/C) ≈ 0, is completely non-hygroscopic, and we postulate a simple linear relationship between κorg and O/C. Under these assumptions, the κ of the entire organic component for bulk aerosols measured by the AMS can be parameterised as κorg=(0.29±0.05)·(O/C), for the range of O/C observed in this study (0.3 to 0.6). These results are averaged over our five-week study at one location using only the AMS for composition analysis. Empirically, our measurements are consistent with κorg generally increasing with increasing particle oxygenation, but high uncertainties preclude us from testing this hypothesis. Lastly, we examine select periods of different aerosol composition, corresponding

  12. Technical Note: Molecular characterization of aerosol-derived water soluble organic carbon using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

    Directory of Open Access Journals (Sweden)

    R. M. Dickhut

    2008-09-01

    Full Text Available Despite the acknowledged relevance of aerosol-derived water-soluble organic carbon (WSOC to climate and biogeochemical cycling, characterization of aerosol WSOC has been limited. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS was utilized in this study to provide detailed molecular level characterization of the high molecular weight (HMW; m/z>223 component of aerosol-derived WSOC collected from rural sites in Virginia and New York, USA. More than 3000 peaks were detected by ESI FT-ICR MS within a m/z range of 223–600 for each sample. Approximately 86% (Virginia and 78% (New York of these peaks were assigned molecular formulas using only carbon (C, hydrogen (H, oxygen (O, nitrogen (N, and sulfur (S as elemental constituents. H/C and O/C molar ratios were plotted on van Krevelen diagrams and indicated a strong contribution of lignin-like and lipid-like compounds to the aerosol-derived WSOC samples. Approximately 1–4% of the peaks in the aerosol-derived WSOC mass spectra were classified as black carbon (BC on the basis of double bond equivalents calculated from the assigned molecular formulas. In addition, several high-magnitude peaks in the mass spectra of samples from both sites corresponded to molecular formulas proposed in previous secondary organic aerosol (SOA laboratory investigations indicating that SOAs are important constituents of the WSOC. Overall, ESI FT-ICR MS provides a level of resolution adequate for detailed compositional and source information of the HMW constituents of aerosol-derived WSOC.

  13. Chemical and isotopic composition of secondary organic aerosol generated by α-pinene ozonolysis

    DEFF Research Database (Denmark)

    Meusinger, Carl; Dusek, Ulrike; King, Stephanie M.

    2017-01-01

    -NOx conditions, with OH scavengers and in the absence of seed particles. The excess of ozone and long residence time in the flow chamber ensured that virtually all α-pinene had reacted. Product SOA was collected on two sequential quartz filters. The filters were analysed offline by heating them stepwise from 100...... it is difficult to apply because neither the isotopic composition of aerosol precursors nor the fractionation of aerosol forming processes is well characterised. In this paper, SOA formation from ozonolysis of α-pinene - an important precursor and perhaps the best-known model system used in laboratory studies...... - was investigated using position-dependent and average determinations of 13C in α-pinene and advanced analysis of reaction products using thermal-desorption proton-transfer-reaction mass spectrometry (PTR-MS). The total carbon (TC) isotopic composition δ13C of the initial α-pinene was measured, and the δ13C...

  14. Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

    Science.gov (United States)

    Jing, Bo; Wang, Zhen; Tan, Fang; Guo, Yucong; Tong, Shengrui; Wang, Weigang; Zhang, Yunhong; Ge, Maofa

    2018-04-01

    While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO3)2) and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA). The nitrate salt / organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH), the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

  15. Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

    Directory of Open Access Journals (Sweden)

    B. Jing

    2018-04-01

    Full Text Available While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO32 and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA. The nitrate salt ∕ organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH, the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

  16. Analysis of organic sulfur compounds in atmospheric aerosols at the HKUST supersite in Hong Kong using HR-ToF-AMS.

    Science.gov (United States)

    Huang, Dan Dan; Li, Yong Jie; Lee, Berto P; Chan, Chak K

    2015-03-17

    Organic sulfur compounds have been identified in ambient secondary organic aerosols, but their contribution to organic mass is not well quantified. In this study, using a high-resolution time-of-flight aerosol mass spectrometer (AMS), concentrations of organic sulfur compounds were estimated based on the high-resolution fragmentation patterns of methanesulfonic acid (MSA), and organosulfates (OS), including alkyl, phenyl, and cycloalkyl sulfates, obtained in laboratory experiments. Mass concentrations of MSA and minimum mass concentrations of OS were determined in a field campaign conducted at a coastal site of Hong Kong in September 2011. MSA and OS together accounted for at least 5% of AMS detected organics. MSA is of marine origin with its formation dominated by local photochemical activities and enhanced by aqueous phase processing. OS concentrations are better correlated with particle liquid water content (LWC) than with particle acidity. High-molecular-weight OS were detected in the continental influenced period probably because they had grown into larger molecules during long-range transport or they were formed from large anthropogenic precursors. This study highlights the importance of both aqueous-phase processing and regional influence, i.e., different air mass origins, on organic sulfur compound formation in coastal cities like Hong Kong.

  17. Aerosol trapping in steam generator (artist): an investigation of aerosol and iodine behaviour in the secondary side of a steam generator

    International Nuclear Information System (INIS)

    Guentay, S.; Birchley, J.; Suckow, D.; Dehbi, A.

