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Sample records for aged organic aerosol

  1. Photochemical Aging of Organic Aerosol Particles

    NASA Astrophysics Data System (ADS)

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

    2007-05-01

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

  2. Molecular transformations accompanying the aging of laboratory secondary organic aerosol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The aging of fresh secondary organic aerosol, generated by alpha-pinene ozonolysis in a flow tube reactor, was studied by passing it through a second reaction chamber where hydroxyl radicals were generated. Two types of experiments were performed: plug injection experiments where the particle mass a...

  3. Aged organic aerosol in the Eastern Mediterranean: the Finokalia aerosol measurement experiment-2008

    NASA Astrophysics Data System (ADS)

    Hildebrandt, L.; Engelhart, G. J.; Mohr, C.; Kostenidou, E.; Lanz, V. A.; Bougiatioti, A.; Decarlo, P. F.; Prévôt, A. S. H.; Baltensperger, U.; Mihalopoulos, N.; Donahue, N. M.; Pandis, S. N.

    2010-01-01

    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 time of day, 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.

  4. Aged organic aerosol in the Eastern Mediterranean: the Finokalia Aerosol Measurement Experiment - 2008

    NASA Astrophysics Data System (ADS)

    Hildebrandt, L.; Engelhart, G. J.; Mohr, C.; Kostenidou, E.; Lanz, V. A.; Bougiatioti, A.; Decarlo, P. F.; Prevot, A. S. H.; Baltensperger, U.; Mihalopoulos, N.; Donahue, N. M.; Pandis, S. N.

    2010-05-01

    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.

  5. OH-initiated heterogeneous aging of highly oxidized organic aerosol

    SciTech Connect

    Kessler, Sean H.; Nah, Theodora; Daumit, Kelly E.; Smith, Jared D.; Leone, Stephen R.; Kolb, Charles E.; Worsnop, Douglas R.; Wilson, Kevin R.; Kroll, Jesse H.

    2011-12-05

    The oxidative evolution (“aging”) of organic species in the atmosphere is thought to have a major influence on the composition and properties of organic particulate matter, but remains poorly understood, particularly for the most oxidized fraction of the aerosol. Here we measure the kinetics and products of the heterogeneous oxidation of highly oxidized organic aerosol, with an aim of better constraining such atmospheric aging processes. Submicron particles composed of model oxidized organics—1,2,3,4-butanetetracarboxylic acid (C{sub 8}H{sub 10}O{sub 8}), citric acid (C{sub 6}H{sub 8}O{sub 7}), tartaric acid (C{sub 4}H{sub 6}O{sub 6}), and Suwannee River fulvic acid—were oxidized by gas-phase OH in a flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to our previous studies of less-oxidized model systems (squalane, erythritol, and levoglucosan), particle mass did not decrease significantly with heterogeneous oxidation. Carbon content of the aerosol always decreased somewhat, but this mass loss was approximately balanced by an increase in oxygen content. The estimated reactive uptake coefficients of the reactions range from 0.37 to 0.51 and indicate that such transformations occur at rates corresponding to 1-2 weeks in the atmosphere, suggesting their importance in the atmospheric lifecycle of organic particulate matter.

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

    PubMed

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

    2011-07-01

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

  7. Kinetic regimes for formation and aging of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Shiraiwa, Manabu; Berkemeier, Thomas; Schilling-Fahnestock, Katherine; Seinfeld, John; Pöschl, Ulrich

    2014-05-01

    Here we present a conceptual framework of kinetic regime and limiting cases for formation and aging of secondary organic aerosol (SOA). The limiting step of SOA formation can be identified following the developed classification scheme, which is based on three fundamental properties of oxidation products: the reaction location, the saturation ratio, and the heterogeneity in the gas and particle phases. Using the kinetic multi-layer model of gas-particle interactions (KM-GAP) (Shiraiwa et al., 2012), we have analyzed the experimental data of photooxidation of dodecane and subsequent SOA formation. We have found that the contribution of intermediate gas-phase oxidation products to SOA formation is most likely limited by gas-phase reaction, validating the assumption of instantaneous equilibrium partitioning. For semi-volatile and low volatility gas-phase oxidation products, partitioning into the particle phase can be limited by surface accommodation, and possibly by bulk diffusion when organic aerosols adopt glassy or amorphous solid state. The formation of low volatility particle-phase products, such as oligomers and other high molar mass compounds, may be limited by reaction and diffusion in the particle. The 2D evolution plot of molar mass vs. volatility is useful to overview SOA formation and aging. The average molar mass of the organic compounds can be used as a yardstick to estimate relative contribution of gas- vs. particle-phase chemistry to SOA formation. The relatively high values of measured average molar mass for ambient and laboratory-generated SOA imply the importance of particle-phase chemistry in SOA formation.

  8. Organic aerosols

    SciTech Connect

    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.

  9. Quantifying the effect of organic aerosol aging and intermediate-volatility emissions on regional-scale aerosol pollution in China

    NASA Astrophysics Data System (ADS)

    Zhao, Bin; Wang, Shuxiao; Donahue, Neil M.; Jathar, Shantanu H.; Huang, Xiaofeng; Wu, Wenjing; Hao, Jiming; Robinson, Allen L.

    2016-06-01

    Secondary organic aerosol (SOA) is one of the least understood constituents of fine particles; current widely-used models cannot predict its loadings or oxidation state. Recent laboratory experiments demonstrated the importance of several new processes, including aging of SOA from traditional precursors, aging of primary organic aerosol (POA), and photo-oxidation of intermediate volatility organic compounds (IVOCs). However, evaluating the effect of these processes in the real atmosphere is challenging. Most models used in previous studies are over-simplified and some key reaction trajectories are not captured, and model parameters are usually phenomenological and lack experimental constraints. Here we comprehensively assess the effect of organic aerosol (OA) aging and intermediate-volatility emissions on regional-scale OA pollution with a state-of-the-art model framework and experimentally constrained parameters. We find that OA aging and intermediate-volatility emissions together increase OA and SOA concentrations in Eastern China by about 40% and a factor of 10, respectively, thereby improving model-measurement agreement significantly. POA and IVOCs both constitute over 40% of OA concentrations, and IVOCs constitute over half of SOA concentrations; this differs significantly from previous apportionment of SOA sources. This study facilitates an improved estimate of aerosol-induced climate and health impacts, and implies a shift from current fine-particle control policies.

  10. Quantifying the effect of organic aerosol aging and intermediate-volatility emissions on regional-scale aerosol pollution in China.

    PubMed

    Zhao, Bin; Wang, Shuxiao; Donahue, Neil M; Jathar, Shantanu H; Huang, Xiaofeng; Wu, Wenjing; Hao, Jiming; Robinson, Allen L

    2016-01-01

    Secondary organic aerosol (SOA) is one of the least understood constituents of fine particles; current widely-used models cannot predict its loadings or oxidation state. Recent laboratory experiments demonstrated the importance of several new processes, including aging of SOA from traditional precursors, aging of primary organic aerosol (POA), and photo-oxidation of intermediate volatility organic compounds (IVOCs). However, evaluating the effect of these processes in the real atmosphere is challenging. Most models used in previous studies are over-simplified and some key reaction trajectories are not captured, and model parameters are usually phenomenological and lack experimental constraints. Here we comprehensively assess the effect of organic aerosol (OA) aging and intermediate-volatility emissions on regional-scale OA pollution with a state-of-the-art model framework and experimentally constrained parameters. We find that OA aging and intermediate-volatility emissions together increase OA and SOA concentrations in Eastern China by about 40% and a factor of 10, respectively, thereby improving model-measurement agreement significantly. POA and IVOCs both constitute over 40% of OA concentrations, and IVOCs constitute over half of SOA concentrations; this differs significantly from previous apportionment of SOA sources. This study facilitates an improved estimate of aerosol-induced climate and health impacts, and implies a shift from current fine-particle control policies. PMID:27350423

  11. Quantifying the effect of organic aerosol aging and intermediate-volatility emissions on regional-scale aerosol pollution in China

    PubMed Central

    Zhao, Bin; Wang, Shuxiao; Donahue, Neil M.; Jathar, Shantanu H.; Huang, Xiaofeng; Wu, Wenjing; Hao, Jiming; Robinson, Allen L.

    2016-01-01

    Secondary organic aerosol (SOA) is one of the least understood constituents of fine particles; current widely-used models cannot predict its loadings or oxidation state. Recent laboratory experiments demonstrated the importance of several new processes, including aging of SOA from traditional precursors, aging of primary organic aerosol (POA), and photo-oxidation of intermediate volatility organic compounds (IVOCs). However, evaluating the effect of these processes in the real atmosphere is challenging. Most models used in previous studies are over-simplified and some key reaction trajectories are not captured, and model parameters are usually phenomenological and lack experimental constraints. Here we comprehensively assess the effect of organic aerosol (OA) aging and intermediate-volatility emissions on regional-scale OA pollution with a state-of-the-art model framework and experimentally constrained parameters. We find that OA aging and intermediate-volatility emissions together increase OA and SOA concentrations in Eastern China by about 40% and a factor of 10, respectively, thereby improving model-measurement agreement significantly. POA and IVOCs both constitute over 40% of OA concentrations, and IVOCs constitute over half of SOA concentrations; this differs significantly from previous apportionment of SOA sources. This study facilitates an improved estimate of aerosol-induced climate and health impacts, and implies a shift from current fine-particle control policies. PMID:27350423

  12. Importance of relative humidity in the oxidative ageing of organic aerosols: case study of the ozonolysis of maleic acid aerosol

    NASA Astrophysics Data System (ADS)

    Gallimore, P. J.; Achakulwisut, P.; Pope, F. D.; Davies, J. F.; Spring, D. R.; Kalberer, M.

    2011-12-01

    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 observations. This

  13. Characterization of particulate products for aging of ethylbenzene secondary organic aerosol in the presence of ammonium sulfate seed aerosol.

    PubMed

    Huang, Mingqiang; Zhang, Jiahui; Cai, Shunyou; Liao, Yingmin; Zhao, Weixiong; Hu, Changjin; Gu, Xuejun; Fang, Li; Zhang, Weijun

    2016-09-01

    Aging of secondary organic aerosol (SOA) particles formed from OH- initiated oxidation of ethylbenzene in the presence of high mass (100-300μg/m(3)) concentrations of (NH4)2SO4 seed aerosol was investigated in a home-made smog chamber in this study. The chemical composition of aged ethylbenzene SOA particles was measured using an aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with a Fuzzy C-Means (FCM) clustering algorithm. Experimental results showed that nitrophenol, ethyl-nitrophenol, 2,4-dinitrophenol, methyl glyoxylic acid, 5-ethyl-6-oxo-2,4-hexadienoic acid, 2-ethyl-2,4-hexadiendioic acid, 2,3-dihydroxy-5-ethyl-6-oxo-4-hexenoic acid, 1H-imidazole, hydrated N-glyoxal substituted 1H-imidazole, hydrated glyoxal dimer substituted imidazole, 1H-imidazole-2-carbaldehyde, N-glyoxal substituted hydrated 1H-imidazole-2-carbaldehyde and high-molecular-weight (HMW) components were the predominant products in the aged particles. Compared to the previous aromatic SOA aging studies, imidazole compounds, which can absorb solar radiation effectively, were newly detected in aged ethylbenzene SOA in the presence of high concentrations of (NH4)2SO4 seed aerosol. These findings provide new information for discussing aromatic SOA aging mechanisms. PMID:27593289

  14. Parameterization of the Cloud Nucleating Activity of Fresh, Aged, and Internally-Mixed Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Kreidenweis, S.; Petters, M.; Demott, P.; Prenni, A.; Ziemann, P.

    2006-12-01

    Carbonaceous particle types affect global climate, visibility, and human health, but their primary and secondary sources, sinks, and tropospheric lifetimes are highly uncertain. The size and hygroscopicity of particles, and in particular their activity as cloud condensation nuclei (CCN), plays a large role in determining their atmospheric impacts and lifetimes. However, hygroscopicity is difficult to parameterize for many organic species for which no thermodynamic data exist, and for complex, multicomponent aerosols of undefined composition. We propose a simple method to describe the relationship between dry particle diameter and CCN activity using a single hygroscopicity parameter, κ. We derive values of κ from fitting of experimental CCN-activity data from the literature and from recent experiments, including oxidation-aged organic particles and secondary organic aerosols. Values of κ are between 0.5 and 2 for highly-CCN- active salts such as sodium chloride, between 0.01 and 0.5 for slightly to very hygroscopic organic aerosols such as those produced in biomass burning and as secondary organic aerosols, and 0 for nonhygroscopic components. The hygroscopicity of internal mixtures can be calculated as a volume fraction weighted average of the hygroscopicity parameters of the individual species comprising the mixture. Aging of aerosol, understood as changes in hygroscopicity due to condensation of hydrophilic species, coagulation of aerosol populations, or heterogeneous chemical reactions, are described conveniently by changes in κ. Our studies show that oxidative aging that proceeds by addition of functional groups to the CHx carbon backbone leads to only small changes in κ, and thus the process alone is inefficient at rendering small, initially- hydrophobic primary organic particles capable of being scavenged by cloud-drop nucleation. Other processes, such as coagulation and condensation, control the rate of hydrophobic-to-hydrophilic conversion of primary

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

    PubMed

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

    2016-04-19

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

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

    NASA Astrophysics Data System (ADS)

    Collier, K.; Brooks, S. D.

    2014-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Sarrafzadeh, M.; Hastie, D. R.

    2013-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    DOE PAGES

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

    2015-07-24

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

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

    SciTech Connect

    Donahue, Neil M.

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

    NASA Astrophysics Data System (ADS)

    Yan, B.; Zheng, M.; Hu, Y. T.; Lee, S.; Kim, H. K.; Russell, A. G.

    2008-11-01

    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.

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

    NASA Astrophysics Data System (ADS)

    Yan, B.; Zheng, M.; Hu, Y. T.; Lee, S.; Kim, H. K.; Russell, A. G.

    2007-12-01

    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, 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 can be used for source apportionment.

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

    NASA Astrophysics Data System (ADS)

    Tasoglou, A.; Pandis, S. N.

    2015-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  6. Evolution of the complex refractive index in the UV spectral region in ageing secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Flores, J. M.; Zhao, D. F.; Segev, L.; Schlag, P.; Kiendler-Scharr, A.; Fuchs, H.; Watne, Å. K.; Bluvshtein, N.; Mentel, Th. F.; Hallquist, M.; Rudich, Y.

    2014-06-01

    The chemical and physical properties of secondary organic aerosol (SOA) formed by the photochemical degradation of biogenic and anthropogenic volatile organic compounds (VOC) are as yet still poorly constrained. The evolution of the complex refractive index (RI) of SOA, formed from purely biogenic VOC and mixtures of biogenic and anthropogenic VOC, was studied over a diurnal cycle in the SAPHIR photochemical outdoor chamber in Jülich, Germany. The correlation of RI with SOA chemical and physical properties such as oxidation level and volatility was examined. The RI was retrieved by a newly developed broadband cavity-enhanced spectrometer for aerosol optical extinction measurements in the UV spectral region (360 to 420 nm). Chemical composition and volatility of the particles were monitored by a high-resolution time-of-flight aerosol mass spectrometer, and a volatility tandem differential mobility analyzer. SOA was formed by ozonolysis of either (i) a mixture of biogenic VOC (α-pinene and limonene), (ii) biogenic VOC mixture with subsequent addition of an anthropogenic VOC (p-xylene-d10), or (iii) a mixture of biogenic and anthropogenic VOC. The SOA aged by ozone/OH reactions up to 29.5 h was found to be non-absorbing in all cases. The SOA with p-xylene-d10 showed an increase of the scattering component of the RI correlated with an increase of the O / C ratio and with an increase in the SOA density. There was a greater increase in the scattering component of the RI when the SOA was produced from the mixture of biogenic VOCs and anthropogenic VOC than from the sequential addition of the VOCs after approximately the same ageing time. The increase of the scattering component was inversely correlated with the SOA volatility. Two RI retrievals determined for the pure biogenic SOA showed a constant RI for up to 5 h of ageing. Mass spectral characterization shows the three types of the SOA formed in this study have a significant amount of semivolatile components. The

  7. OH Radical Aging of Model Primary Organic Aerosols In Smog Chamber Studies

    NASA Astrophysics Data System (ADS)

    Lambe, A. T.; Zhang, J.; Sage, A. M.; Donahue, N. M.

    2006-12-01

    Most of the fine primary organic carbon (OC) in the atmosphere is saturated. Thus, by OC mass balance alone, OH radicals should be important in organic aerosol processing because saturated OC is unreactive to ozone and vulnerable to NO3 oxidation only at night. However, the importance of OH-induced heterogeneous oxidation remains uncertain because laboratory and ambient analysis is a challenge. Most laboratory aging studies have been conducted in flow tube reactors with extremely high radical concentrations and short exposure times. While these pioneering experiments have revealed efficient OH uptake, a confounding issue remains that both oxidant and reagent losses are rate-limited by diffusion of the oxidant to the phase interface. Examining these systems over much longer timescales in smog chamber experiments is therefore desirable, but established methods of OH radical production in smog chamber studies typically require some combination of UV illumination, high NOx, or radical cycling. Thus, employing these methods results in experimental conditions that either do not represent atmospheric conditions or cannot produce a sufficiently high flux of OH radicals - these shortcomings are acceptable for some applications, but are significant hindrances when heterogeneous aging is the experimental objective. Our approach has been to use alkene ozonolysis as a continuous, low-NOx, dark source of OH. Specifically, we use 2,3-dimethyl-2-butene (tetramethylethylene, TME) because ozonolysis results in an OH yield near unity. Furthermore, the organic TME ozonolysis products have high vapor pressures, so they do not participate directly in condensed-phase chemistry. To maintain a constant radical production rate, fresh reagents are delivered to the chamber to replenish TME and O3 as they react. TME is delivered continuously via capillary liquid flow with constant evaporation from a droplet at the capillary tip into a carrier stream. Ozone is held at a constant, high value by

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

    SciTech Connect

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

    2013-05-10

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

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

    PubMed

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

    2013-06-01

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

  10. Modeling the multiday evolution and aging of secondary organic aerosol during MILAGRO 2006.

    PubMed

    Dzepina, Katja; Cappa, Christopher D; Volkamer, Rainer M; Madronich, Sasha; Decarlo, Peter F; Zaveri, Rahul A; Jimenez, Jose L

    2011-04-15

    In this study, we apply several recently proposed models to the evolution of secondary organic aerosols (SOA) and organic gases advected from downtown Mexico City at an altitude of ∼3.5 km during three days of aging, in a way that is directly comparable to simulations in regional and global models. We constrain the model with and compare its results to available observations. The model SOA formed from oxidation of volatile organic compounds (V-SOA) when using a non-aging SOA parameterization cannot explain the observed SOA concentrations in aged pollution, despite the increasing importance of the low-NO(x) channel. However, when using an aging SOA parameterization, V-SOA alone is similar to the regional aircraft observations, highlighting the wide diversity in current V-SOA formulations. When the SOA formed from oxidation of semivolatile and intermediate volatility organic vapors (SI-SOA) is computed following Robinson et al. (2007) the model matches the observed SOA mass, but its O/C is ∼2× too low. With the parameterization of Grieshop et al. (2009), the total SOA mass is ∼2× too high, but O/C and volatility are closer to the observations. Heating or dilution cause the evaporation of a substantial fraction of the model SOA; this fraction is reduced by aging although differently for heating vs dilution. Lifting of the airmass to the free-troposphere during dry convection substantially increases SOA by condensation of semivolatile vapors; this effect is reduced by aging. PMID:21425791

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

    DOE PAGES

    Liu, Jiumeng; Lin, Peng; Laskin, Alexander; Laskin, Julia; Kathmann, Shawn M.; Wise, Matthew; 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 volatile organic carbon (VOC) precursors, NOx concentrations, photolysis time, and relative humidity (RH) on the light absorptionmore » of selected secondary organic aerosols (SOA). Light absorption of chamber-generated SOA samples, especially aromatic SOA, was found to increase with NOx concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficient (MAC) value is observed from toluene SOA products formed under high-NOx conditions at moderate RH, in which nitro-aromatics were previously identified as the major light-absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organic nitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible (Vis) and ultraviolet (UV) light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.« less

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  13. Modeling the Multiday Evolution and Aging of Secondary Organic Aerosol During MILAGRO 2006

    SciTech Connect

    Dzepina, K.; Cappa, Christopher D.; Volkamer, Rainer M.; Madronich, Sasha; DeCarlo, Peter; Zaveri, Rahul A.; Jimenez, Jose L.

    2011-03-22

    In this study we apply several recently-proposed models to the evolution of secondary organic aerosols (SOA) and organic gases advected from downtown Mexico City at an altitude of ~3.5 km during three days of aging. We constrain the model with and compare its results to available observations. The model SOA formed from oxidation of volatile organic compounds (V-SOA) when using the aromatic SOA parameterization of Ng et al. (2007) cannot explain the observed SOA concentrations in aged pollution, even as the low-NOx channel becomes more important away from the city. However, when using the aromatic SOA parameterization of Tsimpidi et al. (2010), V-SOA alone is similar to the regional aircraft observations, highlighting the wide diversity in current V-SOA formulations. When the SOA formed from oxidation of both semivolatile and intermediate volatility organic vapors (SI-SOA) is computed following Robinson et al. (2007) the model matches the observed SOA mass, but its O/C is too low by a factor of 2. With the parameterization of Grieshop et al. (2009) the total SOA mass is overpredicted by a factor of ~2 but O/C and volatility are closer to the observations. Heating or dilution of the air results in evaporation of a substantial fraction of the model SOA; this fraction is reduced by aging although differently for heating vs. dilution. Finally, lifting of the airmass tothe free-troposphere during dry convection results in a substantial increase of SOA bycondensation of semivolatile vapors, with this effect being reduced by aging.

  14. Modeling the Multiday Evolution and Aging of Secondary Organic Aerosol During MILAGRO 2006

    NASA Astrophysics Data System (ADS)

    Dzepina, K.; Cappa, C. D.; Volkamer, R.; Madronich, S.; Decarlo, P. F.; Zaveri, R. A.; Jimenez, J. L.

    2010-12-01

    In this study we apply several recently-proposed models to the evolution of secondary organic aerosols (SOA) and organic gases advected from downtown Mexico City at an altitude of ~3.5 km during three days of aging. We constrain the model with and compare its results to available observations. The model SOA formed from oxidation of volatile organic compounds (V-SOA) alone cannot explain the observed mass loadings in aged pollution. Over the regional scale ~5% of the model SOA is due to the low-NOx aromatic V-SOA pathway, which has a higher yield and produces comparably “low-volatility” species that remain in the particle phase as dilution proceeds and more volatile components evaporate. The model SOA formed from oxidation of both semivolatile and intermediate volatility organic vapors (SI-SOA) accounts for most of the predicted SOA mass concentration. With the SI-SOA parameterization of Robinson et al. (2007) the model matches the observed SOA mass, but its O/C is too low by a factor of 2. With the parameterization of Grieshop et al. (2009) the total SOA mass is overpredicted by a factor of ~2 but O/C and volatility are much closer to the observations. Heating or dilution of the air results in evaporation of a substantial fraction of the model SOA; this fraction is reduced by aging although differently for heating vs. dilution. Finally, lifting of the airmass to the free-troposphere during dry convection results in a substantial increase of SOA by condensation of semivolatile vapors, with this effect being reduced by aging.

  15. Molecular composition of aged secondary organic aerosol generated from a mixture of biogenic volatile compounds using ultrahigh resolution mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Doussin, J.-F.; Giorio, C.; Mahon, B.; Wilson, E. M.; Maurin, N.; Pangui, E.; Venables, D. S.; Wenger, J. C.; Kalberer, M.

    2015-02-01

    Field observations over the past decade indicate that a significant fraction of organic aerosol in remote areas may contain highly oxidised molecules. Aerosol processing or further oxidation (ageing) of organic aerosol has been suggested to be responsible for their formation through heterogeneous uptake of oxidants and multigenerational oxidation of vapours by OH radicals. In this study we investigated the influence of several ageing processes on the molecular composition of secondary organic aerosols (SOA) using direct infusion and liquid chromatography ultrahigh resolution mass spectrometry. SOA was formed in simulation chamber experiments from ozonolysis of a mixture of four biogenic volatile organic compounds (BVOC): α-pinene, β-pinene, Δ3-carene and isoprene. The SOA was subsequently aged under three different sets of conditions: in the dark in the presence of residual ozone, with UV irradiation and OH radicals, and using UV light only. Among all studied conditions, only OH radical-initiated ageing was found to influence the molecular composition of the aerosol and showed an increase in carbon oxidation state (OSC) and elemental O/C ratios of the SOA components. None of the ageing processes produced an observable effect on the oligomers formed from ozonolysis of the BVOC mixture, which were found to be equally abundant in both "fresh" and "aged" SOA. Additional experiments using α-pinene as the sole precursor demonstrated that oligomers are an important group of compounds in SOA produced from both ozonolysis and OH radical-initiated oxidation processes; however, a completely different set of oligomers is formed under these two oxidation regimes. SOA from the OH radical-initiated α-pinene oxidation had a significantly higher overall OSC and O/C compared to that from pure ozonolysis experiments confirming that the OH radical reaction is more likely to be responsible for the occurrence of highly oxidised species in ambient biogenic SOA.

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

    NASA Astrophysics Data System (ADS)

    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. Characterizing the aging of biomass burning organic aerosol by use of mixing ratios: a meta-analysis of four regions.

    PubMed

    Jolleys, Matthew D; Coe, Hugh; McFiggans, Gordon; Capes, Gerard; Allan, James D; Crosier, Jonathan; Williams, Paul I; Allen, Grant; Bower, Keith N; Jimenez, Jose L; Russell, Lynn M; Grutter, Michel; Baumgardner, Darrel

    2012-12-18

    Characteristic organic aerosol (OA) emission ratios (ERs) and normalized excess mixing ratios (NEMRs) for biomass burning (BB) events have been calculated from ambient measurements recorded during four field campaigns. Normalized OA mass concentrations measured using Aerodyne Research Inc. quadrupole aerosol mass spectrometers (Q-AMS) reveal a systematic variation in average values between different geographical regions. For each region, a consistent, characteristic ratio is seemingly established when measurements are collated from plumes of all ages and origins. However, there is evidence of strong regional and local-scale variability between separate measurement periods throughout the tropical, subtropical, and boreal environments studied. ERs close to source typically exceed NEMRs in the far-field, despite apparent compositional change and increasing oxidation with age. The absence of any significant downwind mass enhancement suggests no regional net source of secondary organic aerosol (SOA) from atmospheric aging of BB sources, in contrast with the substantial levels of net SOA formation associated with urban sources. A consistent trend of moderately reduced ΔOA/ΔCO ratios with aging indicates a small net loss of OA, likely as a result of the evaporation of organic material from initial fire emissions. Variability in ERs close to source is shown to substantially exceed the magnitude of any changes between fresh and aged OA, emphasizing the importance of fuel and combustion conditions in determining OA loadings from biomass burning. PMID:23163290

  18. Investigation of a Particle into Liquid Sampler to Study the Formation & Ageing of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

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

    SciTech Connect

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

    2014-05-14

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

  20. Effect of Relative Humidity and Temperature on Photochemical Aging of Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Nizkorodov, S.; Brady, M. V.; Hinks, M. L.; Lignell, H.; Bertram, A. K.; Song, M.; Laskin, A.; Laskin, J.; Lin, P.

    2014-12-01

    The viscosity of secondary organic aerosol material (SOM) is known to depend sensitively on both temperature and relative humidity (RH). This work investigates the effect of these two important environmental variables on photochemical processes occurring inside model SOM. The experiments are designed to test the hypothesis that an increased SOM viscosity, resulting from either lower temperatures or decreased RH, should slow down the rates of photochemical processes in the organic matrix by constraining molecular motion inside the matrix. Photolysis of a probe molecule, 2,4-dinitrophenol, dispersed in SOM made produced through oxidation of alpha-pinene and limonene by ozone is investigated with absorption spectroscopy methods under controlled humidity and temperature. Viscosity of SOM is directly measured using "bead-mobility" technique and "poke-flow" techniques. Finally, the products of 2,4-dinitrophenol are analyzed by liquid chromatography high resolution mass spectrometry methods. The experiments suggest that the presence of water strongly affects photodegradation rates of organic compounds contained in the SOM matrix. Given the paramount role of photochemistry in driving the chemical reactions in the environment, these results will have significant implications for predicting lifetimes of photolabile atmospheric organic compounds trapped in organic particles.

  1. Aging of secondary organic aerosol from small aromatic VOCs. Changes in chemical composition, mass yield, volatility and hygroscopicity

    DOE PAGES

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

    2014-12-12

    Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form and transform SOA from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx. The effects of chemical aging on organic aerosol (OA) composition, mass yield, volatility and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state OSC) and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OSmore » C ranged from -0.29 to 0.45 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  3. Photochemistry of Model Organic Aerosol Systems

    NASA Astrophysics Data System (ADS)

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

    2007-05-01

    Up to 90 percent of urban aerosol particles have been shown to contain organic molecules. Reactions of these particles with atmospheric oxidants and/or sunlight result in large changes in their composition, toxicity, and ability to act as cloud condensation nuclei. For this reason, chemistry of model organic aerosol particles initiated by oxidation and direct photolysis is of great interest to atmospheric, climate, and health scientists. Most studies in this area have focused on identifying the products of oxidation of the organic aerosols, while the products of direct photolysis of the resulting molecules remaining in the aerosol particle have been left mostly unexplored. We have explored direct photolytic processes occurring in selected organic aerosol systems using infrared cavity ringdown spectroscopy to identify small gas phase products of photolysis, and mass-spectrometric and photometric techniques to study the condensed phase products. The first model system was secondary organic aerosol formed from the oxidation of several monoterpenes by ozone in the presence and absence of NOx, under different humidities. The second system modeled after oxidatively aged primary organic aerosol particles was a thin film of either alkanes or saturated fatty acids oxidized in several different ways, with the oxidation initiated by ozone, chlorine atom, or OH. In every case, the general conclusion was that the photochemical processing of model organic aerosols is significant. Such direct photolysis processes are believed to age organic aerosol particles on time scales that are short compared to the particles' atmospheric lifetimes.

  4. Evolution of the complex refractive index in the near UV spectral region in ageing secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Flores, J. M.; Zhao, D. F.; Segev, L.; Schlag, P.; Kiendler-Scharr, A.; Fuchs, H.; Watne, Å. K.; Bluvshtein, N.; Mentel, Th. F.; Hallquist, M.; Rudich, Y.

    2014-02-01

    The chemical and physical properties of secondary organic aerosol (SOA) formed by the photochemical degradation of biogenic and anthropogenic volatile organic compounds (VOC) are yet poorly constrained. The evolution of the complex refractive index (RI) of SOA, formed from purely biogenic VOC and mixtures of biogenic and anthropogenic VOC was studied over a diurnal cycle in the SAPHIR photochemical outdoor chamber in Jülich, Germany. The correlation of RI with SOA chemical and physical properties such as oxidation level and volatility was examined. The RI was retrieved by a newly developed broadband cavity enhanced spectrometer for aerosol optical extinction measurements in the near UV spectral region (360 to 420 nm). Chemical composition and volatility of the particles were monitored by a high resolution time of flight aerosol mass spectrometer, and a volatility tandem differential mobility analyzer. SOA was formed by ozonolysis of either (i) a mixture of biogenic VOC (α-pinene and limonene), (ii) biogenic VOC mixture with subsequent addition of an anthropogenic VOC (p-xylene-d10), or (iii) a mixture of biogenic and anthropogenic VOC. The SOA aged by ozone / OH reactions up to 29.5 h was found to be non-absorbing in all cases. The SOA with p-xylene-d10 showed an increase of the scattering component of the RI correlated with an increase of the O / C ratio and with an increase in the SOA density. There was a greater increase in the scattering component of the RI when the SOA was produced from the mixture of biogenic VOCs and anthropogenic VOC than from the sequential addition of the VOCs after the approximate same ageing time. The increase of the scattering component was inversely correlated with the SOA volatility. Two RI retrievals determined for the pure biogenic SOA showed a constant RI for up to 5 h of ageing. Mass spectral characterization shows the three types of the SOA formed in this study have significant amount of semivolatile components. The influence

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

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

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

  6. Photochemical Aging of α-pinene and β-pinene Secondary Organic Aerosol formed from Nitrate Radical Oxidation.

    PubMed

    Nah, Theodora; Sanchez, Javier; Boyd, Christopher M; Ng, Nga Lee

    2016-01-01

    The nitrate radical (NO3) is the dominant nighttime oxidant in most urban and rural environments and reacts rapidly with biogenic volatile organic compounds to form secondary organic aerosol (SOA) and organic nitrates (ON). Here, we study the formation of SOA and ON from the NO3 oxidation of two monoterpenes (α-pinene and β-pinene) and investigate how they evolve during photochemical aging. High SOA mass loadings are produced in the NO3+β-pinene reaction, during which we detected 41 highly oxygenated gas- and particle-phase ON possessing 4 to 9 oxygen atoms. The fraction of particle-phase ON in the β-pinene SOA remains fairly constant during photochemical aging. In contrast to the NO3+β-pinene reaction, low SOA mass loadings are produced during the NO3+α-pinene reaction, during which only 5 highly oxygenated gas- and particle-phase ON are detected. The majority of the particle-phase ON evaporates from the α-pinene SOA during photochemical aging, thus exhibiting a drastically different behavior from that of β-pinene SOA. Our results indicate that nighttime ON formed by NO3+monoterpene chemistry can serve as either permanent or temporary NOx sinks depending on the monoterpene precursor.

  7. Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

    NASA Astrophysics Data System (ADS)

    Liu, T.; Wang, X.; Deng, W.; Hu, Q.; Ding, X.; Zhang, Y.; He, Q.; Zhang, Z.; Lü, S.; Bi, X.; Chen, J.; Yu, J.

    2015-08-01

    In China, a rapid increase in passenger vehicles has led to the growing concern of vehicle exhaust as an important source of anthropogenic secondary organic aerosol (SOA) in megacities hard hit by haze. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) operated in China was investigated in a 30 m3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with relative humidity at around 50 %. After aging at an OH exposure of 5 × 106 molecules cm-3 h, the formed SOA was 12-259 times as high as primary organic aerosol (POA). The SOA production factors (PF) were 0.001-0.044 g kg-1 fuel, comparable with those from the previous studies at comparable OH exposure. This quite lower OH exposure than that in typical atmospheric conditions might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yields in this study were well fit by a one-product gas-particle partitioning model but quite lower than those of a previous study investigating SOA formation from three idling passenger vehicles (Euro 2-4). Traditional single-ring aromatic precursors and naphthalene could explain 51-90 % of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f43 (ratio of m/z 43, mostly C2H3O+, to the total signal in mass spectrum) and f44 (mostly CO2+) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C / ΔO : C ranged from -0.59 to -0.36, suggesting that the oxidation chemistry in these experiments was a combination of carboxylic acid and alcohol/peroxide formation.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  10. Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

    NASA Astrophysics Data System (ADS)

    Liu, T.; Wang, X.; Deng, W.; Hu, Q.; Ding, X.; Zhang, Y.; He, Q.; Zhang, Z.; Lü, S.; Bi, X.; Chen, J.; Yu, J.

    2015-04-01

    In China, fast increase in passenger vehicles has procured the growing concern about vehicle exhausts as an important source of anthropogenic secondary organic aerosols (SOA) in megacities hard-hit by haze. However, there are still no chamber simulation studies in China on SOA formation from vehicle exhausts. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) in China was investigated in a 30 m3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with the relative humidity around 50%. After aging at an OH exposure of 5 × 106 molecules cm-3 h, the formed SOA was 12-259 times as high as primary OA (POA). The SOA production factors (PF) were 0.001-0.044 g kg-1 fuel, comparable with those from the previous studies at the quite similar OH exposure. This quite lower OH exposure than that in typical atmospheric condition might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yield data in this study were well fit by a one-product gas-particle partitioning model and quite lower than those of a previous study investigating SOA formation form three idling passenger vehicles (Euro 2-Euro 4). Traditional single-ring aromatic precursors and naphthalene could explain 51-90% of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f43 (ratio of m/z 43, mostly C2H3O+, to the total signal in mass spectrum) and f44 (mostly CO2+) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C/ΔO : C ranged from -0.59 to -0.36, suggesting that the oxidation chemistry in these experiments was a

  11. Carbonaceous and inorganic composition in long-range transported aerosols over northern Japan: Implication for aging of water-soluble organic fraction

    NASA Astrophysics Data System (ADS)

    Aggarwal, Shankar Gopala; Kawamura, Kimitaka

    To better understand the influence of sources and atmospheric processing on aerosol chemical composition, we collected atmospheric particles in Sapporo, northern Japan during spring and early summer 2005 under the air mass transport conditions from Siberia, China and surrounding seas. The aerosols were analyzed for inorganic ions, organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and the major water-soluble organic compound classes (i.e., dicarboxylic acids and sugars). SO 42- is the most abundant inorganic constituent (average 44% of the identified inorganic ion mass) followed by NH 4+ (21%) and NO 3- (13%). Concentrations of OC, EC, and WSOC ranged from 2.0-16, 0.24-2.9, and 0.80-7.9 μg m -3 with a mean of 7.4, 1.0, and 3.1 μg m -3, respectively. High OC/EC ratios (range: 3.6-19, mean: 8.7) were obtained, however WSOC/OC ratios (0.23-0.69, 0.44) do not show any significant diurnal changes. These results suggest that the Sapporo aerosols were already aged, but were not seriously affected by local photochemical processes. Identified water-soluble organic compounds (diacids + sugars) account for <10% of WSOC. Based on some marker species and air mass back trajectory analyses, and using stable carbon isotopic compositions of shorter-chain diacids (i.e., C 2-C 4) as photochemical aging factor of organic aerosols, the present study suggests that a fraction of WSOC in OC is most likely influenced by aerosol aging, although the OC loading in aerosols may be more influenced by their sources and source regions.

  12. Molecular composition of fresh and aged secondary organic aerosol from a mixture of biogenic volatile compounds: a high-resolution mass spectrometry study

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Doussin, J.-F.; Giorio, C.; Mahon, B.; Wilson, E. M.; Maurin, N.; Pangui, E.; Venables, D. S.; Wenger, J. C.; Kalberer, M.

    2015-05-01

    Field observations over the past decade indicate that a significant fraction of organic aerosol in remote areas may contain highly oxidized molecules. Aerosol processing or further oxidation (aging) of organic aerosol has been suggested to be responsible for their formation through heterogeneous reaction with oxidants and multigenerational oxidation of vapours by OH radicals. In this study we investigated the influence of several aging processes on the molecular composition of secondary organic aerosols (SOA) using direct infusion and liquid chromatography high-resolution mass spectrometry. SOA was formed in simulation chamber experiments from ozonolysis of a mixture of four biogenic volatile organic compounds (BVOC): α-pinene, β-pinene, Δ3-carene and isoprene. The SOA was subsequently aged under three different sets of conditions: in the dark in the presence of residual ozone, with UV irradiation and OH radicals, and using UV light only. Among all studied conditions, only OH radical-initiated aging was found to influence the molecular composition of the aerosol and showed an increase in carbon oxidation state (OSC) and elemental O / C ratios of the SOA components. None of the aging processes produced an observable effect on the oligomers formed from ozonolysis of the BVOC mixture, which were found to be equally abundant in both "fresh" and "aged" SOA. Additional experiments using α-pinene as the sole precursor demonstrated that oligomers are an important group of compounds in SOA produced from both ozonolysis and OH radical-initiated oxidation processes; however, a completely different set of oligomers is formed under these two oxidation regimes. SOA from the OH-initiated oxidation of α-pinene had a significantly higher overall OSC and O / C compared to that from pure ozonolysis experiments confirming that the OH radical reaction is more likely to be responsible for the occurrence of highly oxidized species in ambient biogenic SOA.

  13. Evolution of Organic Aerosols in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.; Canagaratna, M. R.; Donahue, N. M.; Prevot, A. S. H.; Zhang, Q.; Kroll, J. H.; DeCarlo, P. F.; Allan, J. D.; Coe, H.; Ng, N. L.; Aiken, A. C.; Docherty, K. S.; Ulbrich, I. M.; Grieshop, A. P.; Robinson, A. L.; Duplissy, J.; Smith, J. D.; Wilson, K. R.; Lanz, V. A.; Hueglin, C.; Sun, Y. L.; Tian, J.; Laaksonen, A.; Raatikainen, T.; Rautiainen, J.; Vaattovaara, P.; Ehn, M.; Kulmala, M.; Tomlinson, J. M.; Collins, D. R.; Cubison, M. J.; Dunlea, J.; Huffman, J. A.; Onasch, T. B.; Alfarra, M. R.; Williams, P. I.; Bower, K.; Kondo, Y.; Schneider, J.; Drewnick, F.; Borrmann, S.; Weimer, S.; Demerjian, K.; Salcedo, D.; Cottrell, L.; Griffin, R.; Takami, A.; Miyoshi, T.; Hatakeyama, S.; Shimono, A.; Sun, J. Y.; Zhang, Y. M.; Dzepina, K.; Kimmel, J. R.; Sueper, D.; Jayne, J. T.; Herndon, S. C.; Trimborn, A. M.; Williams, L. R.; Wood, E. C.; Middlebrook, A. M.; Kolb, C. E.; Baltensperger, U.; Worsnop, D. R.

    2009-12-01

    Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework describing the atmospheric evolution of OA that is constrained by high-time-resolution measurements of its composition, volatility, and oxidation state. OA and OA precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. Our model framework captures the dynamic aging behavior observed in both the atmosphere and laboratory: It can serve as a basis for improving parameterizations in regional and global models.

  14. Modeling the formamtion and aging of secondary organic aerosols in Los Angeles during CalNex 2010

    EPA Science Inventory

    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 A...

  15. Slow aging in Secondary Organic Aerosol observed by Liquid Chromatography coupled with High-Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Bones, D. L.; Bateman, A. P.; Nguyen, T. B.; Laskin, J.; Laskin, A.; Nizkorodov, S.

    2009-12-01

    This study investigated long term changes in the chemical composition of model biogenic secondary organic aerosol (SOA) prepared via ozonolysis of the terpene limonene. This SOA has been observed to turn brown when exposed to NH4+. Our hypothesis is that the chromophoric compounds responsible for this color change are suspected to be imidazole-like or pyridinium-like compounds. These compounds are only present in small relative amounts, hence standard mass spectrometry is insufficient to unambiguously detect these compounds. However, a combination of HPLC and high resolution electrospray ionization mass spectrometry allows assignments of chemical formulae to individual peaks. These and other experiments confirm the presence of N-containing compounds in treated SOA. We are in the process of determining the exact identity of these species by MS/MS methods. LC-MS can also provide information about the polarity of the compounds in SOA. Most compounds in limonene-O3 SOA are polar and are detected at short retention times; peaks suggesting trimeric species appear at longer retention times in the case of fresh SOA, but at shorter times with the bulk of the components for aged SOA. Limonene SOA has been shown to be composed of monomers, dimers, trimers and larger oligomers. The appearance of trimers in specific regions of the chromatogram suggests these species are genuine SOA components and not an artifact of electrospray ionization. Changes in biogenic SOA over time are important because of the propensity of SOA to affect direct and indirect radiative forcing.

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

    NASA Astrophysics Data System (ADS)

    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

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

    DOE PAGES

    Hayes, P. L.; Carlton, A. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S.; Rappenglück, B.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; et al

    2014-12-20

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  19. The Statistical Evolution of Multiple Generations of Oxidation Products in the Photochemical Aging of Chemically Reduced Organic Aerosol

    SciTech Connect

    Wilson, Kevin R.; Smith, Jared D.; Kessler, Sean; Kroll, Jesse H.

    2011-10-03

    The heterogeneous reaction of hydroxyl radicals (OH) with squalane and bis(2-ethylhexyl) sebacate (BES) particles are used as model systems to examine how distributions of reactionproducts evolve during the oxidation of chemically reduced organic aerosol. A kinetic model of multigenerational chemistry, which is compared to previously measured (squalane) and new(BES) experimental data, reveals that it is the statistical mixtures of different generations of oxidation products that control the average particle mass and elemental composition during thereaction. The model suggests that more highly oxidized reaction products, although initially formed with low probability, play a large role in the production of gas phase reaction products.In general, these results highlight the importance of considering atmospheric oxidation as a statistical process, further suggesting that the underlying distribution of molecules could playimportant roles in aerosol formation as well as in the evolution of key physicochemical properties such as volatility and hygroscopicity.

  20. Constraining Predicted Secondary Organic Aerosol Formation and Processing Using Real-Time Observations of Aging Urban Emissions in an Oxidation Flow Reactor

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Palm, B. B.; Hayes, P. L.; Day, D. A.; Cubison, M.; Brune, W. H.; Hu, W.; Graus, M.; Warneke, C.; Gilman, J.; De Gouw, J. A.; Jimenez, J. L.

    2014-12-01

    To investigate atmospheric processing of urban emissions, we deployed an oxidation flow reactor with measurements of size-resolved chemical composition of submicron aerosol during CalNex-LA, a field study investigating air quality and climate change at a receptor site in the Los Angeles Basin. The reactor produces OH concentrations up to 4 orders of magnitude higher than in ambient air, achieving equivalent atmospheric aging of hours to ~2 weeks in 5 minutes of processing. The OH exposure (OHexp) was stepped every 20 min to survey the effects of a range of oxidation exposures on gases and aerosols. This approach is a valuable tool for in-situ evaluation of changes in organic aerosol (OA) concentration and composition due to photochemical processing over a range of ambient atmospheric conditions and composition. Combined with collocated gas-phase measurements of volatile organic compounds, this novel approach enables the comparison of measured SOA to predicted SOA formation from a prescribed set of precursors. Results from CalNex-LA show enhancements of OA and inorganic aerosol from gas-phase precursors. The OA mass enhancement from aging was highest at night and correlated with trimethylbenzene, indicating the importance of relatively short-lived VOC (OH lifetime of ~12 hrs or less) as SOA precursors in the LA Basin. Maximum net SOA production is observed between 3-6 days of aging and decreases at higher exposures. Aging in the reactor shows similar behavior to atmospheric processing; the elemental composition of ambient and reactor measurements follow similar slopes when plotted in a Van Krevelen diagram. Additionally, for air processed in the reactor, oxygen-to-carbon ratios (O/C) of aerosol extended over a larger range compared to ambient aerosol observed in the LA Basin. While reactor aging always increases O/C, often beyond maximum observed ambient levels, a transition from net OA production to destruction occurs at intermediate OHexp, suggesting a transition

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

    DOE PAGES

    Hayes, P. L.; Carlton, A. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S.; Rappenglück, B.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; et al

    2015-05-26

    Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidationmore » of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model–measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model–measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model-measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model-measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed

  3. Evolution of Organic Aerosols in the Atmosphere.

    SciTech Connect

    Jimenez, J. L.; Canagaratna, M. R.; Donahue, N. M.; Prevot, A. S. H.; Zhang, Qi; Kroll, Jesse H.; DeCarlo, Peter F.; Allan, James D.; Coe, H.; Ng, N. L.; Aiken, Allison; Docherty, Kenneth S.; Ulbrich, Ingrid M.; Grieshop, A. P.; Robinson, A. L.; Duplissy, J.; Smith, J. D.; Wilson, K. R.; Lanz, V. A.; Hueglin, C.; Sun, Y. L.; Tian, J.; Laaksonen, A.; Raatikainen, T.; Rautiainen, J.; Vaattovaara, P.; Ehn, M.; Kulmala, M.; Tomlinson, Jason M.; Collins, Donald R.; Cubison, Michael J.; Dunlea, E. J.; Huffman, John A.; Onasch, Timothy B.; Alfarra, M. R.; Williams, Paul I.; Bower, K.; Kondo, Yutaka; Schneider, J.; Drewnick, F.; Borrmann, S.; Weimer, S.; Demerjian, K.; Salcedo, D.; Cottrell, L.; Griffin, Robert; Takami, A.; Miyoshi, T.; Hatakeyama, S.; Shimono, A.; Sun, J. Y.; Zhang, Y. M.; Dzepina, K.; Kimmel, Joel; Sueper, D.; Jayne, J. T.; Herndon, Scott C.; Trimborn, Achim; Williams, L. R.; Wood, Ezra C.; Middlebrook, A. M.; Kolb, C. E.; Baltensperger, Urs; Worsnop, Douglas R.

    2009-12-11

    Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework that describes the atmospheric evolution of OA and is constrained and motivated by new, high time resolution, experimental characterizations of their composition, volatility, and oxidation state. OA and OA-precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of large amounts of oxygenated organic aerosol (OOA) mass that has comparable concentrations to sulfate aerosol over the Northern Hemisphere. Our new model framework captures the dynamic aging behavior observed in the atmosphere and the laboratory and can serve as a basis for improving parameterizations in regional and global models.

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  6. Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

    DOE PAGES

    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; et al

    2016-06-15

    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 andmore » 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

  7. Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

    NASA Astrophysics Data System (ADS)

    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

  8. Surface-active organics in atmospheric aerosols.

    PubMed

    McNeill, V Faye; Sareen, Neha; Schwier, Allison N

    2014-01-01

    Surface-active organic material is a key component of atmospheric aerosols. The presence of surfactants can influence aerosol heterogeneous chemistry, cloud formation, and ice nucleation. We review the current state of the science on the sources, properties, and impacts of surfactants in atmospheric aerosols. PMID:23408277

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

    SciTech Connect

    Liu, Xiaohong; Wang, Jian

    2010-12-07

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

  10. Aerosol from Organic Nitrogen in the Southeast United States

    EPA Science Inventory

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

  11. Effect of Hydrophilic Organic Seed Aerosols on Secondary Organic Aerosol Formation from Ozonolysis of α-Pinene

    SciTech Connect

    Song, Chen; Zaveri, Rahul A.; Shilling, John E.; Alexander, M. L.; Newburn, Matthew K.

