WorldWideScience

Sample records for submicron organic aerosol

  1. Submicron organic aerosol in Tijuana, Mexico, from local and Southern California sources during the CalMex campaign

    Science.gov (United States)

    Takahama, S.; Johnson, A.; Guzman Morales, J.; Russell, L. M.; Duran, R.; Rodriguez, G.; Zheng, J.; Zhang, R.; Toom-Sauntry, D.; Leaitch, W. R.

    2013-05-01

    The CalMex campaign was conducted from May 15 to June 30 of 2010 to study the properties and sources of air pollution in Tijuana, Mexico. In this study, submicron organic aerosol mass (OM) composition measured by Fourier Transform Infrared Spectroscopy (FTIR), Aerosol Chemical Speciation Monitor (ACSM), and X-ray spectromicroscopy are combined with statistical analysis and measurements of other atmospheric constituents. The average (±one standard deviation) OM concentration was 3.3 ± 1.7 μg m-3. A large source of submicron aerosol mass at this location was determined to be vehicular sources, which contributed approximately 40% to the submicron OM; largely during weekday mornings. The O/C ratio estimated from ACSM measurements was 0.64 ± 0.19; diurnal variations in this value and the more oxygenated fraction of OM as determined from Positive Matrix Factorization and classification analyses suggest the high degree of oxygenation originates from aged OM, rather than locally-produced secondary organic aerosol. A large contribution of this oxygenated aerosol to Tijuana from various source classes was observed; some fraction of this aerosol mass may be associated with non-refractory components, such as dust or BC. Backtrajectory simulations using the HYSPLIT model suggest that the mean wind vector consistently originated from the northwest region, over the Pacific Ocean and near the Southern California coast, which suggests that the origin of much of the oxygenated organic aerosol observed in Tijuana (as much as 60% of OM) may have been the Southern California Air Basin. The marine aerosol contribution to OM during the period was on average 23 ± 24%, though its contribution varied over synoptic rather than diurnal timescales. BB aerosol contributed 20 ± 20% of the OM during the campaign period, with notable BB events occurring during several weekend evenings.

  2. Beschrijving van een verdampings-condensatie aerosol generator voor de produktie van submicron aerosol

    NARCIS (Netherlands)

    Feijt; A.*; Meulen; A.van der

    1985-01-01

    Dit rapport is een handleiding voor een bedrijfszeker, routinematig gebruik van een zgn. Evaporation-Condensation aerosol Conditioner. Met deze aerosol generatie apparatuur kunnen op stabiele, reproduceerbare manier zeer hoge concentraties (tot 1 miljoen deeltjes per cc) monodispers submicron

  3. Source apportionment of submicron organic aerosol collected from Atlanta, Georgia, during 2014-2015 using the aerosol chemical speciation monitor (ACSM)

    Science.gov (United States)

    Rattanavaraha, Weruka; Canagaratna, Manjula R.; Budisulistiorini, Sri Hapsari; Croteau, Philip L.; Baumann, Karsten; Canonaco, Francesco; Prevot, Andre S. H.; Edgerton, Eric S.; Zhang, Zhenfa; Jayne, John T.; Worsnop, Douglas R.; Gold, Avram; Shaw, Stephanie L.; Surratt, Jason D.

    2017-10-01

    The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was redeployed at the Jefferson Street (JST) site in downtown Atlanta, Georgia (GA) for 1 year (March 20, 2014-February 08, 2015) to chemically characterize non-refractory submicron particulate matter (NR-PM1) in near real-time and to assess whether organic aerosol (OA) types and amounts change from year-to-year. Submicron organic aerosol (OA) mass spectra were analyzed by season using multilinear engine (ME-2) to apportion OA subtypes to potential sources and chemical processes. A suite of real-time collocated measurements from the Southeastern Aerosol Research and Characterization (SEARCH) network was compared with ME-2 factor solutions to aid in the interpretation of OA subtypes during each season. OA tracers measured from high-volume filter samples using gas chromatography interfaced with electron ionization-mass spectrometry (GC/EI-MS) also aided in identifying OA sources. The initial application of ME-2 to the yearlong ACSM dataset revealed that OA source apportionment by season was required to better resolve sporadic OA types. Spring and fall OA mass spectral datasets were separated into finer periods to capture potential OA sources resulting from non-homogeneous emissions during transitioning periods. NR-PM1 was highest in summer (16.7 ± 8.4 μg m-3) and lowest in winter (8.0 ± 5.7 μg m-3), consistent with prior studies. OA dominated NR-PM1 mass (56-74% on average) in all seasons. Hydrocarbon-like OA (HOA) from primary emissions was observed in all seasons, averaging 5-22% of total OA mass. Strong correlations of HOA with carbon monoxide (CO) (R = 0.71-0.88) and oxides of nitrogen (NOx) (R = 0.55-0.79) indicated that vehicular traffic was the likely source. Biomass burning OA (BBOA) was observed in all seasons, with lower contributions (2%) in summer and higher in colder seasons (averaging 8-20% of total OA mass). BBOA correlated strongly with levoglucosan (R = 0.78-0.95) during colder seasons