    2000-01-01

    Incidents such as a steam generator tube rupture (SGTR) with stuck-open relief valve are important accident sequences for analysis by virtue of the open path for release of radioactivity which ensues. The release may be mitigated by deposition of fission products on the steam generator (SG) tubes and other structures, or by scrubbing in the secondary coolant. The absence of empirical data, the complexity of the geometry and controlling processes, however, make the retention difficult to quantify and its full import is typically not taken into account in risk assessment studies. The ARTIST experimental programme at PSI will simulate the flow and retention of aerosol-borne fission products in the SG secondary, and thus provide a unique database to support safety assessments and analytical models. Scaling of the break flow represents a particular challenge since the aerosol retention processes operate at contrasting length scales. Preliminary calculations have identified a baseline set of conditions, and confirmed the feasibility of the rig design and scaling principles. Flexibility of the rig layout enables simulations to be performed for a range of SG designs, accident situations and accident management philosophies. (authors)

  18. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  19. Diurnal Cycles of Aerosol Optical Properties at Pico Tres Padres, Mexico City: Evidences for Changes in Particle Morphology and Secondary Aerosol Formation

    Science.gov (United States)

    Mazzoleni, C.; Dubey, M.; Chakrabarty, R.; Moosmuller, H.; Onasch, T.; Zavala, M.; Herndon, S.; Kolb, C.

    2007-12-01

    Aerosol optical properties affect planetary radiative balance and depend on chemical composition, size distribution, and morphology. During the MILAGRO field campaign, we measured aerosol absorption and scattering in Mexico City using the Los Alamos aerosol photoacoustic (LAPA) instrument operating at 781 nm. The LAPA was mounted on-board the Aerodyne Research Inc. mobile laboratory, which hosted a variety of gaseous and aerosol instruments. During the campaign, the laboratory was moved to different sites, capturing spatial and temporal variability. Additionally, we collected ambient aerosols on Nuclepore filters for scanning electron microscopy (SEM) analysis. SEM images of selected filters were taken to study particle morphology. Between March 7th and 19th air was sampled at the top of Pico Tres Padres, a mountain on the north side of Mexico City. Aerosol absorption and scattering followed diurnal patterns related to boundary layer height and solar insulation. We report an analysis of aerosol absorption, scattering, and morphology for three days (9th, 11th and 12th of March 2006). The single scattering albedo (SSA, ratio of scattering to total extinction) showed a drop in the tens-of-minutes-to-hour time frame after the boundary layer grew above the sampling site. Later in the day the SSA rose steadily reaching a maximum in the afternoon. The SEM images showed a variety of aerosol shapes including fractal-like aggregates, spherical particles, and other shapes. The absorption correlated with the CO2 signal and qualitatively with the fraction of fractal-like particles to the total particle count. In the afternoon the SSA qualitatively correlated with a relative increase in spherical particles and total particle count. These observed changes in optical properties and morphology can be explained by the dominant contribution of freshly emitted particles in the morning and by secondary particle formation in the afternoon. SSA hourly averaged values ranged from ~0.63 in

  20. Bulk and molecular-level characterization of laboratory-aged biomass burning organic aerosol from oak leaf and heartwood fuels

    Directory of Open Access Journals (Sweden)

    C. F. Fortenberry

    2018-02-01

    Full Text Available The chemical complexity of biomass burning organic aerosol (BBOA greatly increases with photochemical aging in the atmosphere, necessitating controlled laboratory studies to inform field observations. In these experiments, BBOA from American white oak (Quercus alba leaf and heartwood samples was generated in a custom-built emissions and combustion chamber and photochemically aged in a potential aerosol mass (PAM flow reactor. A thermal desorption aerosol gas chromatograph (TAG was used in parallel with a high-resolution time-of-flight aerosol mass spectrometer (AMS to analyze BBOA chemical composition at different levels of photochemical aging. Individual compounds were identified and integrated to obtain relative decay rates for key molecules. A recently developed chromatogram binning positive matrix factorization (PMF technique was used to obtain mass spectral profiles for factors in TAG BBOA chromatograms, improving analysis efficiency and providing a more complete determination of unresolved complex mixture (UCM components. Additionally, the recently characterized TAG decomposition window was used to track molecular fragments created by the decomposition of thermally labile BBOA during sample desorption. We demonstrate that although most primary (freshly emitted BBOA compounds deplete with photochemical aging, certain components eluting within the TAG thermal decomposition window are instead enhanced. Specifically, the increasing trend in the decomposition m∕z 44 signal (CO2+ indicates formation of secondary organic aerosol (SOA in the PAM reactor. Sources of m∕z 60 (C2H4O2+, typically attributed to freshly emitted BBOA in AMS field measurements, were also investigated. From the TAG chemical speciation and decomposition window data, we observed a decrease in m∕z 60 with photochemical aging due to the decay of anhydrosugars (including levoglucosan and other compounds, as well as an increase in m∕z 60 due to the formation of

  1. Formation of secondary aerosols from the ozonolysis of styrene: Effect of SO2 and H2O

    Science.gov (United States)

    Díaz-de-Mera, Yolanda; Aranda, Alfonso; Martínez, Ernesto; Rodríguez, Ana Angustias; Rodríguez, Diana; Rodríguez, Ana