    2011-07-26

    Gas-particle partitioning theory is widely used in atmospheric models to predict organic aerosol loadings. This theory predicts that secondary organic aerosol (SOA) yield of an oxidized VOC product will increase as the mass loading of preexisting organic aerosol increases. In a previous study, we showed that the presence of model hydrophobic primary organic aerosol (POA) had no detectable effect on the secondary organic aerosol (SOA) yields from ozonolysis of {alpha}-pinene, suggesting that the condensing SOA compounds form a separate phase from the preexisting POA. However, non-polar, hydrophobic POA may gradually become polar and hydrophilic as it undergoes oxidative aging while POA formed from biomass burning is already somewhat polar and hydrophilic. In this study, we investigate the effects of model hydrophilic POA such as fulvic acid, adipic acid and citric acid on the gas-particle partitioning of SOA from {alpha}-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of {alpha}-pinene SOA into the particle-phase. The other two POA seed particles have negligible effect on the {alpha}-pinene SOA yields, suggesting that {alpha}-pinene SOA forms a well-mixed organic aerosol phase with citric acid while a separate phase with adipic acid and fulvic acid. This finding highlights the need to improve the thermodynamics treatment of organics in current aerosol models that simply lump all hydrophilic organic species into a single phase, thereby potentially introducing an erroneous sensitivity of SOA mass to emitted POA.

  12. The organic aerosols of Titan

    NASA Technical Reports Server (NTRS)

    Khare, B. N.; Sagan, C.; Thompson, W. R.; Arakawa, E. T.; Suits, F.; Calcott, T. A.; Williams, M. W.; Shrader, S.; Ogino, H.; Willingham, T. O.

    1986-01-01

    A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan prepared by continuous dc discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mb is determined from X-ray to microwave frequencies. Values of n (approx. 1.65) and k (approx. 0.004 to 0.08) in the visible are consistent with deductions made by groundbased and spaceborne observations of Titan. Many infrared absorption features are present in k(lambda), including the 4.6 micrometer nitrile band. Molecular analysis of the volatile components of this tholin was performed by sequential and nonsequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycylic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition,acid hydrolysis produces a racemic mixture of biological and nonbiological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.

  13. The organic aerosols of Titan.

    PubMed

    Khare, B N; Sagan, C; Thompson, W R; Arakawa, E T; Suits, F; Callcott, T A; Williams, M W; Shrader, S; Ogino, H; Willingham, T O; Nagy, B

    1984-01-01

    A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan tholin prepared by continuous D.C. discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mb is determined from x-ray to microwave frequencies. Values of n (approximately equal to 1.65) and k (approximately equal to 0.004 to 0.08) in the visible are consistent with deductions made by ground-based and spaceborne observations of Titan. Many infrared absorption features are present in k (lambda), including the 4.6 micrometers nitrile band. Molecular analysis of the volatile component of this tholin was performed by sequential and non-sequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition, acid hydrolysis produces a racemic mixture of biological and non-biological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.

  14. Implementing marine organic aerosols into the GEOS-Chem model

    DOE PAGES

    Gantt, B.; Johnson, M. S.; Crippa, M.; Prévôt, A. S. H.; Meskhidze, N.

    2014-09-09

    Marine organic aerosols (MOA) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Model predictions were also in goodmore » agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOA observed during the summertime at an inland site near Paris, France. Our study shows that MOA have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having > 10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly-emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.« less

  15. Implementing marine organic aerosols into the GEOS-Chem model

    DOE PAGES

    Gantt, B.; Johnson, M. S.; Crippa, M.; Prévôt, A. S. H.; Meskhidze, N.

    2015-03-17

    Marine-sourced organic aerosols (MOAs) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem (Global Earth Observing System Chemistry) model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Modelmore » predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOAs observed during the summertime at an inland site near Paris, France. Our study shows that MOAs have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having >10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.« less

  16. Implementing marine organic aerosols into the GEOS-Chem model

    NASA Astrophysics Data System (ADS)

    Gantt, B.; Johnson, M. S.; Crippa, M.; Prévôt, A. S. H.; Meskhidze, N.

    2015-03-01

    Marine-sourced organic aerosols (MOAs) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem (Global Earth Observing System Chemistry) model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Model predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOAs observed during the summertime at an inland site near Paris, France. Our study shows that MOAs have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having >10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.

  17. Implementing marine organic aerosols into the GEOS-Chem model

    NASA Astrophysics Data System (ADS)

    Gantt, B.; Johnson, M. S.; Crippa, M.; Prévôt, A. S. H.; Meskhidze, N.

    2014-09-01

    Marine organic aerosols (MOA) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Model predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOA observed during the summertime at an inland site near Paris, France. Our study shows that MOA have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having > 10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly-emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.

  18. Chemistry of secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Yee, Lindsay Diana

    The photooxidation of volatile organic compounds (VOCs) in the atmosphere can lead to the formation of secondary organic aerosol (SOA), a major component of fine particulate matter. Improvements to air quality require insight into the many reactive intermediates that lead to SOA formation, of which only a small fraction have been measured at the molecular level. This thesis describes the chemistry of secondary organic aerosol (SOA) formation from several atmospherically relevant hydrocarbon precursors. Photooxidation experiments of methoxyphenol and phenolic compounds and C12 alkanes were conducted in the Caltech Environmental Chamber. These experiments include the first photooxidation studies of these precursors run under sufficiently low NOx levels, such that RO2 + HO2 chemistry dominates, an important chemical regime in the atmosphere. Using online Chemical Ionization Mass Spectrometery (CIMS), key gas-phase intermediates that lead to SOA formation in these systems were identified. With complementary particle-phase analyses, chemical mechanisms elucidating the SOA formation from these compounds are proposed. Three methoxyphenol species (phenol, guaiacol, and syringol) were studied to model potential photooxidation schemes of biomass burning intermediates. SOA yields (ratio of mass of SOA formed to mass of primary organic reacted) exceeding 25% are observed. Aerosol growth is rapid and linear with the organic conversion, consistent with the formation of essentially non-volatile products. Gas and aerosol-phase oxidation products from the guaiacol system show that the chemical mechanism consists of highly oxidized aromatic species in the particle phase. Syringol SOA yields are lower than that of phenol and guaiacol, likely due to unique chemistry dependent on methoxy group position. The photooxidation of several C12 alkanes of varying structure n-dodecane, 2-methylundecane, cyclododecane, and hexylcyclohexane) were run under extended OH exposure to investigate the

  19. Condensing Organic Aerosols in a Microphysical Model

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  20. EVIDENCE FOR ORGANOSULFATES IN SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

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

  1. Photochemical Aging of α-pinene and β-pinene Secondary Organic Aerosol formed from Nitrate Radical Oxidation: New Insights into the Formation and Fates of Highly Oxygenated Gas- and Particle-phase Organic Nitrates

    NASA Astrophysics Data System (ADS)

    Nah, T.; Sanchez, J.; Boyd, C.; Ng, N. L.

    2015-12-01

    The nitrate radical (NO3), one of the most important oxidants in the nocturnal atmosphere, can react rapidly with a variety of biogenic volatile organic compounds (BVOCs) to form high mass concentrations of secondary organic aerosol (SOA) and organic nitrates (ON). Despite its critical importance in aerosol formation, the mechanisms and products from the NO3 oxidation of BVOCs have been largely unexplored, and the fates of their SOA and ON after formation are not well characterized. In this work, we studied the formation of SOA and ON from the NO3 oxidation of α-pinene and β-pinene and investigated for the first time how they evolve during dark and photochemical aging through a series of chamber experiments performed at the Georgia Tech Environmental Chamber (GTEC) facility. The α-pinene and β-pinene SOA are characterized using real-time gas- and particle-phase measurements, which are used to propose mechanisms for SOA and organic nitrate formation and aging. Highly oxygenated gas- and particle-phase ON (containing as many as 9 oxygen atoms) are detected during the NO3 reaction. In addition, the β-pinene SOA and α-pinene SOA exhibited drastically different behavior during photochemical aging. Our results indicate that nighttime ON formed by NO3+monoterpene chemistry can serve as either NOx reservoirs or sinks depending on the monoterpene precursor. Results from this study provide fundamental data for evaluating the contributions of NO3+monoterpene reactions to ambient OA measured in the Southeastern U.S.

  2. Aqueous phase processing of secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Liu, Yao; Tritscher, T.; Praplan, A. P.; Decarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.; Monod, A.

    2011-07-01

    The aging of secondary organic aerosol (SOA) by photooxidation in the aqueous phase was experimentally investigated. To simulate multiphase processes, the following experiments were sequentially performed in a smog chamber and in an aqueous phase photoreactor: (1) Gas-phase photooxidation of three different volatile organic compounds (VOC): isoprene, α-pinene, and 1,3,5-trimethylbenzene (TMB) in the presence of NOx, leading to the formation of SOA which was subjected to on-line physical and chemical analysis; (2) particle-to-liquid transfer of water soluble species of SOA using filter sampling and aqueous extraction; (3) aqueous-phase photooxidation of the obtained water extracts; and (4) nebulization of the solutions for a repetition of the on-line characterization. SOA concentrations in the chamber measured with a scanning mobility particle sizer (SMPS) were higher than 200 μg m-3, as the experiments were conducted under high initial concentrations of volatile organic compounds (VOC) and NOx. The aging of SOA through aqueous phase processing was investigated by measuring the physical and chemical properties of the particles online before and after processing using a high resolution time-of-flight aerosol mass spectrometer (AMS) and a hygroscopicity tandem differential mobility analyzer (H-TDMA). It was shown that, after aqueous phase processing, the particles were significantly more hygroscopic, and contained more fragmentation ions at m/z = 44 and less ions at m/z = 43, thus showing a significant impact on SOA aging for the three different precursors. Additionally, the particles were analyzed with a thermal desorption atmospheric pressure ionization aerosol mass spectrometer (TD-API-AMS). Comparing the smog chamber SOA composition and non processed nebulized aqueous extracts with this technique revealed that sampling, extraction and/or nebulization did not significantly impact the chemical composition of SOA formed from isoprene and α-pinene, whereas it

  3. Field and Laboratory Studies of Atmospheric Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Coggon, Matthew Mitchell

    these conditions to all measurements conducted during E-PEACE demonstrated that a large fraction of cloud droplet (72%) and dry aerosol mass (12%) sampled in the California coastal study region was heavily or moderately influenced by ship emissions. Another study investigated the chemical and physical evolution of a controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed 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

  4. Impact of aging mechanism on model simulated carbonaceous aerosols

    PubMed Central

    Huang, Y.; Wu, S.; Dubey, M.K.; French, N. H. F.

    2013-01-01

    Carbonaceous aerosols including organic carbon and black carbon have significant implications for both climate and air quality. In the current global climate or chemical transport models, a fixed hydrophobic-to-hydrophilic conversion lifetime for carbonaceous aerosol (τ) is generally assumed, which is usually around one day. We have implemented a new detailed aging scheme for carbonaceous aerosols in a chemical transport model (GEOS-Chem) to account for both the chemical oxidation and the physical condensation-coagulation effects, where τ is affected by local atmospheric environment including atmospheric concentrations of water vapor, ozone, hydroxyl radical and sulfuric acid. The updated τ exhibits large spatial and temporal variations with the global average (up to 11 km altitude) calculated to be 2.6 days. The chemical aging effects are found to be strongest over the tropical regions driven by the low ozone concentrations and high humidity there. The τ resulted from chemical aging generally decreases with altitude due to increases in ozone concentration and decreases in humidity. The condensation-coagulation effects are found to be most important for the high-latitude areas, in particular the polar regions, where the τ values are calculated to be up to 15 days. When both the chemical aging and condensation-coagulation effects are considered, the total atmospheric burdens and global average lifetimes of BC, black carbon, (OC, organic carbon) are calculated to increase by 9% (3%) compared to the control simulation, with considerable enhancements of BC and OC concentrations in the Southern Hemisphere. Model evaluations against data from multiple datasets show that the updated aging scheme improves model simulations of carbonaceous aerosols for some regions, especially for the remote areas in the Northern Hemisphere. The improvement helps explain the persistent low model bias for carbonaceous aerosols in the Northern Hemisphere reported in literature. Further

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  6. Multiphase OH oxidation kinetics of organic aerosol: The role of particle phase state and relative humidity

    NASA Astrophysics Data System (ADS)

    Slade, Jonathan H.; Knopf, Daniel A.

    2014-07-01

    Organic aerosol can exhibit different phase states in response to changes in relative humidity (RH), thereby influencing heterogeneous reaction rates with trace gas species. OH radical uptake by laboratory-generated levoglucosan and methyl-nitrocatechol particles, serving as surrogates for biomass burning aerosol, is determined as a function of RH. Increasing RH lowers the viscosity of amorphous levoglucosan aerosol particles enabling enhanced OH uptake. Conversely, OH uptake by methyl-nitrocatechol aerosol particles is suppressed at higher RH as a result of competitive coadsorption of H2O that occupies reactive sites. This is shown to have substantial impacts on organic aerosol lifetimes with respect to OH oxidation. The results emphasize the importance of organic aerosol phase state to accurately describe the multiphase chemical kinetics and thus chemical aging process in atmospheric models to better represent the evolution of organic aerosol and its role in air quality and climate.

  7. Emissions and Secondary Organic Aerosol Production from Semivolatile and Intermediate Volatility Organic Compounds

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

    Organic aerosols are a highly-dynamic system dominated by both variable gas-particle partitioning and chemical evolution. Important classes of organics include semivolatile and intermediate volatility organic compounds (SVOC and IVOC, respectively). SVOCs are compounds that exist in both the gas and particle phases at typical atmospheric conditions while IVOC are low-volatility vapors that exist exclusively in the gas phase. Both classes have saturation concentrations that are orders of magnitude lower than volatile organic compounds (VOC) that are the traditional subjects of atmosphere chemistry, such as monoterpenes, alkyl benzenes, etc. The SVOC and IVOC are poorly represented for in current atmospheric chemistry models. Source testing indicates that SVOC and IVOC emissions from biomass combustion, diesel engines and other sources exceed the primary organic aerosol emissions; thus the oxidation of these vapors could serve as a significant source of organic aerosol in the atmosphere. The formation of secondary organic aerosol (SOA) from the reactions between OH radicals and SVOCs and IVOCs was investigated in the Carnegie Mellon University smog chamber. Experiments were conducted with n-alkanes and emission surrogates (diesel fuel and lubricating oil). SVOC oxidation produces oxidized organic aerosol but little new organic aerosol mass. This behavior can be explained by the coupled effects of partitioning and aging. Oxidation of SVOC vapors creates low volatility species that partition into the condensed phase; this oxidation also reduces the SVOC vapor concentration which, in turn, requires particle-phase SVOC to evaporate to maintain phase equilibrium. In contrast, oxidation of IVOC results in sustained production of SOA consistent with a reaction with relatively slow kinetics and high mass yield. Aerosol Mass Spectrometer data indicates that the SOA formed from IVOC has a mass spectrum that is quite similar to the oxygenated organic aerosol factor observed in

  8. Fluorescent lidar for organic aerosol study

    NASA Astrophysics Data System (ADS)

    Matvienko, G. G.; Timofeev, V. I.; Grishin, A. I.; Fateyeva, N. L.

    2005-10-01

    The paper describes the fluorescent lidar created for monitoring of the atmosphere and for estimating the content of fluorescent components of organic aerosol. The lidar operation is based on the use of ultraviolet radiation of harmonics of Nd:YAG solid state laser for exciting the atmospheric fluorescence and the spectral analysis of the atmospheric fluorescence is used in the near ultraviolet and blue spectral range with the resolution of 2 nm. The lidar was found to be efficient for remote analysis of organic aerosol occurring as a result of vegetation emission of secondary metabolites to the atmosphere. Fluorescence spectra processing allows us to select some organic compounds, which molecules contain 7 and more carbon atoms. Taking into account the availability of interconnection between organic aerosol and vegetation, in lidar the second harmonic of Nd:YAG laser is also used for exciting the fluorescence of vegetation covers. In this case the receiving system detects the fluorescence of vegetation in the red spectral range conditioned by the chlorophyll of vegetation. Simultaneous detection of the fluorescence from the atmosphere and from vegetation makes it possible to obtain data on the interaction of the atmosphere and underlying surface covered by vegetation. It has been found that a disruption in the vegetation feeding or the impact of pollutions on vegetation resulted in a sharp increase of the fluorescence intensity of vegetation chlorophyll in the red spectral range and in the simultaneous appearance of organic aerosol in the atmosphere adjacent to vegetation in the region of negative impact.

  9. THERMAL PROPERTIES OF SECONDARY ORGANIC AEROSOLS

    EPA Science Inventory

    Volume concentrations of steady-state secondary organic aerosol (SOA) were measured in several hydrocarbon/NOx irradiation experiments. These measurements were used to estimate the thermal behavior of the particles that may be formed in the atmosphere. These laborator...

  10. Organosulfate Formation in Biogenic Secondary Organic Aerosol

    EPA Science Inventory

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

  11. Organic aerosol formation in citronella candle plumes

    PubMed Central

    Bothe, Melanie

    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 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. PMID:20700379

  12. Does atmospheric aging of biogenic SOA increase aerosol absorption and brown carbon?

    NASA Astrophysics Data System (ADS)

    Rudich, Yinon

    2014-05-01

    The optical properties of organic aerosols are important in determining their radiative forcing and, subsequently, their impact on climate. Primary or secondary organic aerosols (SOA) from natural and anthropogenic emissions age via photochemical reactions of OH, NO3, and O3. Atmospheric aging of aerosols changes their chemical, physical, and optical properties. Of special interest is the possible formation of absorbing organic species or "brown carbon", which can lead to absorption and heating in the atmosphere, with important consequences to climate and air quality. In this talk we will discuss possible formation pathways of brown carbon by aging of SOA, and its potential effect on radiative forcing. We employed a new broadband aerosol spectrometer that retrieves aerosol optical properties between 360 and 420 nm to probe the aging of biogenic and anthropogenic SOA in a flowtube and photochemical smog chamber. We will discuss the effect of photochemical aging on the optical properties of SOA that form from the ozonolysis of biogenic and anthropogenic VOCs, and subsequent reactions with ammonia with special emphasis on the change in their absorption. Nitration reactions of polyaromatic hydrocarbons that lead to increased absorption will also be presented. Using the wavelength-dependent modified forcing equation we will provide estimates of the radiative impact of the aged biogenic SOA. Our calculation shows that the integrated radiative forcing suggest that the observed changes in refractive index due to photochemical ageing by NH3 reactions can lead to enhanced cooling by the aged aerosol.

  13. Evolved gas analysis of secondary organic aerosols

    SciTech Connect

    Grosjean, D.; Williams, E.L. II; Grosjean, E. ); Novakov, T. )

    1994-11-01

    Secondary organic aerosols have been characterized by evolved gas analysis (EGA). Hydrocarbons selected as aerosol precursors were representative of anthropogenic emissions (cyclohexene, cyclopentene, 1-decene and 1-dodecene, n-dodecane, o-xylene, and 1,3,5-trimethylbenzene) and of biogenic emissions (the terpenes [alpha]-pinene, [beta]-pinene and d-limonene and the sesquiterpene trans-caryophyllene). Also analyzed by EGA were samples of secondary, primary (highway tunnel), and ambient (urban) aerosols before and after exposure to ozone and other photochemical oxidants. The major features of the EGA thermograms (amount of CO[sub 2] evolved as a function of temperature) are described. The usefulness and limitations of EGA data for source apportionment of atmospheric particulate carbon are briefly discussed. 28 refs., 7 figs., 4 tabs.

  14. Regional signatures in the organic composition of marine aerosol particles

    NASA Astrophysics Data System (ADS)

    Frossard, Amanda A.; Russell, Lynn M.; Keene, William C.; Kieber, David J.; Quinn, Patricia K.; Bates, Timothy S.

    2013-05-01

    Marine aerosol particles play an important role in the earth's radiative balance, yet the sources and composition of the organic fraction remain largely unconstrained. Recent measurements have been made in order to characterize the sources, composition, and concentration of aerosol particles in the marine boundary layer. The organic composition of submicron particles derived from multiple seawater regions have been measured using Fourier Transform Infrared (FTIR) spectroscopy. Cluster analysis of FTIR organic spectra suggest different spectral signatures based on collection location, seawater composition, and ambient conditions. Measurements including non-refractory aerosol composition from a high-resolution time of flight aerosol mass spectrometer (HR-ToF-AMS), seawater composition, and wind speed were used to interpret the cluster results, depending on the availability from each campaign. FTIR spectra of ambient particles are compared to FTIR spectra of primary marine particles generated from model ocean systems to infer the ambient particle production mechanisms and aging processes. Recent measurements used in the comparison include ambient and generated marine aerosol particles measured off the coast of California during CalNex in May and June 2010. Remote ambient marine aerosol particles were collected 100 miles off the coast of Monterey in the eastern Pacific during the EPEACE experiment in July 2011. Ambient and generated marine particles were measured in two different seawater types during WACS 2012 including colder, more productive water off the coast of the northeastern United States and warmer, oligotrophic water in the Sargasso Sea. These particles are also compared with those measured in the southeastern Pacific during VOCALS and the north Atlantic during ICEALOT.

  15. Aging and Aged in Organized Crime.

    ERIC Educational Resources Information Center

    Amir, Menachem

    1989-01-01

    Examines problems of the aged in organized crime, basing discussion on organized crime bosses over age 60 operating in Italy, the United States, and Israel. Looks at problems stemming from normative system in organized crime, role of the aged, intergenerational problems, fears of the aged, excuses and justifications, standards of life, and…

  16. Organic Mass to Organic Carbon ratio in Atmospheric Aerosols: Observations and Global Simulations

    NASA Astrophysics Data System (ADS)

    Tsigaridis, K.; Kanakidou, M.; Daskalakis, N.

    2012-12-01

    Organic compounds play an important role in atmospheric chemistry and affect Earth's climate through their impact on oxidants and aerosol formation (e.g. O3 and organic aerosols (OA)). Due to the complexity of the mixture of organics in the atmosphere, the organic-mass-to-organic-carbon ratio (OM/OC) is often used to characterize the organic component in atmospheric aerosols. This ratio varies dependant on the aerosol origin and the chemical processing in the atmosphere. Atmospheric observations have shown that as OA and its precursor gases age in the atmosphere, it leads to the formation of more oxidized (O:C atomic ratio 0.6 to 0.8), less volatile and less hydrophobic compounds (particle growth factor at 95% relative humidity of 0.16 to 0.20) that have more similar properties than fresh aerosols. While reported OM:OC ratios observed over USA range between 1.29 and 1.95, indicating significant contribution of local pollution sources to the OC in that region, high O/C ratio associated with a high OM/OC ratio of 2.2 has been also observed for the summertime East Mediterranean aged aerosol. In global models, the OM/OC ratio is either calculated for specific compounds or estimated for compound groups. In the present study, we review OM/OC observations and compare them with simulations from a variety of models that contributed to the AEROCOM exercise. We evaluate the chemical processing level of atmospheric aerosols simulated by the models. A total of 32 global chemistry transport models are considered in this study with variable complexity of the representation of OM/OC ratio in the OA. The analysis provides an integrated view of the OM/OC ratio in the global atmosphere and of the accuracy of its representation in the global models. Implications for atmospheric chemistry and climate simulations are discussed.

  17. Development of an aerosol microphysical module: Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS)

    SciTech Connect

    Matsui, H.; Koike, Makoto; Kondo, Yutaka; Fast, Jerome D.; Takigawa, M.

    2014-09-30

    Number concentrations, size distributions, and mixing states of aerosols are essential parameters for accurate estimation of aerosol direct and indirect effects. In this study, we developed an aerosol module, designated Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS), that can represent these parameters explicitly by considering new particle formation (NPF), black carbon (BC) aging, and secondary organic aerosol (SOA) processes. A two-dimensional bin representation is used for particles with dry diameters from 40 nm to 10 µm to resolve both aerosol size (12 bins) and BC mixing state (10 bins) for a total of 120 bins. The particles with diameters from 1 to 40 nm are resolved using an additional 8 size bins to calculate NPF. The ATRAS module was implemented in the WRF-chem model and applied to examine the sensitivity of simulated mass, number, size distributions, and optical and radiative parameters of aerosols to NPF, BC aging and SOA processes over East Asia during the spring of 2009. BC absorption enhancement by coating materials was about 50% over East Asia during the spring, and the contribution of SOA processes to the absorption enhancement was estimated to be 10 – 20% over northern East Asia and 20 – 35% over southern East Asia. A clear north-south contrast was also found between the impacts of NPF and SOA processes on cloud condensation nuclei (CCN) concentrations: NPF increased CCN concentrations at higher supersaturations (smaller particles) over northern East Asia, whereas SOA increased CCN concentrations at lower supersaturations (larger particles) over southern East Asia. Application of ATRAS to East Asia also showed that the impact of each process on each optical and radiative parameter depended strongly on the process and the parameter in question. The module can be used in the future as a benchmark model to evaluate the accuracy of simpler aerosol models and examine interactions between NPF, BC aging, and SOA

  18. Characterizing the formation of secondary organic aerosols

    SciTech Connect

    Lunden, Melissa; Black, Douglas; Brown, Nancy

    2004-02-01

    Organic aerosol is an important fraction of the fine particulate matter present in the atmosphere. This organic aerosol comes from a variety of sources; primary organic aerosol emitted directly from combustion process, and secondary aerosol formed in the atmosphere from condensable vapors. This secondary organic aerosol (SOA) can result from both anthropogenic and biogenic sources. In rural areas of the United States, organic aerosols can be a significant part of the aerosol load in the atmosphere. However, the extent to which gas-phase biogenic emissions contribute to this organic load is poorly understood. Such an understanding is crucial to properly apportion the effect of anthropogenic emissions in these rural areas that are sometimes dominated by biogenic sources. To help gain insight on the effect of biogenic emissions on particle concentrations in rural areas, we have been conducting a field measurement program at the University of California Blodgett Forest Research Facility. The field location includes has been used to acquire an extensive suite of measurements resulting in a rich data set, containing a combination of aerosol, organic, and nitrogenous species concentration and meteorological data with a long time record. The field location was established in 1997 by Allen Goldstein, a professor in the Department of Environmental Science, Policy and Management at the University of California at Berkeley to study interactions between the biosphere and the atmosphere. The Goldstein group focuses on measurements of concentrations and whole ecosystem biosphere-atmosphere fluxes for volatile organic compounds (VOC's), oxygenated volatile organic compounds (OVOC's), ozone, carbon dioxide, water vapor, and energy. Another important collaborator at the Blodgett field location is Ronald Cohen, a professor in the Chemistry Department at the University of California at Berkeley. At the Blodgett field location, his group his group performs measurements of the

  19. Heterogeneous OH oxidation of organic aerosols

    NASA Astrophysics Data System (ADS)

    Smith, J.; Kroll, J.; Cappa, C.; Che, D.; Ahmed, M.; Leone, S.; Worsnop, D.; Wilson, K.

    2008-12-01

    The hydroxyl radical (OH) is the most important reactive species in both clean and polluted atmospheres, and therefore gas-phase OH chemistry has been extensively studied for decades. Due to this enormous effort the rates and mechanism of OH reactions with gas phase organics are relatively well understood. However, it unclear whether these well established gas-phase chemical mechanisms apply to the more complex heterogeneous reactions of OH radicals with organic aerosols (OA). Although recent studies have begun to examine OH oxidation of OA, numerous outstanding questions still remain regarding both the rate and chemical mechanism of these reactions. Here we present an in depth investigation of the heterogeneous oxidation of organic squalane particles by OH radicals. By combining a photochemical aerosol flow reactor with a high-resolution aerosol mass spectrometer (AMS), with both electron impact and vacuum ultraviolet photoionization, we investigate OH heterogeneous chemistry in unprecedented detail. Employing elemental composition measurements with detailed kinetics we have arrived at a simple oxidation model which accurately accounts for the evolution of squalane and its" oxidation products. In addition, by exploring a large range of OH concentrations we are able to directly measure the role of secondary particle-phase chain chemistry which can significantly accelerate the oxidation of OA in the atmosphere. Based on these measurements we have arrived at an explicit chemical mechanism for heterogeneous OH oxidation of OA which accurately accounts for our observations over a wide range of reaction conditions.

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

    NASA Astrophysics Data System (ADS)

    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

  1. Organic Aerosols as Cloud Condensation Nuclei

    NASA Astrophysics Data System (ADS)

    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

  2. Organosulfate formation in biogenic secondary organic aerosol.

    PubMed

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

    2008-09-11

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

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

    PubMed

    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

    2014-10-01

    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.

  4. Fast Airborne Size Distribution Measurements of an Aerosol Processes and Aging

    NASA Astrophysics Data System (ADS)

    Kapustin, V.; Clarke, A. D.; Zhou, J.; Brekhovskikh, V.; McNaughton, C. S.; Howell, S.

    2009-12-01

    During MILAGRO/INTEX experiment the Hawaii Group for Environmental Aerosol Research (HIGEAR) deployed a wide range of aerosol instrumentation aboard NSF C-130 and NASA DC-8. These were designed to provide rapid information on aerosol composition, state of mixing (internal or external), spectral optical properties (scattering and absorption), the humidity dependence of light scattering - f(RH), and the role of condensed species in changing the absorption properties of black carbon (BC) and inferred properties of organic carbon (OC). We also flew the Fast Mobility Particle Spectrometer (FMPS, TSI Inc.) to measure aerosol size distributions in a range 5.6 - 560 nm. For all our flights around Mexico City, an aerosol number concentration usually was well above the nominal FMPS sensitivity (from ~100 particles/cc @ Dp = 5.6 nm to 1 part/cc @ 560nm), providing us with reliable size distributions even at 1 sec resolution. FMPS measurements revealed small scale structure of an aerosol and allowed us to examine size distributions varying over space and time associated with mixing processes previously unresolved. These 1-Hz measurements during aircraft profiles captured variations in size distributions within shallow layers. Other dynamic processes observed included orography induced aerosol layers and evolution of the nanoparticles formed by nucleation. We put FMPS high resolution size distribution data in a context of aerosol evolution and aging, using a range of established (for MIRAGE/INTEX) chemical, aerosol and transport aging parameters.

  5. Primary to secondary organic aerosol: evolution of organic emissions from mobile combustion sources

    NASA Astrophysics Data System (ADS)

    Presto, A. A.; Gordon, T. D.; Robinson, A. L.

    2013-09-01

    A series of smog chamber experiments were conducted to investigate the transformation of primary organic aerosol (POA) and formation of secondary organic aerosol (SOA) during the photo-oxidation of dilute gasoline and diesel motor vehicle exhaust. In half of the experiments POA was present in the chamber at the onset of photo-oxidation. In these experiments positive matrix factorization (PMF) was used to determine separate POA and SOA factors from aerosol mass spectrometer data. A two-factor solution, with one POA factor and one SOA factor, was sufficient to describe the organic aerosol in all but one experiment. In the other half of the experiments, POA was not present at the onset of photo-oxidation; these experiments are considered "pure SOA" experiments. The POA mass spectrum was similar to the mass spectra of the hydrocarbon-like organic aerosol factor determined from ambient datasets with one exception, a diesel vehicle equipped with a diesel oxidation catalyst. The SOA in all experiments had a constant composition over the course of photo-oxidation, and did not appear to age with continued oxidation. The SOA mass spectra for the various gasoline and diesel vehicles were similar to each other, but markedly different than ambient oxidized organic aerosol factors. Van Krevelen analysis of the POA and SOA factors for gasoline and diesel experiments reveal slopes of -0.68 and -0.43, respectively. This suggests that the oxidation chemistry in these experiments is a combination of carboxylic acid and alcohol/peroxide formation, consistent with ambient oxidation chemistry. These experiments also provide insight to the mixing behavior of the POA and SOA. Analysis of the time series of the POA factor concentration and a basis-set model both indicate that for all but one of the vehicles tested here, the POA and SOA seem to mix and form a single organic aerosol phase.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    PubMed Central

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

    2016-01-01

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

  8. Field and Laboratory Studies of Atmospheric Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Coggon, Matthew Mitchell

    these conditions to all measurements conducted during E-PEACE demonstrated that a large fraction of cloud droplet (72%) and dry aerosol mass (12%) sampled in the California coastal study region was heavily or moderately influenced by ship emissions. Another study investigated the chemical and physical evolution of a controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed 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

  9. Aged boreal biomass burning aerosol size distributions from BORTAS 2011

    NASA Astrophysics Data System (ADS)

    Sakamoto, K. M.; Allan, J. D.; Coe, H.; Taylor, J. W.; Duck, T. J.; Pierce, J. R.

    2014-09-01

    Biomass-burning aerosols contribute to aerosol radiative forcing on the climate system. The magnitude of this effect is partially determined by aerosol size distributions, which are functions of source fire characteristics (e.g. fuel type, MCE) and in-plume microphysical processing. The uncertainties in biomass-burning emission number size-distributions in climate model inventories lead to uncertainties in the CCN concentrations and forcing estimates derived from these models. The BORTAS-B measurement campaign was designed to sample boreal biomass-burning outflow over Eastern Canada in the summer of 2011. Using these BORTAS-B data, we implement plume criteria to isolate the characteristic size-distribution of aged biomass-burning emissions (aged ∼1-2 days) from boreal wildfires in Northwestern Ontario. The composite median size-distribution yields a single dominant accumulation mode with Dpm = 230 nm (number-median diameter), σ = 1.7, which are comparable to literature values of other aged plumes of a similar type. The organic aerosol enhancement ratios (ΔOA / ΔCO) along the path of Flight b622 show values of 0.05-0.18 μg m-3 ppbv-1 with no significant trend with distance from the source. This lack of enhancement ratio increase/decrease with distance suggests no detectable net OA production/evaporation within the aged plume over the sampling period. A Lagrangian microphysical model was used to determine an estimate of the freshly emitted size distribution corresponding to the BORTAS-B aged size-distributions. The model was restricted to coagulation and dilution processes based on the insignificant net OA production/evaporation derived from the ΔOA / ΔCO enhancement ratios. We estimate that the fresh-plume median diameter was in the range of 59-94 nm with modal widths in the range of 1.7-2.8 (the ranges are due to uncertainty in the entrainment rate). Thus, the size of the freshly emitted particles is relatively unconstrained due to the uncertainties in

  10. Modeling secondary organic aerosol in CMAQ using multigenerational oxidation of semi-volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Baek, Jaemeen; Hu, Yongtao; Odman, M. Talat; Russell, Armistead G.

    2011-11-01

    Chemical transport models have had a historically low bias in simulated organic aerosol concentrations in summer as compared to observed levels, likely due to an underestimate in the formation of secondary organic aerosol (SOA). CMAQ with the AE4 SOA module, the fourth generation aerosol module, was extended using SOA formation produced by the multigenerational photochemical oxidation of semi-volatile organic compound (SVOC) from anthropogenic and biogenic precursors. The updated CMAQ was applied to both a summer and winter episode (2001 July and 2002 January) over the U.S. for evaluation and has been operational in the high resolution air quality forecasting (Hi-Res) system for the Southeast since May 2009. Overall, the updated SOA module significantly improved CMAQ performance on a daily basis, mainly due to the newly added aerosol that contributed more than half of the SOA formed (1.5 μg m-3 in summer on average). SOA contributed 46% (1.24 μg m-3 in the Pacific) to 79% (3.21 μg m-3 in the South) of the total organic aerosol in summer depending upon region. Adding aged aerosol also improved diurnal variation of simulated organic carbon in the Southeast, decreasing a mean fractional error from 74% to 49% and increasing the correlation coefficient from 0.52 to 0.59. Furthermore, the revised CMAQ was shown to improve PM2.5 simulations in the Hi-Res forecasting system that previously had typically underestimated PM2.5 levels during summer simulations. Impacts of using monoterpenes emissions estimated in BEIS version 3.12 on aerosol yields were tested as well.

  11. Ultraviolet Absorption by Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  12. Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

    NASA Astrophysics Data System (ADS)

    Moffet, R. C.; Rödel, T. C.; Kelly, S. T.; Yu, X. Y.; Carroll, G. T.; Fast, J.; Zaveri, R. A.; Laskin, A.; Gilles, M. K.

    2013-04-01

    Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of pollution accumulation event (27-29 June 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm diameter) increased with plume age as did the organic mass per particle. Comparison of the CARES spectro-microscopic data set with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that individual particles in Mexico City contained twice as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (30%) was larger than at the CARES urban site (10%) and the most aged samples from CARES contained less carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro-microscopic measurements

  13. Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

    NASA Astrophysics Data System (ADS)

    Moffet, R. C.; Rödel, T. C.; Kelly, S. T.; Yu, X. Y.; Carroll, G. T.; Fast, J.; Zaveri, R. A.; Laskin, A.; Gilles, M. K.

    2013-10-01

    Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of the Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of a pollution accumulation event (27-29 June 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer-controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near-edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm equivalent circular diameter) increased with plume age, as did the organic mass per particle. Comparison of the CARES spectro-microscopic dataset with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that fresh particles in Mexico City contained three times as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (ranging from 16.6 to 47.3%) was larger than at the CARES urban site (13.4-15.7%), and the most aged samples from CARES contained fewer carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed

  14. Mechanism for production of secondary organic aerosols and their representation in atmospheric models. Final report

    SciTech Connect

    Seinfeld, J.H.; Flagan, R.C.

    1999-06-07

    This document contains the following: organic aerosol formation from the oxidation of biogenic hydrocarbons; gas/particle partitioning of semivolatile organic compounds to model inorganic, organic, and ambient smog aerosols; and representation of secondary organic aerosol formation in atmospheric models.

  15. A naming convention for atmospheric organic aerosol

    NASA Astrophysics Data System (ADS)

    Murphy, B. N.; Donahue, N. M.; Robinson, A. L.; Pandis, S. N.

    2014-06-01

    While the field of atmospheric organic aerosol scientific research has experienced thorough and insightful progress over the last half century, this progress has been accompanied by the evolution of a communicative and detailed yet, at times, complex and inconsistent language. The menagerie of detailed classification that now exists to describe organic compounds in our atmosphere reflects the wealth of observational techniques now at our disposal as well as the rich information provided by state-of-the-science instrumentation. However, the nomenclature in place to communicate these scientific gains is growing disjointed to the point that effective communication within the scientific community and to the public may be sacrificed. We propose standardizing a naming convention for organic aerosol classification that is relevant to laboratory studies, ambient observations, atmospheric models, and various stakeholders for air-quality problems. Because a critical aspect of this effort is to directly translate the essence of complex physico-chemical phenomena to a much broader, policy-oriented audience, we recommend a framework that maximizes comprehension among scientists and non-scientists alike. For example, to classify volatility, it relies on straightforward alphabetic terms (e.g., semivolatile, SV; intermediate volatility, IV; etc.) rather than possibly ambiguous numeric indices. This framework classifies organic material as primary or secondary pollutants and distinguishes among fundamental features important for science and policy questions including emission source, chemical phase, and volatility. Also useful is the addition of an alphabetic suffix identifying the volatility of the organic material or its precursor for when emission occurred. With this framework, we hope to introduce into the community a consistent connection between common notation for the general public and detailed nomenclature for highly specialized discussion. In so doing, we try to maintain

  16. Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 1: measurement and simulation of organic aerosol evolution

    NASA Astrophysics Data System (ADS)

    Grieshop, A. P.; Logue, J. M.; Donahue, N. M.; Robinson, A. L.

    2009-02-01

    Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) emissions from flaming and smoldering hard- and soft-wood fires under plume-like conditions. This was done by exposing the dilute emissions from a small wood stove to UV light in a smog chamber and measuring the gas- and particle-phase pollutant concentrations with a suite of instruments including a Proton Transfer Reaction Mass Spectrometer (PTR-MS), an Aerosol Mass Spectrometer (AMS) and a thermodenuder. The measurements highlight how atmospheric processing can lead to considerable evolution of the mass and volatility of biomass-burning OA. Photochemical oxidation produced substantial new OA, increasing concentrations by a factor of 1.5 to 2.8 after several hours of exposure to typical summertime hydroxyl radical (OH) concentrations. Less than 20% of this new OA could be explained using a state-of-the-art secondary organic aerosol model and the measured decay of traditional SOA precursors. The thermodenuder data indicate that the primary OA is semivolatile; at 50°C between 50 and 80% of the fresh primary OA evaporated. Aging reduced the volatility of the OA; at 50°C only 20 to 40% of aged OA evaporated. The predictions of a volatility basis-set model that explicitly tracks the partitioning and aging of low-volatility organics was compared to the chamber data. The OA production can be explained by the oxidation of low-volatility organic vapors; the model can also reproduce observed changes in OA volatility and composition. The model was used to investigate the competition between photochemical processing and dilution on OA concentrations in plumes.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  19. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

    2015-03-01

    This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOA). Typically only photolysis of smaller organic molecules (e.g. formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low- and high-NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after four days of chemical aging under those conditions (equivalent to eight days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields i.e ~15% (low-NOx) to ~45% (high-NOx) for α-pinene, ~15% for toluene, ~25% for C12-alkane, and ~10% for C16-alkane. The small effect on low volatility n-alkanes such as C16-alkane is due to the rapid partitioning of early-generation products to the particle phase where they are assumed to be protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass seems increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas-phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an estimated SOA photolysis rate of JSOA=4 x 10-4JNO2. Modeling

  20. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

    2015-08-01

    This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low and high NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NOx) to ~45 % (high NOx) for α-pinene, ~15 % for toluene, ~25 % for C12 n-alkane, and ~10 % for C16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of JSOA

  1. Sources and atmospheric transformations of semivolatile organic aerosols

    NASA Astrophysics Data System (ADS)

    Grieshop, Andrew P.

    dilution both cause it to evaporate. Gas-particle partitioning was parameterized using absorptive partitioning theory and the volatility basis-set framework. The dynamics of particle evaporation proved to be much slower than expected and measurements of aerosol composition indicate that particle composition varies with partitioning. These findings have major implications for the measurement and modeling of POA from combustion sources. Source tests need to be conducted at atmospheric concentrations and temperatures. Upon entering the atmosphere, organic aerosol emissions are aged via photochemical reactions. Experiments with dilute wood-smoke demonstrate the dramatic evolution these emissions undergo within hours of emission. Aging produced substantial new OA (doubling or tripling OA levels within hours) and changed particle composition and volatility. These changes are consistent with model predictions based on the partitioning and aging (via gas-phase photochemistry) of semi-volatile species represented with the basis-set framework. Aging of wood-smoke OA made created a much more oxygenated aerosol and formed material spectrally similar to oxygenated OA found widely in the atmosphere. The oxygenated aerosol is also similar that formed with similar experiments conducted with diesel engine emissions. Therefore, aging of emissions from diverse sources may produce chemically similar OA, complicating the establishment of robust source-receptor relationships.

  2. Effect of hydrophilic organic seed aerosols on secondary organic aerosol formation from ozonolysis of α-pinene.

    PubMed

    Song, Chen; Zaveri, Rahul A; Shilling, John E; Alexander, M Lizabeth; Newburn, Matt

    2011-09-01

    Gas-particle partitioning theory is widely used in atmospheric models to predict organic aerosol loadings. This theory predicts that secondary organic aerosol (SOA) yield of an oxidized volatile organic compound product will increase as the mass loading of preexisting organic aerosol increases. In a previous work, we showed that the presence of model hydrophobic primary organic aerosol (POA) had no detectable effect on the SOA yields from ozonolysis of α-pinene, suggesting that the condensing SOA compounds form a separate phase from the preexisting POA. However, a substantial faction of atmospheric aerosol is composed of polar, hydrophilic organic compounds. In this work, we investigate the effects of model hydrophilic organic aerosol (OA) species such as fulvic acid, adipic acid, and citric acid on the gas-particle partitioning of SOA from α-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of α-pinene SOA into the particle-phase. The other two seed particles have a negligible effect on the α-pinene SOA yields, suggesting that α-pinene SOA forms a well-mixed organic aerosol phase with citric acid and a separate phase with adipic acid and fulvic acid. This finding highlights the need to improve the thermodynamics treatment of organics in current aerosol models that simply lump all hydrophilic organic species into a single phase, thereby potentially introducing an erroneous sensitivity of SOA mass to emitted OA species. PMID:21790137

  3. CARES Helps Explain Secondary Organic Aerosols

    SciTech Connect

    Zaveri, Rahul

    2014-03-28

    What happens when urban man-made pollution mixes with what we think of as pristine forest air? To know more about what this interaction means for the climate, the Carbonaceous Aerosol and Radiative Effects Study, or CARES, field campaign was designed in 2010. The sampling strategy during CARES was coordinated with CalNex 2010, another major field campaign that was planned in California in 2010 by the California Air Resources Board (CARB), the National Oceanic and Atmospheric Administration (NOAA), and the California Energy Commission (CEC). "We found two things. When urban pollution mixes with forest pollutions we get more secondary organic aerosols," said Rahul Zaveri, FCSD scientist and project lead on CARES. "SOAs are thought to be formed primarily from forest emissions but only when they interact with urban emissions. The data is saying that there will be climate cooling over the central California valley because of these interactions." Knowledge gained from detailed analyses of data gathered during the CARES campaign, together with laboratory experiments, is being used to improve existing climate models.

  4. CARES Helps Explain Secondary Organic Aerosols

    ScienceCinema

    Zaveri, Rahul

    2016-07-12

    What happens when urban man-made pollution mixes with what we think of as pristine forest air? To know more about what this interaction means for the climate, the Carbonaceous Aerosol and Radiative Effects Study, or CARES, field campaign was designed in 2010. The sampling strategy during CARES was coordinated with CalNex 2010, another major field campaign that was planned in California in 2010 by the California Air Resources Board (CARB), the National Oceanic and Atmospheric Administration (NOAA), and the California Energy Commission (CEC). "We found two things. When urban pollution mixes with forest pollutions we get more secondary organic aerosols," said Rahul Zaveri, FCSD scientist and project lead on CARES. "SOAs are thought to be formed primarily from forest emissions but only when they interact with urban emissions. The data is saying that there will be climate cooling over the central California valley because of these interactions." Knowledge gained from detailed analyses of data gathered during the CARES campaign, together with laboratory experiments, is being used to improve existing climate models.

  5. THERMODYNAMIC MODELING OF LIQUID AEROSOLS CONTAINING DISSOLVED ORGANICS AND ELECTROLYTES

    EPA Science Inventory

    Many tropospheric aerosols contain large fractions of soluble organic material, believed to derive from the oxidation of precursors such alpha-pinene. The chemical composition of aerosol organic matter is complex and not yet fully understood.

    The key properties of solu...

  6. Thermodynamics of water condensation on a primary marine aerosol coated by surfactant organic molecules.

    PubMed

    Djikaev, Yuri S; Ruckenstein, Eli

    2014-10-23

    A large subset of primary marine aerosols can be initially (immediately upon formation) treated using an "inverted micelle" model. We study the thermodynamics of heterogeneous water condensation on such a marine aerosol. Its hydrophobic organic coating can be processed by chemical reactions with atmospheric species; this enables the marine aerosol to serve as a nucleating center for water condensation. The most probable pathway of such "aging" involves atmospheric hydroxyl radicals that abstract hydrogen atoms from organic molecules coating the aerosol (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). Taking these two reactions into account, we derive an expression for the free energy of formation of an aqueous droplet on a marine aerosol. The model is illustrated by numerical calculations. The results suggest that the formation of aqueous droplets on marine aerosols is most likely to occur via Köhler activation rather than via nucleation. The model allows one to determine the threshold parameters necessary for the Köhler activation of such aerosols. Numerical results also corroborate previous suggestions that one can omit some chemical species of aerosols (and other details of their chemical composition) in investigating aerosol effects on climate.

  7. Visibility-reducing organic aerosols in the vicinity of Grand Canyon National Park: Properties observed by high resolution gas chromatography

    SciTech Connect

    Mazurek, M. |; Masonjones, M.C.; Masonjones, H.D.; Salmon, L.G.; Cass, G.R.; Hallock, K.A.; Leach, M.

    1997-02-01

    Fine particle and total airborne particle samples were collected during August 1989 within the Grand Canyon [Indian Gardens (IG)] and on its south rim [Hopi Point (HP)] to define summertime organic aerosol concentration and composition as a function of elevation at Grand Canyon National Park. Inorganic chemical constituents were analyzed also to help place the relative importance of organics in perspective. Fine particle organic aerosols were approximately equal in concentration to sulfate aerosols at both sites. Monthly average mass concentrations for fine aerosol organics ranged from 1.1{mu}gm{sup {minus}3} (IG) to 1.3{mu}gm{sup {minus}3} (HP), while the organic aerosol concentration within total suspended particulate matter samples ranged from 1.9{mu}gm{sup {minus}3} (IG) to 2.1{mu}gm{sup {minus}3} (HP). Aerosol organics that could be evaluated by gas chromatography with flame ionization detection (GC-FID) (elutable organics) constituted 27{percent} to 53{percent} of the total organics mass collected as fine or total aerosol. At each site, roughly half of the elutable organics fine aerosol fraction was composed of highly polar organic compounds. Distributions of the elutable organics were compared to Los Angeles fine aerosol samples and to distributions of authentic sources of aerosol organics. It was found that the Grand Canyon organic aerosol during August 1989 did not resemble diluted aged Los Angeles organic aerosol, indicating that most of the organic particulate matter at the Grand Canyon at the time studied originated from other sources.{copyright} 1997 American Geophysical Union

  8. Relating hygroscopicity and composition of organic aerosol particulate matter

    SciTech Connect

    Duplissy, J.; DeCarlo, P. F.; Dommen, J.; Alfarra, M. R.; Metzger, A.; Barmpadimos, I.; Prevot, A. S. H.; Weingartner, E.; Tritscher, T.; Gysel, M.; Aiken, A. C.; Jimenez, J. L.; Canagaratna, M. R.; Worsnop, D. R.; Collins, D. R.; Tomlinson, J.; 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 (f44). m/z 44 is due mostly to the ion fragment CO2+ 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 Jungfraujoch, and the megacity Mexico City, where similar results were found. A simple empirical linear relation between the hygroscopicity of OA at subsaturated RH, as given by the hygroscopic growth factor (GF) or "κorg" parameter, and f44 was determined and is given by κorg = 2.2 × f44 - 0.13. This approximation can be further verified and refined as the database for AMS and HTDMA measurements is constantly being expanded around the world. Finally, the use of this approximation could introduce an important simplification in the parameterization of hygroscopicity of OA in atmospheric models, since f44 is correlated with the photochemical age of an air mass.