    2017-12-01

    In this work we report the study of the ozonolysis of styrene and the reaction conditions leading to the formation of secondary aerosols. The reactions have been carried out in a Teflon chamber filled with synthetic air mixtures at atmospheric pressure and room temperature. We have found that the ozonolysis of styrene in the presence of low concentrations of SO2 readily produces new particles under concentrations of reactants lower than those required in experiments in the absence of SO2. Thus, nucleation events occur at concentrations around (5.6 ± 1.7) × 108molecule cm-3 (errors are 2σ±20%) and SO2 is consumed during the experiments. The reaction of the Criegee intermediates with SO2 to produce SO3 and then H2SO4 may explain (together with OH reactions' contribution) the high capacity of styrene to produce particulate matter in polluted atmospheres. The formation of secondary aerosols in the smog chamber is inhibited under high H2O concentrations. So, the potential formation of secondary aerosols under atmospheric conditions depends on the concentration of SO2 and relative humidity, with a water to SO2 rate constants ratio kH2O/kSO2 = (2.8 ± 0.7) × 10-5 (errors are 2σ±20%).

  2. Seasonal cycles of secondary organic aerosol tracers in rural Guangzhou, Southern China: The importance of atmospheric oxidants.

    Science.gov (United States)

    Yuan, Qi; Lai, Senchao; Song, Junwei; Ding, Xiang; Zheng, Lishan; Wang, Xinming; Zhao, Yan; Zheng, Junyu; Yue, Dingli; Zhong, Liuju; Niu, Xiaojun; Zhang, Yingyi

    2018-05-21

    Thirteen secondary organic aerosol (SOA) tracers of isoprene (SOA I ), monoterpenes (SOA M ), sesquiterpenes (SOA S ) and aromatics (SOA A ) in fine particulate matter (PM 2.5 ) were measured at a Pearl River Delta (PRD) regional site for one year. The characteristics including their seasonal cycles and the factors influencing their formation in this region were studied. The seasonal patterns of SOA I , SOA M and SOA S tracers were characterized over three enhancement periods in summer (I), autumn (II) and winter (III), while the elevations of SOA A tracer (i.e., 2,3-dihydroxy-4-oxopentanoic acid, DHOPA) were observed in Periods II and III. We found that SOA formed from different biogenic precursors could be driven by several factors during a one-year seasonal cycle. Isoprene emission controlled SOA I formation throughout the year, while monoterpene and sesquiterpene emissions facilitated SOA M and SOA S formation in summer rather than in other seasons. The influence of atmospheric oxidants (O x ) was found to be an important factor of the formation of SOA M tracers during the enhancement periods in autumn and winter. The formation of SOA S tracer was influenced by the precursor emissions in summer, atmospheric oxidation in autumn and probably also by biomass burning in both summer and winter. In this study, we could not see the strong contribution of biomass burning to DHOPA as suggested by previous studies in this region. Instead, good correlations between observed DHOPA and O x as well as [NO 2 ][O 3 ] suggest the involvement of both ozone (O 3 ) and nitrogen dioxide (NO 2 ) in the formation of DHOPA. The results showed that regional air pollution may not only increase the emissions of aromatic precursors but also can greatly promote the formation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Chemical Thermodynamics of Aqueous Atmospheric Aerosols: Modeling and Microfluidic Measurements

    Science.gov (United States)

    Nandy, L.; Dutcher, C. S.

    2017-12-01

    Accurate predictions of gas-liquid-solid equilibrium phase partitioning of atmospheric aerosols by thermodynamic modeling and measurements is critical for determining particle composition and internal structure at conditions relevant to the atmosphere. Organic acids that originate from biomass burning, and direct biogenic emission make up a significant fraction of the organic mass in atmospheric aerosol particles. In addition, inorganic compounds like ammonium sulfate and sea salt also exist in atmospheric aerosols, that results in a mixture of single, double or triple charged ions, and non-dissociated and partially dissociated organic acids. Statistical mechanics based on a multilayer adsorption isotherm model can be applied to these complex aqueous environments for predictions of thermodynamic properties. In this work, thermodynamic analytic predictive models are developed for multicomponent aqueous solutions (consisting of partially dissociating organic and inorganic acids, fully dissociating symmetric and asymmetric electrolytes, and neutral organic compounds) over the entire relative humidity range, that represent a significant advancement towards a fully predictive model. The model is also developed at varied temperatures for electrolytes and organic compounds the data for which are available at different temperatures. In addition to the modeling approach, water loss of multicomponent aerosol particles is measured by microfluidic experiments to parameterize and validate the model. In the experimental microfluidic measurements, atmospheric aerosol droplet chemical mimics (organic acids and secondary organic aerosol (SOA) samples) are generated in microfluidic channels and stored and imaged in passive traps until dehydration to study the influence of relative humidity and water loss on phase behavior.