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

    NASA Technical Reports Server (NTRS)

    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.

  10. Investigating Types and Sources of Organic Aerosol in Rocky Mountain National Park Using Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Schurman, M. I.; Lee, T.; Sun, Y.; Schichtel, B. A.; Kreidenweis, S. M.; Collett, J. L.

    2011-12-01

    The Rocky Mountain Atmospheric Nitrogen and Sulfur Study (RoMANS) focuses on identifying pathways and sources of nitrogen deposition in Rocky Mountain National Park (RMNP). Past work has combined measurements from a range of instrumentation such as annular denuders, PILS-IC, Hi-Vol samplers, and trace gas analyzers. Limited information from early RoMANS campaigns is available regarding organic aerosol. While prior measurements have produced a measure of total organic carbon mass, high time resolution measures of organic aerosol concentration and speciation are lacking. One area of particular interest is characterizing the types, sources, and amounts of organic nitrogen aerosol. Organic nitrogen measurements in RMNP wet deposition reveal a substantial contribution to the total reactive nitrogen deposition budget. In this study an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in summer 2010 at RMNP to investigate organic aerosol composition and its temporal variability. The species timeline and diurnal species variations are combined with meteorological data to investigate local transport events and chemistry; transport from the Colorado Front Range urban corridor appears to be more significant for inorganic species than for the overall organic aerosol mass. Considerable variation in organic aerosol concentration is observed (0.5 to 20 μg/m3), with high concentration episodes lasting between hours and two days. High resolution AMS data are analyzed for organic aerosol, including organic nitrogen species that might be expected from local biogenic emissions, agricultural activities, and secondary reaction products of combustion emissions. Positive matrix factorization reveals that semi-volatile oxidized OA, low-volatility oxidized OA, and biomass burning OA comprise most organic mass; the diurnal profile of biomass burning OA peaks at four and nine pm and may arise from local camp fires, while constant concentrations of

  11. Can scooter emissions dominate urban organic aerosol?

    NASA Astrophysics Data System (ADS)

    El Haddad, Imad; Platt, Stephen; Huang, Ru-Jin; Zardini, Alessandro; Clairotte, Micheal; Pieber, Simone; Pfaffenberger, Lisa; Fuller, Steve; Hellebust, Stig; Temime-Roussel, Brice; Slowik, Jay; Chirico, Roberto; Kalberer, Markus; Marchand, Nicolas; Dommen, Josef; Astorga, Covadonga; Baltensperger, Urs; Prevot, Andre

    2014-05-01

    In urban areas, where the health impact of pollutants increases due to higher population density, traffic is a major source of ambient organic aerosol (OA). A significant fraction of OA from traffic is secondary, produced via the reaction of exhaust volatile organic compounds (VOCs) with atmospheric oxidants. Secondary OA (SOA) has not been systematically assessed for different vehicles and driving conditions and thus its relative importance compared to directly emitted, primary OA (POA) is unknown, hindering the design of effective vehicle emissions regulations. 2-stroke (2S) scooters are inexpensive and convenient and as such a popular means of transportation globally, particularly in Asia. European regulations for scooters are less stringent than for other vehicles and thus primary particulate emissions and SOA precursor VOCs from 2S engines are estimated to be much higher. Assessing the effects of scooters on public health requires consideration of both POA, and SOA production. Here, we quantify POA emission factors and potential SOA EFs from 2S scooters, and the effect of using aromatic free fuel instead of standard gasoline thereon. During the tests, Euro 1 and Euro 2 2S scooters were run in idle or simulated low power conditions. Emissions from a Euro 2 2S scooter were also sampled during regulatory driving cycles on a chassis dynamometer. Vehicle exhaust was introduced into smog chambers, where POA emission and SOA production were quantified using a high-resolution time-of-flight aerosol mass spectrometer. A high resolution proton transfer time-of-flight mass spectrometer was used to investigate volatile organic compounds and a suite of instruments was utilized to quantify CO, CO2, O3, NOX and total hydrocarbons. We show that the oxidation of VOCs in the exhaust emissions of 2S scooters produce significant SOA, exceeding by up to an order of magnitude POA emissions. By monitoring the decay of VOC precursors, we show that SOA formation from 2S scooter

  12. Two Hundred Fifty Years of Aerosols and Climate: The End of the Age of Aerosols

    SciTech Connect

    Smith, Steven J.; Bond, Tami C.

    2014-01-20

    Carbonaceous and sulfur aerosols have a substantial global and regional influence on climate in addition to their impact on health and ecosystems. The magnitude of this influence has changed substantially over the past and is expected to continue to change into the future. An integrated picture of the changing climatic influence of black carbon, organic carbon and sulfate over the period 1850 through 2100, focusing on uncertainty, is presented using updated historical inventories and a coordinated set of emission projections. While aerosols have had a substantial impact on climate over the past century, by the end of the 21st century aerosols will likely be only a minor contributor to radiative forcing due to increases in greenhouse gas forcing and a global decrease in pollutant emissions. This outcome is even more certain under a successful implementation of a policy to limit greenhouse gas emissions as low-carbon energy technologies that do not emit appreciable aerosol or SO2 are deployed.

  13. Organic aerosol formation from photochemical oxidation of diesel exhaust in a smog chamber.

    PubMed

    Weitkamp, Emily A; Sage, Amy M; Pierce, Jeffrey R; Donahue, Neil M; Robinson, Allen L

    2007-10-15

    Diluted exhaust from a diesel engine was photo-oxidized in a smog chamber to investigate secondary organic aerosol (SOA) production. Photochemical aging rapidly produces significant SOA, almost doubling the organic aerosol contribution of primary emissions after several hours of processing at atmospherically relevant hydroxyl radical concentrations. Less than 10% of the SOA mass can be explained using a SOA model and the measured oxidation of known precursors such as light aromatics. However, the ultimate yield of SOA is uncertain because it is sensitive to treatment of particle and vapor losses to the chamber walls. Mass spectra from an aerosol mass spectrometer (AMS) reveal that the organic aerosol becomes progressively more oxidized throughout the experiments, consistent with sustained, multi-generational production. The data provide strong evidence that the oxidation of a wide array of precursors that are currently not accounted for in existing models contributes to ambient SOA formation.

  14. EFFECT OF ACIDITY ON SECONDARY ORGANIC AEROSOL FORMATION FROM ISOPRENE

    EPA Science Inventory

    The effect of particle-phase acidity on secondary organic aerosol (SOA) formation from isoprene is investigated in a laboratory chamber study, in which the acidity of the inorganic seed aerosol was controlled systematically. The observed enhancement in SOA mass concentration is c...

  15. Carbonaceous aerosols influencing atmospheric radiation: Black and organic carbon

    SciTech Connect

    Penner, J.E.

    1994-09-01

    Carbonaceous particles in the atmosphere may both scatter and absorb solar radiation. The fraction associated with the absorbing component is generally referred to as black carbon (BC) and is mainly produced from incomplete combustion processes. The fraction associated with condensed organic compounds is generally referred to as organic carbon (OC) or organic matter and is mainly scattering. Absorption of solar radiation by carbonaceous aerosols may heat the atmosphere, thereby altering the vertical temperature profile, while scattering of solar radiation may lead to a net cooling of the atmosphere/ocean system. Carbonaceous aerosols may also enhance the concentrations of cloud condensation nuclei. This paper summarizes observed concentrations of aerosols in remote continental and marine locations and provides estimates for the fine particle (D < 2.5 {mu}m) source rates of both OC and BC. The source rates for anthropogenic organic aerosols may be as large as the source rates for anthropogenic sulfate aerosols, suggesting a similar magnitude of direct forcing of climate. The role of BC in decreasing the amount of reflected solar radiation by OC and sulfates is discussed. The total estimated forcing depends on the source estimates for organic and black carbon aerosols which are highly uncertain. The role of organic aerosols acting as cloud condensation nuclei (CCN) is also described.

  16. Secondary organic aerosol formation and primary organic aerosol oxidation from biomass burning smoke in a flow reactor during FLAME-3

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Day, D. A.; Cubison, M. J.; Brune, W. H.; Bon, D.; de Gouw, J. A.; Jimenez, J. L.

    2013-05-01

    We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A potential aerosol mass "PAM" flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~ 1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days aging in the atmosphere. VOC observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in an total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net SOA to POA ratio of biomass burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OHexp), typically peaking around three days of equivalent atmospheric photochemical age (OHexp ~ 3.9 × 1011 molecules cm-3 s-1), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors. The mass of SOA formed often exceeds the mass of the known VOC precursors, indicating the likely importance of primary semivolatile/intermediate volatility

  17. Characterisation of regional ambient biomass burning organic aerosol mixing ratios

    NASA Astrophysics Data System (ADS)

    Jolleys, M.; Coe, H.; McFiggans, G.; Capes, G.; Allan, J. D.; Crosier, J.; Williams, P.; Allen, G.; Bower, K.; Jimenez, J. L.; Russell, L. M.; Grutter, M.; Baumgardner, D.

    2012-12-01

    No evidence for a regional additional source of secondary organic aerosol (SOA) has been identified in measurements of biomass burning-influenced ambient air masses. Measurements included in this study were obtained from the deployment of an Aerodyne Quadrupole Aerosol Mass Spectrometer during four field campaigns, involving both research aircraft flights and ground-based measurements. OA concentrations normalised to excess CO (OA/dCO) show strong regional and local scale variability, with a difference of almost a factor of five across fresh OA emissions between campaigns. Average OA/dCO is typically higher in the near-field than at a greater distance from source, indicating an absence of significant SOA formation, despite evidence to suggest OA becomes increasingly oxidized with age. This trend is in contrast with observations of anthropogenic OA in urban environments, where OA/dCO is consistently shown to increase with distance from source. There is no such agreement in the case of biomass burning OA (BBOA) amongst the literature base, with conflicting examples relating to the influence of SOA on aerosol loadings. A wide range of average initial emission ratios (ERs) close to source are observed both within the datasets analysed here and within the literature, together with considerable variability in individual OA/dCO values throughout fresh biomass burning plumes. The extent of this variability far outweighs any increase in OA/dCO in the few instances it is observed here, suggesting that source conditions are of greater importance for the propagation of BBOA loadings within the ambient atmosphere. However, the implications of ageing on OA/dCO variability appear to be highly uncertain, with little consistency between observed trends for different locations. Furthermore, the exact effects of the fire conditions influencing emissions from biomass burning events remain poorly constrained. These uncertainties regarding the evolution of biomass burning emissions

  18. Hydroxyl radicals from secondary organic aerosol decomposition in water

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  19. Hydroxyl radicals from secondary organic aerosol decomposition in water

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  20. Hydroxyl radicals from secondary organic aerosol decomposition in water

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  1. Evaluation of one-dimensional and two-dimensional volatility basis sets in simulating the aging of secondary organic aerosol with smog-chamber experiments.

    PubMed

    Zhao, Bin; Wang, Shuxiao; Donahue, Neil M; Chuang, Wayne; Hildebrandt Ruiz, Lea; Ng, Nga L; Wang, Yangjun; Hao, Jiming

    2015-02-17

    We evaluate the one-dimensional volatility basis set (1D-VBS) and two-dimensional volatility basis set (2D-VBS) in simulating the aging of SOA derived from toluene and α-pinene against smog-chamber experiments. If we simulate the first-generation products with empirical chamber fits and the subsequent aging chemistry with a 1D-VBS or a 2D-VBS, the models mostly overestimate the SOA concentrations in the toluene oxidation experiments. This is because the empirical chamber fits include both first-generation oxidation and aging; simulating aging in addition to this results in double counting of the initial aging effects. If the first-generation oxidation is treated explicitly, the base-case 2D-VBS underestimates the SOA concentrations and O:C increase of the toluene oxidation experiments; it generally underestimates the SOA concentrations and overestimates the O:C increase of the α-pinene experiments. With the first-generation oxidation treated explicitly, we could modify the 2D-VBS configuration individually for toluene and α-pinene to achieve good model-measurement agreement. However, we are unable to simulate the oxidation of both toluene and α-pinene with the same 2D-VBS configuration. We suggest that future models should implement parallel layers for anthropogenic (aromatic) and biogenic precursors, and that more modeling studies and laboratory research be done to optimize the "best-guess" parameters for each layer.

  2. Evaluation of one-dimensional and two-dimensional volatility basis sets in simulating the aging of secondary organic aerosol with smog-chamber experiments.

    PubMed

    Zhao, Bin; Wang, Shuxiao; Donahue, Neil M; Chuang, Wayne; Hildebrandt Ruiz, Lea; Ng, Nga L; Wang, Yangjun; Hao, Jiming

    2015-02-17

    We evaluate the one-dimensional volatility basis set (1D-VBS) and two-dimensional volatility basis set (2D-VBS) in simulating the aging of SOA derived from toluene and α-pinene against smog-chamber experiments. If we simulate the first-generation products with empirical chamber fits and the subsequent aging chemistry with a 1D-VBS or a 2D-VBS, the models mostly overestimate the SOA concentrations in the toluene oxidation experiments. This is because the empirical chamber fits include both first-generation oxidation and aging; simulating aging in addition to this results in double counting of the initial aging effects. If the first-generation oxidation is treated explicitly, the base-case 2D-VBS underestimates the SOA concentrations and O:C increase of the toluene oxidation experiments; it generally underestimates the SOA concentrations and overestimates the O:C increase of the α-pinene experiments. With the first-generation oxidation treated explicitly, we could modify the 2D-VBS configuration individually for toluene and α-pinene to achieve good model-measurement agreement. However, we are unable to simulate the oxidation of both toluene and α-pinene with the same 2D-VBS configuration. We suggest that future models should implement parallel layers for anthropogenic (aromatic) and biogenic precursors, and that more modeling studies and laboratory research be done to optimize the "best-guess" parameters for each layer. PMID:25581402

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

    PubMed

    Ehn, Mikael; Thornton, Joel A; Kleist, Einhard; Sipilä, Mikko; Junninen, Heikki; Pullinen, Iida; Springer, Monika; Rubach, Florian; Tillmann, Ralf; Lee, Ben; Lopez-Hilfiker, Felipe; Andres, Stefanie; Acir, Ismail-Hakki; Rissanen, Matti; Jokinen, Tuija; Schobesberger, Siegfried; Kangasluoma, Juha; Kontkanen, Jenni; Nieminen, Tuomo; Kurtén, Theo; Nielsen, Lasse B; Jørgensen, Solvejg; Kjaergaard, Henrik G; Canagaratna, Manjula; Maso, Miikka Dal; Berndt, Torsten; Petäjä, Tuukka; Wahner, Andreas; Kerminen, Veli-Matti; Kulmala, Markku; Worsnop, Douglas R; Wildt, Jürgen; Mentel, Thomas F

    2014-02-27

    Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar 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 at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

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

    PubMed

    Ehn, Mikael; Thornton, Joel A; Kleist, Einhard; Sipilä, Mikko; Junninen, Heikki; Pullinen, Iida; Springer, Monika; Rubach, Florian; Tillmann, Ralf; Lee, Ben; Lopez-Hilfiker, Felipe; Andres, Stefanie; Acir, Ismail-Hakki; Rissanen, Matti; Jokinen, Tuija; Schobesberger, Siegfried; Kangasluoma, Juha; Kontkanen, Jenni; Nieminen, Tuomo; Kurtén, Theo; Nielsen, Lasse B; Jørgensen, Solvejg; Kjaergaard, Henrik G; Canagaratna, Manjula; Maso, Miikka Dal; Berndt, Torsten; Petäjä, Tuukka; Wahner, Andreas; Kerminen, Veli-Matti; Kulmala, Markku; Worsnop, Douglas R; Wildt, Jürgen; Mentel, Thomas F

    2014-02-27

    Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar 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 at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally. PMID:24572423

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

    NASA Astrophysics Data System (ADS)

    Ehn, Mikael; Thornton, Joel A.; Kleist, Einhard; Sipilä, Mikko; Junninen, Heikki; Pullinen, Iida; Springer, Monika; Rubach, Florian; Tillmann, Ralf; Lee, Ben; Lopez-Hilfiker, Felipe; Andres, Stefanie; Acir, Ismail-Hakki; Rissanen, Matti; Jokinen, Tuija; Schobesberger, Siegfried; Kangasluoma, Juha; Kontkanen, Jenni; Nieminen, Tuomo; Kurtén, Theo; Nielsen, Lasse B.; Jørgensen, Solvejg; Kjaergaard, Henrik G.; Canagaratna, Manjula; Maso, Miikka Dal; Berndt, Torsten; Petäjä, Tuukka; Wahner, Andreas; Kerminen, Veli-Matti; Kulmala, Markku; Worsnop, Douglas R.; Wildt, Jürgen; Mentel, Thomas F.

    2014-02-01

    Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar 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 at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    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.

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

    SciTech Connect

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

    2007-10-16

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

  8. Formation of halogen-induced secondary organic aerosol (XOA)

    NASA Astrophysics Data System (ADS)

    Kamilli, Katharina; Ofner, Johannes; Zetzsch, Cornelius; Held, Andreas

    2013-04-01

    Reactive halogen species (RHS) are very important due to their potential of stratospheric ozone depletion and surface ozone destruction. RHS seem to interact with precursors of secondary organic aerosol (SOA) similarly to common atmospheric oxidants like OH radicals and ozone. The potential interaction of RHS with preformed SOA has recently been studied (Ofner et al., 2012). Although aerosol formation from reaction of RHS with typical SOA precursors was previously studied (e.g. Cai et al., 2006), no data are available on bromine-induced aerosol formation from organic precursors yet. An aerosol smog-chamber was used to examine the halogen-induced secondary organic aerosol (XOA) formation under atmospheric conditions using simulated sunlight. With a concentration of 10 ppb for the organic precursor, 2 ppb for molecular chlorine, and 10 ppb for molecular bromine, the experimental setup is close to ambient conditions. By combined measurements of the aerosol size distribution, ozone and NOx mixing ratios, as well as the decay of the organic precursor, aerosol yields and aerosol growth rates were determined. The decay of the organic precursor was analyzed by capillary gas chromatography coupled with flame-ionization detection (GC-FID) and the aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS). Additionally, with the decay rate of the precursor and the calculated photolysis rates of molecular halogen species, based on the well-known spectrum of the solar simulator, mechanistic details on the XOA formation pathways can be determined. We observed XOA formation even at very low precursor and RHS concentrations with a diameter mode at 10-20 nm and a number concentration up to 1000000 particles cm-3. While the XOA formation from chlorine is very rapid, the interaction of bromine with the organic precursors is about five times slower. The aerosol yield reached maximum values of 0.01 for the reaction of chlorine with α-pinene and 0.0004 for

  9. Organic Aerosol Component (OACOMP) Value-Added Product Report

    SciTech Connect

    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. Is benzene a precursor for secondary organic aerosol?

    PubMed

    Martín-Reviejo, Montserrat; Wirtz, Klaus

    2005-02-15

    It is currently assumed that benzene contributes only negligibly to secondary organic aerosol formation in the atmosphere. Our understanding of the capacity of benzene to generate secondary aerosols is based on the work of Izumi and Fukuyama (Atmos. Environ. 1990, 24A, 1433) in which two photosmog experiments with benzene in the presence of NOx were performed and no particle formation was observed. In contrast to the observations of Izumi and Fukuyama, experiments performed in the EUPHORE large outdoor simulation chamber have clearly shown aerosol formation during the photochemical oxidation of benzene in various NOx regimes. The maximum aerosol yields of 8-25% on a mass basis are comparable to yields obtained during the photochemical oxidation of other aromatic compounds under similar conditions. In addition, a density of 1.35+/-0.04 g/cm3 for the secondary organic aerosol from the benzene photochemical oxidation in the presence of NOx has been determined through the simultaneous measurement of aerosol volume and aerosol mass using two independent measurement techniques. Comparing the results in the present work with previous findings underscores the strong influence that the NOx content in the system has on aerosol formation during the photochemical oxidation of aromatic hydrocarbons and the importance of performing experiments with NOx concentrations relevant to the atmosphere.

  11. Ice Nucleation Properties of Amospherically Aged Biomass Burning Aerosol

    NASA Astrophysics Data System (ADS)

    Polen, M.; Lawlis, E.; Sullivan, R. C.

    2015-12-01

    Biomass burning can sometimes emit surprisingly active ice nucleating particles, though these emissions are not at all consistent between biomass fuel sources and burns. Soot from biomass combustion has been attributed to some but not all of the ice nucleating potential of biomass burning aerosol (BBA), while fossil fuel combustion soot emits very weak ice nucleants. The causes of the sometimes significant but variable ice nucleating ability of BBA are still largely unknown. BBA experiences significant atmospheric aging as the plume evolves and mixes with background air, yet almost no reports exploring the effects of atmospheric aging on the freezing properties of BBA have been made. We have performed some of the first experiments to determine the effects of simulated atmospheric aging on these ice nucleation properties, using a chamber reactor. The fresh and aged BBA was collected for subsequent droplet freezing array analysis using an impinger sampler to collect aerosol in water, and by deposition onto substrates in a MOUDI sampler. Droplets containing the chamber particles were then suspended in oil on a cold plate for freezing temperature spectrum measurement. Aging of Sawgrass flaming-phase combustion BBA by exposure to hydroxyl radicals (from H2O2 photolysis) enhanced the ice nucleation ability, observed by a shift to warmer droplet freezing temperatures by ~2-3°C. The changes in the aerosol's chemical composition during aging were observed using a laser ablation single-particle mass spectrometer and a soot-particle aerosol mass spectrometer. We will report our observations of the effects of other types of simulated aging (including photochemistry under high and low NOx conditions, dark ozonolysis, and nitric acid exposure) on Sawgrass and BBA from other grass and palm fuels.

  12. Investigating water soluble organic aerosols: Sources and evolution

    NASA Astrophysics Data System (ADS)

    Hecobian, Arsineh N.

    Many studies are being conducted on the different properties of organic aerosols (OA-s) as it is first emitted into the atmosphere and the consequent changes in these characteristics as OA-s age and secondary organic aerosol (SOA) is produced and in turn aged. This thesis attempts to address some of the significant and emerging issues that deal with the formation and transformation of water-soluble organic aerosols in the atmosphere. First, a proven method for the measurement of gaseous sulfuric acid, negative ion chemical ionization mass spectrometry (CIMS), has been modified for fast and sensitive measurements of particulate phase sulfuric acid (i.e. sulfate). The modifications implemented on this system have also been the subject of preliminary verifications for measurements of aerosol phase oxalic acid (an organic acid). Second, chemical and physical characteristics of a wide range of biomass-burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS experiment are presented here. A statistical summary of the emission (or enhancement) ratios relative to carbon monoxide is presented for various gaseous and aerosol species. Extensive investigations of fire plume evolutions were undertaken during the second part of this field campaign. For four distinct Boreal fires, where plumes were intercepted by the aircraft over a wide range of down-wind distances, emissions of various compounds and the effect of aging on them were investigated in detail. No clear evidence of production of secondary compounds (e.g., WSOC and OA) was observed. High variability in emissions between the different plumes may have obscured any clear evidence of changes in the mass of various species with increasing plume age. Also, the lack if tropospheric oxidizing species (e.g., O3 and OH) may have contributed to the lack of SOA formation. Individual intercepts of smoke plumes in this study were segregated by source regions. The normalized excess mixing

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  14. a Study of the Origin of Atmospheric Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Hildemann, Lynn Mary

    1990-01-01

    The sources of ambient organic particulate matter in urban areas are investigated through a program of emission source measurements, atmospheric measurements, and mathematical modeling of source/receptor relationships. A dilution sampler intended to collect fine organic aerosol from combustion sources is designed to simulate atmospheric cooling and dilution processes, so that organic vapors which condense under ambient conditions will be collected as particulate matter. This system is used to measure the emissions from a boiler burning distillate oil, a home fireplace, catalyst and noncatalyst automobiles, heavy-duty diesel trucks, natural gas home appliances, and meat cooking operations. Alternate techniques are used to sample the particulate matter emitted from cigarette smoking, a roofing tar pot, paved road dust, brake lining wear, tire wear, and vegetative detritus. The bulk chemical characteristics of the fine aerosol fraction are presented for each source. Over half of the fine aerosol mass emitted from automobiles, wood burning, meat cooking, home appliances, cigarettes, and tar pots is shown to consist of organic compounds. The organic material collected from these sources is analyzed using high-resolution gas chromatography. Using a simple analytical protocol, a quantitative, 50-parameter characterization of the elutable fine organic aerosol emitted from each source type is obtained, which proves to be a unique fingerprint that can be used to distinguish most sources from each other. A mathematical model is used to predict the characteristics of fine ambient organic aerosol in the Los Angeles area that would prevail if the primary organic emissions are transported without chemical reaction. The model is found to track the seasonal variations observed in the ambient aerosol at the three sites studied. Emissions from vehicles and fireplaces are identified as significant sources of solvent-extractable organic aerosol. Differences between the model

  15. Organic nitrate aerosol formation via NO3 + biogenic volatile organic compounds in the southeastern United States

    NASA Astrophysics Data System (ADS)

    Ayres, B. R.; Allen, H. M.; Draper, D. C.; Brown, S. S.; Wild, R. J.; Jimenez, J. L.; Day, D. A.; Campuzano-Jost, P.; Hu, W.; de Gouw, J.; Koss, A.; Cohen, R. C.; Duffey, K. C.; Romer, P.; Baumann, K.; Edgerton, E.; Takahama, S.; Thornton, J. A.; Lee, B. H.; Lopez-Hilfiker, F. D.; Mohr, C.; Wennberg, P. O.; Nguyen, T. B.; Teng, A.; Goldstein, A. H.; Olson, K.; Fry, J. L.

    2015-12-01

    Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOCs) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that a nitrate radical (NO3) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO3 to terpenes are correlated with increase in gas- and aerosol-organic nitrate concentrations made during the campaign. Correlation of NO3 radical consumption to organic nitrate aerosol formation as measured by aerosol mass spectrometry and thermal dissociation laser-induced fluorescence suggests a molar yield of aerosol-phase monoterpene nitrates of 23-44 %. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to BVOCs and show C10H17NO5, likely a hydroperoxy nitrate, is a major nitrate-oxidized terpene product being incorporated into aerosols. The comparable isoprene product C5H9NO5 was observed to contribute less than 1 % of the total organic nitrate in the aerosol phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45 % of the NOy budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO3 uptake produced nitrate aerosol mass loading at a rate comparable to that of organic nitrate produced via NO3 + BVOCs.

  16. Redox activity of naphthalene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    Chamber secondary organic aerosol (SOA) from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. Similar attempts to predict redox behaviour of oxidised two-stroke engine exhaust particles by measuring 1,2-naphthoquinone, 1,4-naphthoquinone and 9,10-phenanthrenequinone predicted DTT decay rates only 4.9 ± 2.5% of those observed. Together, these results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10-4 m3 μg-1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. As well, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

  17. Quantitative estimates of the volatility of ambient organic aerosol

    NASA Astrophysics Data System (ADS)

    Cappa, C. D.; Jimenez, J. L.

    2010-01-01

    Measurements of the sensitivity of organic aerosol (OA, and its components) mass to changes in temperature were recently reported by Huffman et al. (2009) using a tandem thermodenuder-aerosol mass spectrometer (TD-AMS) system in Mexico City and the Los Angeles area. Here, we use these measurements to derive quantitative estimates of aerosol volatility within the framework of absorptive partitioning theory using a kinetic model of aerosol evaporation in the TD. OA volatility distributions (or "basis-sets") are determined using several assumptions as to the enthalpy of vaporization (ΔHvap). We present two definitions of "non-volatile OA," one being a global and one a local definition. Based on these definitions, our analysis indicates that a substantial fraction of the organic aerosol is comprised of non-volatile components that will not evaporate under any atmospheric conditions, on the order of 50-80% when the most realistic ΔHvap assumptions are considered. The sensitivity of the total OA mass to dilution and ambient changes in temperature has been assessed for the various ΔHvap assumptions. The temperature sensitivity is relatively independent of the particular ΔHvap assumptions whereas dilution sensitivity is found to be greatest for the low (ΔHvap = 50 kJ/mol) and lowest for the high (ΔHvap = 150 kJ/mol) assumptions. This difference arises from the high ΔHvap assumptions yielding volatility distributions with a greater fraction of non-volatile material than the low ΔHvap assumptions. If the observations are fit using a 1 or 2-component model the sensitivity of the OA to dilution is unrealistically high. An empirical method introduced by Faulhaber et al. (2009) has also been used to independently estimate a volatility distribution for the ambient OA and is found to give results consistent with the high and variable ΔHvap assumptions. Our results also show that the amount of semivolatile gas-phase organics in equilibrium with the OA could range from ~20

  18. Quantitative estimates of the volatility of ambient organic aerosol

    NASA Astrophysics Data System (ADS)

    Cappa, C. D.; Jimenez, J. L.

    2010-06-01

    Measurements of the sensitivity of organic aerosol (OA, and its components) mass to changes in temperature were recently reported by Huffman et al.~(2009) using a tandem thermodenuder-aerosol mass spectrometer (TD-AMS) system in Mexico City and the Los Angeles area. Here, we use these measurements to derive quantitative estimates of aerosol volatility within the framework of absorptive partitioning theory using a kinetic model of aerosol evaporation in the TD. OA volatility distributions (or "basis-sets") are determined using several assumptions as to the enthalpy of vaporization (ΔHvap). We present two definitions of "non-volatile OA," one being a global and one a local definition. Based on these definitions, our analysis indicates that a substantial fraction of the organic aerosol is comprised of non-volatile components that will not evaporate under any atmospheric conditions; on the order of 50-80% when the most realistic ΔHvap assumptions are considered. The sensitivity of the total OA mass to dilution and ambient changes in temperature has been assessed for the various ΔHvap assumptions. The temperature sensitivity is relatively independent of the particular ΔHvap assumptions whereas dilution sensitivity is found to be greatest for the low (ΔHvap = 50 kJ/mol) and lowest for the high (ΔHvap = 150 kJ/mol) assumptions. This difference arises from the high ΔHvap assumptions yielding volatility distributions with a greater fraction of non-volatile material than the low ΔHvap assumptions. If the observations are fit using a 1 or 2-component model the sensitivity of the OA to dilution is unrealistically high. An empirical method introduced by Faulhaber et al. (2009) has also been used to independently estimate a volatility distribution for the ambient OA and is found to give results consistent with the high and variable ΔHvap assumptions. Our results also show that the amount of semivolatile gas-phase organics in equilibrium with the OA could range from ~20

  19. Visibility-reducing organic aerosols in the vicinity of Grand Canyon National Park: 2. Molecular composition

    SciTech Connect

    Mazurek, M.A.; Newman, L.; Daum, P.H.

    1995-12-31

    In this study we examine the molecular organic constituents (C8 to C40 lipid compounds) collected as aerosol from two sites located in Grand Canyon National Park during summer ambient conditions. Of special interest are molecular species which serve as tracers for possible sources of the observed aerosol organic matter. Ambient samples were collected from Hopi Point (rim site) and from Indian Gardens (in-canyon site) as fine (dp< 2.1 =B5m) and total particle samples. The samples were grouped into fine particle and total particle monthly composites to provide sufficient material for molecular marker analysis then analyzed by capillary gas chromatography/mass spectrometry (GUMS), The molecular constituents of each aerosol composite were screened for key tracer compounds using a computerized data reduction method that was based on molecular ion fragment identification. Comparisons were made to a reference database that included molecular information obtained from authentic sources of primary organic aerosol emissions. Emission sources studied included vehicular exhaust, as well as local sources at the Grand Canyon which included soil dust, wood smoke, and particles from vegetation indigenous to the two Grand Canyon sampling sites. Our results show that summertime ambient aerosols contain many organic molecular compounds which can be related directly to the local vegetation. Another major component found in all samples consists of highly oxidized organic species which are not emitted directly from local primary organic aerosol source types. These oxidized species are thought to be secondary organic aerosols that originate from photochemical transformations involving either locally emitted primary organic compounds or transported aged emissions from source regions upwind of the Grand Canyon.

  20. Apportionment of Primary and Secondary Organic Aerosols in Southern California During the 2005 Study of Organic Aerosols in Riverside (SOAR-1)

    EPA Science Inventory

    Ambient sampling was conducted in Riverside, California during the 2005 Study of Organic Aerosols in Riverside to characterize the composition and sources of organic aerosol using a variety of state-of-the-art instrumentation and source apportionment techniques.

  1. Sources and components of organic aerosols in Central Europe

    NASA Astrophysics Data System (ADS)

    Lanz, V. A.; Prévôt, A. S. H.; Alfarra, M. R.; Hüglin, C.; Mohr, C.; Weimer, S.; Baltensperger, U.

    2009-04-01

    The quadrupole version of the Aerodyne Aerosol Mass Spectrometer (q-AMS) was deployed at several places in Switzerland, Austria, and Liechtenstein. The q-AMS provides real-time information on mass concentration and composition of the non-refractory species in particulate matter smaller than 1 µm (NR-PM1) with high time- and size-resolution at unit mass resolution. The combination of factor analysis and ambient AMS data represents a relatively new approach to identify organic aerosol (OA) sources/components (Zhang et al., 2005). In this study, such an approach (PMF - positive matrix factorization; Lanz et al., 2007, 2008) was applied to various OA data sets covering a wide range of pollution levels (mobile measurements on motorways, urban, rural, and even a high-alpine location) as well as all seasons of the year. Dominating aerosol components were representing oxygenated and secondary organic aerosol (OOA-I and OOA-II), primary particles from wood burning (P-BBOA; especially in residential areas in wintertime with abundances of ~50% OA and more) and primary traffic-related aerosols (usually ~10% of OA, but up to 60% on motorways). Close to sources, charbroiling and potentially food cooking aerosols could be distinguished as well. The OOAs' time series were compared to measurements of AMS inorganics (sulphate, nitrate, and ammonium) in order to facilitate their interpretation as secondary OA (SOA). Diurnal cycles of the estimated source strengths, ancillary gas-phase and meteorological data, estimated emission ratios etc. were also used to validate the interpretations of the factor analytical results. Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., and Prévôt, A. S. H.: Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra, Atmos. Chem. Phys., 7, 1503-1522, 2007, http://www.atmos-chem-phys.net/7/1503/2007/. Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B

  2. New Particle Formation and Secondary Organic Aerosol in Beijing

    NASA Astrophysics Data System (ADS)

    Hu, M.; Yue, D.; Guo, S.; Hu, W.; Huang, X.; He, L.; Wiedensohler, A.; Zheng, J.; Zhang, R.

    2011-12-01

    Air pollution in Beijing has been a major concern due to being a mega-city and green Olympic Games requirements. Both long term and intensive field measurements have been conducted at an Urban Air Quality Monitoring Station in the campus of Peking University since 2004. Aerosol characteristics vary seasonally depending on meteorological conditions and source emissions. Secondary compositions of SNA (sum of sulfate, nitrate, and ammonium) and SOA (secondary organic aerosol) become major fraction of fine particles, which may enhance aerosol impacts on visibility and climate change. The transformation processes of new particle formation (NPF) and secondary organic aerosol have been focused on. It was found that gaseous sulfuric acid, ammonia, and organic compounds are important precursors to NPF events in Beijing and H2SO4-NH3-H2O ternary nucleation is one of the important mechanisms. The contributions of condensation and neutralization of sulfuric acid, coagulation, and organics to the growth of the new particles are estimated as 45%, 34%, and 21%, respectively. Tracer-based method to estimate biogenic and anthropogenic SOA was established by using gas chromatography-mass spectrometry. Secondary organic tracers derived from biogenic (isoprene, α-pinene, β-caryophyllene) and anthropogenic (toluene) contributed 32% at urban site and 35% at rural site, respectively. Other source apportionment techniques were also used to estimate secondary organic aerosols, including EC tracer method, water soluble organic carbon content, chemical mass balance model, and AMS-PMF method.

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

    NASA Technical Reports Server (NTRS)

    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.

  4. Effect of photosensitized chemistry on organic aerosol evolution

    NASA Astrophysics Data System (ADS)

    Rouvière, A.; Decarlo, P. F.; Bartels-Rausch, T.; Ammann, M.

    2009-12-01

    Photochemistry in aerosol particles is an emerging new field of atmospheric science. Up to now, photochemical processes in the condensed phase of atmospheric aerosol particles are not well understood. Primary and secondary compounds in the gas and aerosol phase continuously interact and change phase during their or their descendants life time in the atmosphere. Partially oxised aromatic compounds such as aromatic ketones may act as photosensitizer to promote charge and energy transfer to other organic compounds under conditions, where direct photolysis processes of the latter are not possible. The resulting radicals undergo numerous secondary chemical reactions, some of which may lead to polymerization. In this study we show that the presence of a photosensitizer in the aerosol phase leads to significant processing of simple organic compounds such as small organic acids due to exposure to simulated sunlight. The aerosol flow tube experiments were performed in a photoreactor, which was coupled to a chemical ionization mass spectrometer and a scanning mobility particle sizer. For some experiments an aerosol mass spectrometer was also used. We used ammonium sulfate and organic acids as matrix and Benzoyl Benzoic Acid (BBA) as sensitizer. BBA is a well known photosensitizer absorbing in the UV. The results will be shown and discussed.

  5. Evaluating Organic Aerosol Model Performance: Impact of two Embedded Assumptions

    NASA Astrophysics Data System (ADS)

    Jiang, W.; Giroux, E.; Roth, H.; Yin, D.

    2004-05-01

    Organic aerosols are important due to their abundance in the polluted lower atmosphere and their impact on human health and vegetation. However, modeling organic aerosols is a very challenging task because of the complexity of aerosol composition, structure, and formation processes. Assumptions and their associated uncertainties in both models and measurement data make model performance evaluation a truly demanding job. Although some assumptions are obvious, others are hidden and embedded, and can significantly impact modeling results, possibly even changing conclusions about model performance. This paper focuses on analyzing the impact of two embedded assumptions on evaluation of organic aerosol model performance. One assumption is about the enthalpy of vaporization widely used in various secondary organic aerosol (SOA) algorithms. The other is about the conversion factor used to obtain ambient organic aerosol concentrations from measured organic carbon. These two assumptions reflect uncertainties in the model and in the ambient measurement data, respectively. For illustration purposes, various choices of the assumed values are implemented in the evaluation process for an air quality model based on CMAQ (the Community Multiscale Air Quality Model). Model simulations are conducted for the Lower Fraser Valley covering Southwest British Columbia, Canada, and Northwest Washington, United States, for a historical pollution episode in 1993. To understand the impact of the assumed enthalpy of vaporization on modeling results, its impact on instantaneous organic aerosol yields (IAY) through partitioning coefficients is analysed first. The analysis shows that utilizing different enthalpy of vaporization values causes changes in the shapes of IAY curves and in the response of SOA formation capability of reactive organic gases to temperature variations. These changes are then carried into the air quality model and cause substantial changes in the organic aerosol modeling

  6. Combined effects of organic aerosol loading and fog processing on organic aerosols oxidation and composition

    NASA Astrophysics Data System (ADS)

    Chakraborty, Abhishek; Tripathi, Sachchida; Gupta, Tarun

    2016-04-01

    Fog is a natural meteorological phenomenon that occurs throughout the world, it contains substantial quantity of liquid water and generally seen as a natural cleansing agent but it also has the potential to form highly oxidized secondary organic aerosols (SOA) via aqueous processing of ambient aerosols. On the other hand higher organic aerosols (OA) loading tend to decrease the overall oxidation level (O/C) of the particle phase organics, due to enhanced partitioning of less oxidized organics from gas to particle phase. However, combined impact of these two parameters; aqueous oxidation and OA loading, on the overall oxidation ratio (O/C) of ambient OA has never been studied. To assess this, real time ambient sampling using HR-ToF-AMS was carried out at Kanpur, India from 15 December 2014 - 10 February 2015. In first 3 weeks of this campaign, very high OA loading is (134 ± 42 μg/m3) observed (termed as high loading or HL period) while loading is substantially reduced from 2nd January, 2016 (56 ± 20 μg/m3, termed as low loading or LL period) . However, both the loading period was affected by several fog episodes (10 in HL and 7 in LL), thus providing the opportunity of studying the combined effects of fog and OA loading on OA oxidation. It is found that O/C ratio is very strongly anti-correlated with OA loading in both the loading period, however, slope of this ant-correlation is much steep during HL period than in LL period. Source apportionment of OA revealed that there is drastic change in the types of OA from HL to LL period, clearly indicating difference in OA composition from HL to LL period. During foggy night continuous oxidation of OA is observed from early evening to early morning with 15-20% enhancement in O/C ratio, while the same is absent during non-foggy period, clearly indicating the efficient fog processing of ambient OA. It is also found that night time fog aqueous oxidation can be as effective as daytime photo chemistry in oxidation of OA. Fog

  7. On the source of organic acid aerosol layers above clouds.

    PubMed

    Sorooshian, Armin; Lu, Miao-Ling; Brechtel, Fred J; Jonsson, Haflidi; Feingold, Graham; Flagan, Richard C; Seinfeld, John H

    2007-07-01

    During the July 2005 Marine Stratus/Stratocumulus Experiment (MASE) and the August-September 2006 Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS), the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter probed aerosols and cumulus clouds in the eastern Pacific Ocean off the coast of northern California and in southeastern Texas, respectively. An on-board particle-into-liquid sampler (PILS) quantified inorganic and organic acid species with < or = 5-min time resolution. Ubiquitous organic aerosol layers above cloud with enhanced organic acid levels were observed in both locations. The data suggest that aqueous-phase reactions to produce organic acids, mainly oxalic acid, followed by droplet evaporation is a source of elevated organic acid aerosol levels above cloud. Oxalic acid is observed to be produced more efficiently relative to sulfate as the cloud liquid water content increases, corresponding to larger and less acidic droplets. As derived from large eddy simulations of stratocumulus underthe conditions of MASE, both Lagrangian trajectory analysis and diurnal cloudtop evolution provide evidence that a significant fraction of the aerosol mass concentration above cloud can be accounted for by evaporated droplet residual particles. Methanesulfonate data suggest that entrainment of free tropospheric aerosol can also be a source of organic acids above boundary layer clouds.

  8. Water soluble organic constituents in Arctic aerosols and snow pack

    SciTech Connect

    Li, Shaomeng ); Winchester, J.W. )

    1993-01-08

    Eight water-soluble organic anions were measured in 70 aerosol samples and 10 snow samples at Barrow, Alaska in March-April, 1989. The ranking of the ions in aerosols according to total (coarse + fine aerosol) median concentrations was acetate (44 ng m[sup [minus]3]), oxalate (27), benzoate (23), formate (22), propionate (6), methanesulfonate (5), lactate (4), and pyruvate (4). When added up, the median organic anion mass was 156 ng m[sup [minus]3]. The organic anions/nssSO[sub 4][sup =] mass ratio had a median of 0.18 and 0.07 in the coarse (>1 [mu]m) and fine (<1 [mu]m) size fractions, respectively, but can be very high on occasions. On average, the organic anions made up more than 10% of the water-soluble aerosol mass. A similar ranking in concentration was also found for the organic ions in the snow pack samples. The organic anion/nssSO[sub 4][sup =] mass ratio in these samples was >0.5, substantially higher than in aerosols. 18 refs., 2 tabs.

  9. Research highlights: laboratory studies of the formation and transformation of atmospheric organic aerosols.

    PubMed

    Borduas, Nadine; Lin, Vivian S

    2016-04-01

    Atmospheric particles are emitted from a variety of anthropogenic and natural precursors and have direct impacts on climate, by scattering solar irradiation and nucleating clouds, and on health, by causing oxidative stress in the lungs when inhaled. They may also form from gaseous precursors, creating complex mixtures of organic and inorganic material. The chemical composition and the physical properties of aerosols will evolve during their one-week lifetime which will consequently change their impact on climate and health. The heterogeneity of aerosols is difficult to model and thus atmospheric aerosol research strives to characterize the mechanisms involved in nucleating and transforming particles in the atmosphere. Recent advances in four laboratory studies of aerosol formation and aging are highlighted here.

  10. Secondary organic aerosol from biogenic volatile organic compound mixtures

    NASA Astrophysics Data System (ADS)

    Hatfield, Meagan L.; Huff Hartz, Kara E.

    2011-04-01

    The secondary organic aerosol (SOA) yields from the ozonolysis of a Siberian fir needle oil (SFNO), a Canadian fir needle oil (CFNO), and several SOA precursor mixtures containing reactive and non-reactive volatile organic compounds (VOCs) were investigated. The use of precursor mixtures more completely describes the atmosphere where many VOCs exist. The addition of non-reactive VOCs such as bornyl acetate, camphene, and borneol had very little to no effect on SOA yields. The oxidation of VOC mixtures with VOC mass percentages similar to the SFNO produced SOA yields that became more similar to the SOA yield from SFNO as the complexity and concentration of VOCs within the mixture became more similar to overall SFNO composition. The SOA yield produced by the oxidation of CFNO was within the error of the SOA yield produced by the oxidation of SFNO at a similar VOC concentration. The SOA yields from SFNO were modeled using the volatility basis set (VBS), which predicts the SOA yields for a given mass concentration of mixtures containing similar VOCs.

  11. Organic Aerosol Volatility Parameterizations and Their Impact on Atmospheric Composition and Climate

    NASA Technical Reports Server (NTRS)

    Tsigaridis, Kostas; Bauer, Susanne E.

    2015-01-01

    Despite their importance and ubiquity in the atmosphere, organic aerosols are still very poorly parameterized in global models. This can be explained by two reasons: first, a very large number of unconstrained parameters are involved in accurate parameterizations, and second, a detailed description of semi-volatile organics is computationally very expensive. Even organic aerosol properties that are known to play a major role in the atmosphere, namely volatility and aging, are poorly resolved in global models, if at all. Studies with different models and different parameterizations have not been conclusive on whether the additional complexity improves model simulations, but the added diversity of the different host models used adds an unnecessary degree of variability in the evaluation of results that obscures solid conclusions. Aerosol microphysics do not significantly alter the mean OA vertical profile or comparison with surface measurements. This might not be the case for semi-volatile OA with microphysics.

  12. Chemical characteristics of organic aerosols in Algiers city area: influence of a fat manufacture plant

    NASA Astrophysics Data System (ADS)

    Yassaa, Noureddine; Meklati, Brahim Youcef; Cecinato, Angelo

    Total concentrations and homologue distributions of organic fraction constituents have been determined in particulate matter emitted from different units of a fat manufacturer (i.e. oils refining and conditioning plants, and production and conditioning units of a soap industry) located in Algiers area, as well as in atmospheric aerosols. In particular n-alkanes, n-alkanoic and n-alkenoic acids, n-alkan-2-ones and polycyclic aromatic hydrocarbons (PAH) were investigated. Organic aerosol contents varied broadly among the plant units, depending upon nature of the manufactured products. The percent composition of all classes of compounds investigated in ambient atmosphere was similar to those observed indoor at industrial plant units. Organic acids, n-alkanoic as well as n-alkenoic, appeared by far the most abundant organic constituents of aerosols, both indoor and outdoor, ranging from 7.7 to 19.8 and from 12.7 to 17.1 μg m -3, respectively. The huge occurrence of acids and n-alkanes in ambient aerosols was consistent with their high levels present in oil and fat materials. Among minor components of aerosols, n-alkan-2-ones and PAH, seemed to be related to thermally induced ageing and direct combustion of raw organic material used for oil and soap production.

  13. Light extinction by secondary organic aerosol: an intercomparison of three broadband cavity spectrometers

    NASA Astrophysics Data System (ADS)

    Varma, R. M.; Ball, S. M.; Brauers, T.; Dorn, H.-P.; Heitmann, U.; Jones, R. L.; Platt, U.; Pöhler, D.; Ruth, A. A.; Shillings, A. J. L.; Thieser, J.; Wahner, A.; Venables, D. S.

    2013-11-01

    Broadband optical cavity spectrometers are maturing as a technology for trace-gas detection, but only recently have they been used to retrieve the extinction coefficient of aerosols. Sensitive broadband extinction measurements allow explicit separation of gas and particle phase spectral contributions, as well as continuous spectral measurements of aerosol extinction in favourable cases. In this work, we report an intercomparison study of the aerosol extinction coefficients measured by three such instruments: a broadband cavity ring-down spectrometer (BBCRDS), a cavity-enhanced differential optical absorption spectrometer (CE-DOAS), and an incoherent broadband cavity-enhanced absorption spectrometer (IBBCEAS). Experiments were carried out in the SAPHIR atmospheric simulation chamber as part of the NO3Comp campaign to compare the measurement capabilities of NO3 and N2O5 instrumentation. Aerosol extinction coefficients between 655 and 690 nm are reported for secondary organic aerosols (SOA) formed by the NO3 oxidation of β-pinene under dry and humid conditions. Despite different measurement approaches and spectral analysis procedures, the three instruments retrieved aerosol extinction coefficients that were in close agreement. The refractive index of SOA formed from the β-pinene + NO3 reaction was 1.61, and was not measurably affected by the chamber humidity or by aging of the aerosol over several hours. This refractive index is significantly larger than SOA refractive indices observed in other studies of OH and ozone-initiated terpene oxidations, and may be caused by the large proportion of organic nitrates in the particle phase. In an experiment involving ammonium sulfate particles, the aerosol extinction coefficients as measured by IBBCEAS were found to be in reasonable agreement with those calculated using the Mie theory. The results of the study demonstrate the potential of broadband cavity spectrometers for determining the optical properties of aerosols.

  14. Light extinction by Secondary Organic Aerosol: an intercomparison of three broadband cavity spectrometers

    NASA Astrophysics Data System (ADS)

    Varma, R. M.; Ball, S. M.; Brauers, T.; Dorn, H.-P.; Heitmann, U.; Jones, R. L.; Platt, U.; Pöhler, D.; Ruth, A. A.; Shillings, A. J. L.; Thieser, J.; Wahner, A.; Venables, D. S.