  4. Development and Application of an Oxidation Flow Reactor to Study Secondary Organic Aerosol Formation from Ambient Air

    Science.gov (United States)

    Palm, Brett Brian

    Secondary organic aerosols (SOA) in the atmosphere play an important role in air quality, human health, and climate. However, the sources, formation pathways, and fate of SOA are poorly constrained. In this dissertation, I present development and application of the oxidation flow reactor (OFR) technique for studying SOA formation from OH, O3, and NO3 oxidation of ambient air. With a several-minute residence time and a portable design with no inlet, OFRs are particularly well-suited for this purpose. I first introduce the OFR concept, and discuss several advances I have made in performing and interpreting OFR experiments. This includes estimating oxidant exposures, modeling the fate of low-volatility gases in the OFR (wall loss, condensation, and oxidation), and comparing SOA yields of single precursors in the OFR with yields measured in environmental chambers. When these experimental details are carefully considered, SOA formation in an OFR can be more reliably compared with ambient SOA formation processes. I then present an overview of what OFR measurements have taught us about SOA formation in the atmosphere. I provide a comparison of SOA formation from OH, O3, and NO3 oxidation of ambient air in a wide variety of environments, from rural forests to urban air. In a rural forest, the SOA formation correlated with biogenic precursors (e.g., monoterpenes). In urban air, it correlated instead with reactive anthropogenic tracers (e.g., trimethylbenzene). In mixed-source regions, the SOA formation did not correlate well with any single precursor, but could be predicted by multilinear regression from several precursors. Despite these correlations, the concentrations of speciated ambient VOCs could only explain approximately 10-50% of the total SOA formed from OH oxidation. In contrast, ambient VOCs could explain all of the SOA formation observed from O3 and NO3 oxidation. Evidence suggests that lower-volatility gases (semivolatile and intermediate-volatility organic

  5. Source apportionment of organic compounds in Berlin using positive matrix factorization - assessing the impact of biogenic aerosol and biomass burning on urban particulate matter.

    Science.gov (United States)

    Wagener, Sandra; Langner, Marcel; Hansen, Ute; Moriske, Heinz-Jörn; Endlicher, Wilfried R

    2012-10-01

    Source apportionment of 13 organic compounds, elemental carbon and organic carbon of ambient PM(10) and PM(1) was performed with positive matrix factorization (PMF). Samples were collected at three sites characterized by different vegetation influences in Berlin, Germany in 2010. The aim was to determine organic, mainly biogenic sources and their impact on urban aerosol collected in a densely populated region. A 6-factor solution provided the best data fit for both PM-fractions, allowing the sources isoprene- and α-pinene-derived secondary organic aerosol (SOA), bio primary, primarily attributable to fungal spores, bio/urban primary including plant fragments in PM(10) and cooking and traffic emissions in PM(1), biomass burning and combustion fossil to be identified. With mean concentrations up to 2.6 μg Cm(-3), biomass burning dominated the organic fraction in cooler months. Concentrations for α-pinene-derived SOA exceeded isoprene-derived concentrations. Estimated secondary organic carbon contributions to total organic carbon (OC) were between 7% and 42% in PM(10) and between 11% and 60% in PM(1), which is slightly lower than observed for US- or Asian cities. Primary biogenic emissions reached up to 33% of OC in the PM(10)-fraction in the late summer and autumn months. Temperature-dependence was found for both SOA-factors, correlations with ozone and mix depth only for the α-pinene-derived SOA-factor. Latter indicated input of α-pinene from the borders, highlighting differences in the origin of the precursors of both factors. Most factors were regionally distributed. High regional distribution was found to be associated with stronger influence of ambient parameters and higher concentrations at the background station. A significant contribution of biogenic emissions and biomass burning to urban organic aerosol could be stated. This indicates a considerable impact on PM concentrations also in cities in a densely populated area, and should draw the attention

  6. A GCM study of organic matter in marine aerosol and its potential contribution to cloud drop activation

    NARCIS (Netherlands)

    Roelofs, G.J.H.

    2007-01-01

    With the global aerosol-climate model ECHAM5-HAM we investigate the potential influence of organic aerosol originating from the ocean on aerosol mass and chemical composition and the droplet concentration and size of marine clouds. We present sensitivity simulations in which the uptake of organic

  7. Landscape fires dominate terrestrial natural aerosol - climate feedbacks

    Science.gov (United States)

    Scott, C.; Arnold, S.; Monks, S. A.; Asmi, A.; Paasonen, P.; Spracklen, D. V.

    2017-12-01

    The terrestrial biosphere is an important source of natural aerosol including landscape fire emissions and secondary organic aerosol (SOA) formed from biogenic volatile organic compounds (BVOCs). Atmospheric aerosol alters the Earth's climate by absorbing and scattering radiation (direct radiative effect; DRE) and by perturbing the properties of clouds (aerosol indirect effect; AIE). Natural aerosol sources are strongly controlled by, and can influence, climate; giving rise to potential natural aerosol-climate feedbacks. Earth System Models (ESMs) include a description of some of these natural aerosol-climate feedbacks, predicting substantial changes in natural aerosol over the coming century with associated radiative perturbations. Despite this, the sensitivity of natural aerosols simulated by ESMs to changes in climate or emissions has not been robustly tested against observations. Here we combine long-term observations of aerosol number and a global aerosol microphysics model to assess terrestrial natural aerosol-climate feedbacks. We find a strong positive relationship between the summertime anomaly in observed concentration of particles greater than 100 nm diameter and the anomaly in local air temperature. This relationship is reproduced by the model and driven by variability in dynamics and meteorology, as well as natural sources of aerosol. We use an offline radiative transfer model to determine radiative effects due to changes in two natural aerosol sources: landscape fire and biogenic SOA. We find that interannual variability in the simulated global natural aerosol radiative effect (RE) is negatively related to the global temperature anomaly. The magnitude of global aerosol-climate feedback (sum of DRE and AIE) is estimated to be -0.15 Wm-2 K-1 for landscape fire aerosol and -0.06 Wm-2 K-1 for biogenic SOA. These feedbacks are comparable in magnitude, but opposite in sign to the snow albedo feedback, highlighting the need for natural aerosol feedbacks to

  8. Chemical composition and characteristics of ambient aerosols and rainwater residues during Indian summer monsoon: Insight from aerosol mass spectrometry

    Science.gov (United States)

    Chakraborty, Abhishek; Gupta, Tarun; Tripathi, Sachchida N.