    2013-07-01

    Broadband optical cavity spectrometers are maturing as a technology for trace gas detection, but only recently have they been used to retrieve the extinction coefficient of aerosols. Sensitive broadband extinction measurements allow explicit separation of gas and particle phase spectral contributions, as well as continuous spectral measurements of aerosol extinction in favourable cases. In this work, we report an intercomparison study of the aerosol extinction coefficients measured by three such instruments: a broadband cavity ring-down spectrometer (BBCRDS), a cavity-enhanced differential optical absorption spectrometer (CE-DOAS), and an incoherent broadband cavity-enhanced absorption spectrometer (IBBCEAS). Experiments were carried out in the SAPHIR atmospheric simulation chamber as part of the NO3Comp campaign to compare the measurement capabilities of NO3 and N2O5 instrumentation. Aerosol extinction coefficients between 655 and 690 nm are reported for secondary organic aerosols (SOA) formed by the NO3 oxidation of β-pinene under dry and humid conditions. Despite different measurement approaches and spectral analysis procedures, the three instruments retrieved aerosol extinction coefficients that were in close agreement. The refractive index of SOA formed from the β-pinene + NO3 reaction was 1.61, and was not measurably affected by the chamber humidity or by aging of the aerosol over several hours. This refractive index is significantly larger than SOA refractive indices observed in other studies of OH and ozone-initiated terpene oxidations, and may be caused by the large proportion of organic nitrates in the particle phase. In an experiment involving ammonium sulphate particles the aerosol extinction coefficients as measured by IBBCEAS were found to be in reasonable agreement with those calculated using Mie theory. The results of the study demonstrate the potential of broadband cavity spectrometers for determining the optical properties of aerosols.

  15. Formation of nitrogenated organic aerosols in the Titan upper atmosphere

    PubMed Central

    Imanaka, Hiroshi; Smith, Mark A.

    2010-01-01

    Many aspects of the nitrogen fixation process by photochemistry in the Titan atmosphere are not fully understood. The recent Cassini mission revealed organic aerosol formation in the upper atmosphere of Titan. It is not clear, however, how much and by what mechanism nitrogen is incorporated in Titan’s organic aerosols. Using tunable synchrotron radiation at the Advanced Light Source, we demonstrate the first evidence of nitrogenated organic aerosol production by extreme ultraviolet–vacuum ultraviolet irradiation of a N2/CH4 gas mixture. The ultrahigh-mass-resolution study with laser desorption ionization-Fourier transform-ion cyclotron resonance mass spectrometry of N2/CH4 photolytic solid products at 60 and 82.5 nm indicates the predominance of highly nitrogenated compounds. The distinct nitrogen incorporations at the elemental abundances of H2C2N and HCN, respectively, are suggestive of important roles of H2C2N/HCCN and HCN/CN in their formation. The efficient formation of unsaturated hydrocarbons is observed in the gas phase without abundant nitrogenated neutrals at 60 nm, and this is confirmed by separately using 13C and 15N isotopically labeled initial gas mixtures. These observations strongly suggest a heterogeneous incorporation mechanism via short lived nitrogenated reactive species, such as HCCN radical, for nitrogenated organic aerosol formation, and imply that substantial amounts of nitrogen is fixed as organic macromolecular aerosols in Titan’s atmosphere. PMID:20616074

  16. Cloud condensation nuclei activity of isoprene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Engelhart, Gabriella J.; Moore, Richard H.; Nenes, Athanasios; Pandis, Spyros N.

    2011-01-01

    This work explores the cloud condensation nuclei (CCN) activity of isoprene secondary organic aerosol (SOA), likely a significant source of global organic particulate matter and CCN, produced from the oxidation with OH from HONO/HOOH photolysis in a temperature-controlled SOA chamber. CCN concentrations, activation diameter, and droplet growth kinetic information were monitored as a function of supersaturation (from 0.3% to 1.5%) for several hours using a cylindrical continuous-flow streamwise thermal gradient CCN counter connected to a scanning mobility particle sizer. The initial SOA concentrations ranged from 2 to 30 μg m-3 and presented CCN activity similar to monoterpene SOA with an activation diameter of 35 nm for 1.5% supersaturation and 72 nm for 0.6% supersaturation. The CCN activity improved slightly in some experiments as the SOA aged chemically and did not depend significantly on the level of NOx during the SOA production. The measured activation diameters correspond to a hygroscopicity parameter κ value of 0.12, similar to κ values of 0.1 ± 0.04 reported for monoterpene SOA. Analysis of the water-soluble carbon extracted from filter samples of the SOA suggest that it has a κ of 0.2-0.3 implying an average molar mass between 90 and 150 g mol-1 (assuming a zero and 5% surface tension reduction with respect to water, respectively). These findings are consistent with known oxidation products of isoprene. Using threshold droplet growth analysis, the CCN activation kinetics of isoprene SOA was determined to be similar to pure ammonium sulfate aerosol.

  17. A study of the origin of atmospheric organic aerosols

    SciTech Connect

    Hildemann, L.M.

    1990-01-01

    The sources of ambient organic particulate matter in urban areas are investigated through a program of emission source measurements, atmospheric measurements, and mathematical modeling of source/receptor relationships. A dilution sampler intended to collect fine organic aerosol from combustion sources is designed to simulate atmospheric cooling and dilution processes, so that organic vapors which condense under ambient conditions will be collected as particulate matter. This system is used to measure the emissions from a boiler burning distillate oil, a home fireplace, catalyst and noncatalyst automobiles, heavy-duty diesel trucks, natural gas home appliances, and meat-cooking operations. Alternate techniques are used to sample the particulate matter emitted from cigarette smoking, a roofing tar pot, paved road dust, brake lining wear, tire wear, and vegetative detritus. The bulk chemical characteristics of the fine aerosol fraction are presented for each source. Over half of the fine aerosol mass emitted from automobiles, wood burning, meat cooking, home appliances, cigarettes, and tar pots is shown to consist of organic compounds. The organic material collected from these sources is analyzed using high-resolution gas chromatography. Using a simple analytical protocol, a quantitative, 50-parameter characterization of the elutable fine organic aerosol emitted from each source type is obtained, which proves to be a unique fingerprint that can be used to distinguish most sources from each other. A mathematical model is used to predict the characteristics of fine ambient organic aerosol in the Los Angeles area that would prevail if the primary organic emissions are transported without chemical reaction. The model is found to track the seasonal variations observed in the ambient aerosol at the three sites studied.

  18. Toward Investigating Optically Trapped Organic Aerosols with CARS Microspectroscopy

    NASA Astrophysics Data System (ADS)

    Voss, L. F.

    2009-12-01

    The Intergovernmental Panel on Climate Change notes the huge uncertainty in the effect that atmospheric aerosols play in determining overall global temperature, specifically in their ability to nucleate clouds. To better understand aerosol chemistry, the novel coupling of gradient force optical trapping with broad bandwidth coherent anti-Stokes Raman scattering (CARS) spectroscopy is being developed to study single particles suspended in air. Building on successful designs employed separately for the techniques, this hybrid technology will be used to explain how the oxidation of organic compounds changes the chemical and physical properties of aerosols. By trapping the particles, an individual aerosol can be studied for up to several days. Using a broad bandwidth pulse for one of the incident beams will result in a Raman vibrational spectrum from every laser pulse. Combined with signal enhancement due to resonance and coherence of nonlinear CARS spectroscopy, this technique will allow for acquisition of data on the millisecond time scale, facilitating the study of dynamic processes. This will provide insights on how aerosols react with and absorb species from the gas phase. These experiments will increase understanding of aerosol oxidation and growth mechanisms and the effects that aerosols have on our atmosphere and climate. Progress in efforts developing this novel technique to study model systems is presented.

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

    EPA Science Inventory

    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...

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

    EPA Science Inventory

    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 ...

  1. A Study of Cloud Processing of Organic Aerosols Using Models and CHAPS Data

    SciTech Connect

    Ervens, Barbara

    2012-01-17

    The main theme of our work has been the identification of parameters that mostly affect the formation and modification of aerosol particles and their interaction with water vapor. Our detailed process model studies led to simplifications/parameterizations of these effects that bridge detailed aerosol information from laboratory and field studies and the need for computationally efficient expressions in complex atmospheric models. One focus of our studies has been organic aerosol mass that is formed in the atmosphere by physical and/or chemical processes (secondary organic aerosol, SOA) and represents a large fraction of atmospheric particulate matter. Most current models only describe SOA formation by condensation of low volatility (or semivolatile) gas phase products and neglect processes in the aqueous phase of particles or cloud droplets that differently affect aerosol size and vertical distribution and chemical composition (hygroscopicity). We developed and applied models of aqueous phase SOA formation in cloud droplets and aerosol particles (aqSOA). Placing our model results into the context of laboratory, model and field studies suggests a potentially significant contribution of aqSOA to the global organic mass loading. The second focus of our work has been the analysis of ambient data of particles that might act as cloud condensation nuclei (CCN) at different locations and emission scenarios. Our model studies showed that the description of particle chemical composition and mixing state can often be greatly simplified, in particular in aged aerosol. While over the past years many CCN studies have been successful performed by using such simplified composition/mixing state assumptions, much more uncertainty exists in aerosol-cloud interactions in cold clouds (ice or mixed-phase). Therefore we extended our parcel model that describes warm cloud formation by ice microphysics and explored microphysical parameters that determine the phase state and lifetime of

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

    SciTech Connect

    Fast, J; Zhang, Q; tilp, A; Shippert, T; Parworth, C; Mei, F

    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).

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

    EPA Science Inventory

    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...

  4. Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

    NASA Astrophysics Data System (ADS)

    Pajunoja, Aki; Hu, Weiwei; Leong, Yu J.; Taylor, Nathan F.; Miettinen, Pasi; Palm, Brett B.; Mikkonen, Santtu; Collins, Don R.; Jimenez, Jose L.; Virtanen, Annele

    2016-09-01

    During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmospheric aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O : C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ˜ 50 % RH in the sampling inlets. While the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.

  5. Towards an Understanding of Aerosol Redistribution by Shallow Cumulus Clouds with a Focus on Organics

    NASA Astrophysics Data System (ADS)

    Wonaschuetz, A.; Sorooshian, A.; Murphy, S. M.; Ervens, B.; Chuang, P. Y.; Feingold, G.; Jonsson, H. H.; Flagan, R. C.; Seinfeld, J.

    2010-12-01

    The extent to which clouds alter the vertical distribution of aerosols and concentrations of various inorganic and organic species has important implications for gas phase chemistry, air quality, and radiative forcing of climate. Models have been shown to inaccurately predict the vertical concentrations of organic aerosol mass and its oxidation state, especially in the free troposphere, where measurements usually exceed predictions of mass and underestimate O:C ratios. This work uses an airborne data set from the 2006 Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS) to address the convective redistribution of aerosols by small cumulus clouds, and also to quantify the contribution of aqueous chemistry to the vertical profiles of inorganic and organic particle species. There is evidence for convective pumping of aerosols in regions above cloud tops, where enhanced particle concentrations are observed in addition to high levels of sulfate and organics. Pre-conditioned areas in clear air that were recently processed by clouds exhibit enhanced levels of sulfate and organic acids as compared to other clear air regions. There is a trend towards enrichment of water-soluble organic aerosols (relative to both total organic and inorganic mass) as a function of both altitude (up to 4 km) and relative humidity. The most plausible explanation is that these species are produced by multi-phase chemistry. Modeling analysis will be presented to constrain the chemical aging processes in clouds and aqueous particles in the summertime southeastern Texas atmosphere. The usefulness of utilizing aerosol tracers for estimating the vertical profile of convective mass flux due to clouds is also explored.

  6. The uptake of HO2 radicals to organic aerosols

    NASA Astrophysics Data System (ADS)

    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 < 0.004 to γ = 0.008 ± 0.004. Humic acid was also studied, however, much larger uptake coefficients (γ = 0.007 - 0.09) were measured, probably due to the fact that these aerosols 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

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

    SciTech Connect

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

    2013-02-28

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

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

    SciTech Connect

    Madronich, Sasha

    2015-12-09

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

  9. Effect of Aerosol Age on the Infectivity of Airborne Pasteurella tularensis for Macaca mulatta and Man

    PubMed Central

    Sawyer, William D.; Jemski, Joseph V.; Hogge, Arthur L.; Eigelsbach, Henry T.; Wolfe, Elwood K.; Dangerfield, Harry G.; Gochenour, William S.; Crozier, Dan

    1966-01-01

    Sawyer, William D. (U.S. Army Medical Unit, Fort Detrick, Frederick, Md.), Joseph V. Jemski, Arthur L. Hogge, Jr., Henry T. Eigelsbach, Elwood K. Wolfe, Harry G. Dangerfield, William S. Gochenour, Jr., and Dan Crozier. Effect of aerosol age on the infectivity of airborne Pasteurella tularensis for Macaca mulatta and man. J. Bacteriol. 91:2180–2184. 1966.—In aging aerosols of Pasteurella tularensis SCHU-S4, the respiratory infectivity for man and Macaca mulatta decreased more rapidly than the viability of the organisms. Infectivity was diminished after 120 min, and was reduced 10-fold after 180 min. These findings confirmed previous observations made in mice and guinea pigs, and also revealed that smaller losses of infectivity were detectable in the primate hosts. PMID:4957611

  10. Optical Properties of Polymers Relevant to Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Zhu, Chunmao; Kawamura, Kimitaka; Fukuda, Yasuro; Mochida, Michihiro; Iwamoto, Yoko

    2016-06-01

    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.

  12. The thermodynamic and kinetic impacts of organics on marine aerosols

    NASA Astrophysics Data System (ADS)

    Crahan, Kathleen

    Organics can change the manner in which aerosols scatter radiation directly as hydrated aerosols and indirectly as in-cloud activated aerosols, through changing the solution activity, the surface tension, and the accommodation coefficient of the hydrated aerosol. This work explores the kinetic and thermodynamic impacts of the organic component of marine aerosols through data collected over four field campaigns and through several models used to reproduce observations. The Rough Evaporation Duct (RED) project was conducted in the summer of 2001 off the coast of Oahu using the Twin Otter Aircraft and the Floating Instrument Platform research platform for data collection. The Cloud-Aerosol Research in the Marine Atmosphere (CARMA) campaigns were conducted over three summers (2002, 2004, 2005) off the coast of Monterey, California. During the CARMA campaigns, a thick, moist, stratocumulus deck was present during most days, and the Twin Otter Aircraft was the primary research platform used to collect data. However, the research goals and exact instrumentation onboard the Twin Otter varied from campaign to campaign, and each data set was analyzed individually. Data collected from CARMA I were used to explore the mechanism of oxalic acid production in cloud droplets. Oxalate was observed in the clouds in excess to below cloud concentrations by an average of 0.11 mug m-3, suggesting an in-cloud production. The tentative identification in cloud water of an intermediate species in the aqueous oxalate production mechanism lends further support to an in-cloud oxalate source. The data sets collected during the RED campaign and the CARMA II and CARMA III campaigns were used to investigate the impact of aerosol chemical speciation on aerosol hygroscopic behavior. Several models were used to correlate the observations in the subsaturated regime to theory including an explicit thermodynamic model, simple Kohler theory, and a parameterization of the solution activity. These models

  13. Oxidation enhancement of submicron organic aerosols by fog processing

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Ge, X.; Collier, S.; Setyan, A.; Xu, J.; Sun, Y.

    2011-12-01

    During 2010 wintertime, a measurement study was carried out at Fresno, California, using an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) combined with a Scanning Mobility Particle Sizer (SMPS). Four fog events occurred during the first week of the campaign. While ambient aerosol was sampled into the HR-ToF-AMS, fog water samples were collected, and were later aerosolized and analyzed via HR-TOF-AMS in the laboratory. We performed Positive Matrix Factorization (PMF) on the AMS ambient organic mass spectra, and identified four OA factors: hydrocarbon-like OA (HOA) likely from vehicle emissions, cooking influenced OA (COA), biomass burning OA (BBOA) representing residential wood combustion, and an oxygenated OA (OOA) that has an average O/C ratio of 0.42. The time series of the OOA factor correlates best with that of sulfate (R2 =0.54 ) during fog events, suggesting that aqueous phase processing may have strongly affected OOA production during wintertime in Fresno. We further investigate the OOA compositions and elemental ratios before, during, and after the fog events, as well as those of dissolved organic matter (DOM) in fog waters to study the influence of aqueous phase processing on OA compositions. Results of fog sample analysis shows an enhancement of oxidation of DOM in 11 separate fog samples. Further factor analysis of the fog DOM data will elucidate the possible mechanisms by which fog processing enhances oxidation of aerosol. In addition, in order to investigate the influence of aqueous processing on OA, we used the Extended Aerosol Inorganic Model (E-AIM) (http://www.aim.env.uea.ac.uk/aim/aim.php) to estimate aerosol phase water contents based on the AMS measured aerosol composition. The predicted water content has a good correlation with sulfate and OOA . We will further explore the correlations between particle phase water with organic aerosol characteristics to discuss the influence of aqueous phase processing on

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

    EPA Science Inventory

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

  15. Glass transition measurements in mixed organic and organic/inorganic aerosol particles

    NASA Astrophysics Data System (ADS)

    Dette, Hans Peter; Qi, Mian; Schröder, David; Godt, Adelheid; Koop, Thomas

    2014-05-01

    The recent proposal of a semi-solid or glassy state of secondary organic aerosol (SOA) particles has sparked intense research in that area. In particular, potential effects of a glassy aerosol state such as incomplete gas-to-particle partitioning of semi-volatile organics, inhibited chemical reactions and water uptake, and the potential to act as heterogeneous ice nuclei have been identified so far. Many of these studies use well-studied proxies for oxidized organics such as sugars or other polyols. There are, however, few measurements on compounds that do exist in atmospheric aerosol particles. Here, we have performed studies on the phase state of organics that actually occur in natural SOA particles arising from the oxidation of alpha-pinene emitted in boreal forests. We have investigated the two marker compounds pinonic acid and 3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA) and their mixtures. 3-MBCTA was synthesized from methyl isobutyrate and dimethyl maleate in two steps. In order to transfer these substances into a glassy state we have developed a novel aerosol spray drying technique. Dilute solutions of the relevant organics are atomized into aerosol particles which are dried subsequently by diffusion drying. The dried aerosol particles are then recollected in an impactor and studied by means of differential scanning calorimetry (DSC), which provides unambiguous information on the aerosols' phase state, i.e. whether the particles are crystalline or glassy. In the latter case DSC is used to determine the glass transition temperature Tg of the investigated samples. Using the above setup we were able to determine Tg of various mixtures of organic aerosol compounds as a function of their dry mass fraction, thus allowing to infer a relation between Tg and the O:C ratio of the aerosols. Moreover, we also studied the glass transition behavior of mixed organic/inorganic aerosol particles, including the effects of liquid-liquid phase separation upon drying.

  16. Characterization and source apportionment of organic aerosol using offline aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Daellenbach, K. R.; Bozzetti, C.; Křepelová, A.; Canonaco, F.; Wolf, R.; Zotter, P.; Fermo, P.; Crippa, M.; Slowik, J. G.; Sosedova, Y.; Zhang, Y.; Huang, R.-J.; Poulain, L.; Szidat, S.; Baltensperger, U.; Prévôt, A. S. H.; El Haddad, I.

    2015-08-01

    Field deployments of the Aerodyne Aerosol Mass Spectrometer (AMS) have significantly advanced real-time measurements and source apportionment of non-refractory particulate matter. However, the cost and complex maintenance requirements of the AMS make impractical its deployment at sufficient sites to determine regional characteristics. Furthermore, the negligible transmission efficiency of the AMS inlet for supermicron particles significantly limits the characterization of their chemical nature and contributing sources. In this study, we utilize the AMS to characterize the water-soluble organic fingerprint of ambient particles collected onto conventional quartz filters, which are routinely sampled at many air quality sites. The method was applied to 256 particulate matter (PM) filter samples (PM1, PM2.5, PM10) collected at 16 urban and rural sites during summer and winter. We show that the results obtained by the present technique compare well with those from co-located online measurements, e.g. AMS or Aerosol Chemical Speciation Monitor (ACSM). The bulk recoveries of organic aerosol (60-91 %) achieved using this technique, together with low detection limits (0.8 μg of organic aerosol on the analyzed filter fraction) allow its application to environmental samples. We will discuss the recovery variability of individual hydrocarbon, oxygen containing and other ions. The performance of such data in source apportionment is assessed in comparison to ACSM data. Recoveries of organic components related to different sources as traffic, wood burning and secondary organic aerosol are presented. This technique, while subjected to the limitations inherent to filter-based measurements (e.g. filter artifacts and limited time resolution) may be used to enhance the AMS capabilities in measuring size-fractionated, spatially-resolved long-term datasets.

  17. Characterization and source apportionment of organic aerosol using offline aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Daellenbach, K. R.; Bozzetti, C.; Křepelová, A.; Canonaco, F.; Wolf, R.; Zotter, P.; Fermo, P.; Crippa, M.; Slowik, J. G.; Sosedova, Y.; Zhang, Y.; Huang, R.-J.; Poulain, L.; Szidat, S.; Baltensperger, U.; El Haddad, I.; Prévôt, A. S. H.

    2016-01-01

    Field deployments of the Aerodyne Aerosol Mass Spectrometer (AMS) have significantly advanced real-time measurements and source apportionment of non-refractory particulate matter. However, the cost and complex maintenance requirements of the AMS make its deployment at sufficient sites to determine regional characteristics impractical. Furthermore, the negligible transmission efficiency of the AMS inlet for supermicron particles significantly limits the characterization of their chemical nature and contributing sources. In this study, we utilize the AMS to characterize the water-soluble organic fingerprint of ambient particles collected onto conventional quartz filters, which are routinely sampled at many air quality sites. The method was applied to 256 particulate matter (PM) filter samples (PM1, PM2.5, and PM10, i.e., PM with aerodynamic diameters smaller than 1, 2.5, and 10 µm, respectively), collected at 16 urban and rural sites during summer and winter. We show that the results obtained by the present technique compare well with those from co-located online measurements, e.g., AMS or Aerosol Chemical Speciation Monitor (ACSM). The bulk recoveries of organic aerosol (60-91 %) achieved using this technique, together with low detection limits (0.8 µg of organic aerosol on the analyzed filter fraction) allow its application to environmental samples. We will discuss the recovery variability of individual hydrocarbon ions, ions containing oxygen, and other ions. The performance of such data in source apportionment is assessed in comparison to ACSM data. Recoveries of organic components related to different sources as traffic, wood burning, and secondary organic aerosol are presented. This technique, while subjected to the limitations inherent to filter-based measurements (e.g., filter artifacts and limited time resolution) may be used to enhance the AMS capabilities in measuring size-fractionated, spatially resolved long-term data sets.

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

    PubMed

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

    2013-01-01

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

  19. Organic Aerosols from SÃO Paulo and its Relationship with Aerosol Absorption and Scattering Properties

    NASA Astrophysics Data System (ADS)

    Artaxo, P.; Brito, J. F.; Rizzo, L. V.

    2012-12-01

    The megacity of São Paulo with its 19 million people and 7 million cars is a challenge from the point of view of air pollution. High levels of organic aerosols, PM10, black carbon and ozone and the peculiar situation of the large scale use of ethanol fuel makes it a special case. Little is known about the impact of ethanol on air quality and human health and the increase of ethanol as vehicle fuel is rising worldwide An experiment was designed to physico-chemical properties of aerosols in São Paulo, as well as their optical properties. Aerosol size distribution in the size range of 1nm to 10 micrometers is being measured with a Helsinki University SMPS (Scanning Mobility Particle Sizer), an NAIS (Neutral ion Spectrometer) and a GRIMM OPC (Optical Particle Counter). Optical properties are being measured with a TSI Nephelometer and a Thermo MAAP (Multi Angle Absorption Photometer). A CIMEL sunphotometer from the AERONET network measure the aerosol optical depth. Furthermore, a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) and an Aerosol Chemical Speciation Monitor (ACSM) are used to real-time VOC analysis and aerosol composition, respectively. The ACSM was operated for 3 months continuosly during teh wintertime of 2012. The measured total particle concentration typically varies between 10,000 and 30,000 cm-3 being the lowest late in the night and highest around noon and frequently exceeding 50,000 cm-3. Clear diurnal patterns in aerosol optical properties were observed. Scattering and absorption coefficients typically range between 20 and 100 Mm-1 at 450 nm, and between 10 to 40 Mm-1 at 637 nm, respectively, both of them peaking at 7:00 local time, the morning rush hour. The corresponding single scattering albedo varies between 0.50 and 0.85, indicating a significant contribution of primary absorbing particles to the aerosol population. During the first month a total of seven new particle formation events were observed with growth rates ranging from 9 to 25

  20. Impacts of sources and aging on submicrometer aerosol properties in the marine boundary layer across the Gulf of Maine

    NASA Astrophysics Data System (ADS)

    Quinn, P. K.; Bates, T. S.; Coffman, D.; Onasch, T. B.; Worsnop, D.; Baynard, T.; de Gouw, J. A.; Goldan, P. D.; Kuster, W. C.; Williams, E.; Roberts, J. M.; Lerner, B.; Stohl, A.; Pettersson, A.; Lovejoy, E. R.

    2006-12-01

    Measurements were made on board the NOAA RV Ronald H. Brown during the second New England Air Quality Study (NEAQS 2004) to determine the source of the aerosol in the region and how sources and aging processes affect submicrometer aerosol chemical composition and optical properties. Using the Lagrangian particle dispersion model FLEXPART in combination with gas phase tracer compounds, local (urban), regional (NE U.S. urban corridor of Washington, D.C.; New York; and Boston), and distant (midwest industries and North American forest fires) sources were identified. Submicrometer aerosol measured near the source region (Boston Harbor) had a molar equivalence ratio near one with respect to NH4+, NO3-, and SO4=, had a large mass fraction of particulate organic matter (POM) relative to SO4=, and had relatively unoxidized POM. As distance from the source region increased, the submicrometer aerosol measured in the marine boundary layer became more acidic and had a lower POM mass fraction, and the POM became more oxidized. The relative humidity dependence of light extinction reflected the change in aerosol composition being lower for the near-source aerosol and higher for the more processed aerosol. A factor analysis performed on a combined data set of aerosol and gas phase parameters showed that the POM measured during the experiment was predominantly of secondary anthropogenic origin.

  1. SECONDARY ORGANIC AEROSOL FORMATION FROM THE IRRADIATION OF SIMULATED AUTOMOBILE EXHAUST

    EPA Science Inventory

    A laboratory study was conducted to evaluate the potential for secondary organic aerosol formation from emissions from automotive exhaust. The goal was to determine to what extent photochemical oxidation products of these hydrocarbons contribute to secondary organic aerosol (SO...

  2. A Review of Secondary Organic Aerosol (SOA) Formation from Isoprene

    EPA Science Inventory

    Recent field and laboratory evidence indicates that the oxidation of isoprene forms secondary organic aerosol (SOA). Global biogenic emissions of isoprene (600 Tg yr-1) are sufficiently large the formation of SOA is even small yields results in substantial production ...

  3. EVALUATION OF SECONDARY ORGANIC AEROSOL FORMATION IN WINTER. (R823514)

    EPA Science Inventory

    Three different methods are used to predict secondary organic aerosol (SOA)
    concentrations in the San Joaquin Valley of California during the winter of 1995-1996 [Integrated
    Monitoring Study, (IMS95)]. The first of these methods estimates SOA by using elemental carbon as

  4. Secondary organic aerosol formation from gasoline passenger vehicle emissions investigated in a smog chamber

    NASA Astrophysics Data System (ADS)

    Nordin, E. Z.; Eriksson, A. C.; Roldin, P.; Nilsson, P. T.; Carlsson, J. E.; Kajos, M. K.; Hellén, H.; Wittbom, C.; Rissler, J.; Löndahl, J.; Swietlicki, E.; Svenningsson, B.; Bohgard, M.; Kulmala, M.; Hallquist, M.; Pagels, J.

    2012-12-01

    Gasoline vehicles have elevated emissions of volatile organic compounds during cold starts and idling and have recently been pointed out as potentially the main source of anthropogenic secondary organic aerosol (SOA) in megacities. However, there is a lack of laboratory studies to systematically investigate SOA formation in real-world exhaust. In this study, SOA formation from pure aromatic precursors, idling and cold start gasoline exhaust from one Euro II, one Euro III and one Euro IV passenger vehicles were investigated using photo-oxidation experiments in a 6 m3 smog chamber. The experiments were carried out at atmospherically relevant organic aerosol mass concentrations. The characterization methods included a high resolution aerosol mass spectrometer and a proton transfer mass spectrometer. It was found that gasoline exhaust readily forms SOA with a signature aerosol mass spectrum similar to the oxidized organic aerosol that commonly dominates the organic aerosol mass spectra downwind urban areas. After 4 h aging the formed SOA was 1-2 orders of magnitude higher than the Primary OA emissions. The SOA mass spectrum from a relevant mixture of traditional light aromatic precursors gave f43 (mass fraction at m/z = 4 3) approximately two times higher than to the gasoline SOA. However O : C and H : C ratios were similar for the two cases. Classical C6-C9 light aromatic precursors were responsible for up to 60% of the formed SOA, which is significantly higher than for diesel exhaust. Important candidates for additional precursors are higher order aromatic compounds such as C10, C11 light aromatics, naphthalene and methyl-naphthalenes.

  5. Aqueous phase processing of secondary organic aerosol from isoprene photooxidation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Monod, A.; Tritscher, T.; Praplan, A. P.; DeCarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.

    2012-07-01

    Transport of reactive air masses into humid and wet areas is highly frequent in the atmosphere, making the study of aqueous phase processing of secondary organic aerosol (SOA) very relevant. We have investigated the aqueous phase processing of SOA generated from gas-phase photooxidation of isoprene using a smog chamber. The SOA collected on filters was extracted by water and subsequently oxidized in the aqueous phase either by H2O2 under dark conditions or by OH radicals in the presence of light, using a photochemical reactor. Online and offline analytical techniques including SMPS, HR-AMS, H-TDMA, TD-API-AMS, were employed for physical and chemical characterization of the chamber SOA and nebulized filter extracts. After aqueous phase processing, the particles were significantly more hygroscopic, and HR-AMS data showed higher signal intensity at m/z 44 and a lower signal intensity at m/z 43, thus showing the impact of aqueous phase processing on SOA aging, in good agreement with a few previous studies. Additional offline measurement techniques (IC-MS, APCI-MS2 and HPLC-APCI-MS) permitted the identification and quantification of sixteen individual chemical compounds before and after aqueous phase processing. Among these compounds, small organic acids (including formic, glyoxylic, glycolic, butyric, oxalic and 2,3-dihydroxymethacrylic acid (i.e. 2-methylglyceric acid)) were detected, and their concentrations significantly increased after aqueous phase processing. In particular, the aqueous phase formation of 2-methylglyceric acid and trihydroxy-3-methylbutanal was correlated with the consumption of 2,3-dihydroxy-2-methyl-propanal, and 2-methylbutane-1,2,3,4-tetrol, respectively, and an aqueous phase mechanism was proposed accordingly. Overall, the aging effect observed here was rather small compared to previous studies, and this limited effect could possibly be explained by the lower liquid phase OH concentrations employed here, and/or the development of oligomers

  6. Organic aerosol mixing observed by single-particle mass spectrometry.

    PubMed

    Robinson, Ellis Shipley; Saleh, Rawad; Donahue, Neil M

    2013-12-27

    We present direct measurements of mixing between separately prepared organic aerosol populations in a smog chamber using single-particle mass spectra from the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Docosane and docosane-d46 (22 carbon linear solid alkane) did not show any signs of mixing, but squalane and squalane-d62 (30 carbon branched liquid alkane) mixed on the time scale expected from a condensational-mixing model. Docosane and docosane-d46 were driven to mix when the chamber temperature was elevated above the melting point for docosane. Docosane vapors were shown to mix into squalane-d62, but not the other way around. These results are consistent with low diffusivity in the solid phase of docosane particles. We performed mixing experiments on secondary organic aerosol (SOA) surrogate systems finding that SOA derived from toluene-d8 (a surrogate for anthropogenic SOA (aSOA)) does not mix into squalane (a surrogate for hydrophobic primary organic aerosol (POA)) but does mix into SOA derived from α-pinene (biogenic SOA (bSOA) surrogate). For the aSOA/POA, the volatility of either aerosol does not limit gas-phase diffusion, indicating that the two particle populations do not mix simply because they are immiscible. In the aSOA/bSOA system, the presence of toluene-d8-derived SOA molecules in the α-pinene-derived SOA provides evidence that the diffusion coefficient in α-pinene-derived SOA is high enough for mixing on the time scale of 1 min. The observations from all of these mixing experiments are generally invisible to bulk aerosol composition measurements but are made possible with single-particle composition data.

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

    SciTech Connect

    Ziemann, Paul J.; Kreidenweis, Sonia M.; Petters, Markus D.

    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. Organic Aerosols in Rural and Remote Atmospheric Environments: Insights from Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Jimenez, J.; Ulbrich, I.; Dunlea, E.; Decarlo, P.; Huffman, A.; Allan, J.; Coe, H.; Alfarra, R.; Canagaratna, M.; Onasch, T.; Jayne, J.; Worsnop, D.; Takami, A.; Miyoshi, T.; Shimono, A.; Hatakeyama, S.; Weimer, S.; Demerjian, K.; Drewnick, F.; Schneider, J.; Middlebrook, A.; Bahreini, R.; Cotrell, L.; Griffin, R.; Leaitch, R.; Li, S.; Hayden, K.; Rautiainen, J.

    2006-12-01

    Organic matter usually accounts for a large fraction of the fine particle mass in rural and remote atmospheres. However, little is known about the sources and properties of this material. Here we report findings on the characteristics and the major types of organic aerosols (OA) in urban downwind, high elevation, forested, and marine atmospheres based on analyses of more than 20 highly time resolved AMS datasets sampled from various locations in the mid-latitude Northern Hemisphere. Organic aerosol components are extracted from these datasets using a custom multiple component mass spectral analysis technique and the Positive Matrix Factorization (PMF) method. These components are evaluated according to their extracted mass spectra and correlations to aerosol species, such as sulfate, nitrate, and elemental carbon, and gas-phase tracer compounds, such as CO and NOx. We have identified a hydrocarbon-like organic aerosol (HOA) component similar in mass spectra to the hydrocarbon substances observed at urban locations. We have also identified several oxygenated OA (OOA) components that show different fragmentation patterns and oxygen to carbon ratios in their mass spectra. Two OOA components a highly oxygenated that has mass spectrum resembling that of fulvic acid (a model compound representative for highly processed/oxidized organics in the environment) and a less oxygenated OOA component, whose spectrum is dominated with ions that are mainly associated with carbonyls and alcohols, are very frequently observed at various rural/remote sites. The oxygenated OOA component is more prevalent at downwind sites influenced by urban transport and the less oxygenated shows correlation to biogenic chamber OA at some locations. Compared to the total OOA concentration, HOA is generally very small and accounts for < 10% of the total OA mass at rural/remote sites. The comparisons between the concentrations of HOA and primary OA (POA) that would be predicted according to inert

  9. Composition of Secondary Organic Aerosols Produced by Photo-Oxidation of Biomass Burning Emissions in a Smog Chamber

    NASA Astrophysics Data System (ADS)

    Desyaterik, Y.; Sullivan, A.; Hennigan, C. J.; Robinson, A. L.; Collett, J. L.

    2009-12-01

    Knowledge of the chemical composition of atmospheric organic aerosols (OA) is essential for accurate representation of OA in air quality and climate models. Both the sources of OA and their properties and effects remain poorly understood. In particular, we still know relatively little about the atmospheric formation of secondary organic aerosols (SOA). There is growing interest in the impact of biomass burning emissions on air quality, human health, and radiative forcing. Through a series of experiments, we are working to quantify changes in the chemical composition of wood smoke particles as a result of photochemical aging under well-controlled laboratory conditions. One specific objective of this study is to identify markers for biomass burning SOA and test whether these markers can be used in atmospheric samples to quantify SOA formation from aging of biomass burning emissions. We analyzed SOA generated in a smog chamber by photooxidation of smoke produced by burning oak wood. In order to initiate photochemistry, the chamber was irradiated with UV light. Aqueous extracts of collected aerosol samples were analyzed with Electrospray Ionization Time-of-Flight Mass Spectrometry. The high mass accuracy of these measurements reduces ambiguity in the assignment of elemental compositions for observed ions. Analysis has shown that primary oak smoke aerosol includes products of the thermal decomposition of cellulose (levoglucosan, cyclotene etc.) and lignin (guaiacol and syringol derivatives, mostly aldehydes and alcohols). After 2 hours of aging at typical summertime hydroxyl radical concentrations, the aerosol mass increased 2.5 fold due to the production of secondary organic aerosol. Mass spectra of the secondary organic aerosol formed are dominated by organic nitrates (nitrophenol, nitrocresol, nitrocatechol, and nitroguaiacol) and aromatic acids (benzoic acid, mono and di-hydroxybenzoic acid). Both nitrates and acids most likely are formed due to oxidation of the

  10. Molecular Markers of Secondary Organic Aerosol in Mumbai, India.

    PubMed

    Fu, Pingqing; Aggarwal, Shankar G; Chen, Jing; Li, Jie; Sun, Yele; Wang, Zifa; Chen, Huansheng; Liao, Hong; Ding, Aijun; Umarji, G S; Patil, R S; Chen, Qi; Kawamura, Kimitaka

    2016-05-01

    Biogenic secondary organic aerosols (SOA) are generally considered to be more abundant in summer than in winter. Here, polar organic marker compounds in urban background aerosols from Mumbai were measured using gas chromatography-mass spectrometry. Surprisingly, we found that concentrations of biogenic SOA tracers at Mumbai were several times lower in summer (8-14 June 2006; wet season; n = 14) than in winter (13-18 February 2007; dry season; n = 10). Although samples from less than 10% of the season are extrapolated to the full season, such seasonality may be explained by the predominance of the southwest summer monsoon, which brings clean marine air masses to Mumbai. While heavy rains are an important contributor to aerosol removal during the monsoon season, meteorological data (relative humidity and T) suggest no heavy rains occurred during our sampling period. However, in winter, high levels of SOA and their day/night differences suggest significant contributions of continental aerosols through long-range transport together with local sources. The winter/summer pattern of SOA loadings was further supported by results from chemical transport models (NAQPMS and GEOS-Chem). Furthermore, our study suggests that monoterpene- and sesquiterpene-derived secondary organic carbon (SOC) were more significant than those of isoprene- and toluene-SOC at Mumbai. PMID:27045808

  11. Aged boreal biomass-burning aerosol size distributions from BORTAS 2011

    NASA Astrophysics Data System (ADS)

    Sakamoto, K. M.; Allan, J. D.; Coe, H.; Taylor, J. W.; Duck, T. J.; Pierce, J. R.

    2015-02-01

    Biomass-burning aerosols contribute to aerosol radiative forcing on the climate system. The magnitude of this effect is partially determined by aerosol size distributions, which are functions of source fire characteristics (e.g. fuel type, MCE) and in-plume microphysical processing. The uncertainties in biomass-burning emission number-size distributions in climate model inventories lead to uncertainties in the CCN (cloud condensation nuclei) concentrations and forcing estimates derived from these models. The BORTAS-B (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellite) measurement campaign was designed to sample boreal biomass-burning outflow over eastern Canada in the summer of 2011. Using these BORTAS-B data, we implement plume criteria to isolate the characteristic size distribution of aged biomass-burning emissions (aged ~ 1-2 days) from boreal wildfires in northwestern Ontario. The composite median size distribution yields a single dominant accumulation mode with Dpm = 230 nm (number-median diameter) and σ = 1.5, which are comparable to literature values of other aged plumes of a similar type. The organic aerosol enhancement ratios (ΔOA / ΔCO) along the path of Flight b622 show values of 0.09-0.17 μg m-3 ppbv-1 (parts per billion by volume) with no significant trend with distance from the source. This lack of enhancement ratio increase/decrease with distance suggests no detectable net OA (organic aerosol) production/evaporation within the aged plume over the sampling period (plume age: 1-2 days), though it does not preclude OA production/loss at earlier stages. A Lagrangian microphysical model was used to determine an estimate of the freshly emitted size distribution corresponding to the BORTAS-B aged size distributions. The model was restricted to coagulation and dilution processes based on the insignificant net OA production/evaporation derived from the ΔOA / ΔCO enhancement ratios. We

  12. Identification of significant precursor gases of secondary organic aerosols from residential wood combustion

    PubMed Central

    Bruns, Emily A.; El Haddad, Imad; Slowik, Jay G.; Kilic, Dogushan; Klein, Felix; Baltensperger, Urs; Prévôt, André S. H.

    2016-01-01

    Organic gases undergoing conversion to form secondary organic aerosol (SOA) during atmospheric aging are largely unidentified, particularly in regions influenced by anthropogenic emissions. SOA dominates the atmospheric organic aerosol burden and this knowledge gap contributes to uncertainties in aerosol effects on climate and human health. Here we characterize primary and aged emissions from residential wood combustion using high resolution mass spectrometry to identify SOA precursors. We determine that SOA precursors traditionally included in models account for only ~3–27% of the observed SOA, whereas for the first time we explain ~84–116% of the SOA by inclusion of non-traditional precursors. Although hundreds of organic gases are emitted during wood combustion, SOA is dominated by the aging products of only 22 compounds. In some cases, oxidation products of phenol, naphthalene and benzene alone comprise up to ~80% of the observed SOA. Identifying the main precursors responsible for SOA formation enables improved model parameterizations and SOA mitigation strategies in regions impacted by residential wood combustion, more productive targets for ambient monitoring programs and future laboratories studies, and links between direct emissions and SOA impacts on climate and health in these regions. PMID:27312480

  13. Identification of significant precursor gases of secondary organic aerosols from residential wood combustion.

    PubMed

    Bruns, Emily A; El Haddad, Imad; Slowik, Jay G; Kilic, Dogushan; Klein, Felix; Baltensperger, Urs; Prévôt, André S H

    2016-01-01

    Organic gases undergoing conversion to form secondary organic aerosol (SOA) during atmospheric aging are largely unidentified, particularly in regions influenced by anthropogenic emissions. SOA dominates the atmospheric organic aerosol burden and this knowledge gap contributes to uncertainties in aerosol effects on climate and human health. Here we characterize primary and aged emissions from residential wood combustion using high resolution mass spectrometry to identify SOA precursors. We determine that SOA precursors traditionally included in models account for only ~3-27% of the observed SOA, whereas for the first time we explain ~84-116% of the SOA by inclusion of non-traditional precursors. Although hundreds of organic gases are emitted during wood combustion, SOA is dominated by the aging products of only 22 compounds. In some cases, oxidation products of phenol, naphthalene and benzene alone comprise up to ~80% of the observed SOA. Identifying the main precursors responsible for SOA formation enables improved model parameterizations and SOA mitigation strategies in regions impacted by residential wood combustion, more productive targets for ambient monitoring programs and future laboratories studies, and links between direct emissions and SOA impacts on climate and health in these regions. PMID:27312480

  14. Identification of significant precursor gases of secondary organic aerosols from residential wood combustion

    NASA Astrophysics Data System (ADS)

    Bruns, Emily A.; El Haddad, Imad; Slowik, Jay G.; Kilic, Dogushan; Klein, Felix; Baltensperger, Urs; Prévôt, André S. H.

    2016-06-01

    Organic gases undergoing conversion to form secondary organic aerosol (SOA) during atmospheric aging are largely unidentified, particularly in regions influenced by anthropogenic emissions. SOA dominates the atmospheric organic aerosol burden and this knowledge gap contributes to uncertainties in aerosol effects on climate and human health. Here we characterize primary and aged emissions from residential wood combustion using high resolution mass spectrometry to identify SOA precursors. We determine that SOA precursors traditionally included in models account for only ~3–27% of the observed SOA, whereas for the first time we explain ~84–116% of the SOA by inclusion of non-traditional precursors. Although hundreds of organic gases are emitted during wood combustion, SOA is dominated by the aging products of only 22 compounds. In some cases, oxidation products of phenol, naphthalene and benzene alone comprise up to ~80% of the observed SOA. Identifying the main precursors responsible for SOA formation enables improved model parameterizations and SOA mitigation strategies in regions impacted by residential wood combustion, more productive targets for ambient monitoring programs and future laboratories studies, and links between direct emissions and SOA impacts on climate and health in these regions.

  15. Microscopic Characterization of Carbonaceous Aerosol Particle Aging in the Outflow from Mexico City

    SciTech Connect

    Moffet, R. C.; Henn, T. R.; Tivanski, A. V.; Hopkins, R. J.; Desyaterik, Y.; Kilcoyne, A. L. D.; Tyliszczak, T.; Fast, J.; Barnard, J.; Shutthanandan, V.; Cliff, S.S.; Perry, K. D.; Laskin, A.; Gilles, M. K.

    2009-09-16

    This study was part of the Megacities Initiative: Local and Global Research Observations (MILAGRO) field campaign conducted in Mexico City Metropolitan Area during spring 2006. The physical and chemical transformations of particles aged in the outflow from Mexico City were investigated for the transport event of 22 March 2006. A detailed chemical analysis of individual particles was performed using a combination of complementary microscopy and micro-spectroscopy techniques. The applied techniques included scanning transmission X-ray microscopy (STXM) coupled with near edge X-ray absorption fine structure spectroscopy (NEXAFS) and computer controlled scanning electron microscopy with an energy dispersive X-ray analyzer (CCSEM/EDX). As the aerosol plume evolves from the city center, the organic mass per particle increases and the fraction of carbon-carbon double bonds (associated with elemental carbon) decreases. Organic functional groups enhanced with particle age include: carboxylic acids, alkyl groups, and oxygen bonded alkyl groups. At the city center (T0) the most prevalent aerosol type contained inorganic species (composed of sulfur, nitrogen, oxygen, and potassium) coated with organic material. At the T1 and T2 sites, located northeast of T0 (~;;29 km and ~;;65 km, respectively), the fraction of homogenously mixed organic particles increased in both size and number. These observations illustrate the evolution of the physical mixing state and organic bonding in individual particles in a photochemically active environment.

  16. Glass formation processes in mixed inorganic/organic aerosol particles.

    PubMed

    Dette, Hans P; Koop, Thomas

    2015-05-14

    Recent experiments suggest that organic aerosol particles may transform into a glassy state at room temperature under dry conditions. Information on glass forming processes in mixed inorganic/organic aerosol particles is sparse, however, because inorganic crystal nucleation is usually very likely in such mixtures. Here we investigate the glass transition temperatures Tg of various organics (trehalose, sucrose, citric acid, sorbitol, and glycerol as well as 3-MBTCA) in binary mixtures with either NaNO3 or NH4HSO4 at different mass fractions. The glassy samples were prepared with the MARBLES technique by atomizing dilute aqueous solutions into aerosol particles and subsequent diffusion drying. The resulting aerosol particles were collected and their phase behavior was investigated using differential scanning calorimetry. At small and intermediate inorganic mass fractions salt crystallization did not occur. Instead, the single-phase mixtures remained in an amorphous state upon drying such that determination of their Tg was possible. From these measurements the Tg value of pure NaNO3 and pure NH4HSO4 could be inferred through extrapolation, resulting in values of Tg(NaNO3) ≈ 290 K and Tg(NH4HSO4) ≈ 220 K. Upon drying of NH4HSO4/3-MBTCA mixtures, phase-separated samples formed in which the inorganic-rich and organic-rich phases each show an independent glass transition. Our measurements provide a route toward establishing Tg values of inorganic salts that usually crystallize readily, and they may explain the reported contradicting observations of NaNO3 aerosol particles to either crystallize or remain amorphous upon drying at room temperature. PMID:25490407

  17. A Study on the Aqueous Formation of Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Sinclair, K.; Tsigaridis, K.

    2013-12-01

    The effect aerosols have on radiative forcing in the atmosphere is recognized as one of the largest uncertainties in the radiation budget. About 80% of organic aerosol mass in the atmosphere is estimated to be created though secondary processes. Recently, the aqueous formation of secondary organic aerosols (SOA) has become recognized as important when considering the source, transformation and radiative impacts of SOA. This work focuses on implementing a mechanism for aqueous SOA formation that can be used in atmospheric chemistry and models of all scales, from box to global. A box model containing a simplified chemical mechanism for the aqueous production of precursors of aqueous SOA (Myriokefalitakis et al. (2011) is coupled to gas-phase chemistry which uses the carbon bond mechanism (CBM) IV is presented. The model implements aqueous chemistry of soluble gases, both in-cloud and aerosol water, including organic compounds such as glyoxal and methylglyoxal, which have been shown as potentially significant sources for dissolved secondary organic aerosols. This mechanism implements aqueous phase mass transfer and molecular dissociation. The model's performance is evaluated against previous box model studies from the literature. A comparison is conducted between the detailed GAMMA model (McNeill et al., 2012), which is constrained with chamber experiments and the one developed here. The model output under different atmospheric conditions is explored and differences and sensitivities are assessed. The objective of this work is to create a robust framework for simulating aqueous phase formation of SOA and maximizing the computational efficiency of the model, while maintaining accuracy, in order to later use the exact mechanism in global climate simulations.

  18. Organic acids in continental background aerosols

    NASA Astrophysics Data System (ADS)

    Limbeck, Andreas; Puxbaum, Hans

    With a newly developed method aerosol samples from three distinctly different continental sites were analyzed: an urban site (Vienna), a savanna site in South Africa (Nylsvley Nature Reserve, NNR) and a free tropospheric continental background site (Sonnblick Observatory, SBO). In all samples a range of monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) has been identified and quantified. The three most abundant MCAs in Vienna were the C18, C16 and C14 acids with concentrations of 66, 45 and 36 ng m -3, respectively. At the mid tropospheric background site (SBO) the three most abundant MCAs were the C18, C16 and C12 acid. For the DCAs at all three sites oxalic, malonic and succinic acid were the dominant compounds. For some individual compounds an information about the sources could be obtained. For example the determined unsaturated MCAs in South Africa appear to result from biogenic sources whereas in Vienna those acids are considered to be derived from combustion processes. Oxalic and glyoxalic acid appear to have a free tropospheric air chemical source. The relative high amounts at SBO in comparison to Vienna can only be explained by secondary formation of oxalic acid in the atmosphere.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  1. Aerosol Size Distribution Response to Anthropogenically Driven Historical Changes in Biogenic Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Pierce, J. R.; D'Andrea, S.; Acosta Navarro, J. C.; Farina, S.; Scott, C.; Farmer, D. K.; Spracklen, D. V.; Riipinen, I.

    2014-12-01

    Emissions of biological volatile organic compounds (BVOC) have changed in the past millennium due to changes in land use, temperature and CO2 concentrations. A recent model reconstruction of BVOC emissions over the past millennium predicted the changes in the three dominant secondary organic aerosol (SOA) producing BVOC classes (isoprene, monoterpenes and sesquiterpenes). The reconstruction predicted that in global averages isoprene emissions have decreased (land-use changes to crop/grazing land dominate the reduction), while monoterpene and sesquiterpene emissions have increased (temperature increases dominate the increases); however, all three show both increases and decreases in certain regions due to competition between the various influencing factors. These BVOC changes have largely been anthropogenic in nature, and land-use change was shown to have the most dramatic effect by decreasing isoprene emissions. We use these modeled estimates of these three dominant BVOC classes' emissions from the years 1000 to 2000 to test the effect of anthropogenic changes to BVOC emissions on SOA formation and global aerosol size distributions using the GEOS-Chem-TOMAS global aerosol microphysics model. With anthropogenic emissions (e.g. SO2, NOx, primary aerosols) held at present day values and BVOC emissions changed from year 1000 to year 2000 values, decreases in the number concentration of particles of size Dp > 80 nm (N80) of >25% in year 2000 relative to year 1000 were predicted in regions with extensive land-use changes since year 1000. This change in N80 was predominantly driven by a shift towards crop/grazing land that produces less BVOC than the natural vegetation. Similar sensitivities to year 1000 vs. year 2000 BVOC emissions exist when anthropogenic emissions are turned off. This large decrease in N80 could be a largely overlooked and important anthropogenic aerosol effect on regional climates.

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  3. Organic Aerosol Volatility Parameterizations and Their Impact on Atmospheric Composition and Climate

    NASA Technical Reports Server (NTRS)

    Tsigaridis, Konsta; Bauer, Susanne E.

    2015-01-01

    Despite their importance and ubiquity in the atmosphere, organic aerosols are still very poorly parameterized in global models. This can be explained by two reasons: first, a very large number of unconstrained parameters are involved in accurate parameterizations, and second, a detailed description of semi-volatile organics is computationally very expensive. Even organic aerosol properties that are known to play a major role in the atmosphere, namely volatility and aging, are poorly resolved in global models, if at all. Studies with different models and different parameterizations have not been conclusive on whether the additional complexity improves model simulations, but the added diversity of the different host models used adds an unnecessary degree of variability in the evaluation of results that obscures solid conclusions.

  4. Multiphase processing of organic hydroxynitrates in secondary organic aerosol from the radical-initiated oxidation of multi-olefinic monoterpenes

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Lee, L. S.; Shepson, P. B.; De Perre, C.

    2015-12-01

    One of the greatest challenges facing atmospheric and climate science is understanding the impacts human activities have on the natural environment and atmospheric chemistry. The production of condensable organic compounds due to interactions between atmospheric oxidants, nitrogenous pollutants, and biogenic volatile organic compounds (BVOCs) emitted from the terrestrial biosphere can contribute significantly to the formation and growth of secondary organic aerosol (SOA). Aerosol particles influence atmospheric radiative transfer, cloud formation, and thus atmospheric temperatures. Due to their solubility in water and adsorptive nature, hydroxylated organic nitrates (HORONO2) may contribute significantly to the formation and chemical aging of SOA, and serve as an important sink for NOx (NO+NO2). We recently observed that a monoterpene β-hydroxy-organic nitrate (C10H17NO4), produced from the OH oxidation of α-pinene in the presence of NOx, undergoes rapid processing in the aerosol phase via an acid-catalyzed and pH-dependent hydrolysis mechanism, potentially impacting SOA growth and molecular composition. Further processing in the aerosol phase via polymerization and formation of organosulfates is expected, yet studies related to product identification and their formation mechanisms are limited. In this presentation, I will discuss recent laboratory-based reaction chamber studies of gas-phase organic nitrate production, SOA formation, and acidity-dependent aerosol-phase processing of organic nitrates produced from the NO3 oxidation of γ-terpinene. This BVOC is a diolefin, which as modeling studies suggest, may be an important nighttime organic nitrate precursor. Gas-phase organic nitrate compounds resulting from NO3 oxidation were qualitatively identified applying I- chemical ionization mass spectrometry (CIMS) and quantified via calibration using synthetic standards generated in our laboratory. Aerosol-phase analysis was carried out employing Fourier transform

  5. Light absorption of organic aerosol from pyrolysis of corn stalk

    NASA Astrophysics Data System (ADS)

    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.

  6. Organic aerosol evolution and transport observed at Mt. Cimone (2165 m a.s.l.), Italy, during the PEGASOS campaign

    NASA Astrophysics Data System (ADS)

    Rinaldi, M.; Gilardoni, S.; Paglione, M.; Sandrini, S.; Fuzzi, S.; Massoli, P.; Bonasoni, P.; Cristofanelli, P.; Marinoni, A.; Poluzzi, V.; Decesari, S.

    2015-10-01

    High-resolution aerosol mass spectrometer measurements were performed, for the first time, at the Mt. Cimone Global Atmosphere Watch (GAW) station between June and July 2012, within the EU project PEGASOS and the ARPA-Emilia-Romagna project SUPERSITO. Submicron aerosol was dominated by organics (63 %), with sulfate, ammonium and nitrate contributing the remaining 20, 9 and 7 %, respectively. Organic aerosol (OA) was in general highly oxygenated, consistent with the remote character of the site; our observations suggest that oxidation and secondary organic aerosol (SOA) formation processes occurred during aerosol transport to high altitudes. All of the aerosol component concentrations as well as the OA elemental ratios showed a clear daily trend, driven by the evolution of the planetary boundary layer (PBL) and by the mountain wind regime. Higher loadings and lower OA oxidation levels were observed during the day, when the site was within the PBL, and therefore affected by relatively fresh aerosol transported from lower altitudes. Conversely, lower loadings and higher OA oxidation levels were observed at night, when the top of Mt. Cimone resided in the free troposphere although affected by the transport of residual layers on several days of the campaign. Analysis of the elemental ratios in a Van Krevelen space shows that OA oxidation follows a slope comprised between -0.5 and -1, consistent with addition of carboxylic groups, with or without fragmentation of the parent molecules. The increase of carboxylic groups during OA ageing is confirmed by the increased contribution of organic fragments containing more than one oxygen atom in the free troposphere night-time mass spectra. Finally, positive matrix factorization was able to deconvolve the contributions of relatively fresh OA (OOAa) originating from the PBL, more aged OA (OOAb) present at high altitudes during periods of atmospheric stagnation, and very aged aerosols (OOAc) transported over long distances in the

  7. Effect of secondary organic aerosol amount and condensational behavior on global aerosol size distributions

    NASA Astrophysics Data System (ADS)

    D'Andrea, S. D.; Häkkinen, S. A. K.; Westervelt, D. M.; Kuang, C.; Spracklen, D. V.; Riipinen, I.; Pierce, J. R.

    2013-05-01

    Recent research has shown that secondary organic aerosols (SOA) are major contributors to ultrafine particle growth to climatically relevant sizes, increasing global cloud condensation nuclei (CCN) concentrations within the continental boundary layer. Many models treat SOA solely as semivolatile, which leads to condensation of SOA proportional to the aerosol mass distribution; however, recent closure studies with field measurements show that a significant fraction of SOA condenses proportional to the aerosol surface area, which suggests a very low volatility. Additionally, while many global models contain only biogenic sources of SOA (with emissions generally 10-30 Tg yr-1), recent studies have shown a need for an additional source of SOA around 100 Tg yr-1 correlated with anthropogenic carbon monoxide (CO) emissions is required to match measurements. Here, we explore the significance of these two findings using the GEOS-Chem-TOMAS global aerosol microphysics model. The percent change in the number of particles of size Dp > 40 nm (N40) within the continental boundary layer between the surface-area-and massdistribution condensation schemes, both with the base biogenic SOA only, yielded a global increase of 8% but exceeds 100% in biogenically active regions. The percent change in N40 within the continental boundary layer between the base simulation (19 Tg yr-1) and the additional SOA (100 Tg yr-1) both using the surface area condensation scheme (very low volatility) yielded a global increase of 14%, and a global decrease in the number of particles of size Dp > 10 nm (N10) of 32%. These model simulations were compared to measured data from Hyytiälä, Finland and other global locations and confirmed a decrease in the model-measurement bias. Thus, treating SOA as very low volatile as well as including additional SOA correlated with anthropogenic CO emissions causes a significant global increase in the number of climatically relevant sized particles, and therefore we

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

    NASA Astrophysics Data System (ADS)

    Dreyfus, Matthew A.

    Analytical methods developed to sample and characterize ambient organic aerosols often face the trade-off between long sampling times and the loss of detailed information regarding specific chemical species present. The soft, universal ionization scheme of the Photoionization Aerosol Mass Spectrometer (PIAMS) allows for identification of various chemical compounds by a signature ion, often the molecular ion. The goal of this thesis work is to apply PIAMS to both laboratory and field experiments to answer questions regarding the formation, composition, and behavior of organic aerosols. To achieve this goal, a variety of hardware and software upgrades were administered to PIAMS to optimize the instrument. Data collection and processing software were either refined or built from the ground up to simplify difficult or monotonous tasks. Additional components were added to PIAMS with the intent to automate the instrument, enhance the results, and make the instrument more rugged and user-friendly. These changes, combined with the application of an external particle concentration system (mini-Versatile Aerosol Concentration Enrichment System, m-VACES), allowed PIAMS to be suitable for field measurements of organic aerosols. Two such field campaigns were completed, both at the State of Delaware Air Quality Monitoring Site in Wilmington, Delaware: a one week period in June, 2006, and an 18 day period in October and November of 2007. A sampling method developed was capable of collecting sufficient ambient organic aerosol and analyzing it with a time resolution of 3.5 minutes. Because of this method, short term concentration changes of individual species can be tracked. Combined with meteorological data, the behavior of these species can be analyzed as a function of time or wind direction. Many compounds are found at enhanced levels during the evening/night-time hours; potentially due to the combined effects of temperature inversion, and fresh emissions in a cooler environment

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  11. On the Interpretation of Oxygenated Organic Aerosols (and their Subtypes) Arising from Factor Analysis of Aerosol Mass Spectrometer Data

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.; Zhang, Q.; Canagaratna, M. R.; Ulbrich, I. M.; Ng, N. L.; Aiken, A. C.; Decarlo, P. F.; Kroll, J.; Mohr, C.; Allan, J. D.; Worsnop, D. R.

    2008-12-01

    Zhang et al. (ES&T 2005; ACP 2005) first performed factor analysis (FA) of Aerodyne Aerosol Mass Spectrometer (AMS) complete organic aerosol (OA) mass spectra. This study showed that an oxygenated organic aerosol (OOA) factor accounted for 2/3 of the OA mass at an urban site in Pittsburgh and strongly linked OOA to secondary organic aerosols (SOA). Many subsequent studies and the application of more powerful solution algorithms such as Positive Matrix Factorization (PMF) to the same FA problem have demonstrated the importance of OOA at most locations (e.g. Volkamer et al., GRL, 2006; Zhang et al., GRL, 2007; Lanz et al., ACP, 2007 and ES&T, 2008; Ulbrich et al., ACPD, 2008). Multiple studies have also identified several subtypes of OOA (e.g. OOA-1 and OOA-2). This type of analysis offers new insights because it provides some chemical resolution on the total OA mass with high time and size resolution, and bypasses the limitations of techniques that only analyze tracers and which may favor more reduced species. However the chemical resolution is limited and careful interpretation of the FA output is required, including the use of database spectra, time series of external tracers, tracer ratios, back-trajectory analyses, size- distribution analyses, etc. This presentation will address the interpretation of total OOA and its subfactors across a large range of locations in urban, suburban, rural, remote, and forested areas, and will compare with the results of other source apportionment techniques. Based on data from multiple datasets we conclude that (1) anthropogenic SOA in and downwind of urban areas is an important source of OOA; (2) motor vehicles, meat cooking, and trash burning are unlikely to be sources of primary OOA; (3) SOA from biogenic and biomass burning precursors are also clear sources of OOA; (4) primary biomass burning OA (P-BBOA) typically shows significant differences with ambient OOA factors; (5) heterogeneous oxidation of urban POA may give rise to

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

    PubMed

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

    2011-09-01

    Carbonaceous species, meteorological parameters, trace gases, and fogwater chemistry were measured during winter in the Indian city of Kanpur to study secondary organic aerosol (SOA) during foggy and clear (nonfoggy) days. Enhanced SOA production was observed during fog episodes. It is hypothesized that aqueous phase chemistry in fog drops is responsible for increasing SOA production. SOA concentrations on foggy days exceeded those on clear days at all times of day; peak foggy day SOA concentrations were observed in the evening vs peak clear day SOA concentrations which occurred in the afternoon. Changes in biomass burning emissions on foggy days were examined because of their potential to confound estimates of SOA production based on analysis of organic to elemental carbon (OC/EC) ratios. No evidence of biomass burning influence on SOA during foggy days was found. Enhanced oxidation of SO(2) to sulfate during foggy days was observed, possibly causing the regional aerosol to become more acidic. No evidence was found in this study, either, for effects of temperature or relative humidity on SOA production. In addition to SOA production, fogs can also play an important role in cleaning the atmosphere of carbonaceous aerosols. Preferential scavenging of water-soluble organic carbon (WSOC) by fog droplets was observed. OC was found to be enriched in smaller droplets, limiting the rate of OC deposition by droplet sedimentation. Lower EC concentrations were observed on foggy days, despite greater stagnation and lower mixing heights, suggesting fog scavenging and removal of EC was active as well. PMID:21790145

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

    PubMed

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

    2011-09-01

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

  14. BrO loss due to secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Buxmann, Joelle; Bleicher, Sergej; Zetzsch, Cornelius; Held, Andreas; Sommariva, Roberto; von Glasow, Roland; Platt, Ulrich; Ofner, Johannes

    2013-04-01

    One major source of heterogeneous released reactive halogen species (RHS) is primary aerosol from sea-salt particles, ejected by sea spray. Photoactivated RHS emissions, such as atomic Br and BrO radicals, can play a key role in the destruction of atmospheric ozone, influencing HOx and NOx chemistry. Through aerosol interaction they show potential indirect effects on global climate. The formation of RHS can be significantly reduced in the presence of organic aerosols. Additionally, halogen species were found to change the aerosol size distribution, the presence of functional groups and the optical properties. Furthermore, they may form halogenated species in the condensed phase of the organic aerosol - although the inhibition of the formation of RHS has not been quantified before. The interaction of secondary organic aerosols (SOA) from predominantly aliphatic (α-pinene) or aromatic (catechol and guaiacol) precursors and heterogeneously released halogens was studied in smog-chamber experiments. BrO and OClO released from salt aerosols were detected by a White system in combination with Differential Optical Absorption Spectroscopy (DOAS). The size and number distribution of aerosols from salt droplets (~150nm-1000nm) and from SOA (~5nm-150nm) was quantified by a SMPS (Scanning Mobility Particle Sizer) to obtain typical surface areas of 103μm2/cm3 and 2 x 102μm2/cm3, respectively. In the absence of SOA a BrO production rate per salt aerosol surface area of 5.2 x 1011 molec/cm2s =8500 pmol/m2s has been measured. This confirms model assumptions for BrO formation over the Dead Sea, where the Br2 flux of 80-154 pmol/m2s and HOBr flux= 800 pmol/m2s was increased by a factor of 20-30 to explain high BrO mixing ratios. In the presence of SOA from α-pinene, catechol and guaiacol the formation rate was significantly reduced. In a first approximation, neglecting gas phase reactions, the BrO loss rate regarding the surface area of SOA was calculated to be 42 x 1011 molec

  15. Fog scavenging of organic and inorganic aerosol in the Po Valley

    NASA Astrophysics Data System (ADS)

    Gilardoni, S.; Massoli, P.; Giulianelli, L.; Rinaldi, M.; Paglione, M.; Pollini, F.; Lanconelli, C.; Poluzzi, V.; Carbone, S.; Hillamo, R.; Russell, L. M.; Facchini, M. C.; Fuzzi, S.

    2014-07-01

    The interaction of aerosol with atmospheric water affects the processing and wet removal of atmospheric particles. Understanding such interaction is mandatory to improve model description of aerosol lifetime and ageing. We analyzed the aerosol-water interaction at high relative humidity during fog events in the Po Valley within the framework of the Agenzia Regionale per la Prevenzione e l'Ambiente (ARPA) - Emilia Romagna supersite project. For the first time in this area, the changes in particle chemical composition caused by fog are discussed along with changes in particle microphysics. During the experiment, 14 fog events were observed. The average mass scavenging efficiency was 70% for nitrate, 68% for ammonium, 61% for sulfate, 50% for organics, and 39% for black carbon. After fog formation, the interstitial aerosol was dominated by particles smaller than 200 nm Dva (vacuum aerodynamic diameter) and enriched in carbonaceous aerosol, mainly black carbon and water-insoluble organic aerosol. For each fog event, the size-segregated scavenging efficiency of nitrate and organic aerosol (OA) was calculated by comparing chemical species size distribution before and after fog formation. For both nitrate and OA, the size-segregated scavenging efficiency followed a sigmoidal curve, with values close to zero below 100 nm Dva and close to 1 above 700 nm Dva. OA was able to affect scavenging efficiency of nitrate in particles smaller than 300 nm Dva. A linear correlation between nitrate scavenging and particle hygroscopicity (κ) was observed, indicating that 44-51% of the variability of nitrate scavenging in smaller particles (below 300 nm Dva) was explained by changes in particle chemical composition. The size-segregated scavenging curves of OA followed those of nitrate, suggesting that organic scavenging was controlled by mixing with water-soluble species. In particular, functional group composition and OA elemental analysis indicated that more oxidized OA was scavenged

  16. Limited Effect of Anthropogenic Nitrogen Oxides on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Knote, C. J.; Tilmes, S.; Emmons, L. K.; Lamarque, J. F.; Yu, P.

    2014-12-01

    Globally secondary organic aerosol (SOA) is mostly formed from biogenic vegetation emissions and as such is regarded as natural aerosol that cannot be reduced by emission control legislation. However, recent research implies that human activities facilitate SOA formation by affecting the amount of precursor emission, the chemical processing and the partitioning into the aerosol phase. Among the multiple human influences, nitrogen oxides (NO + NO2 = NOx) have been assumed to play a critical role in the chemical formation of low volatile compounds. The goal of this study is to improve the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-Chem) by implementing an updated 4-product Volatility Basis Set (VBS) scheme, and apply it to investigate the impact of anthropogenic NOx on SOA. We first compare three different SOA parameterizations: a 2-product model and the updated VBS model both with and without a SOA aging parameterization. Secondly we evaluate predicted organic aerosol amounts against surface measurement from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network and Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns. We then perform sensitivity experiments to examine how the SOA loading responds to a 50% reduction in anthropogenic NOx in different regions. We find limited SOA reductions of -2.3%, -5.6% and -4.0% for global, southeastern U.S. and Amazon NOx perturbations, respectively. To investigate the chemical processes in more detail, we also use a simplified box model with the same gas-phase chemistry and gas-aerosol partitioning mechanism as in CAM4-Chem to examine the SOA yields dependence on initial precursor emissions and background NOx level. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- versus high-NOx pathways, OH versus NO3-initiated oxidation) and to offsetting

  17. Observations and analysis of organic aerosol evolution in some prescribed fire smoke plumes

    NASA Astrophysics Data System (ADS)

    May, A. A.; Lee, T.; McMeeking, G. R.; Akagi, S.; Sullivan, A. P.; Urbanski, S.; Yokelson, R. J.; Kreidenweis, S. M.

    2015-06-01

    Open biomass burning is a significant source of primary air pollutants such as particulate matter (PM) and non-methane organic gases (NMOG). However, the physical and chemical atmospheric processing of these emissions during transport is poorly understood. Atmospheric transformations of biomass burning emissions have been investigated in environmental chambers, but there have been limited opportunities to investigate these transformations in the atmosphere. In this study, we deployed a suite of real-time instrumentation on a Twin Otter aircraft to sample smoke from prescribed fires in South Carolina, conducting measurements at both the source and downwind to characterize smoke evolution with atmospheric aging. Organic aerosol (OA) within the smoke plumes was quantified using an aerosol mass spectrometer (AMS); refractory black carbon (rBC) was quantified using a single-particle soot photometer, and carbon monoxide (CO) and carbon dioxide (CO2) were measured using a cavity ring-down spectrometer. During the two fires for which we were able to obtain aerosol aging data, normalized excess mixing ratios and "export factors" of conserved species (rBC, CO, CO2) suggested that changes in emissions at the source did not account for most of the differences observed in samples of increasing age. An investigation of AMS mass fragments indicated that the in-plume fractional contribution (fm/z) to OA of the primary fragment (m/z 60) decreased downwind, while the fractional contribution of the secondary fragment (m/z 44) increased. Increases in f44 are typically interpreted as indicating chemical aging of OA. Likewise, we observed an increase in the O : C elemental ratio downwind, which is usually associated with aerosol aging. However, the rapid mixing of these plumes into the background air suggests that these chemical transformations may be attributable to the different volatilities of the compounds that fragment to these m/z in the AMS. The gas-particle partitioning behavior

  18. Industrial age to information age organizations: Changing business ethic

    SciTech Connect

    Stinson, J.E.

    1994-12-31

    In this paper, we argue that Informatoin age organizations both allow and require a higher level of moral development on the part of the members of the organizations. We describe industrial age and information age organization structure charactreistics and identify moral values consistent with each structure.

  19. The Dominance of Organic Aerosols During NEAQS 2002

    NASA Astrophysics Data System (ADS)

    Bates, T. S.; Quinn, P. K.; Middlebrook, A. M.

    2003-12-01

    Aerosol chemical, physical and optical measurements were made aboard the NOAA RV Ronald H. Brown off the coast of New England during July/August 2002 as part of the New England Air Quality Study (NEAQS). Measurements (generally 20 to 100 km from the coast) were made downwind of urban centers (NYC, Boston) and rural areas, and in air masses that had not been in contact with land for several days ("marine"). On average during NEAQS, 72+/-9% of the dry aerosol mass sampled 18 m above the sea surface was in the < 1 μ m fraction (size cut at 55% RH). This submicron fraction accounted for 84+/- 14% of the aerosol light scattering. The major sub-micron aerosol components were ammonium sulfate and particulate organic matter (POM, defined here as 1.6 times the concentration of organic carbon). The ammonium to non-sea-salt (nss) sulfate ratio increased in the urban air masses. The mass ratio of POM to nss sulfate plus ammonium ranged from 0.38 to 8.8 with values generally higher in the rural/marine air masses. POM was the dominant aerosol component in 75% of the samples. Even considering the water associated with ammonium sulfate at ambient RH and assuming no water uptake of the POM, POM was often the major source of the regional haze. These data are similar to that found off the mid-Atlantic states during TARFOX but contrary to the current understanding that the New England haze is primarily a result of sulfate aerosol. The data raise two important questions: Are these data representative of "normal" conditions along the New England Coast? And, what is the source of the POM? We can not address the first question from our single cruise but will attempt to address the latter using other measurements made aboard the ship. We will address both questions during the summer of 2004 using ship and aircraft measurements in this region along with a more detailed study of the organic POM species.

  20. Water-Soluble Organic Species in Biomass Burning Aerosols in Southern Africa: Their Chemical Identification and Spatial Distribution

    NASA Astrophysics Data System (ADS)

    Gao, S.; Hegg, D. A.; Hobbs, P. V.; Kirchstetter, T. W.; Magi, B.

    2001-12-01

    During the SAFARI-2000 field campaign, 14 aerosol samples were collected from an aircraft in plumes from biomass fires (under both flaming and smoldering conditions), at various distances from the fire source. Also collected were 36 aerosol samples in haze layers ranging from the surface to 16,000 feet, some of which could be associated with specific fires. The samples were collected on teflon membrane filters (lower size limit of about 30nm in diameter) which were analyzed for total aerosol mass loading and chemical composition using several analytical techniques. Particular effort was made to speciate the water-soluble portion of the aerosol organics. Seven organic acids and seven carbohydrate species (and their possible stereoisomers) were identified and quantified, along with three inorganic anions and five inorganic cations. The identified organic species accounted for up to 32% of the total aerosol mass; compared with concurrent total carbon and organic carbon measurements, the identified organics constituted at least 5% to 30% of the mass of the total aerosol organics. A number of conspicuous spatial distribution patterns were observed for these species. For instance, using K+ to correct for dilution, it was found that gluconate, oxalate, succinate, and glutarate, along with sulfate and nitrate, all increased significantly in mass concentration from the fire source going downwind. This suggests secondary formation of these species during aerosol aging. On the other hand, formate and acetate showed decreasing trends downwind, probably due to the loss of these volatile species to the gas phase. Another striking pattern is that anhydrosugars (e.g. levoglucosan) had the highest aerosol mass fraction near smoldering fires but a very low fraction in the haze layers, whereas, dicarboxylic acids showed an almost opposite trend. This implies possible chemical reaction processes converting intermediate organic products, such as levoglucosan, to smaller products like

  1. Uptake of Ambient Organic Gases to Acidic Sulfate Aerosols

    NASA Astrophysics Data System (ADS)

    Liggio, J.; Li, S.

    2009-05-01

    The formation of secondary organic aerosols (SOA) in the atmosphere has been an area of significant interest due to its climatic relevance, its effects on air quality and human health. Due largely to the underestimation of SOA by regional and global models, there has been an increasing number of studies focusing on alternate pathways leading to SOA. In this regard, recent work has shown that heterogeneous and liquid phase reactions, often leading to oligomeric material, may be a route to SOA via products of biogenic and anthropogenic origin. Although oligomer formation in chamber studies has been frequently observed, the applicability of these experiments to ambient conditions, and thus the overall importance of oligomerization reactions remain unclear. In the present study, ambient air is drawn into a Teflon smog chamber and exposed to acidic sulfate aerosols which have been formed in situ via the reaction of SO3 with water vapor. The aerosol composition is measured with a High Resolution Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS), and particle size distributions are monitored with a scanning mobility particle sizer (SMPS). The use of ambient air and relatively low inorganic particle loading potentially provides clearer insight into the importance of heterogeneous reactions. Results of experiments, with a range of sulfate loadings show that there are several competing processes occurring on different timescales. A significant uptake of ambient organic gases to the particles is observed immediately followed by a slow shift towards higher m/z over a period of several hours indicating that higher molecular weight products (possibly oligomers) are being formed through a reactive process. The results suggest that heterogeneous reactions can occur with ambient organic gases, even in the presence of ammonia, which may have significant implications to the ambient atmosphere where particles may be neutralized after their formation.

  2. Secondary organic aerosol formation from road vehicle emissions

    NASA Astrophysics Data System (ADS)

    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

  3. Incremental Reactivity Effects of Anthropogenic and Biogenic Volatile Organic Compounds on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Kacarab, M.; Li, L.; Carter, W. P. L.; Cocker, D. R., III

    2015-12-01

    Two surrogate reactive organic gas (ROG) mixtures were developed to create a controlled reactivity environment simulating different urban atmospheres with varying levels of anthropogenic (e.g. Los Angeles reactivity) and biogenic (e.g. Atlanta reactivity) influences. Traditional chamber experiments focus on the oxidation of one or two volatile organic compound (VOC) precursors, allowing the reactivity of the system to be dictated by those compounds. Surrogate ROG mixtures control the overall reactivity of the system, allowing for the incremental aerosol formation from an added VOC to be observed. The surrogate ROG mixtures were developed based on that used to determine maximum incremental reactivity (MIR) scales for O3 formation from VOC precursors in a Los Angeles smog environment. Environmental chamber experiments were designed to highlight the incremental aerosol formation in the simulated environment due to the addition of an added anthropogenic (aromatic) or biogenic (terpene) VOC. All experiments were conducted in the UC Riverside/CE-CERT dual 90m3 environmental chambers. It was found that the aerosol precursors behaved differently under the two altered reactivity conditions, with more incremental aerosol being formed in the anthropogenic ROG system than in the biogenic ROG system. Further, the biogenic reactivity condition inhibited the oxidation of added anthropogenic aerosol precursors, such as m-xylene. Data will be presented on aerosol properties (density, volatility, hygroscopicity) and bulk chemical composition in the gas and particle phases (from a SYFT Technologies selected ion flow tube mass spectrometer, SIFT-MS, and Aerodyne high resolution time of flight aerosol mass spectrometer, HR-ToF-AMS, respectively) comparing the two controlled reactivity systems and single precursor VOC/NOx studies. Incremental aerosol yield data at different controlled reactivities provide a novel and valuable insight in the attempt to extrapolate environmental chamber

  4. Secondary organic aerosol formation and primary organic aerosol oxidation from biomass-burning smoke in a flow reactor during FLAME-3

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Day, D. A.; Cubison, M. J.; Brune, W. H.; Bon, D.; de Gouw, J. A.; Jimenez, J. L.

    2013-11-01

    We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A "potential aerosol mass" (PAM) flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer-reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days of aging in the atmosphere, and allowing for us to extend the investigation of smoke aging beyond the oxidation levels achieved in traditional smog chambers. Volatile organic compound (VOC) observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net-SOA-to-POA ratio of biomass-burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OHexp), typically peaking around three days of equivalent atmospheric photochemical age (OHexp~3.9 × 1011 molecules cm-3 s), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors

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

    SciTech Connect

    Mei, Fan; Hayes, Patrick L.; Ortega, Amber; Taylor, Jonathan W.; Allan, James D.; Gilman, Jessica; Kuster, William; de Gouw, Joost; Jimenez, Jose L.; Wang, Jian

    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.

  6. On the Physicochemical Processes Controlling Organic Aerosol Hygroscopicity

    NASA Astrophysics Data System (ADS)

    Petters, Sarah Suda

    Aerosol particles in the atmosphere can influence air quality and climate through their interaction with water. Aerosols are an important factor in cloud formation because they serve as cloud condensation nuclei (CCN). Organic compounds contribute a large fraction of the atmospheric aerosol mass but their ability to serve as CCN is less certain relative to inorganic compounds. Limitations of the measurement techniques and theoretical gaps in understanding have prevented agreement between predicted and measured CCN. One way to quantify a compound's CCN activity is by the hygroscopicity parameter, kappa. This dissertation presents research towards constraining the variability of organic aerosol kappa at the process level using three approaches: developing a measurement technique; measuring the dependence of kappa on molecular functional groups; and measuring the effect of surface active molecules on kappa for mixtures. Chapter 2 presents a Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) instrument to measure aerosol water uptake at high relative humidity (RH). Measurements up to 99% RH were achieved by improving the precision of aerosol sizing, actively controlling temperature, and calibrating RH between measurements. Osmotic coefficients were obtained within +/-20% for organic aerosols sized between 30 and 200 nanometers. These results may improve water uptake models by providing accurate data at high RH. Chapter 3 presents a study of the sensitivity of kappa to changes in molecular functional group composition for pure compounds. Molecules were synthesized via gas and liquidphase reactions varying the type and location of functional groups, purified by High Performance Liquid Chromatography (HPLC), and routed for CCN measurement. The hydroxyl (-OH) and carbon chain length (-CH2-) changed kappa most, where hydroxyl groups increase kappa and longer carbon chains decrease kappa. This suggests that hydroxyl groups and molecular size dominate the

  7. Effects of aerosol phase and water uptake for understanding organic aerosol oxidation

    NASA Astrophysics Data System (ADS)

    Fitzgerald, C.; Gallimore, P. J.; Fuller, S.; Lee, J.; Garrascon, V.; Achakulwisut, P.; Björkegren, A.; Spring, D. R.; Pope, F. D.; Kalberer, M.

    2012-04-01

    Oxidation reactions of atmospheric organic aerosols strongly influence many important processes in the atmosphere such as aerosol-cloud interactions or heterogeneous chemistry. We present results of an experimental laboratory study with three organic model aerosol systems (maleic, arachidonic and oleic acid) investigating the effect of particle phase and humidity on the oxidative processing of the particle. Two experimental techniques are combined in this investigation. An electrodynamic balance is used to levitate single particles and assess changes in particle size and mass (due to water uptake and/or loss of volatile oxidation products) and phase (liquid or solid) during and after chemical processing with ozone. An aerosol flow tube was used to investigate the detailed chemical composition of the oxidized aerosol with offline ultra-high resolution mass spectrometry. The role of water (i.e., relative humidity) in the oxidation scheme of the three carboxylic acids is very compound specific and the particle phase has a strong effect on the particle processing. Relative humidity was observed to have a major influence on the oxidation scheme of maleic acid and arachidonic acid, whereas no dependence was observed for the oxidation of oleic acid. In both, maleic acid and arachidonic acid, an evaporation of volatile oxidation products could only be observed when the particle was exposed to high relative humidities. Maleic and arachidonic acid change their phase from liquid to solid upon oxidation or upon changes in humidity and efficient oxidative processing of the particle bulk can only occur when the particle is in liquid form. A detailed oxidation mechanism for maleic acid is presented taking the strong effects of water into account. In contrast, oleic acid is liquid under all conditions at room temperature (dry or elevated humidity, pure or oxidized particle). Thus ozone can easily diffuse into the bulk of the particle irrespective of the oxidation conditions. In

  8. Investigating types and sources of organic aerosol in Rocky Mountain National Park using aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schurman, M. I.; Lee, T.; Sun, Y.; Schichtel, B. A.; Kreidenweis, S. M.; Collett, J. L., Jr.

    2015-01-01

    The environmental impacts of atmospheric particles are highlighted in remote areas where visibility and ecosystem health can be degraded by even relatively low particle concentrations. Submicron particle size, composition, and source apportionment were explored at Rocky Mountain National Park using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer. This summer campaign found low average, but variable, particulate mass (PM) concentrations (max = 93.1 μg m-3, avg. = 5.13 ± 2.72 μg m-3) of which 75.2 ± 11.1% is organic. Low-volatility oxidized organic aerosol (LV-OOA, 39.3% of PM1 on average) identified using Positive Matrix Factorization appears to be mixed with ammonium sulfate (3.9% and 16.6% of mass, respectively), while semi-volatile OOA (27.6%) is correlated with ammonium nitrate (nitrate: 4.3%); concentrations of these mixtures are enhanced with upslope (SE) surface winds from the densely populated Front Range area, indicating the importance of transport. A local biomass burning organic aerosol (BBOA, 8.4%) source is suggested by mass spectral cellulose combustion markers (m/z 60 and 73) limited to brief, high-concentration, polydisperse events (suggesting fresh combustion), a diurnal maximum at 22:00 local standard time when campfires were set at adjacent summer camps, and association with surface winds consistent with local campfire locations. The particle characteristics determined here represent typical summertime conditions at the Rocky Mountain site based on comparison to ~10 years of meteorological, particle composition, and fire data.

  9. Investigating types and sources of organic aerosol in Rocky Mountain National Park using aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schurman, M. I.; Lee, T.; Sun, Y.; Schichtel, B. A.; Kreidenweis, S. M.; Collett, J. L., Jr.

    2014-07-01

    The environmental impacts of atmospheric particles are highlighted in remote areas where visibility and ecosystem health can be degraded by even relatively low particle concentrations. Submicron particle size, composition, and source apportionment were explored at Rocky Mountain National Park using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer. This summer campaign found low average, but variable, particulate mass (PM) concentrations (max = 93.1 μg m-3, avg. = 5.13 ± 2.72 μg m-3) of which 75.2 ± 11.1% is organic. Low-volatility oxidized organic aerosol (LV-OOA, 39.3% of PM1 on average) identified using Positive Matrix Factorization appears to be mixed with ammonium sulfate (3.9 and 16.6% of mass, respectively), while semi-volatile OOA (27.6%) is correlated with ammonium nitrate (nitrate: 4.3%); concentrations of these mixtures are enhanced with upslope (SE) surface winds from the densely populated Front Range area, indicating the importance of transport. A local biomass burning organic aerosol (BBOA, 8.4%) source is suggested by mass spectral cellulose combustion markers (m/zs 60 and 73) limited to brief, high-concentration, polydisperse events (suggesting fresh combustion), a diurnal maximum at 22:00 local standard time (LST) when campfires were set at adjacent summer camps, and association with surface winds consistent with local campfire locations. The particle characteristics determined here represent typical summertime conditions at the Rocky Mountain site based on comparison to ∼10 years of meteorological, particle composition, and fire data.

  10. Ice nucleation in sulfuric acid/organic aerosols: implications for cirrus cloud formation

    NASA Astrophysics Data System (ADS)

    Beaver, M. R.; Elrod, M. J.; Garland, R. M.; Tolbert, M. A.

    2006-03-01

    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 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.

  11. Ice nucleation in sulfuric acid/organic aerosols: implications for cirrus cloud formation

    NASA Astrophysics Data System (ADS)

    Beaver, M. R.; Elrod, M. J.; Garland, R. M.; Tolbert, M. A.

    2006-08-01

    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.

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

    NASA Astrophysics Data System (ADS)

    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. Water Activity Limits the Hygroscopic Growth Factor of Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Rodriguez, L. I.; Cabrera, J. A.; Golden, D.; Tabazadeh, A.

    2007-12-01

    In this work we study the hygroscopic behavior of organic aerosols, which has important implications for Earth's climate. The hygroscopic growth factor (HGF) is defined as the ratio of the diameter of a spherical particle when it is exposed to dry conditions to that at humid conditions. We present a new formulation to express the HGF of an aerosol particle as a function of water activity (aw) in the aqueous phase. This new formulation matches reported HGFs for common inorganic salts and water-miscible organic particles that are known to deliquesce into aqueous drops at high relative humidities (RH). Many studies use tandem differential mobility analyzers (TDMA) to determine the HGF of organic aerosols. For example, Brooks et al. used a TDMA to measure a HGF of 1.2 for 2 μm phthalic acid (PA) particles at 90% RH (aw= 0.9). However, water activity limits the growth of a particle that can be attributed to water uptake. We have assembled a vapor pressure apparatus to measure aw of aqueous solutions at room temperature. Measured water activities for PA, used in our growth formulation, yield a HGF of ~ 1.0005 for 2 μm PA particles at 90% RH. Comparing our results against Brooks et al. suggests that TDMA experiments may grossly overestimate the HGF of PA particles since water activity limits this growth to below 1.0005. Alternatively, we suggest that the adsorption of a negligible mass of water by a highly porous PA particle can lead to an apparent growth in particle size by changing its morphology. Other studies also use TDMAs to measure HGFs of secondary organic aerosols (SOAs). HGFs reported for SOAs are very similar to PA, suggesting that the observed growth may be due to morphological changes in particle size rather than water uptake as commonly assumed. We built a smog chamber where an organic precursor, such as d-limonene, reacts with nitrogen oxides under UV radiation to produce SOAs. We compare the HGFs for SOAs obtained with our method to those obtained with

  14. Organic peroxides' gas-particle partitioning and rapid heterogeneous decomposition on secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Li, Huan; Chen, Zhongming; Huang, Liubin; Huang, Dao

    2016-02-01

    Organic peroxides, important species in the atmosphere, promote secondary organic aerosol (SOA) aging, affect HOx radicals cycling, and cause adverse health effects. However, the formation, gas-particle partitioning, and evolution of organic peroxides are complicated and still unclear. In this study, we investigated in the laboratory the production and gas-particle partitioning of peroxides from the ozonolysis of α-pinene, which is one of the major biogenic volatile organic compounds in the atmosphere and an important precursor for SOA at a global scale. We have determined the molar yields of hydrogen peroxide (H2O2), hydromethyl hydroperoxide (HMHP), peroxyformic acid (PFA), peroxyacetic acid (PAA), and total peroxides (TPOs, including unknown peroxides) and the fraction of peroxides in α-pinene/O3 SOA. Comparing the gas-phase peroxides with the particle-phase peroxides, we find that gas-particle partitioning coefficients of PFA and PAA are 104 times higher than the values from the theoretical prediction, indicating that organic peroxides play a more important role in SOA formation than previously expected. Here, the partitioning coefficients of TPO were determined to be as high as (2-3) × 10-4 m3 µg-1. Even so, more than 80 % of the peroxides formed in the reaction remain in the gas phase. Water changes the distribution of gaseous peroxides, while it does not affect the total amount of peroxides in either the gas or the particle phase. Approx. 18 % of gaseous peroxides undergo rapid heterogeneous decomposition on SOA particles in the presence of water vapor, resulting in the additional production of H2O2. This process can partially explain the unexpectedly high H2O2 yields under wet conditions. Transformation of organic peroxides to H2O2 also preserves OH in the atmosphere, helping to improve the understanding of OH cycling.

  15. Organic peroxides gas-particle partitioning and rapid heterogeneous decomposition on secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Li, H.; Chen, Z. M.; Huang, L. B.; Huang, D.

    2015-10-01

    Organic peroxides, important species in the atmosphere, will promote secondary organic aerosols (SOA) aging, affect HOx radicals cycling, and cause adverse health effects. However, the formation, gas-particle partitioning, and evolution of organic peroxides are extremely complicated and still unclear. In this study, we investigate in the laboratory the production and gas-particle partitioning of peroxides from the ozonolysis of α-pinene, which is one of the major biogenic volatile organic compounds in the atmosphere and is an important precursor for SOA at a global scale. We have determined the molar yields of hydrogen peroxide (H2O2), hydroxymethyl hydroperoxide (HMHP), peroxyformic acid (PFA), peroxyacetic acid (PAA) and total peroxides (TPO, including unknown peroxides) and the fraction of peroxides in SOA. Comparing the gas-phase and particle-phase peroxides, we find that gas-particle partitioning coefficients of PFA and PAA are 104 times higher than theoretical prediction, indicating that organic peroxides play a more important role in the SOA formation than expected previously. Here, we give the partitioning coefficients of TPO as (2-3) × 10-4 m3μg-1. Even so, more than 80 % of the peroxides formed in the reaction remain in the gas phase. Water does not affect the total amount of peroxides in either the gas or particle phase, but can change the distribution of gaseous peroxides. About 18 % gaseous peroxides undergo rapid heterogeneous decomposition on SOA particles in the presence of water vapor, resulting in the additional production of H2O2. This process can partially interpret the unexpected high H2O2 yield under wet conditions. Transformation of organic peroxides to H2O2 also saves OH in the atmosphere, helping to improve the understanding of OH cycling.

  16. Predicting secondary organic aerosol formation rates in southeast Texas

    NASA Astrophysics Data System (ADS)

    Russell, Matthew; Allen, David T.

    2005-04-01

    Rates of secondary organic aerosol (SOA) formation, due to the reactions of aromatics and monoterpenes, were estimated for southeast Texas by incorporating a modified version of the Statewide Air Pollution Research Center's chemical mechanism (SAPRC99) into the Comprehensive Air Quality Model with extensions (CAMx version 3.10). The model included explicit representation of the reactions of five SOA precursors (α-pinene, β-pinene, sabinene, d-limonene, and Δ3-carene). Reactions of each SOA precursor with O3, OH radical, and NO3 radical were included. The model also included separate reactions for low- and high-SOA-yield aromatic groups with the OH radical. SOA yields in the mechanisms were estimated using compound-specific yield information (ΔSOA/ΔHC) derived from smog chamber experiments conducted by J. R. Odum and colleagues and R. J. Griffin and colleagues. The form of the SOA yield model was based on the work of J. R. Odum and colleagues and is a function of existing organic aerosol concentrations. Existing organic aerosol concentrations were estimated on the basis of ambient measurements of total organic carbon in southeast Texas. The reactions of monoterpenes (predominantly α-pinene and β-pinene) with ozone led to the most regional SOA formation, followed by monoterpenes with the nitrate radical. Aromatic-OH reactions led to less regional SOA formation compared to monoterpenes; however, this formation occurs close to the urban and industrial areas of Houston. In contrast, SOA formation due to the reactions of monoterpenes occurred in the forested areas north of the urban area. The results of this study are in qualitative agreement with estimates of SOA formation based on ambient data from the same time period.

  17. Chemical composition of emissions from urban sources of fine organic aerosol

    SciTech Connect

    Hildemann, L.M.; Markowski, G.R.; Cass, G.R. )

    1991-04-01

    A dilution source sampling system was used to collect primary fine aerosol emissions from important sources of urban organic aerosol, including a boiler burning No. 2 fuel oil, a home fireplace, a fleet of catalyst-equipped and noncatalyst automobiles, heavy-duty diesel trucks, natural gas home appliances, and meat cooking operations. Alternative dilution sampling techniques were used to collect emissions from cigarette smoking and a roofing tar pot, and grab sample techniques were employed to characterize paved road dust, brake lining wear, and vegetative detritus. Organic aerosol constituted the majority of the fine aerosol mass emitted from many of the sources tested. Fine primary organic aerosol emissions within the heavily urbanized western portion of the Los Angeles Basin were determined to total 29.8 metric ton/day. Over 40% of these organic aerosol emissions are from anthropogenic pollution sources that are expected to emit contemporary (nonfossil) aerosol carbon, in good agreement with the available ambient monitoring data.

  18. Molecular dynamics studies of organic-coated nano aerosols

    NASA Astrophysics Data System (ADS)

    Chakraborty, Purnendu

    2008-10-01

    Atmospheric aerosols play an important role in atmospheric processes. These aerosol particles can affect climate through scattering, transmission and absorption of radiation as well as acting as cloud condensation nuclei. It has recently been found that fatty acids reside on the surfaces of marine and continental aerosols. In this research, an attempt has been made to understand the structures and properties of such organic coated aerosols using Molecular Dynamics simulation. The model particle consisted of a water droplet coated with fatty acid. The density profile (using both Coarse-Grained and Atomistic/United atom models) demonstrated that such aerosol particles have an inverted micelle structure consisting of an aqueous core and with the hydrophobic hydrocarbon tails exposed to the atmosphere. For smaller chains, with the organic molecules directed radially outwards from the water---organic interface) the normal pressure profile showed that the organic coating is under tension resulting in a 'negative' surface tension. As a result, such particles would have an inverse Kelvin vapor pressure effect and would be able to process water vapor despite the hydrophobic surface. Following the work on surface tension, the rate of water uptake by coated aerosols was computed. It was found that the sticking coefficient of water vapor on such particles was about a sixth of that on pure water droplets. This may seem to imply that the net condensation rate is lower, but we also need to take into account the evaporation of water from such particles. With a significant reduction in the evaporation rate (the coating lends greater stability to the particle resulting in reduced evaporation rate), the equilibrium vapor pressure of water on such particles reduced, resulting in a "net water attractor". Thus if such structures were created in sufficient concentration, they might be important contributors in the cloud condensation process. Next the effect of longer Fatty acid molecules

  19. OZONE-ISOPRENE REACTION: RE-EXAMINATION OF THE FORMATION OF SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    The reaction of ozone and isoprene has been studied to examine physical and chemical characteristics of the secondary organic aerosol formed. Using a scanning mobility particle sizer, the volume distribution of the aerosol was found in the range 0.05 - 0.2 µm. The aerosol yield w...

  20. Seasonal differences of urban organic aerosol composition - an ultra-high resolution mass spectrometry study

    NASA Astrophysics Data System (ADS)

    Rincon, A. G.; Calvo, A. I.; Dietzel, M.; Kalberer, M.

    2012-04-01

    The understanding of the chemical composition of atmospheric aerosols, their properties and reactivity are important for assessing aerosol effects upon both global climate change and human health. The composition of organic aerosols is poorly understood mainly due to their highly complex chemical composition with several thousand compounds. In the present study the water-soluble organic fraction of ambient particles collected at an urban site in Cambridge, UK, during different seasons were analysed with ultra-high resolution mass spectrometry. For several thousand peaks in the mass specta (between 3000-6000) an elemental composition could be assigned and summer samples generally contained more components than winter samples. Up to 80% of the peaks in the mass spectra contain nitrogen and/or sulphur functional groups and only about 20% of the compounds contain only C, H and O atoms. In summer the fraction of compounds with oxidized nitrogen and sulphur groups increases compared to winter indicating a photo-chemical formation route of these multifunctional compounds. In addition to oxidized nitrogen compounds a large number of highly unsaturated reduced nitrogen-containing compounds were detected, corresponding likely to cyclic amines. A significant number of oxidized PAHs have been detected in summer samples, which were not present in winter, indicating again photo-chemical aging processes. Both, amines and long-chain aliphatic acids (also frequently observed in these urban samples) are likely signatures of biomass burning and primary biological sources. Potential biomass burning markers are discussed. Particle-phase oligomerisation reactions have only been observed to a very limited degree. Compounds larger than m/z 350 almost exclusively contained N and/or S functional groups indicating that the high molecular weight compounds in these organic aerosol extracts might be mainly due to particle-phase heterogeneous reactions of organic compounds with inorganic

  1. Organic Aerosol Nucleation and Growth at the CERN CLOUD chamber

    NASA Astrophysics Data System (ADS)

    Tröstl, Jasmin; Lethipalo, Katrianne; Bianchi, Federico; Sipilä, Mikko; Nieminen, Tuomo; Wagner, Robert; Frege, Carla; Simon, Mario; Weingartner, Ernest; Gysel, Martin; Dommen, Josef; Baltensperger, Urs

    2014-05-01

    It is well known that atmospheric aerosols influence the climate by changing Earth's radiation balance (IPCC 2007 and 2013). Recent models have shown (Merikanto et al. 2009) that aerosol nucleation is one of the biggest sources of low level cloud condensation nuclei. Still, aerosol nucleation and growth are not fully understood. The driving force of nucleation and growth is sulfuric acid. However ambient nucleation and growth rates cannot be explained by solely sulfuric acid as precursor. Recent studies have shown that only traces of precursors like ammonia and dimethylamine enhance the nucleation rates dramatically (Kirkby et al. 2011, Almeida et al., 2013). Thus the role of different aerosol precursor needs to be studied not only in ambient but also in very well controlled chamber experiments. The CLOUD (Cosmics Leaving OUtdoor Droplets) experiment enables conducting experiments very close to atmospheric conditions and with a very low contaminant background. The latest CLOUD experiments focus on the role of organics in aerosol nucleation and growth. For this purpose, numerous experiments with alpha-pinene have been conducted at the CERN CLOUD chamber. Several state-of-the-art instruments were used to cover the whole complexity of the experiment. Chamber conditions were set to 40% relative humidity and 5° C. Atmospheric concentrations of SO2, O3, HONO, H2O and alpha-pinene were injected to the chamber. Different oxidation conditions were used, yielding different levels of oxidized organics: (1) OH radicals, (2) Ozone with the OH scavenger H2 (pure ozonolysis) and (3) both. SO2 was injected to allow for sulfuric acid production. Optical UV fibers were used to enable photochemical reactions. A high field cage (30 kV) can be turned on to remove all charged particles in the chamber to enable completely neutral conditions. Comparing neutral conditions to the beam conditions using CERN's proton synchrotron, the fraction of ion-induced nucleation can be studied. Using

  2. Burning of olive tree branches: a major organic aerosol source in the Mediterranean

    NASA Astrophysics Data System (ADS)

    Kostenidou, E.; Kaltsonoudis, C.; Tsiflikiotou, M.; Louvaris, E.; Russell, L. M.; Pandis, S. N.