    2016-07-01

    Real time composition of non-refractory submicron aerosol (NR-PM1) is measured via Aerosol mass spectrometer (AMS) for the first time during Indian summer monsoon at Kanpur, a polluted urban location located at the heart of Indo Gangetic Plain (IGP). Submicron aerosols are found to be dominated by organics followed by nitrate. Source apportionment of organic aerosols (OA) via positive matrix factorization (PMF) revealed several types of secondary/oxidized and primary organic aerosols. On average, OA are completely dominated by oxidized OA with a very little contribution from biomass burning OA. During rain events, PM1 concentration is decreased almost by 60%, but its composition remains nearly the same. Oxidized OA showed slightly more decrease than primary OAs, probably due to their higher hygroscopicity. The presence of organo nitrates (ON) is also detected in ambient aerosols. Apart from real-time sampling, collected fog and rainwater samples were also analyzed via AMS in offline mode and in the ICP-OES (Inductively coupled plasma - Optical emission spectrometry) for elements. The presence of sea salt, organo nitrates and sulfates has been observed. Rainwater residues are also dominated by organics but their O/C ratios are 15-20% lower than the observed values for ambient OA. Alkali metals such as Ca, Na, K are found to be most abundant in the rainwater followed by Zn. Rainwater residues are also found to be much less oxidized than the aerosols present inside the fog water, indicating presence of less oxidized organics. These findings indicate that rain can act as an effective scavenger of different types of pollutants even for submicron particle range. Rainwater residues also contain organo sulfates which indicate that some portion of the dissolved aerosols has undergone aqueous processing, possibly inside the cloud. Highly oxidized and possibly hygroscopic OA during monsoon period compared to other seasons (winter, post monsoon), indicates that they can act

  9. Quantitative characterization of urban sources of organic aerosol by high-resolution gas chromatography

    International Nuclear Information System (INIS)

    Hildemann, L.M.; Mazurek, M.A.; Cass, G.R.; Simoneit, B.R.T.

    1991-01-01

    Fine aerosol emissions have been collected from a variety of urban combustion sources, including an industrial boiler, a fireplace, automobiles, diesel trucks, gas-fired home appliances, and meat cooking operations, by use of a dilution sampling system. Other sampling techniques have been utilized to collect fine aerosol samples of paved road dust, brake wear, tire wear, cigarette smoke, tar pot emissions, and vegetative detritus. The organic matter contained in each of these samples has been analyzed via high-resolution gas chromatography. By use of a simple computational approach, a quantitative, 50-parameter characterization of the elutable fine organic aerosol emitted from each source type has been determined. The organic mass distribution fingerprints obtained by this approach are shown to differ significantly from each other for most of the source types tested, using hierarchical cluster analysis

  10. A seasonal time history of the size resolved composition of fine aerosol in Manchester UK

    Science.gov (United States)

    Choularton, Thomas; Martin, Claire; Allan, James; Coe, Hugh; Bower, Keith; Gallagher, Martin

    2010-05-01

    Numerous studies have been conducted in urban centres now using sophisticated instruments that measure aerosol properties needed to determine their effects on human health, air quality and climate change) showing that a significant fraction of urban aerosols (mainly from automotive sources) are composed of organic compounds with implications for human health. In this project we have produced the first seasonal aerosol composition and emission database for the City of Manchester in the UK Several recent projects have been conducted by SEAES looking at fundamental properties of urban atmospheric aerosol to understand their influence on climate. This work is now expanding through collaboration with the School of Geography & Centre for Occupational & Environmental Health to investigate urban aerosol emission impacts on human health In this paper we present a compendium of data from field campaigns in Manchester city centre over the past decade. The data are from six different campaigns, between 2001 - 2007, each campaign was between 2 weeks and 2 months long predominantly from January and June periods . The data analysis includes air parcel trajectory examination and comparisons with external data, including PM10, CO and NOx data from AURN fixed monitoring sites Six Manchester fine aerosol datasets from the past decade have been quality controlled and analysed regarding averages of the size distributions of Organic, NO3, NH4 and SO4 mass loadings. It was found that: Organic material is the largest single component of the aerosol with primary aliphatic material dominating the smallest sizes, but with oxygenated secondary organic material being important in the accumulation mode. In the accumulation mode the organic material seems to be internally mixed with sulphate and nitrate. The accumulation mode particles were effective as cloud condensation nuclei. Seasonal effects surrounding atmospheric stability and photochemistry were found to play an important role in the

  11. Influence of organic films on the evaporation and condensation of water in aerosol.

    Science.gov (United States)