    2013-09-01

    Aerosol produced during the burning of olive tree branches was characterized with both direct source sampling (using a mobile smog chamber) and with ambient measurements during the burning season. The fresh particles were composed of 80% organic matter, 8-10% black carbon (BC), 5% potassium, 3-4% sulfate, 2-3% nitrate and 0.8% chloride. Almost half of the fresh olive tree branches burning organic aerosol (otBB-OA) consisted of alkane groups. Their mode diameter was close to 70 nm. The oxygen to carbon (O : C) ratio of the fresh otBB-OA was 0.29 ± 0.04. The mass fraction of levoglucosan in PM1 was 0.034-0.043, relatively low in comparison with most fuel types. This may lead to an underestimation of the otBB-OA contribution if levoglucosan is being used as a wood burning tracer. Chemical aging was observed during smog chamber experiments, as f44 and O : C ratio increased, due to reactions with OH radicals and O3. The otBB-OA AMS mass spectrum differs from the other published biomass burning spectra, with a main difference at m/z 60, used as levoglucosan tracer. In addition to particles, volatile organic compounds (VOCs) such as methanol, acetonitrile, acrolein, benzene, toluene and xylenes are also emitted. Positive matrix factorization (PMF) was applied to the ambient organic aerosol data and 3 factors could be identified: OOA (oxygenated organic aerosol, 55%), HOA (hydrocarbon-like organic aerosol, 11.3%) and otBB-OA 33.7%. The fresh chamber otBB-OA AMS spectrum is close to the PMF otBB-OA spectrum and resembles the ambient mass spectrum during olive tree branches burning periods. We estimated an otBB-OA emission factor of 3.5 ± 0.9 g kg-1. Assuming that half of the olive tree branches pruned is burned in Greece, 2300 ± 600 tons of otBB-OA are emitted every year. This activity is one of the most important fine aerosol sources during the winter months in Mediterranean countries.

  3. Burning of olive tree branches: a major organic aerosol source in the Mediterranean

    NASA Astrophysics Data System (ADS)

    Kostenidou, E.; Kaltsonoudis, C.; Tsiflikiotou, M.; Louvaris, E.; Russell, L. M.; Pandis, S. N.

    2013-03-01

    Aerosol produced during the burning of olive tree branches was characterized with both direct source-sampling (using a mobile smog chamber) and with ambient measurements during the burning season. The fresh particles were composed of 80% organic matter, 8-10% black carbon (BC), 5% potassium, 3-4% sulfate, 2-3% nitrate and 0.8% chloride. Almost half of the fresh olive tree branches burning organic aerosol (otBB-OA) consisted of alkane groups. Their mode diameter was close to 70 nm. The oxygen to carbon (O:C) ratio of the fresh otBB-OA was 0.29 ± 0.04. The mass fraction of levoglucosan in PM1 was 0.034-0.043, relatively low in comparison with most fuel types. This may lead to an underestimation of the otBB-OA contribution if levoglucosan is being used as a wood burning tracer. Chemical aging was observed during smog chamber experiments, as f44 and O:C ratio increased, due to reactions with OH radicals and O3. The otBB-OA AMS mass spectrum differs from the other published biomass burning spectra, with a main difference at m/z 60, used as levoglucosan tracer. In addition to particles, volatile organic compounds (VOCs) such as methanol, acetonitrile, acrolein, benzene, toluene and xylenes are also emitted. Positive matrix factorization (PMF) was applied to the ambient organic aerosol data and 3 factors could be identified: OOA (oxygenated organic aerosol, 55%), HOA (hydrocarbon-like organic aerosol, 11.3%) and otBB-OA 33.7%. The fresh chamber otBB-OA AMS spectrum is close to the PMF otBB-OA spectrum and resembles the ambient mass spectrum during olive tree branches burning periods. We estimated an otBB-OA emission factor of 3.5 ± 0.2 g kg-1. Assuming that half of the olive tree branches pruned is burned in Greece 2280 ± 140 tons of otBB-OA are emitted every year. This activity is one of the most important fine aerosol sources during the winter months in the Mediterranean countries.

  4. Deconvolution and Quantification of Primary and Oxygenated Organic Aerosols: Technique Development and Applications to the Pittsburgh AMS Datasets

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Jimenez, J.; Alfarra, R.; Allan, J.; Coe, H.; Worsnop, D.; Canagaratna, M.

    2004-12-01

    A new technique has been developed to deconvolve and quantify the mass concentrations of primary and oxygenated organic aerosol (POA and OOA) using highly time-resolved organic mass spectral data obtained with an Aerodyne Aerosol Mass Spectrometer (AMS). OOA may comprise secondary organic aerosol (SOA) as well as oxidized POA. This technique involves a series of multivariate linear regressions that use mass-to-charge ratios (m/z's) 57 (mostly C4H9+) and 44 (mostly CO2+), the identified AMS mass spectral tracers for POA and OOA, respectively, as the initial principal components followed by an iterative algorithm to evaluate and "purify" POA and OOA mass spectral tracers. We have applied this technique to the AMS organic aerosol data acquired at the EPA Pittsburgh Supersite during September 2002 and have observed excellent agreement between the reconstructed organic concentrations (= POA + OOA) and the measured values (r2 = 0.997, slope = 0.998). The reconstructed organic data matrix (size = 3199 time steps x 300 m/z's) explains 99% of the variance in the measured time series. The extracted mass spectrum of POA shows high similarity to those of diesel exhaust sampled during a chase study, lab-measured lubricating oil, and freshly emitted traffic aerosols measured in urban environments. The spectrum of OOA closely resembles those of aged organic aerosols sampled in remote areas and also shows similarity with the spectrum of fulvic acid-a humic-like substance that is ubiquitous in the environment and has previously been used as an analogue to represent polyacid compounds found in highly processed and oxidized atmospheric organic aerosols. Organic aerosols in Pittsburgh during Sept. 2002 are mainly oxygenated, on average consisting of ~ 70% OOA (likely mainly secondary in nature). Pronounced diurnal variations in the POA/OOA contributions to organic mass have been observed, with the contribution of POA peaking in the morning rush hours while that of OOA is largest in

  5. Secondary Organic Aerosol Formation from the Ozonolysis of Cycloalkenes

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  6. Secondary organic aerosol formation through fog processing of VOCs

    NASA Astrophysics Data System (ADS)

    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.

  7. Evaluating the potential impact of marine organic aerosols on climate assessments

    NASA Astrophysics Data System (ADS)

    Meskhidze, N.; Gantt, B.; Xu, J.

    2011-12-01

    Natural aerosols influence clouds and the hydrological cycle by their ability to act as cloud condensation nuclei (CCN). Because the anthropogenic contribution to climate forcing represents the difference between the total forcing and that from natural aerosols, understanding background aerosols is necessary to evaluate the influences of anthropogenic aerosols on cloud reflectivity and persistence (so-called indirect radiative forcing) and on precipitation. The effects of marine organic aerosols on microphysical properties of shallow clouds are explored using the NCAR Community Atmosphere Model (CAM5.0), coupled with the PNNL Modal Aerosol Model. Organic enrichment of sea spray is estimated using newly developed wind speed dependent size-resolved source function, while production of secondary organic aerosol of marine origin is inferred from the ocean emissions of biogenic trace gases. Model-predicted abundance of CCN in remote marine atmosphere is compared to satellite and in-situ data. Simulations show that over biologically productive ocean waters organic aerosols of marine origin can contribute up to 20% increase in CCN (at a supersaturation of 0.2%) number concentrations. Corresponding changes associated with cloud properties (liquid water path and droplet number) can reduce global annual mean indirect radiative forcing of anthropogenic aerosol by 0.1 Wm-2 or 8%. This study suggests that neglecting the effects of marine organic aerosol in climate models could result in overprediction of aerosol indirect effect.

  8. Small molecules as tracers in atmospheric secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    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. Improving Molecular Level Chemical Speciation of Organic Aerosols

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  10. Dosimeter for monitoring vapors and aerosols of organic compounds

    DOEpatents

    Vo-Dinh, T.

    1987-07-14

    A dosimeter is provided for collecting and detecting vapors and aerosols of organic compounds. The dosimeter comprises a lightweight, passive device that can be conveniently worn by a person as a badge or placed at a stationary location. The dosimeter includes a sample collector comprising a porous web treated with a chemical for inducing molecular displacement and enhancing phosphorescence. Compounds are collected onto the web by molecular diffusion. The web also serves as the sample medium for detecting the compounds by a room temperature phosphorescence technique. 7 figs.

  11. Dosimeter for monitoring vapors and aerosols of organic compounds

    DOEpatents

    Vo-Dinh, Tuan

    1987-01-01

    A dosimeter is provided for collecting and detecting vapors and aerosols of organic compounds. The dosimeter comprises a lightweight, passive device that can be conveniently worn by a person as a badge or placed at a stationary location. The dosimeter includes a sample collector comprising a porous web treated with a chemical for inducing molecular displacement and enhancing phosphorescence. Compounds are collected onto the web by molecular diffusion. The web also serves as the sample medium for detecting the compounds by a room temperature phosphorescence technique.

  12. Organic nitrate aerosol formation via NO3 + BVOC in the Southeastern US

    NASA Astrophysics Data System (ADS)

    Ayres, B. R.; Allen, H. M.; Draper, D. C.; Brown, S. S.; Wild, R. J.; Jimenez, J. L.; Day, D. A.; Campuzano-Jost, P.; Hu, W.; de Gouw, J.; Koss, A.; Cohen, R. C.; Duffey, K. C.; Romer, P.; Baumann, K.; Edgerton, E.; Takahama, S.; Thornton, J. A.; Lee, B. H.; Lopez-Hilfiker, F. D.; Mohr, C.; Goldstein, A. H.; Olson, K.; Fry, J. L.

    2015-06-01

    Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOC) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that nitrate radical (NO3) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO3 to terpenes are calculated and correlated to gas and aerosol organic nitrate concentrations made during the campaign. Correlation of NO3 radical consumption to organic nitrate aerosol as measured by Aerosol Mass Spectrometry (AMS) and Thermal Dissociation - Laser Induced Fluorescence (TD-LIF) suggests a range of molar yield of aerosol phase monoterpene nitrates of 23-44 %. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to terpenes and show C10H17NO5, likely a hydroperoxy nitrate, is a major nitrate oxidized terpene product being incorporated into aerosols. The comparable isoprene product C5H9NO5 was observed to contribute less than 0.5 % of the total organic nitrate in the aerosol-phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45 % of the NOy budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO3 uptake produced nitrate aerosol mass loading comparable to that of organic nitrate produced via NO3 + BVOC.

  13. Effects of NOx on the volatility of secondary organic aerosol from isoprene photooxidation

    SciTech Connect

    Xu, Lu; Kollman, Matthew S.; Song, Chen; Shilling, John E.; Ng, L. N.

    2014-01-28

    The effects of NOx on the volatility of the secondary organic aerosol (SOA) formed from isoprene photooxidation are investigated in environmental chamber experiments. Two types of experiments are performed. In HO2-dominant experiments, organic peroxy radicals (RO2) primarily react with HO2. In mixed experiments, RO2 reacts through multiple pathways. The volatility and oxidation state of isoprene SOA is sensitive to and displays a non-linear dependence on NOx levels. When initial NO/isoprene ratio is approximately 3 (ppbv:ppbv), SOA are shown to be most oxidized and least volatile, associated with the highest SOA yield. A High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) is applied to characterize the key chemical properties of aerosols. While the composition of SOA in mixed experiments does not change substantially over time, SOA become less volatile and more oxidized as oxidation progresses in HO2-dominant experiments. Analysis of the SOA composition suggests that the further reactions of organic peroxides and alcohols may produce carboxylic acids, which might play a strong role in SOA aging.

  14. Transboundary secondary organic aerosol in western Japan: An observed limitation of the f44 oxidation indicator

    NASA Astrophysics Data System (ADS)

    Irei, Satoshi; Takami, Akinori; Sadanaga, Yasuhiro; Miyoshi, Takao; Arakaki, Takemitsu; Sato, Kei; Kaneyasu, Naoki; Bandow, Hiroshi; Hatakeyama, Shiro

    2015-11-01

    To obtain evidence for secondary organic aerosol formation during the long-range transport of air masses over the East China Sea, we conducted field measurements in March 2012 at the Fukue atmospheric monitoring station, Nagasaki, in western Japan. The relative abundance of m/z 44 in fine organic aerosol (f44) was measured by an Aerodyne aerosol chemical speciation monitor. The stable carbon isotope ratio (δ13C) of low-volatile water-soluble organic carbon (LV-WSOC) in the daily filter samples of total suspended particulate matter was also analyzed using an elemental-analyzer coupled with an isotope ratio mass spectrometer. Additionally, in situ measurements of NOx and NOy were performed using NOx and NOy analyzers. The measurements showed that, unlike the systematic trends observed in a previous field study, a scatter plot for δ13C of LV-WSOC versus f44 indicated a random variation. Comparison of f44 with the estimated photochemical age by the NOx/NOy ratio revealed that the random distribution of f44 values near 0.2 is likely an indication of saturation already. Such f44 values were significantly lower than the observed f44 (∼0.3) at Hedo in the previous study. These findings imply that the saturation point of f44, and the use of f44 as an oxidation indicator, is case dependent.

  15. Aerosol transport from Chiang Mai, Thailand to Mt. Lulin, Taiwan - Implication of aerosol aging during long-range transport

    NASA Astrophysics Data System (ADS)

    Chuang, Ming-Tung; Lee, Chung-Te; Chou, Charles C.-K.; Engling, Guenter; Chang, Shih-Yu; Chang, Shuenn-Chin; Sheu, Guey-Rong; Lin, Neng-Huei; Sopajaree, Khajornsak; Chang, You-Jia; Hong, Guo-Jun

    2016-07-01

    The transport of biomass burning (BB) aerosol from Indochina may cause a potential effect on climate change in Southeast Asia, East Asia, and the Western Pacific. Up to now, the understanding of BB aerosol composition modification during long-range transport (LRT) is still very limited due to the lack of observational data. In this study, atmospheric aerosols were collected at the Suthep/Doi Ang Khang (DAK) mountain sites in Chiang Mai, Thailand and the Lulin Atmospheric Background Station (Mt. Lulin) in central Taiwan from March to April 2010 and from February to April 2013, respectively. During the study period, an upwind and downwind relationship between the Suthep/DAK and Lulin sites (2400 km apart) was validated by backward trajectories. Comprehensive aerosol properties were resolved for PM2.5 water-soluble inorganic ions, carbonaceous content, water-soluble/insoluble organic carbon (WSOC/WIOC), dicarboxylic acids and their salts (DCAS), and anhydrosugars. A Modification Factor (MF) is proposed by employing non-sea-salt potassium ion (nss-K+) or fractionalized elemental carbon evolved at 580 °C after pyrolized OC correction (EC1-OP) as a BB aerosol tracer to evaluate the mass fraction changes of aerosol components from source to receptor regions during LRT. The MF values of nss-SO42-, NH4+, NO3-, OC1 (fractionalized organic carbon evolved from room temperature to 140 °C), OP (pyrolized OC fraction), DCAS, and WSOC were above unity, which indicated that these aerosol components were enhanced during LRT as compared with those in the near-source region. In contrast, the MF values of anhydrosugars ranged from 0.1 to 0.3, indicating anhydrosugars have degraded during LRT.

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  17. Photochemical evolution of organic aerosols observed in urban plumes from Hong Kong and the Pearl River Delta of China

    NASA Astrophysics Data System (ADS)

    Zhou, Shengzhen; Wang, Tao; Wang, Zhe; Li, Weijun; Xu, Zheng; Wang, Xinfeng; Yuan, Chao; Poon, C. N.; Louie, Peter K. K.; Luk, Connie W. Y.; Wang, Wenxing

    2014-05-01

    Organic aerosols influence human health and global radiative forcing. However, their sources and evolution processes in the atmosphere are not completely understood. To study the aging and production of organic aerosols in a subtropical environment, we measured hourly resolved organic carbon (OC) and element carbon (EC) in PM2.5 at a receptor site (Tung Chung, TC) in Hong Kong from August 2011 to May 2012. The average OC concentrations exhibited the highest values in late autumn and were higher during the daytime than at night. The secondary organic carbon (SOC) concentrations, which were estimated using an EC-tracer method, comprised approximately half of the total OC on average. The SOC showed good correlation with odd oxygen (Ox = O3 + NO2) in the summer and autumn seasons, suggestive of contribution of photochemical activities to the formation of secondary organic aerosols (SOA). We calculated production rates of SOA using the photochemical age (defined as -Log10(NOx/NOy)) in urban plumes from the Pearl River Delta (PRD) region and Hong Kong during pollution episodes in summer and autumn. The CO-normalized SOC increased with the photochemical age, with production rates ranging from 1.31 to 1.82 μg m-3 ppmv-1 h-1 in autumn and with a larger rate in summer (3.86 μg m-3 ppmv-1 h-1). The rates are in the range of the rates observed in the outflow from Mexico City, the eastern U.S. and Los Angeles. Microscopic analyses of the individual aerosol particles revealed large contrasts of aerosol physico-chemical properties on clean and smoggy days, with thick organic coatings internally mixed with inorganic sulfate for all particle sizes in the aged plumes from the PRD region.

  18. Evaporation Kinetics and Phase of Laboratory and Ambient Secondary Organic Aerosol

    SciTech Connect

    Vaden, Timothy D.; Imre, Dan G.; Beranek, Josef; Shrivastava, ManishKumar B.; Zelenyuk, Alla

    2011-02-08

    Field measurements of secondary organic aerosol (SOA) find higher mass loads than predicted by models, sparking intense efforts to find additional SOA sources but leaving the assumption of rapid SOA evaporation unchallenged. We characterized room-temperature evaporation of pure SOA and SOA formed in the presence of spectator organic vapors with and without aging. We find that it takes ~24 hrs for pure SOA particles to evaporate 75% of their mass, which is in sharp contrast to the ~10 minutes timescales predicted by models. The presence of spectator organic vapors and aging dramatically reduces the evaporation, and in some cases nearly stops it. For all cases, SOA evaporation behavior is size independent and does not follow the liquid droplet evaporation kinetics assumed by models.

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

    SciTech Connect

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

    2013-10-25

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

  20. New evidence of an organic layer on marine aerosols

    NASA Astrophysics Data System (ADS)

    Tervahattu, Heikki; Hartonen, Kari; Kerminen, Veli-Matti; Kupiainen, Kaarle; Aarnio, Päivi; Koskentalo, Tarja; Tuck, Adrian F.; Vaida, Veronica

    2002-04-01

    An extraordinary episode of fine particles (diameter mainly <2.5 μm) occurred in Helsinki, southern Finland, at the end of February 1998. The air masses came from the North Atlantic Ocean and passed over France, Germany, and southern Scandinavia. Particles were collected during the episode as well as before and after it. Uncoated particle samples were adhered to an indium substrate and were studied by a scanning electron microscope (SEM) coupled with an energy dispersive X-ray microanalyzer (EDX). A great proportion of the particles behaved differently than aerosols previously studied by microscopic techniques. The particles (size mainly 0.5-1 μm) did not exhibit solid shape. They were ``bubbling'' or ``pulsating'' continually, enlarging in one part and shrinking in another. Some particles were broken down, especially when the beam of the electron microscope was focused on them. EDX analyses showed that the particles contained much carbon together with oxygen, sulfur, and sodium. Ion analyses by ion chromatography revealed high concentrations of sodium, sulfate, nitrate, and ammonium. The particles were identified as marine sea-salt aerosols, which had accumulated anthropogenic emissions and lost chloride during their flow through continental polluted air. The shape fluctuations and the high carbon content observed by SEM/EDX led to the conclusion that the aerosols were enclosed by an organic membrane. Direct insertion probe/mass spectrometry investigations showed remarkable amounts of fragmented aliphatic hydrocarbons, which were considered as an evidence of a lipid membrane on the surface of the particles. The impact of the posited organic film on the properties of sea-salt particles, as well as on Earth's climate, is discussed.

  1. Biotic stress: a significant contributor to organic aerosol in Europe?

    NASA Astrophysics Data System (ADS)

    Bergström, R.; Hallquist, M.; Simpson, D.; Wildt, J.; Mentel, T. F.

    2014-12-01

    We have investigated the potential impact on organic aerosol formation from biotic stress-induced emissions (SIE) of organic molecules from forests in Europe (north of lat. 45° N). Emission estimates for sesquiterpenes (SQT), methyl salicylate (MeSA) and unsaturated C17 compounds, due to different stressors, are based on experiments in the Jülich Plant Atmosphere Chamber (JPAC), combined with estimates of the fraction of stressed trees in Europe based on reported observed tree damage. SIE were introduced in the EMEP MSC-W chemical transport model and secondary organic aerosol (SOA) yields from the SIE were taken from the JPAC experiments. Based on estimates of current levels of infestation and the JPAC aerosol yields, the model results suggest that the contribution to SOA in large parts of Europe may be substantial. It is possible that SIE contributes as much, or more, to organic aerosol than the constitutive biogenic VOC emissions, at least during some periods. Based on the assumptions in this study, SIE-SOA are estimated to constitute between 50 and 70 % of the total biogenic SOA (BSOA) in a current-situation scenario where the biotic stress in northern and central European forests causes large SIE of MeSA and SQT. An alternative current-situation scenario with lower SIE, consisting solely of SQT, leads to lower SIE-SOA, between 20 and 40 % of the total BSOA. Hypothetical future scenarios with increased SIE, due to higher degrees of biotic stress, show that SOA formation due to SIE can become even larger. Unsaturated C17 BVOC (biogenic volatile organic compounds) emitted by spruce infested by the forest-honey generating bark louse, Cinara pilicornis, have a high SOA-forming potential. A model scenario investigating the effect of a regional, episodic infestation of Cinara pilicornis in Baden-Württemberg, corresponding to a year with high production of forest honey, shows that these types of events could lead to very large organic aerosol formation in the

  2. Air quality impact and physicochemical aging of biomass burning aerosols during the 2007 San Diego wildfires.

    PubMed

    Zauscher, Melanie D; Wang, Ying; Moore, Meagan J K; Gaston, Cassandra J; Prather, Kimberly A

    2013-07-16

    Intense wildfires burning >360000 acres in San Diego during October, 2007 provided a unique opportunity to study the impact of wildfires on local air quality and biomass burning aerosol (BBA) aging. The size-resolved mixing state of individual particles was measured in real-time with an aerosol time-of-flight mass spectrometer (ATOFMS) for 10 days after the fires commenced. Particle concentrations were high county-wide due to the wildfires; 84% of 120-400 nm particles by number were identified as BBA, with particles <400 nm contributing to mass concentrations dangerous to public health, up to 148 μg/m(3). Evidence of potassium salts heterogeneously reacting with inorganic acids was observed with continuous high temporal resolution for the first time. Ten distinct chemical types shown as BBA factors were identified through positive matrix factorization coupled to single particle analysis, including particles comprised of potassium chloride and organic nitrogen during the beginning of the wildfires, ammonium nitrate and amines after an increase of relative humidity, and sulfate dominated when the air mass back trajectories passed through the Los Angeles port region. Understanding BBA aging processes and quantifying the size-resolved mass and number concentrations are important in determining the overall impact of wildfires on air quality, health, and climate.

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

    SciTech Connect

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

    2009-09-22

    The meso-scale chemistry-transport model CHIMERE is used to assess our understanding of major sources and formation processes leading to a fairly large amount of organic aerosols [OA, including primary OA (POA) and secondary OA (SOA)] observed in Mexico City during the MILAGRO field project (March 2006). Chemical analyses of submicron aerosols from aerosol mass spectrometers (AMS) indicate that organic particles found in the Mexico City basin have a large fraction of oxygenated organic species (OOA), which have strong correspondence with SOA, and that their production actively continues downwind of the city. The SOA formation is modeled here by the first-generation oxidation of anthropogenic (i.e., aromatics, alkanes) and biogenic (i.e., monoterpenes and isoprene) precursors and their partitioning into both organic and aqueous phases. The near-surface model evaluation shows that predicted OA correlates reasonably well with measurements during the campaign, however it remains a factor of 2 lower than the measured total OA. Fairly good agreement is found between predicted and observed POA within the city suggesting that anthropogenic and biomass burning emissions are reasonably captured. Consistent with previous studies in Mexico City, large discrepancies are encountered for SOA species, with a factor of 5-10 model underestimate. When only anthropogenic SOA precursors were considered, the model was able to reproduce within a factor of two the sharp increase in SOA concentrations during the late morning at both urban and near-urban locations. However, predicted SOA concentrations were unrealistically low when photochemistry was not active, especially overnight. These nighttime discrepancies were not significantly reduced when greatly enhanced partitioning to the aerosol phase was assumed. Model sensitivity results suggest that observed nighttime SOA concentrations are strongly influenced by the regional background (~2µg/m3) from biogenic origin, which is transported

  4. Changes in droplet surface tension affect the observed hygroscopicity of photochemically aged biomass burning aerosol.

    PubMed

    Giordano, Michael R; Short, Daniel Z; Hosseini, Seyedehsan; Lichtenberg, William; Asa-Awuku, Akua A

    2013-10-01

    This study examines the hygroscopic and surface tension properties as a function of photochemical aging of the aerosol emissions from biomass burning. Experiments were conducted in a chamber setting at the UC-Riverside Center for Environmental Research and Technology (CE-CERT) Atmospheric Processes Lab using two biomass fuel sources, manzanita and chamise. Cloud condensation nuclei (CCN) measurements and off-line filter sample analysis were conducted. The water-soluble organic carbon content and surface tension of the extracted filter samples were measured. Surface tension information was then examined with Köhler theory analysis to calculate the hygroscopicity parameter, κ. Laboratory measurement of biomass burning smoke from two chaparral fuels is shown to depress the surface tension of water by 30% or more at organic matter concentrations relevant at droplet activation. Accounting for surface tension depression can lower the calculated κ by a factor of 2. This work provides evidence for surface tension depression in an important aerosol system and may provide closure for differing sub- and supersaturated κ measurements. PMID:23957441

  5. Changes in droplet surface tension affect the observed hygroscopicity of photochemically aged biomass burning aerosol.

    PubMed

    Giordano, Michael R; Short, Daniel Z; Hosseini, Seyedehsan; Lichtenberg, William; Asa-Awuku, Akua A

    2013-10-01

    This study examines the hygroscopic and surface tension properties as a function of photochemical aging of the aerosol emissions from biomass burning. Experiments were conducted in a chamber setting at the UC-Riverside Center for Environmental Research and Technology (CE-CERT) Atmospheric Processes Lab using two biomass fuel sources, manzanita and chamise. Cloud condensation nuclei (CCN) measurements and off-line filter sample analysis were conducted. The water-soluble organic carbon content and surface tension of the extracted filter samples were measured. Surface tension information was then examined with Köhler theory analysis to calculate the hygroscopicity parameter, κ. Laboratory measurement of biomass burning smoke from two chaparral fuels is shown to depress the surface tension of water by 30% or more at organic matter concentrations relevant at droplet activation. Accounting for surface tension depression can lower the calculated κ by a factor of 2. This work provides evidence for surface tension depression in an important aerosol system and may provide closure for differing sub- and supersaturated κ measurements.

  6. Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

    DOE PAGES

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-12-08

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. Small differences are found for themore » no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9–5.6, 6.4–12.0 and 0.9–2.8 % for global, southeast US and Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

  7. Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-12-01

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. Small differences are found for the no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9-5.6, 6.4-12.0 and 0.9-2.8 % for global, southeast US and Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

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

    SciTech Connect

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

    2010-03-01

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

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

    SciTech Connect

    Hodzic, A.; Kleinman, L.; Jimenez, J. L.; Madronich, S.; Canagaratna, M. R.; DeCarlo, P. F.; Fast, J.

    2010-06-01

    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 downwind. Similar

  10. Aerosol size distribution and radiative forcing response to anthropogenically driven historical changes in biogenic secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    D'Andrea, S. D.; Acosta Navarro, J. C.; Farina, S. C.; Scott, C. E.; Rap, A.; Farmer, D. K.; Spracklen, D. V.; Riipinen, I.; Pierce, J. R.

    2015-03-01

    Emissions of biogenic volatile organic compounds (BVOCs) have changed in the past millennium due to changes in land use, temperature, and CO2 concentrations. Recent reconstructions of BVOC emissions have predicted that global isoprene emissions have decreased, while monoterpene and sesquiterpene emissions have increased; however, all three show regional variability due to competition between the various influencing factors. In this work, we use two modeled estimates of BVOC emissions from the years 1000 to 2000 to test the effect of anthropogenic changes to BVOC emissions on secondary organic aerosol (SOA) formation, global aerosol size distributions, and radiative effects using the GEOS-Chem-TOMAS (Goddard Earth Observing System; TwO-Moment Aerosol Sectional) global aerosol microphysics model. With anthropogenic emissions (e.g., SO2, NOx, primary aerosols) turned off and BVOC emissions changed from year 1000 to year 2000 values, decreases in the number concentration of particles of size Dp > 80 nm (N80) of > 25% in year 2000 relative to year 1000 were predicted in regions with extensive land-use changes since year 1000 which led to regional increases in the combined aerosol radiative effect (direct and indirect) of > 0.5 W m-2 in these regions. We test the sensitivity of our results to BVOC emissions inventory, SOA yields, and the presence of anthropogenic emissions; however, the qualitative response of the model to historic BVOC changes remains the same in all cases. Accounting for these uncertainties, we estimate millennial changes in BVOC emissions cause a global mean direct effect of between +0.022 and +0.163 W m-2 and the global mean cloud-albedo aerosol indirect effect of between -0.008 and -0.056 W m-2. This change in aerosols, and the associated radiative forcing, could be a largely overlooked and important anthropogenic aerosol effect on regional climates.

  11. Natural organic compounds as tracers for biomass combustion in aerosols

    SciTech Connect

    Simoneit, B.R.T. |; Abas, M.R. bin |; Cass, G.R. |; Rogge, W.F. |; Mazurek, M.A.; Standley, L.J.; Hildemann, L.M.

    1995-08-01

    Biomass combustion is an important primary source of carbonaceous particles in the global atmosphere. Although various molecular markers have already been proposed for this process, additional specific organic tracers need to be characterized. The injection of natural product organic tracers to smoke occurs primarily by direct volatilization/steam stripping and by thermal alteration based on combustion temperature. The degree of alteration increases as the burn temperature rises and the moisture content of the fuel decreases. Although the molecular composition of organic matter in smoke particles is highly variable, the molecular structures of the tracers are generally source specific. The homologous compound series and biomarkers present in smoke particles are derived directly from plant wax, gum and resin by volatilization and secondarily from pyrolysis of biopolymers, wax, gum and resin. The complexity of the organic components of smoke aerosol is illustrated with examples from controlled burns of temperate and tropical biomass fuels. Burning of biomass from temperate regions (i.e., conifers) yields characteristic tracers from diterpenoids as well as phenolics and other oxygenated species, which are recognizable in urban airsheds. The major organic components of smoke particles from tropical biomass are straight-chain, aliphatic and oxygenated compounds and triterpenoids. The precursor-to-product approach of organic geochemistry can be applied successfully to provide tracers for studying smoke plume chemistry and dispersion.

  12. Interpretation of Secondary Organic Aerosol Formation from Diesel Exhaust Photooxidation in an Environmental Chamber

    SciTech Connect

    Nakao, Shunsuke; Shrivastava, ManishKumar B.; Nguyen, Anh; Jung, Hee-Jung; Cocker, David R.

    2011-04-14

    Secondary organic aerosol (SOA) formation from diesel exhaust in a smog chamber was investigated. Particle volume measurement based on mobility diameter is shown to underestimate SOA formation from diesel exhaust due to the external void space of agglomerate particles, in which case mass-based measurement technique is necessary. Rapid determination of particle effective density as a function of particle mass was performed by an Aerosol Particle Mass analyzer – Scanning Mobility Particle Sizer (APM-SMPS) to obtain particle mass concentration and fractal dimension. Continuous aging of aerosol was observed in terms of atomic ratio (O/C), from 0.05 to 0.25 in 12 hours, underscoring the importance of multi-generational oxidation of low-volatile organic vapors emitted from diesel engine as the significant source of oxygenated SOA. Experimental conditions possibly have strong impacts on physical evolution of diesel particulates in a smog chamber. Higher particle effective densities were observed when raw exhaust was injected into a full bag as opposed to filling a bag with diluted exhaust using an ejector diluter. When longer transfer line was used for injecting diesel exhaust into the smog chamber, rapid particle coagulation was observed, leading to increasing particle volume concentration in dark while its mass concentration is decreasing.

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

    NASA Astrophysics Data System (ADS)

    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.

    2011-10-01

    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 in the m/z range 12-250 showing Pearson's r values >0.94 for the correlations between the different SOA types after 5 h 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 oxidized 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 5 h 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 based on their carbon number revealed that the SOA source with the highest O : C ratio had the largest fraction of small ions. Fragment ions containing up to 3 carbon atoms accounted for 66%, 68%, 72% and 76% of the organic spectrum of the SOA produced by the diesel car, wood burner, α-pinene and

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

    NASA Astrophysics Data System (ADS)

    Gómez-González, Y.; Wang, W.; Vermeylen, R.; Chi, X.; Neirynck, J.; Janssens, I. A.; Maenhaut, W.; Claeys, M.

    2012-01-01

    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 (0.7organic 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.

  15. Observations and analysis of organic aerosol evolution in some prescribed fire smoke plumes

    NASA Astrophysics Data System (ADS)

    May, A. A.; Lee, T.; McMeeking, G. R.; Akagi, S.; Sullivan, A. P.; Urbanski, S.; Yokelson, R. J.; Kreidenweis, S. M.

    2015-01-01

    Open biomass burning is a significant source of primary air pollutants such as particulate matter and non-methane organic gases. However, the physical and chemical atmospheric processing of these emissions during transport is poorly understood. Atmospheric transformations of biomass burning emissions have been investigated in environmental chambers, but there have been limited opportunities to investigate these transformations in the atmosphere. In this study, we deployed a suite of real-time instrumentation on a Twin Otter aircraft to sample smoke from prescribed fires in South Carolina, conducting measurements at both the source and downwind to characterize smoke evolution with atmospheric aging. Organic aerosol (OA) within the smoke plumes was quantified using an Aerosol Mass Spectrometer (AMS), along with refractory black carbon (rBC) using a Single Particle Soot Photometer and carbon monoxide (CO) and carbon dioxide (CO2) using a Cavity Ring-Down Spectrometer. During the two fires for which we were able to obtain aerosol aging data, normalized excess mixing ratios and "export factors" of conserved species (rBC, CO, CO2) were unchanged with increasing sample age. Investigation of AMS mass fragments indicated that the in-plume fractional contribution (fm/z) to OA of the primary fragment (m/z 60) decreased downwind, while the fractional contribution of the secondary fragment (m/z 44) increased. Increases in f44 are typically interpreted as indicating chemical production of secondary OA (SOA). Likewise, we observed an increase in the O : C elemental ratio downwind, which is usually associated with aerosol aging. However, the rapid mixing of these plumes into the background air suggests that these chemical transformations may be attributable to the different volatilities of the compounds that fragment to these m/z in the AMS. The gas-particle partitioning behavior of the bulk OA observed during the study was consistent with the predictions from a parameterization

  16. Do primary marine aerosol organics play a role in the biological regulation of climate?

    NASA Astrophysics Data System (ADS)

    Quinn, P.; Bates, T. S.; Coffman, D. J.; Russell, L. M.; Modini, R. L.

    2015-12-01

    Field and laboratory observations reveal a source of primary marine organic aerosol that is emitted to the atmosphere along with inorganic sea salt during the wind-driven production of sea spray aerosol (SSA). Surface seawater processes and properties that control the amount and the composition of organics emitted to the atmosphere are not well understood. Ramifications of the emission of primary marine organic aerosol on clouds and climate have been suggested but not confirmed. An oceanic, biological impact on clouds and climate by primary marine aerosol requires that a) the organic fraction of SSA is controlled by surface ocean biological processes and b) that primary marine aerosol makes up a significant number fraction of CCN in the marine boundary layer. Generation and characterization of freshly emitted SSA in the laboratory and at sea have revealed information about the size, composition, volatility, and hygroscopicity of primary marine aerosol. It has been shown that SSA is an internal mixture of sea salt and organics with the organic fraction increasing with decreasing particle size. In addition, quantification of the enrichment of organic matter in freshly emitted SSA relative to seawater has shown that high enrichments occur in regions of both eutrophic and oligotrophic waters, indicating that enrichment can be decoupled from local biological activity. Measurements of ambient (not generated) marine aerosol number size distributions and size-segregated chemical composition can be used to estimate the number fraction of CCN attributable to primary marine aerosol. An analysis of Eastern Pacific, Northern Atlantic, and Southern Ocean marine aerosol indicates that the primary marine aerosol makes up only a small fraction of the total CCN in the marine atmosphere. This presentation will consider current evidence derived from generation of freshly emitted SSA and measurements of ambient marine aerosol to assess the role of primary marine aerosol organics in the

  17. Chemical sinks of organic aerosol: kinetics and products of the heterogeneous oxidation of erythritol and levoglucosan.

    PubMed

    Kessler, Sean H; Smith, Jared D; Che, Dung L; Worsnop, Douglas R; Wilson, Kevin R; Kroll, Jesse H

    2010-09-15

    The heterogeneous oxidation of pure erythritol (C(4)H(10)O(4)) and levoglucosan (C(6)H(10)O(5)) particles was studied in order to evaluate the effects of atmospheric aging on the mass and chemical composition of atmospheric organic aerosol. In contrast to what is generally observed for the heterogeneous oxidation of reduced organics, substantial volatilization is observed in both systems. However, the ratio of the decrease in particle mass to the decrease in the concentration of the parent species is about three times higher for erythritol than for levoglucosan, indicating that details of chemical structure (such as carbon number, cyclic moieties, and oxygen-containing functional groups) play a governing role in the importance of volatilization reactions. The kinetics of the reaction indicate that while both compounds react at approximately the same rate, reactions of their oxidation products appear to be slowed substantially. Estimates of volatilities of organic species based on elemental composition measurements suggest that the heterogeneous oxidation of oxygenated organics may be an important loss mechanism of organic aerosol.

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

    SciTech Connect

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

    2015-01-06

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

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

    PubMed

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

    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 result in new functional groups, changed UV/VIS absorption, 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.

  1. Observed secondary organic aerosol (SOA) and organic nitrate yields from NO3 oxidation of isoprene

    NASA Astrophysics Data System (ADS)

    Rollins, A. W.; Fry, J. L.; Kiendler-Scharr, A.; Wooldridge, P. J.; Brown, S. S.; Fuchs, H.; Dube, W.; Mensah, A.; Tillmann, R.; Dorn, H.; Brauers, T.; Cohen, R. C.

    2008-12-01

    Formation of organic nitrates and secondary organic aerosol (SOA) from the NO3 oxidation of isoprene has been studied at atmospheric concentrations of VOC (10 ppb) and oxidant (<100 ppt NO3) in the presence of ammonium sulfate seed aerosol in the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich. Cavity Ringdown (CaRDS) and thermal dissociation - CaRDS measurements of NO3 and N2O5 as well as Thermal Dissociation - Laser Induced Fluorescence (TD-LIF) detection of alkyl nitrates (RONO2) and Aerodyne Aerosol Mass Spectrometer (AMS) measurements of aerosol composition were all used in comparison to a Master Chemical Mechanism (MCM) based chemical kinetics box model to quantify the product yields from two stages in isoprene oxidation. We find significant yields of organic nitrate formation from both the initial isoprene + NO3 reaction (71%) as well as from the reaction of NO3 with the initial oxidation products (30% - 60%). Under these low concentration conditions (~1 μg / m3), measured SOA production was greater than instrument noise only for the second oxidation step. Based on the modeled chemistry, we estimate an SOA mass yield of 10% (relative to isoprene mass reacted) for the reaction of the initial oxidation products with NO3. This yield is found to be consistent with the estimated saturation concentration (C*) of the presumed gas products of the doubly oxidized isoprene, where both oxidations lead to the addition of nitrate, carbonyl, and hydroxyl groups.

  2. Chemical aging of single and multicomponent biomass burning aerosol surrogate particles by OH: implications for cloud condensation nucleus activity

    DOE PAGES

    Slade, J. H.; Thalman, R.; Wang, J.; Knopf, D. A.

    2015-09-14

    Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low-soluble single-component OA by OH and O3 can increase their water solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate particles exposed tomore » OH and O3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH and O3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~ 0.1, indicating that chemically aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH-exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions

  3. Chemical aging of single and multicomponent biomass burning aerosol surrogate-particles by OH: implications for cloud condensation nucleus activity

    DOE PAGES

    Slade, J. H.; Thalman, R.; Wang, J.; Knopf, D. A.

    2015-03-06

    Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low soluble single-component OA by OH and O3 can increase their water-solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water-solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate-particles exposed to OH andmore » O3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH/O3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~0.1, indicating that chemically-aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally-mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical

  4. Chemical aging of single and multicomponent biomass burning aerosol surrogate-particles by OH: implications for cloud condensation nucleus activity

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Thalman, R.; Wang, J.; Knopf, D. A.

    2015-03-01

    Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low soluble single-component OA by OH and O3 can increase their water-solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water-solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate-particles exposed to OH and O3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH/O3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~0.1, indicating that chemically-aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally-mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical aging

  5. Chemical aging of single and multicomponent biomass burning aerosol surrogate particles by OH: implications for cloud condensation nucleus activity

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Thalman, R.; Wang, J.; Knopf, D. A.

    2015-09-01

    Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low-soluble single-component OA by OH and O3 can increase their water solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate particles exposed to OH and O3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH and O3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~ 0.1, indicating that chemically aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH-exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical

  6. Cloud condensation nuclei activation of limited solubility organic aerosol

    NASA Astrophysics Data System (ADS)

    Huff Hartz, Kara E.; Tischuk, Joshua E.; Chan, Man Nin; Chan, Chak K.; Donahue, Neil M.; Pandis, Spyros N.

    The cloud condensation nuclei (CCN) activation of 19 organic species with water solubilities ( Csat) ranging from 10 -4 to 10 2 g solute 100 g -1 H 2O was measured. The organic particles were generated by nebulization of an aqueous or an alcohol solution. Use of alcohols as solvents enables the measurement of low solubility, non-volatile organic CCN activity and reduces the likelihood of residual water in the aerosol. The activation diameter of organic species with very low solubility in water ( Csat<0.3 g 100 g -1 H 2O) is in agreement with Köhler theory using the bulk solubility (limited solubility case) of the organic in water. Many species, including 2-acetylbenzoic acid, aspartic acid, azelaic acid, glutamic acid, homophthalic acid, phthalic acid, cis-pinonic acid, and salicylic acid are highly CCN active in spite of their low solubility (0.3 g 100 g -1 H 2O< Csat<1 g 100 g -1 H 2O), and activate almost as if completely water soluble. The CCN activity of most species is reduced, if the particles are produced using non-aqueous solvents. The existence of the particles in a metastable state at low RH can explain the observed enhancement in CCN activity beyond the levels suggested by their solubility.

  7. Composition and major sources of organic compounds in urban aerosols

    NASA Astrophysics Data System (ADS)

    Bi, Xinhui; Simoneit, Bernd R. T.; Sheng, Guoying; Ma, Shexia; Fu, Jiamo

    Total suspended particles (TSP), collected during June 2002 to July 2003 in Guangzhou, a typical economically developed city in South China, were analyzed for the organic compound compositions using gas chromatography-mass spectrometry (GC/MS). Over 140 organic compounds were detected in the aerosols and grouped into different classes including n-alkanes, hopanoids, polycyclic aromatic hydrocarbons, alkanols, fatty acids, dicarboxylic acids excluding oxalic acid, polyols/polyacids, lignin products, phytosterols, phthalates and water-soluble sugars. The total amounts of the identified organic compounds including unresolved complex mixture (UCM) ranged from 3112 ng/m 3 in spring to 5116 ng/m 3 in winter, comprising on seasonal average 2.8% of TSP. Primary organic compounds peaked in winter although there are no heating systems burning fuels in Guangzhou. The highest saccharide levels occurred in fall due to agricultural activities. This study demonstrated that utilization of fossil fuels, biomass burning, soil resuspension and plastic/refuse burning are the major contributors to the identified organic compounds in the urban atmosphere of South China.

  8. Secondary organic aerosol formation from gasoline vehicle emissions in a new mobile environmental reaction chamber

    NASA Astrophysics Data System (ADS)

    Platt, S. M.; El Haddad, I.; Zardini, A. A.; Clairotte, M.; Astorga, C.; Wolf, R.; Slowik, J. G.; Temime-Roussel, B.; Marchand, N.; Ježek, I.; Drinovec, L.; Močnik, G.; Möhler, O.; Richter, R.; Barmet, P.; Bianchi, F.; Baltensperger, U.; Prévôt, A. S. H.

    2012-10-01

    We present a new mobile environmental reaction chamber for the simulation of the atmospheric aging of aerosols from different emissions sources without limitation from the instruments or facilities available at any single site. The chamber can be mounted on a trailer for transport to host facilities or for mobile measurements. Photochemistry is simulated using a set of 40 UV lights (total power 4 KW). Characterisation of the emission spectrum of these lights shows that atmospheric photochemistry can be accurately simulated over a range of temperatures from -7-25 °C. A photolysis rate of NO2, JNO2, of (8.0 ± 0.7) × 10-3 molecules cm-3 s-1 was determined at 25 °C. Further, we present the first application of the mobile chamber and demonstrate its utility by quantifying primary organic aerosol (POA) emission and secondary organic aerosol (SOA) production from a Euro 5 light duty gasoline vehicle. Exhaust emissions were sampled during the New European Driving Cycle (NEDC), the standard driving cycle for European regulatory purposes, and injected into the chamber. The relative concentrations of oxides of nitrogen (NOx) and total hydrocarbon (THC) during the aging of emissions inside the chamber were controlled using an injection system developed as a part of the new mobile chamber set up. Total OA (POA + SOA) emission factors of (370 ± 18) × 10-3 g kg-1 fuel, or (14.6 ± 0.8) × 10-3 g km-1, after aging, were calculated from concentrations measured inside the smog chamber during two experiments. The average SOA/POA ratio for the two experiments was 15.1, a much larger increase than has previously been seen for diesel vehicles, where smog chamber studies have found SOA/POA ratios of 1.3-1.7. Due to this SOA formation, carbonaceous particulate matter (PM) emissions from a gasoline vehicle may approach those of a diesel vehicle of the same class. Furthermore, with the advent of emission controls requiring the use of diesel particle filters, gasoline vehicle emissions

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

    NASA Astrophysics Data System (ADS)

    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 < 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 principal component analysis (PCA). The model showed a significant separation of the four SOA types and clustering of the duplicate

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

    EPA Science Inventory

    Data from a mountain location intercepting the Mexico City emission plume demonstrate a strong correlation between secondary organic aerosol and odd-oxygen (O3 + NO2). The measured oxygenated-organic aerosol correlates with odd-oxygen measurements with an a...

  11. Ageing of aerosol and their radiative properties in the Mediterranean Basin

    NASA Astrophysics Data System (ADS)

    Roberts, Greg; Léon, Jean-François; Pont, Véronique; Mallet, Marc; Augustin, Patrick; Dulac, François; Junkermann, Wolfgang

    2014-05-01

    The VESSAER campaign (VErtical Structure and Sources of AERosols in the Mediterranean Region) identified different sources of aerosol in the Mediterranean Basin and assessed the regional impact of aerosol on cloud microphysical and radiative properties. The airborne aspect of VESSAER was conducted on an ultra-light aircraft in summer 2012. Ground-based activities included observations in the central and northern regions of Corsica, as well as aerosol LIDAR and sun photometer measurements on the eastern coast. The main scientific goals were to investigate local versus long-range sources of aerosol and cloud condensation nuclei (CCN) and their vertical structure in the lower troposphere, study evolution and ageing related to atmospheric processes, and determine aerosol direct radiative impacts over a larger spatial scale in the Mediterranean Basin. Even though Corsica is separated by from the European continent by ca. 100 km with no immediate sources of urban aerosol, the background concentrations in Corsica were similar to those in the continental European boundary layer. The background total aerosol concentrations within the boundary layer in Corsica are nearly 2000 cm-3. Nearly all of the particles in the boundary layer (> 90%) are CCN-active at 0.37% supersaturation as they had become hygroscopic during their transport. Ageing (with respect to CCN-activity) of European emissions occurred exclusively in the boundary layer and not in aerosol layers aloft. In contrast, aerosol hygroscopicity did not change as a function of transport time in elevated aerosol layers, suggesting that photochemical ageing of less hygroscopic material is relatively slow compared to ageing processes in the boundary layer. The vertical profiles clearly show the long-range transport of dust from the Saharan Desert and pollution from the European continent -- which were the two major sources of aerosol during the campaign. Two of the research flights coincided with CALIPSO overpasses, when

  12. Properties and evolution of biomass burning organic aerosol from Canadian boreal forest fires

    NASA Astrophysics Data System (ADS)

    Jolleys, M. D.; Coe, H.; McFiggans, G.; Taylor, J. W.; O'Shea, S. J.; Le Breton, M.; Bauguitte, S. J.-B.; Moller, S.; Di Carlo, P.; Aruffo, E.; Palmer, P. I.; Lee, J. D.

    2014-10-01

    Airborne measurements of biomass burning organic aerosol (BBOA) from boreal forest fires reveal highly contrasting properties for plumes of different ages. These measurements, performed using an Aerodyne Research Inc. compact time-of-flight aerosol mass spectrometer (C-ToF-AMS) during the BORTAS (quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment in the summer of 2011, have been used to derive normalised excess organic aerosol (OA) mass concentrations (ΔOA/ΔCO), with higher average ratios observed closer to source (0.190 ± 0.010) than in the far-field (0.097 ± 0.002). The difference in ΔOA/ΔCO between fresh and aged plumes is influenced by a change in dominant combustion conditions throughout the campaign. Measurements at source sampled largely smouldering fires, while plumes encountered in the far-field originated from fires occurring earlier in the campaign when fire activity had been more intense. Changing combustion conditions also affect the vertical distribution of biomass burning emissions, as aged plumes from more flaming-dominated fires are injected to higher altitudes of up to 6000 m. Proportional contributions of the mass-to-charge ratio (m/z) 60 and 44 peaks in the AMS mass spectra to the total OA mass (denoted f60 and f44) are used as tracers for primary and oxidized BBOA, respectively. Given the shorter aging times associated with near-field plumes, f44 is lower on average than in more aged, transported plumes. However, high levels of ΔO3/ΔCO and -log(NOx/NOy) close to source indicate that emissions can be subject to very rapid oxidation over short timescales. Conversely, the lofting of plumes into the upper troposphere can lead to the retention of source profiles after transportation over extensive temporal and spatial scales, with f60 also higher on average in aged plumes. Evolution of OA composition with aging is comparable to observations of BB tracers in

  13. Apportionment of primary and secondary organic aerosols in southern California during the 2005 study of organic aerosols in riverside (SOAR-1).

    PubMed

    Docherty, Kenneth S; Stone, Elizabeth A; Ulbrich, Ingrid M; DeCarlo, Peter F; Snyder, David C; Schauer, James J; Peltier, Richard E; Weber, Rodney J; Murphy, Shane M; Seinfeld, John H; Grover, Brett D; Eatough, Delbert J; Jimenez, Jose L

    2008-10-15

    Ambient sampling was conducted in Riverside, California during the 2005 Study of Organic Aerosols in Riverside to characterize the composition and sources of organic aerosol using a variety of state-of-the-art instrumentation and source apportionmenttechniques. The secondary organic aerosol (SOA) mass is estimated by elemental carbon and carbon monoxide tracer methods, water soluble organic carbon content, chemical mass balance of organic molecular markers, and positive matrix factorization of high-resolution aerosol mass spectrometer data. Estimates obtained from each ofthese methods indicate that the organic fraction in ambient aerosol is overwhelmingly secondary in nature during a period of several weeks with moderate ozone concentrations and that SOA is the single largest component of PM1 aerosol in Riverside. Average SOA/OA contributions of 70-90% were observed during midday periods, whereas minimum SOA contributions of approximately 45% were observed during peak morning traffic periods. These results are contraryto previous estimates of SOAthroughout the Los Angeles Basin which reported that, other than during severe photochemical smog episodes, SOA was lower than primary OA. Possible reasons for these differences are discussed. PMID:18983089

  14. Biotic stress: a significant contributor to organic aerosol in Europe?

    NASA Astrophysics Data System (ADS)

    Bergström, R.; Hallquist, M.; Simpson, D.; Wildt, J.; Mentel, T. F.

    2014-05-01

    We have investigated the potential impact on organic aerosol formation from biotic stress-induced emissions (SIE) of organic molecules from forests in Europe (North of Lat. 45° N). Emission estimates for sesquiterpenes (SQT), methyl salicylate (MeSA) and unsaturated C17-compounds, due to different stressors, are based on experiments in the Jülich Plant Atmosphere Chamber (JPAC), combined with estimates of the fraction of stressed trees in Europe based on reported observed tree damage. SIE were introduced in the EMEP MSC-W chemical transport model and secondary organic aerosol (SOA) yields from the SIE were taken from the JPAC experiments. The estimated current-situation SIE in Central and Northern European forests are found to contribute substantially to SOA in large parts of Europe. It is possible that the SIE contributes as much, or more, to organic aerosol than the constitutive biogenic VOC-emissions, at least during some periods. Based on the assumptions in this study, SIE-SOA are estimated to constitute between 50 and 70% of the total biogenic SOA (BSOA) in a current-situation scenario where the biotic stress in Northern and Central European forests causes large SIE of MeSA and SQT. An alternative current-situation scenario with lower SIE, consisting solely of SQT, leads to lower SIE-SOA, between 20 and 40% of the total BSOA. Hypothetical future scenarios with increased SIE, due to higher degrees of biotic stress, show that SOA formation due to SIE can become even larger. Unsaturated C17-BVOCs emitted by spruce infested by the forest honey generating bark louse Cinara pilicornis have a high SOA-forming potential. A model scenario investigating the effect of a regional, episodic infestation of Cinara pilicornis in Baden-Württemberg, corresponding to a year with high production of forest honey, shows that these types of events could lead to very large organic aerosol formation in the infested region. We have used the best available laboratory data on biotic

  15. A Systematic Evaluation of the Extent of Photochemical Processing in Different Types of Secondary Organic Aerosols in the Aqueous Phase

    NASA Astrophysics Data System (ADS)

    Romonosky, D.; Lee, H.; Epstein, S. A.; Nizkorodov, S.; Laskin, J.; Laskin, A.

    2013-12-01

    A significant fraction of atmospheric organic compounds are predominantly found in condensed phases, such as organic phase in aerosol particles or aqueous phase in cloud droplets. The oxidation of VOCs followed by the condensation of products into particles was thought to be the main mechanism of organic aerosol (OA) formation. However, in the last several years, scientists have realized that a large fraction, if not the majority of organic particles, is produced through cloud and fog photochemical processes. Many of these organic compounds are photolabile, and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of droplets (hours) and particles (days). We previously reported that compounds in secondary organic aerosol (SOA) from ozonolysis of d-limonene efficiently photodegrade in both organic (Walser et al., 2007) and aqueous phases (Bateman et al., 2011). Significant photolysis was also observed in an aqueous extract of SOA from high-NOx photooxidation of isoprene (Nguyen et al., 2012). More recent experiments studying the response to irradiation of complex aqueous mixtures (as opposed to solutions of isolated compounds) found surprising resilience to photodegradation in aqueous extracts of SOA prepared by photooxidation of alpha-pinene (Romonosky et al., unpublished). We present a systematic investigation of the extent of photochemical processing in different types of SOA from various biogenic and anthropogenic precursors. Chamber- or flowtube-generated SOA is collected on an inert substrate, extracted in a methanol/water solution (70:30), photolyzed in the aqueous solution, and the extent of change in the molecular level composition of the material is assessed with high-resolution mass spectrometry (HR-MS). The outcome of this study will be improved understanding of the role of condensed-phase photochemistry in chemical aging of aerosol particles and cloud droplets. Bateman et

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

    SciTech Connect

    Hodzic, Alma; Jimenez, Jose L.; Madronich, Sasha; Canagaratna, M. R.; DeCarlo, Peter F.; Kleinman, Lawrence I.; Fast, Jerome D.

    2010-06-21

    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 traditional anthropogenic and biogenic VOC precursors. In this study, the 3D regional air quality model CHIMERE is applied to quantify the contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic vapors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to explicitly include 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. For the first time, 3D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS) data, but also against and oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (3-6 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. The predicted anthropogenic POA levels are found to agree within 20% with the observed HOA concentrations for both the ROB and GRI simulations, consistent with the interpretation of the emissions inventory by previous studies. The impact of biomass burning POA within the city is underestimated in comparison to the AMS BBOA, presumably due to insufficient nighttime smoldering emissions. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The production from anthropogenic and biomass burning

  17. Individual Aerosol Particles from Biomass Burning in Southern Africa Compositions and Aging of Inorganic Particles. 2; Compositions and Aging of Inorganic Particles

    NASA Technical Reports Server (NTRS)

    Li, Jia; Posfai, Mihaly; Hobbs, Peter V.; Buseck, Peter R.

    2003-01-01

    Individual aerosol particles collected over southern Africa during the SAFARI 2000 field study were studied using transmission electron microscopy and field-emission scanning electron microscopy. The sizes, shapes, compositions, mixing states, surface coatings, and relative abundances of aerosol particles from biomass burning, in boundary layer hazes, and in the free troposphere were compared, with emphasis on aging and reactions of inorganic smoke particles. Potassium salts and organic particles were the predominant species in the smoke, and most were internally mixed. More KCl particles occur in young smoke, whereas more K2SO4 and KNO3 particles were present in aged smoke. This change indicates that with the aging of the smoke, KCl particles from the fires were converted to K2SO4 and KNO3 through reactions with sulfur- and nitrogen- bearing species from biomass burning as well as other sources. More soot was present in smoke from flaming grass fires than bush and wood fires, probably due to the predominance of flaming combustion in grass fires. The high abundance of organic particles and soluble salts can affect the hygroscopic properties of biomass-burning aerosols and therefore influence their role as cloud condensation nuclei. Particles from biomass burning were important constituents of the regional hazes.

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

    SciTech Connect

    John H. Seinfeld

    2011-12-08

    Organic material constitutes about 50% of global atmospheric aerosol mass, and the dominant source of organic aerosol is the oxidation of volatile hydrocarbons, to produce secondary organic aerosol (SOA). Understanding the formation of SOA is crucial to predicting present and future climate effects of atmospheric aerosols. The goal of this program is to significantly increase our understanding of secondary organic aerosol (SOA) formation in the atmosphere. Ambient measurements indicate that the amount of SOA in the atmosphere exceeds that predicted in current models based on existing laboratory chamber data. This would suggest that either the SOA yields measured in laboratory chambers are understated or that all major organic precursors have not been identified. In this research program we are systematically exploring these possibilities.

  19. Organic functional groups in aerosol particles from burning and non-burning forest emissions at a high-elevation mountain site

    NASA Astrophysics Data System (ADS)

    Takahama, S.; Schwartz, R. E.; Russell, L. M.; MacDonald, A. M.; Sharma, S.; Leaitch, W. R.

    2011-07-01

    Ambient particles collected on teflon filters at the Peak of Whistler Mountain, British Columbia (2182 m a.s.l.) during spring and summer 2009 were measured by Fourier transform infrared (FTIR) spectroscopy for organic functional groups (OFG). The project mean and standard deviation of organic aerosol mass concentrations (OM) for all samples was 3.2±3.3 (μg m-3). Measurements of aerosol mass fragments, size, and number concentrations were used to separate fossil-fuel combustion and burning and non-burning forest sources of the measured organic aerosol. The OM was composed of the same anthropogenic and non-burning forest components observed at Whistler mid-valley in the spring of 2008; during the 2009 campaign, biomass burning aerosol was additionally observed from fire episodes occurring between June and September. On average, organic hydroxyl, alkane, carboxylic acid, ketone, and primary amine groups represented 31 %±11 %, 34 %±9 %, 23 %±6 %, 6 %±7 %, and 6 %±3 % of OM, respectively. Ketones in aerosols were associated with burning and non-burning forest origins, and represented up to 27 % of the OM. The organic aerosol fraction resided almost entirely in the submicron fraction without significant diurnal variations. OM/OC mass ratios ranged mostly between 2.0 and 2.2 and O/C atomic ratios between 0.57 and 0.76, indicating that the organic aerosol reaching the site was highly aged and possibly formed through secondary formation processes.

  20. Exploring matrix effects on photochemistry of organic aerosols.

    PubMed

    Lignell, Hanna; Hinks, Mallory L; Nizkorodov, Sergey A

    2014-09-23

    This work explores the effect of the environment on the rate of photolysis of 2,4-dinitrophenol (24-DNP), an important environmental toxin. In stark contrast to the slow photolysis of 24-DNP in an aqueous solution, the photolysis rate is increased by more than an order of magnitude for 24-DNP dissolved in 1-octanol or embedded in secondary organic material (SOM) produced by ozonolysis of α-pinene. Lowering the temperature decreased the photolysis rate of 24-DNP in SOM much more significantly than that of 24-DNP in octanol, with effective activation energies of 53 kJ/mol and 12 kJ/mol, respectively. We discuss the possibility that the increasing viscosity of the SOM matrix constrains the molecular motion, thereby suppressing the hydrogen atom transfer reaction to the photo-excited 24-DNP. This is, to our knowledge, the first report of a significant effect of the matrix, and possibly viscosity, on the rate of an atmospheric photochemical reaction within SOM. It suggests that rates of photochemical processes in organic aerosols will depend on both relative humidity and temperature and thus altitude. The results further suggest that photochemistry in SOM may play a key role in transformations of atmospheric organics. For example, 24-DNP and other nitro-aromatic compounds should readily photodegrade in organic particulate matter, which has important consequences for predicting their environmental fates and impacts. PMID:25201953

  1. Exploring matrix effects on photochemistry of organic aerosols

    PubMed Central

    Lignell, Hanna; Hinks, Mallory L.; Nizkorodov, Sergey A.

    2014-01-01

    This work explores the effect of the environment on the rate of photolysis of 2,4-dinitrophenol (24-DNP), an important environmental toxin. In stark contrast to the slow photolysis of 24-DNP in an aqueous solution, the photolysis rate is increased by more than an order of magnitude for 24-DNP dissolved in 1-octanol or embedded in secondary organic material (SOM) produced by ozonolysis of α-pinene. Lowering the temperature decreased the photolysis rate of 24-DNP in SOM much more significantly than that of 24-DNP in octanol, with effective activation energies of 53 kJ/mol and 12 kJ/mol, respectively. We discuss the possibility that the increasing viscosity of the SOM matrix constrains the molecular motion, thereby suppressing the hydrogen atom transfer reaction to the photo-excited 24-DNP. This is, to our knowledge, the first report of a significant effect of the matrix, and possibly viscosity, on the rate of an atmospheric photochemical reaction within SOM. It suggests that rates of photochemical processes in organic aerosols will depend on both relative humidity and temperature and thus altitude. The results further suggest that photochemistry in SOM may play a key role in transformations of atmospheric organics. For example, 24-DNP and other nitro-aromatic compounds should readily photodegrade in organic particulate matter, which has important consequences for predicting their environmental fates and impacts. PMID:25201953

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  3. Spectroscopic investigations of organic aerosol and its reaction with halogens, released by sea-salt activation

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Zetzsch, C.

    2009-04-01

    The release of reactive halogen species from sea-salt aerosol offers a class of reactants for heterogeneous reactions of utmost importance. These heterogeneous reactions have been overlooked so far, although they may occur with internal and external mixtures of sea-salt aerosol and organic aerosol or organic matter. Such reactions might constitute sources of gaseous organohalogen compounds or halogenated organic aerosol in the atmospheric boundary layer. Infrared and UV/VIS spectroscopy provide an insight into chemical processes at reactive sites of the organic phase on a molecular level. Model studies of heterogeneous reactions of halogens with different kinds of (secondary) organic aerosols and organic matter were performed using a 700L smog chamber with a solar simulator. The model compounds alpha-pinene, catechol and humic acid have been chosen as precursors/material for the condensed, organic phase of the aerosol. After formation of the secondary organic aerosol or preparation of the organic material and the sea-salt solution the reaction was carried out using molecular chlorine and bromine in the presence of simulated sunlight. Chemical transformation of the organic material was studied using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) on a ZnSe crystal and diffuse reflectance UV/VIS spectroscopy. An electrostatic precipitator was developed to deposit the aerosol particles on the ATR crystal as a thin film. On the other hand, longpath-FTIR spectroscopy with a 40m White-cell allows us to monitor both the condensed and gas phase of the aerosol in situ in the smog chamber directly. These spectroscopic techniques enable us to characterize different organic aerosol particles and their functional groups at reactive sites on these particles as well as to study aerosol formation and transformation directly. The heterogeneous reaction of reactive halogen species with organic material at atmospheric conditions leads to small reactive

  4. Insights Into Water-Soluble Organic Aerosol Sources From Carbon-13 Ratios of Size Exclusion Chromatography Fractions

    NASA Astrophysics Data System (ADS)

    Ruehl, C. R.; Chuang, P. Y.; McCarthy, M. D.

    2008-12-01

    Many sources of organic aerosols have been identified and quantified, and much of this work has used individual (mosty water-insoluble) compounds as tracers of primary sources. However, most organic aerosol cannot be molecularly characterized, and the water-soluble organic carbon (WSOC) in many aerosols is thought to originate from gaseous precursors (i.e., it is secondary in nature). It can therefore be difficult to infer aerosol sources, particularly of background (i.e., aged) aerosols, and of the relatively high-MW component of aerosols. The stable isotope ratios (δ13C) of organic aerosols have been used to distinguish between sources, with lighter values (-30‰ to -25‰) interpreted as having originated from fossil fuel combustion and C4 biogenic emission, and heavier values (-25‰ to - 20‰) indicating a marine or C3 biogenic source. Most published measurements were of either total suspended particulates or PM2.5, however, and it is unknown to what extent these fractions differ from submicron WSOC. We report δ13C for submicron WSOC collected at a variety of sites, ranging from marine to polluted to background continental. Bulk marine organic δ13C ranged from -30.4 to - 27.6‰, slightly lighter than previously published results. This could be due to the elimination of supermicron cellular material or other biogenic primary emissions from the sample. Continental WSOC δ13C ranged from -19.1 to -29.8‰, with heavier values (-19.8 ± 1.0‰) in Oklahoma and lighter values at Great Smoky Mountain National Park in Tennessee (-25.8 ± 2.6‰) and Illinois (-24.5 ± 1.0‰). This likely results from the greater proportional of C3 plant material in the Oklahoma samples. In addition to bulk samples, we used size exclusion chromatography (SEC) to report δ13C of organic aerosols as a function of hydrodynamic diameter. Variability and magnitude of hydrodynamic diameter was greatest at low SEC pH, indicative of the acidic character of submicron WSOC. Tennessee

  5. Contribution of Primary and Secondary Sources to Organic Aerosol and PM2.5 at SEARCH Network Sites

    EPA Science Inventory

    Chemical tracer methods for determining contributions to primary organic aerosol (POA) are fairly well established, whereas similar techniques for secondary organic aerosol (SOA), inherently complicated by time-dependent atmospheric processes, are only beginning to be studied. La...

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  8. Wet Removal of Organic and Black Carbon Aerosols

    NASA Astrophysics Data System (ADS)

    Torres, A.; Bond, T. C.; Lehmann, C.

    2012-12-01

    Organic carbon (OC) and black carbon (BC) aerosols derived from the combustion of fossil fuels and biomass are significant atmospheric pollutants that alter the Earth's radiation balance and affect human health. Carbonaceous aerosol lifetime and extent of its effects are mainly controlled by its wet removal, especially by rain. Limited work has been done to measure both BC and OC from rain events even though these aerosols are co-emitted and exist together in the atmosphere. The choices of analytical techniques for measuring OC and BC in water are limited, and researchers often employ the same techniques used for measuring atmospheric carbon particles. There is no agreement in the methods employed for monitoring carbon concentration in precipitation. As part of the method development, the Single Particle Soot Photometer (SP2), Thermal-Optical Analysis (TOA), Ultraviolet/Visible (UV/VIS) Spectrophotometer, and the Total Organic Carbon (TOC) Analyzer were evaluated for measuring BC suspended in water, water insoluble OC (WIOC) and dissolved OC (DOC). The study also monitored the concentration of BC, WIOC, and DOC in rainwater collected at Bondville (Illinois) for 18 months. Results indicated that 34% (±3%) of the BC mass was lost in the SP2 analysis, most probably during the nebulization process. Filtration required for TOA also had large losses (>75%) because quartz fiber filters were ineffective for capturing BC particles from water. Addition of NH4H2PO4 as a coagulant improved (>95%) the capture efficiency of the filters. UV/VIS spectrophotometry had good linearity, but the sensitivity for detecting BC particles (±20 μg/L) suspended in water was inadequate. TOC analysis was a robust technique for measuring both DOC and total carbon (BC + OC). The chosen techniques were TOC analysis for DOC, and TOA with an optimized filtration procedure for BC and WIOC. The mean concentrations in rainwater were 8.72 (±9.84) μg/L of BC, 88.97 (±62.64) μg/L of WIOC, and 1

  9. An amorphous solid state of biogenic secondary organic aerosol particles.

    PubMed

    Virtanen, Annele; Joutsensaari, Jorma; Koop, Thomas; Kannosto, Jonna; Yli-Pirilä, Pasi; Leskinen, Jani; Mäkelä, Jyrki M; Holopainen, Jarmo K; Pöschl, Ulrich; Kulmala, Markku; Worsnop, Douglas R; Laaksonen, Ari

    2010-10-14

    Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs). On a global scale, biogenic VOCs account for about 90% of VOC emissions and of SOA formation (90 billion kilograms of carbon per year). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate. They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid, but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles. Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate.

  10. An amorphous solid state of biogenic secondary organic aerosol particles.

    PubMed

    Virtanen, Annele; Joutsensaari, Jorma; Koop, Thomas; Kannosto, Jonna; Yli-Pirilä, Pasi; Leskinen, Jani; Mäkelä, Jyrki M; Holopainen, Jarmo K; Pöschl, Ulrich; Kulmala, Markku; Worsnop, Douglas R; Laaksonen, Ari

    2010-10-14

    Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs). On a global scale, biogenic VOCs account for about 90% of VOC emissions and of SOA formation (90 billion kilograms of carbon per year). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate. They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid, but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles. Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate. PMID:20944744

  11. Aircraft observations of aerosol composition and ageing in New England and Mid-Atlantic States during the summer 2002 New England Air Quality Study field campaign

    NASA Astrophysics Data System (ADS)

    Kleinman, Lawrence I.; Daum, Peter H.; Lee, Yin-Nan; Senum, Gunnar I.; Springston, Stephen R.; Wang, Jian; Berkowitz, Carl; Hubbe, John; Zaveri, Rahul A.; Brechtel, Fred J.; Jayne, John; Onasch, Timothy B.; Worsnop, Douglas

    2007-05-01

    Aerosol chemical composition, size distribution, and optical properties were measured during 17 aircraft flights in New England and Middle Atlantic States as part of the summer 2002 New England Air Quality Study field campaign. An Aerodyne aerosol mass spectrometer (AMS) was operated with a measurement cycle of 30 s, about an order of magnitude faster than used for ground-based measurements. Noise levels within a single measurement period were sub μg m-3. Volume data derived from the AMS were compared with volume measurements from a Passive Cavity Aerosol Spectrometer (PCASP) optical particle detector and a Twin Scanning Electrical Mobility Spectrometer (TSEMS); calculated light scattering was compared with measured values from an integrating nephelometer. The median ratio for AMS/TSEMS volume was 1.25 (1.33 with an estimated refractory component); the median ratio for AMS/nephelometer scattering was 1.18. A dependence of the AMS collection efficiency on aerosol acidity was quantified by a comparison between AMS and PCASP volumes in two high sulfate plumes. For the entire field campaign, the average aerosol concentration was 11 μg m-3. Compared with monitoring data from the IMPROVE network, the organic component made up a large fraction of total mass, varying from 70% in clean air to 40% in high concentration sulfate plumes. In combination with other optical and chemical measurements, the AMS gave information on secondary organic aerosol (SOA) production and the time evolution of aerosol light absorption. CO is taken as a conservative tracer of urban emissions and the ratios of organic aerosol and aerosol light absorption to CO examined as a function of photochemical age. Comparisons were made to ratios determined from surface measurements under conditions of minimal atmospheric processing. In air masses in which the NOx to NOy ratio has decreased to 10%, the ratio of organic aerosol to CO has quadrupled indicating that 75% of the organic aerosol is secondary

  12. Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke

    NASA Astrophysics Data System (ADS)

    Sleiman, Mohamad; Destaillats, Hugo; Smith, Jared D.; Liu, Chen-Lin; Ahmed, Musahid; Wilson, Kevin R.; Gundel, Lara A.

    2010-11-01

    We used controlled laboratory experiments to evaluate the aerosol-forming potential of ozone reactions with nicotine and secondhand smoke. Special attention was devoted to real-time monitoring of the particle size distribution and chemical composition of SOA as they are believed to be key factors determining the toxicity of SOA. The experimental approach was based on using a vacuum ultraviolet photon ionization time-of-flight aerosol mass spectrometer (VUV-AMS), a scanning mobility particle sizer (SMPS) and off-line thermal desorption coupled to mass spectrometry (TD-GC-MS) for gas-phase byproducts analysis. Results showed that exposure of SHS to ozone induced the formation of ultrafine particles (<100 nm) that contained high molecular weight nitrogenated species ( m/ z 400-500), which can be due to accretion/acid-base reactions and formation of oligomers. In addition, nicotine was found to contribute significantly (with yields 4-9%) to the formation of secondary organic aerosol through reaction with ozone. The main constituents of the resulting SOA were tentatively identified and a reaction mechanism was proposed to elucidate their formation. These findings identify a new component of thirdhand smoke that is associated with the formation of ultrafine particles (UFP) through oxidative aging of secondhand smoke. The significance of this chemistry for indoor exposure and health effects is highlighted.

  13. Chemical composition, sources, and aging process of submicron aerosols in Beijing: Contrast between summer and winter

    NASA Astrophysics Data System (ADS)

    Hu, Weiwei; Hu, Min; Hu, Wei; Jimenez, Jose L.; Yuan, Bin; Chen, Wentai; Wang, Ming; Wu, Yusheng; Chen, Chen; Wang, Zhibin; Peng, Jianfei; Zeng, Limin; Shao, Min

    2016-02-01

    To investigate the seasonal characteristics of submicron aerosol (PM1) in Beijing urban areas, a high-resolution time-of-flight aerosol-mass-spectrometer (HR-ToF-AMS) was utilized at an urban site in summer (August to September 2011) and winter (November to December 2010), coupled with multiple state of the art online instruments. The average mass concentrations of PM1 (60-84 µg m-3) and its chemical compositions in different campaigns of Beijing were relatively consistent in recent years. In summer, the daily variations of PM1 mass concentrations were stable and repeatable. Eighty-two percent of the PM1 mass concentration on average was composed of secondary species, where 62% is secondary inorganic aerosol and 20% secondary organic aerosol (SOA). In winter, PM1 mass concentrations changed dramatically because of the different meteorological conditions. The high average fraction (58%) of primary species in PM1 including primary organic aerosol (POA), black carbon, and chloride indicates primary emissions usually played a more important role in the winter. However, aqueous chemistry resulting in efficient secondary formation during occasional periods with high relative humidity may also contribute substantially to haze in winter. Results of past OA source apportionment studies in Beijing show 45-67% of OA in summer and 22-50% of OA in winter can be composed of SOA. Based on the source apportionment results, we found 45% POA in winter and 61% POA in summer are from nonfossil sources, contributed by cooking OA in both seasons and biomass burning OA (BBOA) in winter. Cooking OA, accounting for 13-24% of OA, is an important nonfossil carbon source in all years of Beijing and should not be neglected. The fossil sources of POA include hydrocarbon-like OA from vehicle emissions in both seasons and coal combustion OA (CCOA) in winter. The CCOA and BBOA were the two main contributors (57% of OA) for the highest OA concentrations (>100 µg m-3) in winter. The POA

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  15. Oxygenated products of sesquiterpenes in secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    van Eijck, A.; Kampf, C.; Hoffmann, T.

    2012-04-01

    Secondary organic aerosol (SOA) has a huge impact on air quality and climate change. It influences the Earth radiative budget through absorbing, scattering and reflecting radiation as well as the formation of clouds because the particulates can act as cloud condensation nuclei (CCN). Furthermore, it plays an important role for human health. SOA is formed from gaseous precursors which get oxidized by ozone, OH- and NO3-radicals in the atmosphere. Due to their low vapor pressure these degradation products can nucleate to form new particles or they can condense on existing aerosol particles. Despite the major progress in research during the last few years the actual chemical composition as well as the contribution of various volatile organic compounds (VOCs) to the formation of secondary organic aerosol is still partially unknown. Recent studies indicate that sesquiterpenes play an important role in the formation of SOA because of the low volatility of their oxygenated products (Lee et al., 2006). Their emission is estimated to be about 14,8 Tg per year (Henze et al., 2008), however, these emission rates remain highly uncertain due to the lack of quantitative emission rate measurements. In addition, the knowledge about the actual atmospheric degradation mechanism and the main oxidation products of sesquiterpenes is quite limited. β-Caryophyllene, α-humulene, α-farnesene and β-farnesene are the most abundant sequiterpenes in many sesquiterpene emission profiles. But also aromadendren, α-bergamotene and δ-cadinene and germacrene-D can contribute significantly to some emission profiles (Duhl et al., 2008). To determine the major oxygenated products of sesquiterpenes in SOA, reaction chamber experiments with different sesquiterpenes and ozone were performed in a 100 L reaction chamber. To measure the time dependent formation of initial oxidation products, an APCI-IT-MS was directly connected to the reaction chamber. After 2 hours the APCI-IT-MS was replaced by a

  16. Use of the NASA GEOS-5 SEAC4RS Meteorological and Aerosol Reanalysis for assessing simulated aerosol optical properties as a function of smoke age

    NASA Astrophysics Data System (ADS)

    Randles, C. A.; da Silva, A. M., Jr.; Colarco, P. R.; Darmenov, A.; Buchard, V.; Govindaraju, R.; Chen, G.; Hair, J. W.; Russell, P. B.; Shinozuka, Y.; Wagner, N.; Lack, D.

    2014-12-01

    The NASA Goddard Earth Observing System version 5 (GEOS-5) Earth system model, which includes an online aerosol module, provided chemical and weather forecasts during the SEAC4RS field campaign. For post-mission analysis, we have produced a high resolution (25 km) meteorological and aerosol reanalysis for the entire campaign period. In addition to the full meteorological observing system used for routine NWP, we assimilate 550 nm aerosol optical depth (AOD) derived from MODIS (both Aqua and Terra satellites), ground-based AERONET sun photometers, and the MISR instrument (over bright surfaces only). Daily biomass burning emissions of CO, CO2, SO2, and aerosols are derived from MODIS fire radiative power retrievals. We have also introduced novel smoke "age" tracers, which provide, for a given time, a snapshot histogram of the age of simulated smoke aerosol. Because GEOS-5 assimilates remotely sensed AOD data, it generally reproduces observed (column) AOD compared to, for example, the airborne 4-STAR instrument. Constraining AOD, however, does not imply a good representation of either the vertical profile or the aerosol microphysical properties (e.g., composition, absorption). We do find a reasonable vertical structure for aerosols is attained in the model, provided actual smoke injection heights are not much above the planetary boundary layer, as verified with observations from DIAL/HRSL aboard the DC8. The translation of the simulated aerosol microphysical properties to total column AOD, needed in the aerosol assimilation step, is based on prescribed mass extinction efficiencies that depend on wavelength, composition, and relative humidity. Here we also evaluate the performance of the simulated aerosol speciation by examining in situ retrievals of aerosol absorption/single scattering albedo and scattering growth factor (f(RH)) from the LARGE and AOP suite of instruments. Putting these comparisons in the context of smoke age as diagnosed by the model helps us to

  17. Effect of SO2 and Photolysis on Photooxidized Diesel Fuel Secondary Organic Aerosol Composition

    NASA Astrophysics Data System (ADS)

    MacMillan, A. C.; Blair, S. L.; Lin, P.; Laskin, A.; Laskin, J.; Nizkorodov, S.

    2014-12-01

    Diesel fuel (DSL) and sulfur dioxide (SO2) are important precursors to secondary organic aerosol (SOA) formation. DSL is often co-emitted with SO2 and NO2, thus it is important to understand the possible effects of SO2 on DSL SOA composition. Additionally, DSL SOA composition can be affected by photochemical aging processes such as photolysis. In this study, DSL SOA was first prepared under dry, high-NOx conditions with various concentrations of SO2 by photooxidation in a smog chamber. The SOA was then stripped of excess oxidants and gaseous organics with a denuder train and the resulting particles were photolyzed at various photolysis times in a quartz flow tube. The SOA composition, photochemical aging, properties, and mass concentration, before and after direct photolysis in the flow tube, were examined using several techniques. High-resolution mass spectrometry (HR-MS) was performed on DSL SOA samples to investigate the effect of SO2 on molecular level composition. SOA composition as a function of photolysis time was measured with an aerosol mass spectrometer (AMS). HR-MS results show that organosulfates are produced in DSL SOA. Both AMS and HR-MS results show that photolysis also has an effect on composition; though, this is more apparent in the HR-MS results than in the AMS results. In summary, both the presence of SO2 and solar radiation has an effect on DSL SOA composition.

  18. Nonequilibrium Atmospheric Secondary Organic Aerosol Formation and Growth

    SciTech Connect

    Perraud, Veronique M.; Bruns, Emily A.; Ezell, Michael J.; Johnson, Stanley N.; Yu, Yong; Alexander, M. L.; Zelenyuk, Alla; Imre, D.; Chang, W. L.; Dabdub, Donald; Pankow, James F.; Finlayson-Pitts, Barbara J.

    2012-02-21

    Airborne particles play a critical role in air quality, human health effects, visibility and climate. Secondary organic aerosols (SOA) account for a significant portion of total airborne particles. They are formed in reactions of organic gases that produce low volatility and semi-volatile organic compounds (SVOCs). Current atmospheric models assume that SOA are liquids into which SVOCs undergo equilibrium partitioning and grow the particles. However a large discrepancy between model predictions and field measurements of SOA is commonly observed. We report here laboratory studies of the oxidation of a-pinene by ozone and nitrate radicals and show that particle composition is actually consistent with a kinetically determined growth mechanism, and not with equilibrium partitioning between the gas phase and liquid particles. If this is indeed a general phenomenon in air, the formulation of atmospheric SOA models will have to be revised to reflect this new paradigm. This will have significant impacts on quantifying the role of SOA in air quality, visibility, and climate.

  19. Organic composition of aerosols from controlled forest fires

    NASA Astrophysics Data System (ADS)

    Mirante, F.; Gonçalves, C.; Rocha, A. C.; Alves, C.; Evtyugina, M.; Nunes, T.; Pio, C.; Puxbaum, H.

    2009-04-01

    Controlled field fires were carried-out in May 2008 in the Gestosa area, in the upper zone of the Serra da Lousã mountain range in central Portugal. Particulate matter (PM2.5-10/PM2.5) in the smoke plume of these burnings has been sampled. A portion of the filters was analysed by a thermal-optical method to determine the elemental and organic carbon (EC and OC). The PM2.5 in the smoke plumes reached average levels up to 13,000 g.m-3. The total carbon in the coarse fraction concentration (PM2.5-10) was find to range between 49 and 331 µg.m-3. The elemental carbon represented less than 3% of the carbonaceous content in PM2.5-10 varying from 0.02 to 0.58 µg.m-3. The total carbon in the fine fraction (PM2.5) ranged between 295 and 6,126 µg.m-3. More than 95% of total carbon in PM2.5 is organic presenting concentrations between 0.42 and 0.94 µg.m-3. The particulate organic matter was then solvent extracted and fractionated by vacuum flash chromatography into 5 different classes of compounds whose structure were characterised by Gas Chromatography - Mass Spectrometry (GC-MS). The chromatographic results were dominated by odd -numbered alkanes and acids with and even number of carbon atoms. The organic speciation also enabled the quantification of specific molecular tracers (e.g. steradienes and amyryl-alkanoates) The carbon preference index (CPI) for higher plant waxes was 2.32 and is 12.19 for PM2.5 and PM2.5-10, respectively, indicating a major incorporation of recent biological components into aerosol samples. Sugar alcohols and anhydrosugars, which also represented a significant aerosol component, were analysed by HPLC with electrochemical (amperometric) detection. The Levoglucosan-to-mannosan ratio to this burnings carried out at shrub-dominated Mediterranean forest was 11.65, 6.09 for PM2.5-10 and PM10 respectively. This information could be conducive to source apportionment studies.

  20. 2-Hydroxyterpenylic acid: An oxygenated marker compound for a-pinene secondary organic aerosol in ambient fine aerosol

    EPA Science Inventory

    An oxygenated MW 188 compound is commonly observed in substantial abundance in atmospheric aerosol samples and was proposed in previous studies as an α-pinene-related marker compound that is associated with aging processes. Owing to difficulties in producing this compound in suff...

  1. Molecular distributions and stable carbon isotopic compositions of dicarboxylic acids and related compounds in aerosols from Sapporo, Japan: Implications for photochemical aging during long-range atmospheric transport

    NASA Astrophysics Data System (ADS)

    Aggarwal, Shankar G.; Kawamura, Kimitaka

    2008-07-01

    Molecular and stable carbon isotopic (δ13C value) compositions of dicarboxylic acids, ketoacids, and dicarbonyls in aerosol samples (i.e., total suspended particles) collected in Sapporo, northern Japan during spring and summer were determined to better understand the photochemical aging of organic aerosols during long-range transport from East Asia and Siberia. Their molecular distributions were characterized by the predominance of oxalic acid (C2) followed by malonic (C3) or occasionally succinic (C4) acids. Concentrations of total diacids ranged from 106-787 ng m-3 with ketoacids (13-81 ng m-3) and dicarbonyls (2.6-28 ng m-3) being less abundant. Water-soluble organic carbon (WSOC) comprised 23-69% of aerosol organic carbon (OC). OC to elemental carbon (EC) ratios were high (3.6-19, mean: 8.7). The ratios of C3/C4 and WSOC/OC did not show significant diurnal changes, suggesting that the Sapporo aerosols were not seriously affected by local photochemical processes and instead they were already aged. δ13C values of the dominant diacids (C2 - C4) ranged from -14.0 to -25.3‰. Largest δ13C values (-14.0 to -22.4‰, mean: -18.8‰) were obtained for C2, whereas smallest values (-25.1 to -31.4‰, mean: -28.1‰) were for azelaic acid (C9). In general, δ13C values of C2 - C4 diacids became less negative with aerosol aging (i.e., WSOC/OC), presumably due to isotopic fractionation during photochemical degradation of diacids. By comparing the δ13C values of diacids in the Sapporo aerosols with different air mass source regions, we suggest that although initial δ13C values of diacids depend on their precursor sources, the enrichment in 13C can be ascribed to aerosol photochemical aging.

  2. [Aging and mixing state of particulate matter during aerosol pollution episode in autumn Shanghai using a single particle aerosol mass spectrometer (SPAMS)].

    PubMed

    Mu, Ying-Ying; Lou, Sheng-Rong; Chen, Chang-Hong; Zhou, Min; Wang, Hong-Li; Zhou, Zhen; Qiao, Li-Ping; Huang, Cheng; Li, Mei; Li, Li; Wang, Qian; Huang, Hai-Ying; Zou, Lan-Jun

    2013-06-01

    A single particle aerosol mass spectrometer (SPAMS) was applied to characterize the size distribution (200 nm-2.0 microm) and chemical compositions of ambient particles during a polluted event from 11th to 18th, November 2011. OCEC, METAL, EC, SECONDARY and K-Na types of particulates were the dominant groups observed in hazy day period, which were 27.4%, 3.4%, 7.3% , 45.6% and 5.4% of the overall measured particles, respectively. The observed five types of particles contained the secondary composition such as 18NH4(+), 80SO3(-), 96SO4(-), 97HSO4(-), 46NO2(-), 62NO3(-) and 125H (NO3) -, showing that they probably went through different aging processes, and the increasing of the SECONDARY particles during the event clearly indicated a secondary aerosol pollution. Heterogeneous reactions of SO2 and particles could be the reason of strong 97HSO4(-) signals in the mass spectrums of OCEC type particles while the existence of organic compounds might have an important influence on the aerosol formation with the gas-phase sulfuric acid. Fresh EC particles in the environment tended to be aging with above-mentioned secondary ions by the analysis of particle size distribution and eventually lead to a particle type conversion from EC to SECONDARY. Organic amine in marine environment was brought to the land by the warm, moist marine air mass that dramatically removed atmospheric SECONDARY and OCEC particles from the air with a heavy rain and leading to the observation of amine particles in the clean day period. PMID:23947016

  3. [Aging and mixing state of particulate matter during aerosol pollution episode in autumn Shanghai using a single particle aerosol mass spectrometer (SPAMS)].

    PubMed

    Mu, Ying-Ying; Lou, Sheng-Rong; Chen, Chang-Hong; Zhou, Min; Wang, Hong-Li; Zhou, Zhen; Qiao, Li-Ping; Huang, Cheng; Li, Mei; Li, Li; Wang, Qian; Huang, Hai-Ying; Zou, Lan-Jun

    2013-06-01

    A single particle aerosol mass spectrometer (SPAMS) was applied to characterize the size distribution (200 nm-2.0 microm) and chemical compositions of ambient particles during a polluted event from 11th to 18th, November 2011. OCEC, METAL, EC, SECONDARY and K-Na types of particulates were the dominant groups observed in hazy day period, which were 27.4%, 3.4%, 7.3% , 45.6% and 5.4% of the overall measured particles, respectively. The observed five types of particles contained the secondary composition such as 18NH4(+), 80SO3(-), 96SO4(-), 97HSO4(-), 46NO2(-), 62NO3(-) and 125H (NO3) -, showing that they probably went through different aging processes, and the increasing of the SECONDARY particles during the event clearly indicated a secondary aerosol pollution. Heterogeneous reactions of SO2 and particles could be the reason of strong 97HSO4(-) signals in the mass spectrums of OCEC type particles while the existence of organic compounds might have an important influence on the aerosol formation with the gas-phase sulfuric acid. Fresh EC particles in the environment tended to be aging with above-mentioned secondary ions by the analysis of particle size distribution and eventually lead to a particle type conversion from EC to SECONDARY. Organic amine in marine environment was brought to the land by the warm, moist marine air mass that dramatically removed atmospheric SECONDARY and OCEC particles from the air with a heavy rain and leading to the observation of amine particles in the clean day period.

  4. Sources and source processes of organic nitrogen aerosols in the atmosphere

    NASA Astrophysics Data System (ADS)

    Erupe, Mark E.

    The research in this dissertation explored the sources and chemistry of organic nitrogen aerosols in the atmosphere. Two approaches were employed: field measurements and laboratory experiments. In order to characterize atmospheric aerosol, two ambient studies were conducted in Cache Valley in Northern Utah during strong winter inversions of 2004 and 2005. The economy of this region is heavily dependent on agriculture. There is also a fast growing urban population. Urban and agricultural emissions, aided by the valley geography and meteorology, led to high concentrations of fine particles that often exceeded the national ambient air quality standards. Aerosol composition was dominated by ammonium nitrate and organic species. Mass spectra from an aerosol mass spectrometer revealed that the organic ion peaks were consistent with reduced organic nitrogen compounds, typically associated with animal husbandry practices. Although no direct source characterization studies have been undertaken in Cache Valley with an aerosol mass spectrometer, spectra from a study at a swine facility in Ames, Iowa, did not show any evidence of reduced organic nitrogen species. This, combined with temporal and diurnal characteristics of organic aerosol peaks, was a pointer that the organic nitrogen species in Cache Valley likely formed from secondary chemistry. Application of multivariate statistical analyses to the organic aerosol spectra further supported this hypothesis. To quantify organic nitrogen signals observed in ambient studies as well as understand formation chemistry, three categories of laboratory experiments were performed. These were calibration experiments, smog chamber studies, and an analytical method development. Laboratory calibration experiments using standard calibrants indicated that quantifying the signals from organic nitrogen species was dependent on whether they formed through acid-base chemistry or via secondary organic aerosol pathway. Results from smog chamber

  5. Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

    DOE PAGES

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-08-28

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitude and distribution ofmore » US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

  6. Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-08-01

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

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

    NASA Astrophysics Data System (ADS)

    Li, Ying; Pöschl, Ulrich; Shiraiwa, Manabu

    2016-03-01

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

  8. Estimates of non-traditional secondary organic aerosols from aircraft SVOC and IVOC emissions using CMAQ

    NASA Astrophysics Data System (ADS)

    Woody, M. C.; West, J. J.; Jathar, S. H.; Robinson, A. L.; Arunachalam, S.

    2014-12-01

    Utilizing an aircraft-specific parameterization based on smog chamber data in the Community Multiscale Air Quality (CMAQ) model with the Volatility Basis Set (VBS), we estimated contributions of non-traditional secondary organic aerosols (NTSOA) for aircraft emissions during landing and takeoff (LTO) activities at the Hartsfield-Jackson Atlanta International Airport. NTSOA, formed from the oxidation of semi-volatile and intermediate volatility organic compounds (S/IVOCs), is a heretofore unaccounted component of fine particulate matter (PM2.5) in most air quality models. We expanded a prerelease version of CMAQ with VBS implemented for the Carbon Bond 2005 (CB05) chemical mechanism to use the Statewide Air Pollution Research Center 2007 (SAPRC-07) chemical mechanism, and added species representing aircraft S/IVOCs and corresponding NTSOA oxidation products. Results indicated the maximum monthly average NTSOA contributions occurred at the airport, and ranged from 2.4 ng m-3 (34% from idle and 66% from non-idle aircraft activities) in January to 9.1 ng m-3 (33 and 67%) in July. This represents 1.7% (of 140 ng m-3) in January and 7.4% in July (of 122 ng m-3) of aircraft-attributable PM2.5, compared to 41.0-42.0% from elemental carbon and 42.8-58.0% from inorganic aerosols. As a percentage of PM2.5, impacts were higher downwind of the airport, where NTSOA averaged 4.6-17.9% of aircraft-attributable PM2.5 and, considering alternative aging schemes, was high as 24.0% - thus indicating the increased contribution of aircraft-attributable SOA, as a component of PM2.5. However, NTSOA contributions were generally low compared to smog chamber results, particularly at idle, due to the considerably lower ambient organic aerosol concentrations in CMAQ, vs. those in the smog chamber experiments.

  9. Estimates of non-traditional secondary organic aerosols from aircraft SVOC and IVOC emissions using CMAQ

    NASA Astrophysics Data System (ADS)

    Woody, M. C.; West, J. J.; Jathar, S. H.; Robinson, A. L.; Arunachalam, S.

    2015-06-01

    Utilizing an aircraft-specific parameterization based on smog chamber data in the Community Multiscale Air Quality (CMAQ) model with the volatility basis set (VBS), we estimated contributions of non-traditional secondary organic aerosols (NTSOA) for aircraft emissions during landing and takeoff (LTO) activities at the Hartsfield-Jackson Atlanta International Airport. NTSOA, formed from the oxidation of semi-volatile and intermediate volatility organic compounds (S/IVOCs), is a heretofore unaccounted component of fine particulate matter (PM2.5) in most air quality models. We expanded a prerelease version of CMAQ with VBS implemented for the Carbon Bond 2005 (CB05) chemical mechanism to use the Statewide Air Pollution Research Center 2007 (SAPRC-07) chemical mechanism and added species representing aircraft S/IVOCs and corresponding NTSOA oxidation products. Results indicated that the maximum monthly average NTSOA contributions occurred at the airport and ranged from 2.4 ng m-3 (34 % from idle and 66 % from non-idle aircraft activities) in January to 9.1 ng m-3 (33 and 67 %) in July. This represents 1.7 % (of 140 ng m-3) in January and 7.4 % in July (of 122 ng m-3) of aircraft-attributable PM2.5 compared to 41.0-42.0 % from elemental carbon and 42.8-58.0 % from inorganic aerosols. As a percentage of PM2.5, impacts were higher downwind of the airport, where NTSOA averaged 4.6-17.9 % of aircraft-attributable PM2.5 and, considering alternative aging schemes, was as high as 24.0 % - thus indicating the increased contribution of aircraft-attributable SOA as a component of PM2.5. However, NTSOA contributions were generally low compared to smog chamber results, particularly at idle, due to the considerably lower ambient organic aerosol concentrations in CMAQ compared to those in the smog chamber experiments.

  10. Heterogeneous ice nucleation on simulated secondary organic aerosol.

    PubMed

    Schill, Gregory P; De Haan, David O; Tolbert, Margaret A

    2014-01-01

    In this study, we have explored the phase behavior and the ice nucleation properties of secondary organic aerosol made from aqueous processing (aqSOA). AqSOA was made from the dark reactions of methylglyoxal with methylamine in simulated evaporated cloud droplets. The resulting particles were probed from 215 to 250 K using Raman spectroscopy coupled to an environmental cell. We find these particles are in a semisolid or glassy state based upon their behavior when exposed to mechanical pressure as well as their flow behavior. Further, we find that these aqSOA particles are poor depositional ice nuclei, in contrast to previous studies on simple mixtures of glassy organics. Additionally, we have studied the effect of ammonium sulfate on the phase, morphology, and ice nucleation behavior of the aqSOA. We find that the plasticizing effect of ammonium sulfate lowers the viscosity of the aqSOA, allowing the ammonium sulfate to effloresce within the aqSOA matrix. Upon humidification, the aqSOA matrix liquefies before it can depositionally nucleate ice, and the effloresced ammonium sulfate can act as an immersion mode ice nucleus. This change in the mode of nucleation is accompanied by an increase in the overall ice nucleation efficiency of the aqSOA particles.