    Davies, James F; Miles, Rachael E H; Haddrell, Allen E; Reid, Jonathan P

    2013-05-28

    Uncertainties in quantifying the kinetics of evaporation and condensation of water from atmospheric aerosol are a significant contributor to the uncertainty in predicting cloud droplet number and the indirect effect of aerosols on climate. The influence of aerosol particle surface composition, particularly the impact of surface active organic films, on the condensation and evaporation coefficients remains ambiguous. Here, we report measurements of the influence of organic films on the evaporation and condensation of water from aerosol particles. Significant reductions in the evaporation coefficient are shown to result when condensed films are formed by monolayers of long-chain alcohols [C(n)H(2n+1)OH], with the value decreasing from 2.4 × 10(-3) to 1.7 × 10(-5) as n increases from 12 to 17. Temperature-dependent measurements confirm that a condensed film of long-range order must be formed to suppress the evaporation coefficient below 0.05. The condensation of water on a droplet coated in a condensed film is shown to be fast, with strong coherence of the long-chain alcohol molecules leading to islanding as the water droplet grows, opening up broad areas of uncoated surface on which water can condense rapidly. We conclude that multicomponent composition of organic films on the surface of atmospheric aerosol particles is likely to preclude the formation of condensed films and that the kinetics of water condensation during the activation of aerosol to form cloud droplets is likely to remain rapid.

  12. Influence of organic films on the evaporation and condensation of water in aerosol

    Science.gov (United States)

    Davies, James F.; Miles, Rachael E. H.; Haddrell, Allen E.; Reid, Jonathan P.

    2013-01-01

    Uncertainties in quantifying the kinetics of evaporation and condensation of water from atmospheric aerosol are a significant contributor to the uncertainty in predicting cloud droplet number and the indirect effect of aerosols on climate. The influence of aerosol particle surface composition, particularly the impact of surface active organic films, on the condensation and evaporation coefficients remains ambiguous. Here, we report measurements of the influence of organic films on the evaporation and condensation of water from aerosol particles. Significant reductions in the evaporation coefficient are shown to result when condensed films are formed by monolayers of long-chain alcohols [CnH(2n+1)OH], with the value decreasing from 2.4 × 10−3 to 1.7 × 10−5 as n increases from 12 to 17. Temperature-dependent measurements confirm that a condensed film of long-range order must be formed to suppress the evaporation coefficient below 0.05. The condensation of water on a droplet coated in a condensed film is shown to be fast, with strong coherence of the long-chain alcohol molecules leading to islanding as the water droplet grows, opening up broad areas of uncoated surface on which water can condense rapidly. We conclude that multicomponent composition of organic films on the surface of atmospheric aerosol particles is likely to preclude the formation of condensed films and that the kinetics of water condensation during the activation of aerosol to form cloud droplets is likely to remain rapid. PMID:23674675

  13. Primary Emission and the Potential of Secondary Aerosol Formation from Chinese Gasoline Engine Exhaust

    Science.gov (United States)

    Hu, Min; Peng, Jianfei; Qin, Yanhong; Du, Zhuofei; Li, Mengjin; Zheng, Rong; Zheng, Jing; Shang, Dongjie; Lu, Sihua; Wu, Yusheng; Zeng, Limin; Guo, Song; Shao, Min; Wang, Yinhui; Shuai, Shijin

    2017-04-01

    Along with the urbanization and economic growth, vehicle population in China reached 269 million, ranked the second in the world in 2015. Gasoline vehicle is identified to be the main source for urban PM2.5 in China, accounting for 15%-31%. In this study the impact of fuel components on PM2.5 and volatile organic compounds (VOCs) emissions from a gasoline port fuel injection (PFI) engine and a gasoline direct injection (GDI) engine are discussed. Results show that, higher proportion of aromatics, alkenes or sulfur in gasoline fuel will lead to higher PM emissions. The PM from the PFI engine mainly consists of OC and a small amount of EC and inorganic ions, while the PM discharge from the GDI engine mainly consists of EC, OM and a small amount of inorganic ions. Since the GDI engines can reduce fuel consumption and CO2 emissions, and it would become more and more popular in the near future. The characteristics of POM component, emission factors and source profile were investigated from GDI engine, particularly focused on the effect of engine speed, load and the catalyst, which will be very much helpful for source identification as source indicators. Chamber experiments were conducted to quantify the potential of secondary aerosol formation from exhaust of a PFI gasoline engine and China V gasoline fuel. During 4-5 h simulation, equivalent to10 days of atmospheric photo-oxidation in Beijing, the extreme SOA production was 426 ± 85 mg/kg fuel, with high precursors and OH exposure. 14% of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatility organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reduction of emissions of aerosol precursor gases from vehicles is essential to mediate pollution in China.

  14. Intercomparison and closure calculations using measurements of aerosol species and optical properties during the Yosemite Aerosol Characterization Study

    Science.gov (United States)

    Malm, William C.; Day, Derek E.; Carrico, Christian; Kreidenweis, Sonia M.; Collett, Jeffrey L.; McMeeking, Gavin; Lee, Taehyoung; Carrillo, Jacqueline; Schichtel, Bret

    2005-07-01

    Physical and optical properties of inorganic aerosols have been extensively studied, but less is known about carbonaceous aerosols, especially as they relate to the non-urban settings such as our nation's national parks and wilderness areas. Therefore an aerosol characterization study was conceived and implemented at one national park that is highly impacted by carbonaceous aerosols, Yosemite. The primary objective of the study was to characterize the physical, chemical, and optical properties of a carbon-dominated aerosol, including the ratio of total organic matter weight to organic carbon, organic mass scattering efficiencies, and the hygroscopic characteristics of a carbon-laden ambient aerosol, while a secondary objective was to evaluate a variety of semi-continuous monitoring systems. Inorganic ions were characterized using 24-hour samples that were collected using the URG and Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring systems, the micro-orifice uniform deposit impactor (MOUDI) cascade impactor, as well as the semi-continuous particle-into-liquid sampler (PILS) technology. Likewise, carbonaceous material was collected over 24-hour periods using IMPROVE technology along with the thermal optical reflectance (TOR) analysis, while semi-continuous total carbon concentrations were measured using the Rupprecht and Patashnick (R&P) instrument. Dry aerosol number size distributions were measured using a differential mobility analyzer (DMA) and optical particle counter, scattering coefficients at near-ambient conditions were measured with nephelometers fitted with PM10 and PM2.5 inlets, and "dry" PM2.5 scattering was measured after passing ambient air through Perma Pure Nafion® dryers. In general, the 24-hour "bulk" measurements of various aerosol species compared more favorably with each other than with the semi-continuous data. Semi-continuous sulfate measurements correlated well with the 24-hour measurements, but were biased low by

  15. Carbonaceous Aerosols in Fine Particulate Matter of Santiago Metropolitan Area, Chile

    Science.gov (United States)

    Toro Araya, Richard; Flocchini, Robert; Morales Segura, Rául G. E.; Leiva Guzmán, Manuel A.

    2014-01-01

    Measurements of carbonaceous aerosols in South American cities are limited, and most existing data are of short term and limited to only a few locations. For 6 years (2002–2007), concentrations of fine particulate matter and organic and elemental carbon were measured continuously in the capital of Chile. The contribution of carbonaceous aerosols to the primary and secondary fractions was estimated at three different sampling sites and in the warm and cool seasons. The results demonstrate that there are significant differences in the levels in both the cold (March to August) and warm (September to February) seasons at all sites studied. The percent contribution of total carbonaceous aerosol fine particulate matter was greater in the cool season (53 ± 41%) than in the warm season (44 ± 18%). On average, the secondary organic carbon in the city corresponded to 29% of the total organic carbon. In cold periods, this proportion may reach an average of 38%. A comparison of the results with the air quality standards for fine particulate matter indicates that the total carbonaceous fraction alone exceeds the World Health Organization standard (10 µg/m3) and the United States Environmental Protection Agency standard (15 µg/m3) for fine particulate matter. PMID:24587753

  16. Carbonaceous Aerosols in Fine Particulate Matter of Santiago Metropolitan Area, Chile

    Directory of Open Access Journals (Sweden)

    Richard Toro Araya

    2014-01-01

    Full Text Available Measurements of carbonaceous aerosols in South American cities are limited, and most existing data are of short term and limited to only a few locations. For 6 years (2002–2007, concentrations of fine particulate matter and organic and elemental carbon were measured continuously in the capital of Chile. The contribution of carbonaceous aerosols to the primary and secondary fractions was estimated at three different sampling sites and in the warm and cool seasons. The results demonstrate that there are significant differences in the levels in both the cold (March to August and warm (September to February seasons at all sites studied. The percent contribution of total carbonaceous aerosol fine particulate matter was greater in the cool season (53 ± 41% than in the warm season (44 ± 18%. On average, the secondary organic carbon in the city corresponded to 29% of the total organic carbon. In cold periods, this proportion may reach an average of 38%. A comparison of the results with the air quality standards for fine particulate matter indicates that the total carbonaceous fraction alone exceeds the World Health Organization standard (10 µg/m3 and the United States Environmental Protection Agency standard (15 µg/m3 for fine particulate matter.

  17. Carbonaceous aerosols in fine particulate matter of Santiago Metropolitan Area, Chile.

    Science.gov (United States)

    Toro Araya, Richard; Flocchini, Robert; Morales Segura, Rául G E; Leiva Guzmán, Manuel A

    2014-01-01

    Measurements of carbonaceous aerosols in South American cities are limited, and most existing data are of short term and limited to only a few locations. For 6 years (2002-2007), concentrations of fine particulate matter and organic and elemental carbon were measured continuously in the capital of Chile. The contribution of carbonaceous aerosols to the primary and secondary fractions was estimated at three different sampling sites and in the warm and cool seasons. The results demonstrate that there are significant differences in the levels in both the cold (March to August) and warm (September to February) seasons at all sites studied. The percent contribution of total carbonaceous aerosol fine particulate matter was greater in the cool season (53 ± 41%) than in the warm season (44 ± 18%). On average, the secondary organic carbon in the city corresponded to 29% of the total organic carbon. In cold periods, this proportion may reach an average of 38%. A comparison of the results with the air quality standards for fine particulate matter indicates that the total carbonaceous fraction alone exceeds the World Health Organization standard (10 µg/m(3)) and the United States Environmental Protection Agency standard (15 µg/m(3)) for fine particulate matter.