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  12. Complex organic matter in Titan's atmospheric aerosols from in situ pyrolysis and analysis.

    PubMed

    Israël, G; Szopa, C; Raulin, F; Cabane, M; Niemann, H B; Atreya, S K; Bauer, S J; Brun, J-F; Chassefière, E; Coll, P; Condé, E; Coscia, D; Hauchecorne, A; Millian, P; Nguyen, M-J; Owen, T; Riedler, W; Samuelson, R E; Siguier, J-M; Steller, M; Sternberg, R; Vidal-Madjar, C

    2005-12-01

    Aerosols in Titan's atmosphere play an important role in determining its thermal structure. They also serve as sinks for organic vapours and can act as condensation nuclei for the formation of clouds, where the condensation efficiency will depend on the chemical composition of the aerosols. So far, however, no direct information has been available on the chemical composition of these particles. Here we report an in situ chemical analysis of Titan's aerosols by pyrolysis at 600 degrees C. Ammonia (NH3) and hydrogen cyanide (HCN) have been identified as the main pyrolysis products. This clearly shows that the aerosol particles include a solid organic refractory core. NH3 and HCN are gaseous chemical fingerprints of the complex organics that constitute this core, and their presence demonstrates that carbon and nitrogen are in the aerosols.

  13. Complex organic matter in Titan's atmospheric aerosols from in situ pyrolysis and analysis.

    PubMed

    Israël, G; Szopa, C; Raulin, F; Cabane, M; Niemann, H B; Atreya, S K; Bauer, S J; Brun, J-F; Chassefière, E; Coll, P; Condé, E; Coscia, D; Hauchecorne, A; Millian, P; Nguyen, M-J; Owen, T; Riedler, W; Samuelson, R E; Siguier, J-M; Steller, M; Sternberg, R; Vidal-Madjar, C

    2005-12-01

    Aerosols in Titan's atmosphere play an important role in determining its thermal structure. They also serve as sinks for organic vapours and can act as condensation nuclei for the formation of clouds, where the condensation efficiency will depend on the chemical composition of the aerosols. So far, however, no direct information has been available on the chemical composition of these particles. Here we report an in situ chemical analysis of Titan's aerosols by pyrolysis at 600 degrees C. Ammonia (NH3) and hydrogen cyanide (HCN) have been identified as the main pyrolysis products. This clearly shows that the aerosol particles include a solid organic refractory core. NH3 and HCN are gaseous chemical fingerprints of the complex organics that constitute this core, and their presence demonstrates that carbon and nitrogen are in the aerosols. PMID:16319825

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

    PubMed

    Kalberer, Markus; Sax, Mirjam; Samburova, Vera

    2006-10-01

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

  15. Functional group composition of organic aerosol from combustion emissions and secondary processes at two contrasted urban environments

    NASA Astrophysics Data System (ADS)

    El Haddad, Imad; Marchand, Nicolas; D'Anna, Barbara; Jaffrezo, Jean Luc; Wortham, Henri

    2013-08-01

    The quantification of major functional groups in atmospheric organic aerosol (OA) provides a constraint on the types of compounds emitted and formed in atmospheric conditions. This paper presents functional group composition of organic aerosol from two contrasted urban environments: Marseille during summer and Grenoble during winter. Functional groups were determined using a tandem mass spectrometry approach, enabling the quantification of carboxylic (RCOOH), carbonyl (RCOR‧), and nitro (RNO2) functional groups. Using a multiple regression analysis, absolute concentrations of functional groups were combined with those of organic carbon derived from different sources in order to infer the functional group contents of different organic aerosol fractions. These fractions include fossil fuel combustion emissions, biomass burning emissions and secondary organic aerosol (SOA). Results clearly highlight the differences between functional group fingerprints of primary and secondary OA fractions. OA emitted from primary sources is found to be moderately functionalized, as about 20 carbons per 1000 bear one of the functional groups determined here, whereas SOA is much more functionalized, as in average 94 carbons per 1000 bear a functional group under study. Aging processes appear to increase both RCOOH and RCOR‧ functional group contents by nearly one order of magnitude. Conversely, RNO2 content is found to decrease with photochemical processes. Finally, our results also suggest that other functional groups significantly contribute to biomass smoke and SOA. In particular, for SOA, the overall oxygen content, assessed using aerosol mass spectrometer measurements by an O:C ratio of 0.63, is significantly higher than the apparent O:C* ratio of 0.17 estimated based on functional groups measured here. A thorough examination of our data suggests that this remaining unexplained oxygen content can be most probably assigned to alcohol (ROH), organic peroxides (ROOH

  16. Organic nitrogen in PM2.5 aerosol at a forest site in the Southeast US

    EPA Science Inventory

    There is growing evidence that organo-nitrogen compounds may constitute a significant fraction of the aerosol nitrogen (N) budget. In this study, the concentration of organic nitrogen (ON) and major inorganic ions in PM2.5 aerosol were measured at the Duke Forest Research Facilit...

  17. Optical Properties of Mixed Black Carbon, Inorganic and Secondary Organic Aerosols

    SciTech Connect

    Paulson, S E

    2012-05-30

    Summarizes the achievements of the project, which are divided into four areas: 1) Optical properties of secondary organic aerosols; 2) Development and of a polar nephelometer to measure aerosol optical properties and theoretical approaches to several optical analysis problems, 3) Studies on the accuracy of measurements of absorbing carbon by several methods, and 4) Environmental impacts of biodiesel.

  18. Contribution of Isoprene Epoxydiol to Urban Organic Aerosol: Evidence from Modeling and Measurements

    EPA Science Inventory

    In a region heavily influenced by anthropogenic and biogenic atmospheric emissions, recent field measurements have attributed one third of urban organic aerosol by mass to isoprene epoxydiols (IEPOX). These aerosols arise from the gas phase oxidation of isoprene, the formation of...

  19. Airborne observations of aerosol microphysical properties and particle ageing processes in the troposphere above Europe

    NASA Astrophysics Data System (ADS)

    Hamburger, T.; McMeeking, G.; Minikin, A.; Petzold, A.; Coe, H.; Krejci, R.

    2012-08-01

    In-situ measurements of aerosol microphysical properties were performed in May 2008 during the EUCAARI-LONGREX campaign. Two aircraft, the FAAM BAe-146 and DLR Falcon 20, operated from Oberpfaffenhofen, Germany. A comprehensive data set was obtained comprising the wider region of Europe north of the Alps throughout the whole tropospheric column. Prevailing stable synoptic conditions enabled measurements of accumulating emissions inside the continental boundary layer reaching a maximum total number concentration of 19 000 particles cm-3 stp. Nucleation events were observed within the boundary layer during high pressure conditions and after updraft of emissions induced by frontal passages above 8 km altitude in the upper free troposphere. Aerosol ageing processes during air mass transport are analysed using trajectory analysis. The ratio of particles containing a non-volatile core (250 °C) to the total aerosol number concentration was observed to increase within the first 12 to 48 h from the particle source from 50 to 85% due to coagulation. Aged aerosol also features an increased fraction of accumulation mode particles of approximately 40% of the total number concentration. The presented analysis provides an extensive data set of tropospheric aerosol microphysical properties on a continental scale which can be used for atmospheric aerosol models and comparisons of satellite retrievals.

  20. Airborne observations of aerosol microphysical properties and particle ageing processes in the troposphere above Europe

    NASA Astrophysics Data System (ADS)

    Hamburger, T.; McMeeking, G.; Minikin, A.; Petzold, A.; Coe, H.; Krejci, R.

    2012-12-01

    In-situ measurements of aerosol microphysical properties were performed in May 2008 during the EUCAARI-LONGREX campaign. Two aircraft, the FAAM BAe-146 and DLR Falcon 20, operated from Oberpfaffenhofen, Germany. A comprehensive data set was obtained comprising the wider region of Europe north of the Alps throughout the whole tropospheric column. Prevailing stable synoptic conditions enabled measurements of accumulating emissions inside the continental boundary layer reaching a maximum total number concentration of 19 000 particles cm-3 stp. Ultra-fine particles as indicators for nucleation events were observed within the boundary layer during high pressure conditions and after updraft of emissions induced by frontal passages above 8 km altitude in the upper free troposphere. Aerosol ageing processes during air mass transport are analysed using trajectory analysis. The ratio of particles containing a non-volatile core (250 °C) to the total aerosol number concentration was observed to increase within the first 12 to 48 h from the particle source from 50 to 85% due to coagulation. Aged aerosol also features an increased fraction of accumulation mode particles of approximately 40% of the total number concentration. The presented analysis provides an extensive data set of tropospheric aerosol microphysical properties on a continental scale which can be used for atmospheric aerosol models and comparisons of satellite retrievals.

  1. Estimating the influence of the secondary organic aerosols on present climate using ECHAM5-HAM

    NASA Astrophysics Data System (ADS)

    O'Donnell, D.; Tsigaridis, K.; Feichter, J.

    2011-01-01

    In recent years, several field measurement campaigns have highlighted the importance of the organic fraction of aerosol mass, and with such spatial diversity that one may assert that these aerosols are ubiquitous in the troposphere, with particular importance in continental areas. Investigation of the chemical composition of organic aerosol remains a work in progress, but it is now clear that a significant portion of the total organic mass is composed of secondary organic material, that is, aerosol chemically formed from gaseous volatile organic carbon (VOC) precursors. A number of such precursors, of both biogenic and anthropogenic origin, have been identified. Experimental, inventory building and modelling studies have followed. Laboratory studies have yielded information on the chemical pathways that lead to secondary organic aerosol (SOA) formation, and provided the means to estimate the aerosol yields from a given precursor-oxidant reaction. Global inventories of anthropogenic VOC emissions, and of biogenic VOC emitter species distribution and their emission potential have been constructed. Models have been developed that provide global estimates of precursor VOC emissions, SOA formation and atmospheric burdens of these species. This paper estimates the direct and indirect effects of these aerosols using the global climate-aerosol model ECHAM5-HAM. For year 2000 conditions, we estimate a global annual mean shortwave (SW) aerosol direct effect due to SOA of -0.3 W m-2. The model predicts a positive SW indirect effect due to SOA amounting to +0.23 W m-2, arising from enlargement of particles due to condensation of SOA, together with an enhanced coagulation sink for small particles. Longwave effects are small. Finally, we indicate of areas of research into SOA that are required in order to better constrain our estimates of the influence of aerosols on the climate system.

  2. Seasonal variations of biogenic secondary organic aerosol tracers in ambient aerosols from Alaska

    NASA Astrophysics Data System (ADS)

    Haque, Md. Mozammel; Kawamura, Kimitaka; Kim, Yongwon

    2016-04-01

    We investigated total suspended particles (TSP) collected from central Alaska, USA for molecular compositions of secondary organic aerosol (SOA) derived from the oxidation of biogenic volatile organic compounds (BVOCs). Isoprene-, α-/β-pinene- and β-caryophyllene-SOA tracers were determined using gas chromatography-mass spectrometry. The concentration ranges of isoprene, α-/β-pinene and β-caryophyllene oxidation products were 0.02-18.6 ng m-3 (ave. 4.14 ng m-3), 0.42-8.24 ng m-3 (2.01 ng m-3) and 0.10-9 ng m-3 (1.53 ng m-3), respectively. Isoprene-SOA tracers showed higher concentrations in summer (ave. 8.77 ng m-3), whereas α-/β-pinene- and β-caryophyllene-SOA tracers exhibited highest levels in spring (3.55 ng m-3) and winter (4.04 ng m-3), respectively. β-Caryophyllinic acid and levoglucosan showed a positive correlation, indicating that biomass burning may be a major source for β-caryophyllene. We found that mean contributions of isoprene oxidation products to organic carbon (OC) and water-soluble organic (WSOC) (0.56% and 1.2%, respectively) were higher than those of α-/β-pinene (0.31% and 0.55%) and β-caryophyllene (0.08% and 0.13%). Using a tracer-based method, we estimated the concentrations of secondary organic carbon (SOC) produced from isoprene, α-/β-pinene and β-caryophyllene to be 0.66-718 ngC m-3 (ave. 159 ngC m-3), 7.4-143 ngC m-3 (35 ngC m-3) and 4.5-391 ngC m-3 (66.3 ngC m-3), respectively. Based on SOA tracers, this study suggests that isoprene is a more important precursor for the production of biogenic SOA than α-/β-pinene and β-caryophyllene in subarctic Alaska.

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

    NASA Astrophysics Data System (ADS)

    Sun, Y. L.; Zhang, Q.; Schwab, J. J.; Yang, T.; Ng, N. L.; Demerjian, K. L.

    2012-09-01

    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 inorganic and organic aerosol signals may enable the deconvolution of more OA factors and gain more insights into the

  4. Secondary organic aerosol formation and organic nitrate yield from NO3 oxidation of biogenic hydrocarbons.

    PubMed

    Fry, Juliane L; Draper, Danielle C; Barsanti, Kelley C; Smith, James N; Ortega, John; Winkler, Paul M; Lawler, Michael J; Brown, Steven S; Edwards, Peter M; Cohen, Ronald C; Lee, Lance

    2014-10-21

    The secondary organic aerosol (SOA) mass yields from NO3 oxidation of a series of biogenic volatile organic compounds (BVOCs), consisting of five monoterpenes and one sesquiterpene (α-pinene, β-pinene, Δ-3-carene, limonene, sabinene, and β-caryophyllene), were investigated in a series of continuous flow experiments in a 10 m(3) indoor Teflon chamber. By making in situ measurements of the nitrate radical and employing a kinetics box model, we generate time-dependent yield curves as a function of reacted BVOC. SOA yields varied dramatically among the different BVOCs, from zero for α-pinene to 38-65% for Δ-3-carene and 86% for β-caryophyllene at mass loading of 10 μg m(-3), suggesting that model mechanisms that treat all NO3 + monoterpene reactions equally will lead to errors in predicted SOA depending on each location's mix of BVOC emissions. In most cases, organonitrate is a dominant component of the aerosol produced, but in the case of α-pinene, little organonitrate and no aerosol is formed.

  5. Secondary Organic Aerosol Formation and Organic Nitrate Yield from NO3 Oxidation of Biogenic Hydrocarbons

    PubMed Central

    2014-01-01

    The secondary organic aerosol (SOA) mass yields from NO3 oxidation of a series of biogenic volatile organic compounds (BVOCs), consisting of five monoterpenes and one sesquiterpene (α-pinene, β-pinene, Δ-3-carene, limonene, sabinene, and β-caryophyllene), were investigated in a series of continuous flow experiments in a 10 m3 indoor Teflon chamber. By making in situ measurements of the nitrate radical and employing a kinetics box model, we generate time-dependent yield curves as a function of reacted BVOC. SOA yields varied dramatically among the different BVOCs, from zero for α-pinene to 38–65% for Δ-3-carene and 86% for β-caryophyllene at mass loading of 10 μg m–3, suggesting that model mechanisms that treat all NO3 + monoterpene reactions equally will lead to errors in predicted SOA depending on each location’s mix of BVOC emissions. In most cases, organonitrate is a dominant component of the aerosol produced, but in the case of α-pinene, little organonitrate and no aerosol is formed. PMID:25229208

  6. Molecular Chemistry of Organic Aerosols Through the Application of High Resolution Mass Spectrometry

    SciTech Connect

    Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2011-01-05

    Understanding of molecular composition and fundamental chemical transformations of organic aerosols (OA) during their formation and aging is both a major challenge and the area of greatest uncertainty in atmospheric research. Particularly little is known about fundamental relationship between the chemical composition and physicochemical properties of OA, their atmospheric history, evolution, and impact on the environment. Ambient soft-ionization methods combined with high-resolution mass spectrometry (HR-MS) analysis provide detailed information on the molecular content of OA that is pivotal for improved understanding of their complex composition, multi-phase aging chemistry, direct (light absorption and scattering) and indirect (aerosol-cloud interactions) effects on atmospheric radiation and climate, and health effects. The HR-MS methods can detect thousands of individual OA constituents at once, provide their elemental formulae from accurate mass measurements, and provide structural information based on tandem mass spectrometry. Integration with additional analytical tools, such as chromatography and UV/Vis absorption spectroscopy, makes it possible to further separate OA compounds by their polarity and ability to absorb solar radiation. The goal of this perspective is to describe modern HR-MS methods, review recent applications to field and laboratory studies of OA, and explain how the information obtained from HR-MS methods can be translated into improved understanding of OA chemistry.

  7. Quantifying the Reactive Uptake of OH by Organic Aerosols in aContinuous Flow Stirred Tank Reactor

    SciTech Connect

    Che, Dung L.; Smith, Jared D.; Leone, Stephen R.; Ahmed, Musahid; Wilson, Kevin R.

    2009-03-01

    Here we report a new method for measuring the heterogeneous chemistry of submicron organic aerosol particles using a continuous flow stirred tank reactor. This approach is designed to quantify the real time heterogeneous kinetics, using a relative rate method, under conditions of low oxidant concentration and long reaction times that more closely mimic the real atmosphere. A general analytical expression, which couples the aerosol chemistry with the flow dynamics in the chamber is developed and applied to the heterogeneous oxidation of squalane particles by hydroxyl radicals (OH) in the presence of O2. The particle phase reaction is monitored via photoionization aerosol mass spectrometry and yields a reactive uptake coefficient of 0.51+-0.10, using OH concentrations of 1-7x108 molec cdot cm-3 and reaction times of 1.5+-3 hours. This uptake coefficient is larger than that found for the reaction carried out under high OH concentrations (~;;1x1010 molec cdot cm-3) and short reaction times in a flow tube reactor. This difference suggests that oxidant concentration and reaction time are not interchangeable quantities in reactions of organic aerosols with radicals. In general, this approach provides a new way to examine how the chemical aging of organic particles measured at short reaction times and high oxidant concentrations in flow tubes might differ from the long reaction times and low oxidant levels found in the real atmosphere.

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

    PubMed Central

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

    2014-01-01

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

  9. Investigating the Formation of Ambient Secondary Organic Aerosol in Southeastern USA

    NASA Astrophysics Data System (ADS)

    Weber, R.; Sullivan, A.; Peltier, R.; Hennigan, C.; Yan, B.; Zheng, M.; Kaynak, B.; Russell, J.; Brock, C.; de Gouw, J.; Warneke, C.; Holloway, J.; Atlas, E.; Edgerton, E.

    2006-12-01

    It is well known that during periods of intense photochemistry the formation of secondary organic aerosol (SOA) is a major source for fine particle mass, and a significant contributor to poor air quality. This process is thought to be especially important in the southeastern United States due to high concentrations of both anthropogenic and biogenic precursor organic compounds. SOA formation, however, is poorly understood. Recent studies by a number of investigators in widely different urban regions show that model simulations based on SOA yields from smog chamber experiments under predict the organic aerosol by factors of roughly 5 to 15. These studies also show organic aerosol can be formed rapidly within 5 to 20 hours following emission. We have found similar results based on data collected from a suite of instrumentation deployed on the NOAA WP-3B aircraft during the New England Air Quality Study of August 2004. Throughout the mission plumes transported from New York City were intercepted various distances downwind. For plumes less that roughly 20 hrs old concentrations of water-soluble organic compounds (WSOC) in fine particles rapidly increased relative to carbon monoxide with increasing plume age. WSOC concentrations were 8 +/- 2 times higher than expected based on calculations using current SOA yields, and although WSOC was highly correlated with anthropogenic tracers, no correlation was found to biogenic VOCs. Subsequent measurements with the same suite of instruments over metropolitan Atlanta and a large region of north Georgia resulted in similar findings despite measured biogenic VOC concentrations higher by factors of 10 to 100. WSOC was only correlated with anthropogenic emissions, chemically aged air masses had WSOC concentrations relative to CO similar to that found in the northeast, and WSOC concentrations were roughly 5 +/- 1 times higher than that predicted by the Community Multi-scale Air Quality Model (CMAQ). In contrast, radiocarbon analysis

  10. Secondary Organic Aerosol formation from the gas-phase reaction of catechol with ozone

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, C.; Tomas, A.; Guilloteau, A.; Henry, F.; Ledoux, F.; Visez, N.; Riffault, V.; Wenger, J. C.; Bedjanian, Y.; Foulon, V.

    2009-04-01

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers (at the LPCA in France and at the CRAC in Ireland). Aerosol production was monitored using a scanning mobility particle sizer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm-3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The aerosol yields determined in the LPCA and CRAC smog chambers were comparable and were also in accordance with those determined in a previous study performed in EUPHORE (EUropean PHOto REactor, Spain).

  11. The sources, properties, and evolution of organic aerosols in the atmosphere

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.

    2015-12-01

    Organic aerosols (OA) account for about 1/2 of the submicron particle mass in the atmosphere leading to important impacts on climate, human health, and other issues, but their sources, properties, and evolution are poorly understood. OA is comprised of primary OA (POA, emitted in the particle phase) and secondary OA (SOA, formed by gas-to-particle conversion). Together with others in the community and contrary to the understanding at the time, we demonstrated in the mid-2000s that SOA dominates over POA at most locations. This paradigm shift has led to intense research on the sources, processing, properties, and fate of SOA. Because pre-existing and commercial instruments were very limited for the analysis of the complex mixtures of highly oxidized species comprising real OA, we developed or co-developed several experimental and data analysis techniques aimed at extracting more information out of ambient and laboratory air, and pioneered their application in field experiments. We proposed a new paradigm (Jimenez et al., Science, 2009) that is consistent with worldwide measurements and in which OA and OA precursor gases evolve continuously by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. The amount of SOA formed from urban air is remarkably consistent across the world, although the contributions of different sources remain a subject of debate. Biomass burning emissions rarely form additional OA mass after emission, although rapid chemical aging is always observed. Global model-measurement comparisons suggest the need for a large (100 Tg/yr) "anthropogenically-controlled" SOA source, thought to be dominated by anthropogenically-enhanced biogenic SOA. SOA formed from several pathways from biogenic emissions is starting to be better characterized, as are key SOA properties such as

  12. Organic aggregate formation in aerosols and its impact on the physicochemical properties of atmospheric particles

    NASA Astrophysics Data System (ADS)

    Tabazadeh, Azadeh

    Fatty acid salts and "humic" materials, found in abundance in atmospheric particles, are both anionic surfactants. Such materials are known to form organic aggregates or colloids in solution at very low aqueous concentrations. In a marine aerosol, micelle aggregates can form at a low fatty acid salt molality of ˜10 -3 m. In other types of atmospheric particles, such as biomass burning, biogenic, soil dust, and urban aerosols, "humic-like" materials exist in sufficient quantities to form micelle-like aggregates in solution. I show micelle formation limits the ability of surface-active organics in aerosols to reduce the surface tension of an atmospheric particle beyond about 10 dyne cm -1. A general phase diagram is presented for anionic surfactants to explain how surface-active organics can change the water uptake properties of atmospheric aerosols. Briefly such molecules can enhance and reduce water uptake by atmospheric aerosols at dry and humid conditions, respectively. This finding is consistent with a number of unexplained field and laboratory observations. Dry electron microscope images of atmospheric particles often indicate that organics may coat the surface of particles in the atmosphere. The surfactant phase diagram is used to trace the particle path back to ambient conditions in order to determine whether such coatings can exist on wet ambient aerosols. Finally, I qualitatively highlight how organic aggregate formation in aerosols may change the optical properties and chemical reactivity of atmospheric particles.

  13. Single-particle measurements of phase partitioning between primary and secondary organic aerosols.

    PubMed

    Robinson, Ellis Shipley; Donahue, Neil M; Ahern, Adam T; Ye, Qing; Lipsky, Eric

    2016-07-18

    Organic aerosols provide a measure of complexity in the urban atmosphere. This is because the aerosols start as an external mixture, with many populations from varied local sources, that all interact with each other, with background aerosols, and with condensing vapors from secondary organic aerosol formation. The externally mixed particle populations start to evolve immediately after emission because the organic molecules constituting the particles also form thermodynamic mixtures - solutions - in which a large fraction of the constituents are semi-volatile. The external mixtures are thus well out of thermodynamic equilibrium, with very different activities for many constituents, and yet also have the capacity to relax toward equilibrium via gas-phase exchange of semi-volatile vapors. Here we describe experiments employing quantitative single-particle mass spectrometry designed to explore the extent to which various primary organic aerosol particle populations can interact with each other or with secondary organic aerosols representative of background aerosol populations. These methods allow us to determine when these populations will and when they will not mix with each other, and then to constrain the timescales for that mixing.

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

    NASA Astrophysics Data System (ADS)

    Li, Yunchun

    Organic aerosols, as an important fraction of airborne particulate mass, significantly affect the environment, climate, and human health. Compared with inorganic species, characterization of individual organic compounds is much less complete and comprehensive because they number in thousands or more and are diverse in chemical structures. The source contributions of organic aerosols are far from being well understood because they can be emitted from a variety of sources as well as formed from photochemical reactions of numerous precursors. This thesis work aims to improve the characterization of polar organic compounds and source apportionment analysis of fine organic carbon (OC) in Hong Kong, which consists of two parts: (1) An improved analytical method to determine monocarboxylic acids, dicarboxylic acids, ketocarboxylic acids, and dicarbonyls collected on filter substrates has been established. These oxygenated compounds were determined as their butyl ester or butyl acetal derivatives using gas chromatography-mass spectrometry. The new method made improvements over the original Kawamura method by eliminating the water extraction and evaporation steps. Aerosol materials were directly mixed with the BF 3/BuOH derivatization agent and the extracting solvent hexane. This modification improves recoveries for both the more volatile and the less water-soluble compounds. This improved method was applied to study the abundances and sources of these oxygenated compounds in PM2.5 aerosol samples collected in Hong Kong under different synoptic conditions during 2003-2005. These compounds account for on average 5.2% of OC (range: 1.4%-13.6%) on a carbon basis. Oxalic acid was the most abundant species. Six C2 and C3 oxygenated compounds, namely oxalic, malonic, glyoxylic, pyruvic acids, glyoxal, and methylglyoxal, dominated this suite of oxygenated compounds. More efforts are therefore suggested to focus on these small compounds in understanding the role of oxygenated

  15. Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

    DOE PAGES

    Woody, Matthew C.; Baker, Kirk R.; Hayes, Patrick L.; Jimenez, Jose L.; Koo, Bonyoung; Pye, Havala O. T.

    2016-03-29

    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 asmore » 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

  16. Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

    NASA Astrophysics Data System (ADS)

    Woody, Matthew C.; Baker, Kirk R.; Hayes, Patrick L.; Jimenez, Jose L.; Koo, Bonyoung; Pye, Havala O. T.

    2016-03-01

    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 for that model is

  17. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    SciTech Connect

    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).

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

    NASA Astrophysics Data System (ADS)

    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 (<1%) observed could not explain observational concentrations

  19. Organic peroxide and OH formation in aerosol and cloud water: laboratory evidence for this aqueous chemistry

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    Aqueous chemistry in atmospheric waters (e.g., cloud droplets or wet aerosols) is well accepted as an atmospheric pathway to produce secondary organic aerosol (SOAaq). Water-soluble organic compounds with small carbon numbers (C2-C3) are precursors for SOAaq and products include organic acids, organic sulfates, and high molecular weight compounds/oligomers. Fenton reactions and the uptake of gas-phase OH radicals are considered to be the major oxidant sources for aqueous organic chemistry. However, the sources and availability of oxidants in atmospheric waters are not well understood. The degree to which OH is produced in the aqueous phase affects the balance of radical and non-radical aqueous chemistry, the properties of the resulting aerosol, and likely its atmospheric behavior. This paper demonstrates organic peroxide formation during aqueous photooxidation of methylglyoxal using ultra high resolution Fourier Transform Ion Cyclotron Resonance electrospray ionization mass spectrometry (FTICR-MS). Organic peroxides are known to form through gas-phase oxidation of volatile organic compounds. They contribute secondary organic aerosol (SOA) formation directly by forming peroxyhemiacetals, and epoxides, and indirectly by enhancing gas-phase oxidation through OH recycling. We provide simulation results of organic peroxide/peroxyhemiacetal formation in clouds and wet aerosols and discuss organic peroxides as a source of condensed-phase OH radicals and as a contributor to aqueous SOA.

  20. CCN Activity of Organic Aerosols Observed Downwind of Urban Emissions during CARES

    SciTech Connect

    Mei, Fan; Setyan, Ari; Zhang, Qi; Wang, J. X.

    2013-12-17

    During the Carbonaceous Aerosols and Radiative Effects Study (CARES), activation fraction of size-resolved aerosol particles and aerosol chemical composition were characterized at the T1 site (~60 km downwind of Sacramento, California) from 10 June to 28 June 2010. The hygroscopicity of CCN-active particles (KCCN) with diameter from 100 to 170 nm, derived from the size-resolved activated fraction, varied from 0.10 to 0.21, with an average of 0.15, which was substantially lower than that proposed for continental sites in earlier studies. The low KCCN value was due to the high organic volume fraction, averaged over 80% at the T1 site. The derived KCCN exhibited little diurnal variation, consistent with the relatively constant organic volume fraction observed. At any time, over 90% of the size selected particles with diameter between 100 and 171nm were CCN active, suggesting most particles within this size range were aged background particles. Due to the large organic volume fraction, organic hygroscopicity (Korg) strongly impacted particle hygroscopicity and therefore calculated CCN concentration. For vast majority of the cases, an increase of Korg from 0.03 to 0.18, which are within the typical range, doubled the calculated CCN concentration. Organic hygroscopicity was derived from KCCN and aerosol chemical composition, and its variations with the fraction of total organic mass spectral signal at m/z 44 (f44) and O:C were compared to results from previous studies. Overall, the relationships between Korg and f44 are quite consistent for organic aerosol (OA) observed during field studies and those formed in smog chamber. Compared to the relationship between Korg and f44, the relationship between Korg and O:C exhibits more significant differences among different studies, suggesting korg may be better parameterized using f44. A

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  2. Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

    NASA Astrophysics Data System (ADS)

    Hayes, P. L.; Ortega, A. M.; Cubison, M. J.; Froyd, K. D.; Zhao, Y.; Cliff, S. S.; Hu, W. W.; Toohey, D. W.; Flynn, J. H.; Lefer, B. L.; Grossberg, N.; Alvarez, S.; Rappenglück, B.; Taylor, J. W.; Allan, J. D.; Holloway, J. S.; Gilman, J. B.; Kuster, W. C.; Gouw, J. A.; Massoli, P.; Zhang, X.; Liu, J.; Weber, R. J.; Corrigan, A. L.; Russell, L. M.; Isaacman, G.; Worton, D. R.; Kreisberg, N. M.; Goldstein, A. H.; Thalman, R.; Waxman, E. M.; Volkamer, R.; Lin, Y. H.; Surratt, J. D.; Kleindienst, T. E.; Offenberg, J. H.; Dusanter, S.; Griffith, S.; Stevens, P. S.; Brioude, J.; Angevine, W. M.; Jimenez, J. L.

    2013-08-01

    Organic aerosols (OA) in Pasadena are characterized using multiple measurements from the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign. Five OA components are identified using positive matrix factorization including hydrocarbon-like OA (HOA) and two types of oxygenated OA (OOA). The Pasadena OA elemental composition when plotted as H : C versus O : C follows a line less steep than that observed for Riverside, CA. The OOA components from both locations follow a common line, however, indicating similar secondary organic aerosol (SOA) oxidation chemistry at the two sites such as fragmentation reactions leading to acid formation. In addition to the similar evolution of elemental composition, the dependence of SOA concentration on photochemical age displays quantitatively the same trends across several North American urban sites. First, the OA/ΔCO values for Pasadena increase with photochemical age exhibiting a slope identical to or slightly higher than those for Mexico City and the northeastern United States. Second, the ratios of OOA to odd-oxygen (a photochemical oxidation marker) for Pasadena, Mexico City, and Riverside are similar, suggesting a proportional relationship between SOA and odd-oxygen formation rates. Weekly cycles of the OA components are examined as well. HOA exhibits lower concentrations on Sundays versus weekdays, and the decrease in HOA matches that predicted for primary vehicle emissions using fuel sales data, traffic counts, and vehicle emission ratios. OOA does not display a weekly cycle—after accounting for differences in photochemical aging —which suggests the dominance of gasoline emissions in SOA formation under the assumption that most urban SOA precursors are from motor vehicles.

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

    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.

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

    PubMed

    McNeill, V Faye

    2015-02-01

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

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  7. Photolytic processing of secondary organic aerosols dissolved in cloud droplets

    SciTech Connect

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

    2011-05-26

    The effect of UV irradiation on the molecular composition of aqueous extracts of secondary organic aerosol (SOA) was investigated. SOA was prepared by the dark reaction of ozone and d-limonene at 0.05 - 1 ppm precursor concentrations and collected with a particle-into-liquid sampler (PILS). The PILS extracts were photolyzed by 300 - 400 nm radiation for up to 24 hours. Water-soluble SOA constituents were analyzed using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) at different stages of photolysis for all SOA precursor concentrations. Exposure to UV radiation increased the average O/C ratio and decreased the average double bond equivalent (DBE) of the dissolved SOA compounds. Oligomeric compounds were significantly reduced by photolysis relative to the monomeric compounds. Direct pH measurements showed that compounds containing carboxylic acids increased upon photolysis. Methanol reactivity analysis revealed significant photodissociation of molecules containing carbonyl groups and formation of carboxylic acids. Aldehydes, such as limononaldehyde, were almost completely removed. The removal of carbonylswas confirmed by the UV-Vis absorption spectroscopy of the SOA extracts where the absorbance in the carbonyl n→π* band decreased significantly upon photolysis. The effective quantum yield (the number of carbonyls destroyed per photon absorbed) was estimated as ~ 0.03. The concentration of peroxides did not change significantly during photolysis as quantified with an iodometric test. Although organic peroxides were photolyzed, the likely end products of photolysis were smaller peroxides, including hydrogen peroxide, resulting in a no net change in the peroxide content.

  8. Estimating Black Carbon Aging Time-Scales with a Particle-Resolved Aerosol Model

    SciTech Connect

    Riemer, Nicole; West, Matt; Zaveri, Rahul A.; Easter, Richard C.

    2010-01-13

    Understanding the aging process of aerosol particles is important for assessing their chemical reactivity, cloud condensation nuclei activity, radiative properties and health impacts. In this study we investigate the aging of black carbon containing particles in an idealized urban plume using a new approach, the particleresolved aerosol model PartMC-MOSAIC. We present a method to estimate aging time-scales using an aging criterion based on cloud condensation nuclei activation. The results show a separation into a daytime regime where condensation dominates and a nighttime regime where coagulation dominates. For the chosen urban plume scenario, depending on the supersaturation threshold, the values for the aging timescales vary between 0.06 hours and 10 hours during the day, and between 6 hours and 20 hours during the night.

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

    SciTech Connect

    Meskhidze, N.; Xu, J.; Gantt, Brett; Zhang, Yang; Nenes, Athanasios; Ghan, Steven J.; Liu, Xiaohong; Easter, Richard C.; Zaveri, Rahul A.

    2011-11-23

    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), phytoplanktonproduced isoprene- and monoterpenes-derived secondary organic aerosols (SOA) and methane sulfonate (MS{sup -}) 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{sup -1}, for the Gantt et al. (2011) and Vignati et al. (2010) emission parameterizations, respectively. Marine sources of SOA and particulate MS{sup -} (containing both sulfur and carbon atoms) contribute an additional 0.2 and 5.1 Tg yr{sup -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 ngm{sup -3}, with values up to 400 ngm{sup -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 marine organics are internally-mixed with sea

  10. Aerosol size distribution and radiative forcing response to anthropogenically driven historical changes in biogenic secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    D'Andrea, S. D.; Acosta Navarro, J. C.; Farina, S. C.; Scott, C. E.; Rap, A.; Farmer, D. K.; Spracklen, D. V.; Riipinen, I.; Pierce, J. R.

    2014-10-01

    Emissions of biogenic volatile organic compounds (BVOC) have changed in the past millennium due to changes in land use, temperature and CO2 concentrations. Recent model reconstructions of BVOC emissions over the past millennium predicted changes in dominant secondary organic aerosol (SOA) producing BVOC classes (isoprene, monoterpenes and sesquiterpenes). The reconstructions predicted that global isoprene emissions have decreased (land-use changes to crop/grazing land dominate the reduction), while monoterpene and sesquiterpene emissions have increased (temperature increases dominate the increases); however, all three show regional variability due to competition between the various influencing factors. These BVOC changes have largely been anthropogenic in nature, and land-use change was shown to have the most dramatic effect by decreasing isoprene emissions. In this work, we use two modeled estimates of BVOC emissions from the years 1000 to 2000 to test the effect of anthropogenic changes to BVOC emissions on SOA formation, global aerosol size distributions, and radiative effects using the GEOS-Chem-TOMAS global aerosol microphysics model. With anthropogenic emissions (e.g. SO2, NOx, primary aerosols) held at present day values and BVOC emissions changed from year 1000 to year 2000 values, decreases in the number concentration of particles of size Dp > 80 nm (N80) of >25% in year 2000 relative to year 1000 were predicted in regions with extensive land-use changes since year 1000 which led to regional increases in direct plus indirect aerosol radiative effect of >0.5 W m-2 in these regions. We test the sensitivity of our results to BVOC emissions inventory, SOA yields and the presence of anthropogenic emissions; however, the qualitative response of the model to historic BVOC changes remains the same in all cases. Accounting for these uncertainties, we estimate millennial changes in BVOC emissions cause a global mean direct effect of between +0.022 and +0.163 W m-2

  11. Reconciling Organic Aerosol Volatility, Hygroscopicity, and Oxidation State During the Colorado DISCOVER-AQ Deployment

    NASA Astrophysics Data System (ADS)

    Hite, J. R.; Moore, R.; Martin, R.; Thornhill, K. L., II; Winstead, E.; Anderson, B. E.; Nenes, A.

    2014-12-01

    The organic fraction of submicron aerosol can profoundly impact radiative forcing on climate directly, through enhancement of extinction, or indirectly through modulation of cloud formation. Semi-volatile constituents of organic ambient aerosol are of particular interest as their partitioning between the vapor and aerosol phases is not well constrained by current atmospheric models and appears to play an important role in the formation of cloud condensation nuclei (CCN) as suggested by recent research. An experimental setup consisting of a DMT CCN counter and SMPS downstream of a custom-built thermodenuder assembly was deployed during the summer 2014 DISCOVER-AQ field campaign to retrieve simultaneous, size-resolved volatility and hygroscopicity - through the use of scanning mobility CCN analysis (SMCA). Housed in the NASA Langley mobile laboratory, a suite of complimentary measurements were made available onboard including submicron aerosol composition and oxidation state provided by an HR-ToF-AMS, and aerosol optical properties provided by a range of other instruments including an SP2. Air masses sampled from locations across the Central Colorado region include influences from regional aerosol nucleation/growth events, long-range transport of Canadian biomass burning aerosols, cattle feedlot emissions and influences of the Denver urban plume - amidst a backdrop of widespread oil and gas exploration. The analysis focuses on the reconciliation of the retrieved aerosol volatility distributions and corresponding hygroscopicity and oxidation state observations, including the use of AMS factor analysis.

  12. Ozonolysis of a series of biogenic organic volatile compounds and secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Bernard, François; Quilgars, Alain; Cazaunau, Mathieu; Grosselin, Benoît.; Daele, Véronique; Mellouki, Abdelwahid; Winterhalter, Richard; Moortgat, Geert K.

    2010-05-01

    Secondary organic aerosols are formed via nucleation of atmospheric organic vapours on pre-existing particles observed in various rural environments where the organic fraction represents the major part of the observed nano-particle (Kavouras and Stephanou, 2002; Kulmala et al., 2004a). However, nucleation of organic vapors appears to be unlikely thermodynamically in relevant atmospheric conditions (Kulmala et al., 2004b). In this work, a systematic study has been conducted to investigate the aerosol formation through the ozonolysis of a series of monotepenes using a newly developed aerosol flow reactor and the ICARE indoor simulation chamber. The nucleation thresholds have been determined for SOA formed through the reaction of ozone with a-Pinene, sabinene, myrcene and limonene in absence of any observable existing particles. The measurements were performed using the flow reactor combined to a particle counter (CPC 3022). Number concentrations of SOA have been measured for different concentration of consumed monoterpenes. The data obtained allow us to estimate the nucleation threshold for a range of 0.2 - 45 ppb of consumed monoterpenes. The nucleation threshold values obtained here (≤ 1 ppb of the consumed monoterpenes) have been found to be lower than the previously reported ones (Berndt et al., 2003; Bonn and Moortgat, 2003; Koch et al., 2000; Lee and Kamens, 2005). The ICARE simulation chamber has been used to study the mechanism of the reaction of ozone with various acyclic terpenes (myrcene, ocimene, linalool and a-farnesene) and to derive the SOA mass formation yield. The time-concentration profiles of reactants and products in gas-phase were obtained using in-situ Fourier Transform Infrared Spectroscopy. In addition, the number and mass concentrations of SOA have been monitored with a Scanning Mobility Particle Sizer. The chemical composition of the SOA formed has been tentatively characterised using Liquid Chromatography - Mass Spectrometry. The results

  13. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol.

    PubMed

    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

    2011-02-01

    A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles and the 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, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, 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.

  14. Concentrations and sources of organic carbon aerosols in the free troposphere over North America

    NASA Astrophysics Data System (ADS)

    Heald, Colette L.; Jacob, Daniel J.; Turquety, SolèNe; Hudman, Rynda C.; Weber, Rodney J.; Sullivan, Amy P.; Peltier, Richard E.; Atlas, Eliot L.; de Gouw, Joost A.; Warneke, Carsten; Holloway, John S.; Neuman, J. Andrew; Flocke, Frank M.; Seinfeld, John H.

    2006-12-01

    Aircraft measurements of water-soluble organic carbon (WSOC) aerosol over NE North America during summer 2004 (ITCT-2K4) are simulated with a global chemical transport model (GEOS-Chem) to test our understanding of the sources of organic carbon (OC) aerosol in the free troposphere (FT). Elevated concentrations were observed in plumes from boreal fires in Alaska and Canada. WSOC aerosol concentrations outside of these plumes average 0.9 ± 0.9 μg C m-3 in the FT (2-6 km). The corresponding model value is 0.7 ± 0.6 μg C m-3, including 42% from biomass burning, 36% from biogenic secondary organic aerosol (SOA), and 22% from anthropogenic emissions. Previous OC aerosol observations over the NW Pacific in spring 2001 (ACE-Asia) averaged 3.3 ± 2.8 μg C m-3 in the FT, compared to a model value of 0.3 ± 0.3 μg C m-3. WSOC aerosol concentrations in the boundary layer (BL) during ITCT-2K4 are consistent with OC aerosol observed at the IMPROVE surface network. The model is low in the boundary layer by 30%, which we attribute to secondary formation at a rate comparable to primary anthropogenic emission. Observed WSOC aerosol concentrations decrease by a factor of 2 from the BL to the FT, as compared to a factor of 10 decrease for sulfate, indicating that most of the WSOC aerosol in the FT originates in situ. Despite reproducing mean observed WSOC concentrations in the FT to within 25%, the model cannot account for the variance in the observations (R = 0.21). Covariance analysis of FT WSOC aerosol with other measured chemical variables suggests an aqueous-phase mechanism for SOA generation involving biogenic precursors.

  15. A smog chamber study coupling a photoionization aerosol electron/ion spectrometer to VUV synchrotron radiation: organic and inorganic-organic mixed aerosol analysis

    NASA Astrophysics Data System (ADS)

    Baeza-Romero, María Teresa; Gaie-Levrel, Francois; Mahjoub, Ahmed; López-Arza, Vicente; Garcia, Gustavo A.; Nahon, Laurent

    2016-07-01

    A reaction chamber was coupled to a photoionization aerosol time-of-flight mass spectrometer based on an electron/ion coincidence scheme and applied for on-line analysis of organic and inorganic-organic mixed aerosols using synchrotron tunable vacuum ultraviolet (VUV) photons as the ionization source. In this proof of principle study, both aerosol and gas phase were detected simultaneously but could be differentiated. Present results and perspectives for improvement for this set-up are shown in the study of ozonolysis ([O3] = 0.13-3 ppm) of α-pinene (2-3 ppm), and the uptake of glyoxal upon ammonium sulphate. In this work the ozone concentration was monitored in real time, together with the particle size distributions and chemical composition, the latter taking advantage of the coincidence spectrometer and the tuneability of the synchrotron radiation as a soft VUV ionization source.

  16. Organic Composition and Morphology of Sea Spray Aerosols as a Function of Biological Life during IMPACTS

    NASA Astrophysics Data System (ADS)

    Pham, D.; Moffet, R.; Fraund, M. W.; O'Brien, R.; Laskina, O.; Prather, K. A.; Grassian, V. H.; Beall, C.; Wang, X.; Forestieri, S.; Cappa, C. D.

    2015-12-01

    Aerosols influence climate by directly reflecting or absorbing sunlight, or indirectly by affecting clouds. A major source of aerosols is from oceanic wave breaking. Due to their complexity, the effects of marine aerosol on climate are uncertain. To provide more detailed measurements of the chemical composition of marine aerosols, Scanning Transmission X-Ray Microscopy coupled with Near Edge X-Ray Absorption Fine Structure (SXTM-NEXAFS) was used to give spatially resolved molecular information for carbon and oxygen. Application of STXM/NEXAFS to particles collected during a mesocosm study using a unique wave channel facility to generate aerosols shows that the organic volume fraction of aerosols at the aerodynamic diameter size range of 0.18-0.32 μm are a direct function of the biological activity in the sea water. Aerosol organic volume fraction increased from 0.32 for particles generated from seawater containing low biolife to 0.49 and 0.40 for particles produced during phytoplankton blooms. However, the organic volume fraction of aerosols at the aerodynamic diameter size range of 0.56-1 μm did not change with biological activity. Measurements also show that different types of organics can concentrate into aerosols depending on the enzyme activity expressed at the time. Enhanced spectral signatures for aliphatic hydrocarbons were observed during the first phytoplankton bloom compared to a second phytoplankton bloom occurring directly thereafter. The decreased signature of aliphatic organics in the second phytoplankton bloom was correlated with increased lipase activity from heterobacteria. Organic aggregates having similar morphology also differ in composition from their carbon spectra from the two blooms. For July 17, organic aggregates were much richer in hydrocarbons, which showed a remarkably intense C-H absorbance and a broad C-C absorbance. Organic aggregates observed for July 26-27, did not have the C-H and C-C signatures, but contained more polar

  17. Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

    NASA Astrophysics Data System (ADS)

    Woody, M. C.; Baker, K. R.; Hayes, P. L.; Jimenez, J. L.; Koo, B.; Pye, H. O. T.

    2015-10-01

    Community Multiscale Air Quality (CMAQ) model simulations utilizing the volatility basis set (VBS) treatment for organic aerosols (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 organic aerosol (OA) in southern California. CMAQ-VBS (OA lumped by volatility, semivolatile POA) underpredicted total organic carbon (OC) at CSN (-25.5 % Normalized Median Bias (NMdnB)) and IMPROVE (-63.9 % NMdnB) locations and total OC was underpredicted to a greater degree compared to the CMAQ-AE6 (9.9 and -55.7 % NMdnB, respectively; semi-explicit OA treatment, SOA lumped by parent hydrocarbon, nonvolatile POA). However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA indicated that CMAQ-VBS better represented the diurnal profile and the primary/secondary split of OA. CMAQ-VBS secondary organic aerosol (SOA) underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate of SOA) concentration by a factor of 5.2 (4.7 μg m-3 measured vs. 0.9 μg m-3 modeled), a considerable improvement to CMAQ-AE6 SOA predictions, which were approximately 24× lower than the average AMS OOA concentration. We use two new methods, based on species ratios and on a simplified SOA parameterization from the observations, to apportion the SOA underprediction for CMAQ-VBS to too 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 too low emissions or too high dispersion for the Pasadena site (estimated to be 1.6 to 2.3× too low/high). The first and third factors will be similar for CMAQ-AE6, while the intrinsic SOA formation

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

    SciTech Connect

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

    2010-10-01

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

  19. Secondary Organic Aerosol formation from the gas-phase ozonolysis of 3-methylcatechol and 4-methylcatechol

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, Cécile; Foulon, Valentine; Laréal, Michel; Cassez, Andy; Zhao, Weixiong

    2010-05-01

    Secondary Organic Aerosol (SOA) formation during the ozonolysis of 3-methylcatechol (3-methyl-1,2-dihydroxybenzene) and 4-methylcatechol (3-methyl-1,2-dihydroxybenzene) was investigated using a simulation chamber (8 m3) at atmospheric pressure, room temperature (294 ± 2 K) and low relative humidity (5-10%). The initial mixing ratios were as follows (in ppb): 3-methylcatechol (194-1059), 4-methylcatechol (204-1188) and ozone (93-531). The ozone and methylcatechol concentrations were followed by UV photometry and GC-FID (Gas Chromatography - Flame ionization detector), respectively and the aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer). The SOA yields (Y) were determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted methylcatechol concentrations assuming a particle density of 1.4 g cm-3. The aerosol formation yield increases as the initial methylcatechol concentration increases, and leads to aerosol yields ranging from 32% to 67% and from 30% to 64% for 3-methylcatechol and 4-methylcatechol, respectively. Y is a strong function of Mo and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. These data are comparable to those published in a recent study on secondary organic aerosol formation from catechol ozonolysis. To our knowledge, this work represents the first investigation of SOA formation from the ozone reaction with methylcatechols.

  20. Speciation of Organic Aerosols in the Tropical Mid-Pacific and Their Relationship to Light Scattering.

    NASA Astrophysics Data System (ADS)

    Crahan, Kathleen K.; Hegg, Dean A.; Covert, David S.; Jonsson, Haflidi; Reid, Jeffrey S.; Khelif, Djamal; Brooks, Barbara J.

    2004-11-01

    Although the importance of the aerosol contribution to the global radiative budget has been recognized, the forcings of aerosols in general, and specifically the role of the organic component in these forcings, still contain large uncertainties. In an attempt