  18. The effect of gas-phase polycyclic aromatic hydrocarbons on the formation and properties of biogenic secondary organic aerosol particles

    Energy Technology Data Exchange (ETDEWEB)

    Zelenyuk, Alla [Pacific Northwest National Laboratory; USA; Imre, Dan G. [Imre Consulting; USA; Wilson, Jacqueline [Pacific Northwest National Laboratory; USA; Bell, David M. [Pacific Northwest National Laboratory; USA; Suski, Kaitlyn J. [Pacific Northwest National Laboratory; USA; Shrivastava, Manish [Pacific Northwest National Laboratory; USA; Beránek, Josef [Pacific Northwest National Laboratory; USA; Alexander, M. Lizabeth [Pacific Northwest National Laboratory; USA; Kramer, Amber L. [Department of Chemistry; Oregon State University; USA; Massey Simonich, Staci L. [Department of Chemistry; Oregon State University; USA; Environmental and Molecular Toxicology; Oregon State University

    2017-01-01

    When secondary organic aerosol (SOA) particles are formed by ozonolysis in the presence of gas-phase polycyclic aromatic hydrocarbons (PAHs), their formation and properties are significantly different from SOA particles formed without PAHs. For all SOA precursors and all PAHs, discussed in this study, the presence of the gas-phase PAHs during SOA formation significantly affects particle mass loadings, composition, growth, evaporation kinetics, and viscosity. SOA particles formed in the presence of PAHs have, as part of their compositions, trapped unreacted PAHs and products of heterogeneous reactions between PAHs and ozone. Compared to ‘pure’ SOA particles, these particles exhibit slower evaporation kinetics, have higher fractions of non-volatile components, like oligomers, and higher viscosities, assuring their longer atmospheric lifetimes. In turn, the increased viscosity and decreased volatility provide a shield that protects PAHs from chemical degradation and evaporation, allowing for the long-range transport of these toxic pollutants. The magnitude of the effect of PAHs on SOA formation is surprisingly large. The presence of PAHs during SOA formation increases mass loadings by factors of two to five, and particle number concentrations, in some cases, by more than a factor of 100. Increases in SOA mass, particle number concentrations, and lifetime have important implications to many atmospheric processes related to climate, weather, visibility, and human health, all of which relate to the interactions between biogenic SOA and anthropogenic PAHs. The synergistic relationship between SOA and PAHs presented here are clearly complex and call for future research to elucidate further the underlying processes and their exact atmospheric implications.

  19. Characterization of urban aerosol in Cork city (Ireland) using aerosol mass spectrometry

    Science.gov (United States)

    Dall'Osto, M.; Ovadnevaite, J.; Ceburnis, D.; Martin, D.; Healy, R. M.; O'Connor, I. P.; Kourtchev, I.; Sodeau, J. R.; Wenger, J. C.; O'Dowd, C.

    2013-05-01

    Ambient wintertime background urban aerosol in Cork city, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the ca. 1 350 000 single particles characterized by an Aerosol Time-of-Flight Mass Spectrometer (TSI ATOFMS) were classified into five organic-rich particle types, internally mixed to different proportions with elemental carbon (EC), sulphate and nitrate, while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was characterized using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS) and was also found to comprise organic aerosol as the most abundant species (62%), followed by nitrate (15%), sulphate (9%) and ammonium (9%), and chloride (5%). Positive matrix factorization (PMF) was applied to the HR-ToF-AMS organic matrix, and a five-factor solution was found to describe the variance in the data well. Specifically, "hydrocarbon-like" organic aerosol (HOA) comprised 20% of the mass, "low-volatility" oxygenated organic aerosol (LV-OOA) comprised 18%, "biomass burning" organic aerosol (BBOA) comprised 23%, non-wood solid-fuel combustion "peat and coal" organic aerosol (PCOA) comprised 21%, and finally a species type characterized by primary {m/z} peaks at 41 and 55, similar to previously reported "cooking" organic aerosol (COA), but possessing different diurnal variations to what would be expected for cooking activities, contributed 18%. Correlations between the different particle types obtained by the two aerosol mass spectrometers are also discussed. Despite wood, coal and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosol mass and non-refractory total PM1, respectively).

  20. Characterization of urban aerosol in Cork city (Ireland using aerosol mass spectrometry

    Directory of Open Access Journals (Sweden)

    M. Dall'Osto

    2013-05-01

    Full Text Available Ambient wintertime background urban aerosol in Cork city, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the ca. 1 350 000 single particles characterized by an Aerosol Time-of-Flight Mass Spectrometer (TSI ATOFMS were classified into five organic-rich particle types, internally mixed to different proportions with elemental carbon (EC, sulphate and nitrate, while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was characterized using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS and was also found to comprise organic aerosol as the most abundant species (62%, followed by nitrate (15%, sulphate (9% and ammonium (9%, and chloride (5%. Positive matrix factorization (PMF was applied to the HR-ToF-AMS organic matrix, and a five-factor solution was found to describe the variance in the data well. Specifically, "hydrocarbon-like" organic aerosol (HOA comprised 20% of the mass, "low-volatility" oxygenated organic aerosol (LV-OOA comprised 18%, "biomass burning" organic aerosol (BBOA comprised 23%, non-wood solid-fuel combustion "peat and coal" organic aerosol (PCOA comprised 21%, and finally a species type characterized by primary extit{m/z}~peaks at 41 and 55, similar to previously reported "cooking" organic aerosol (COA, but possessing different diurnal variations to what would be expected for cooking activities, contributed 18%. Correlations between the different particle types obtained by the two aerosol mass spectrometers are also discussed. Despite wood, coal and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosol mass and non-refractory total PM1, respectively.