  4. The role of jet and film drops in controlling the mixing state of submicron sea spray aerosol particles

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaofei; Deane, Grant B.; Moore, Kathryn A.; Ryder, Olivia S.; Stokes, M. Dale; Beall, Charlotte M.; Collins, Douglas B.; Santander, Mitchell V.; Burrows, Susannah M.; Sultana, Camille M.; Prather, Kimberly A.

    2017-06-19

    Covering 71% of the Earth’s surface, oceans represent a significant global source of atmospheric aerosols. The size and composition of sea spray aerosols (SSA) affect their ability to serve as cloud seeds and thus understanding the factors controlling their composition is critical to predicting their impact on clouds and climate. SSA particles have been shown to be an external mixture of particles with different compositions. Film and jet drop production mechanisms ultimately determine the individual particle compositions which are comprised of an array of salt/organic mixtures ranging from pure sea salt to nearly pure organic particles. It is often assumed that the majority of submicron SSA are formed by film drops produced from bursting hydrophobic organic-rich bubble film caps at the sea surface, and in contrast, jet drops are postulated to produce larger supermicron particles from underlying seawater comprised largely of salts and water soluble organic species. However, here we show that jet drops produced by bursting sub-100 m bubbles account for up to 40 % of all submicron particles. They have distinct chemical compositions, organic volume fractions and ice nucleating activities from submicron film drops. Thus a substantial fraction of submicron particles will not necessarily be controlled by the composition of the sea surface microlayer as has been assumed in many studies. This finding has significant ramifications for the size-resolved mixing states of SSA particles which must be taken into consideration when accessing SSA impacts on clouds.

  5. Evaluating model parameterizations of submicron aerosol scattering and absorption with in situ data from ARCTAS 2008

    Directory of Open Access Journals (Sweden)

    M. J. Alvarado

    2016-07-01

    Full Text Available Accurate modeling of the scattering and absorption of ultraviolet and visible radiation by aerosols is essential for accurate simulations of atmospheric chemistry and climate. Closure studies using in situ measurements of aerosol scattering and absorption can be used to evaluate and improve models of aerosol optical properties without interference from model errors in aerosol emissions, transport, chemistry, or deposition rates. Here we evaluate the ability of four externally mixed, fixed size distribution parameterizations used in global models to simulate submicron aerosol scattering and absorption at three wavelengths using in situ data gathered during the 2008 Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS campaign. The four models are the NASA Global Modeling Initiative (GMI Combo model, GEOS-Chem v9-02, the baseline configuration of a version of GEOS-Chem with online radiative transfer calculations (called GC-RT, and the Optical Properties of Aerosol and Clouds (OPAC v3.1 package. We also use the ARCTAS data to perform the first evaluation of the ability of the Aerosol Simulation Program (ASP v2.1 to simulate submicron aerosol scattering and absorption when in situ data on the aerosol size distribution are used, and examine the impact of different mixing rules for black carbon (BC on the results. We find that the GMI model tends to overestimate submicron scattering and absorption at shorter wavelengths by 10–23 %, and that GMI has smaller absolute mean biases for submicron absorption than OPAC v3.1, GEOS-Chem v9-02, or GC-RT. However, the changes to the density and refractive index of BC in GC-RT improve the simulation of submicron aerosol absorption at all wavelengths relative to GEOS-Chem v9-02. Adding a variable size distribution, as in ASP v2.1, improves model performance for scattering but not for absorption, likely due to the assumption in ASP v2.1 that BC is present at a constant mass

  6. Submicron aerosol source apportionment of wintertime pollution in Paris, France by double positive matrix factorization (PMF2) using an aerosol chemical speciation monitor (ACSM) and a multi-wavelength Aethalometer

    International Nuclear Information System (INIS)

    Petit, J.E.; Favez, O.; Leoz-Garziandia, E.; Sciare, J.

    2014-01-01

    Online non-refractory submicron aerosol mass spectrometer (AMS) measurements in urban areas have successfully allowed the apportionment of specific sources and/or physical and chemical properties of the organic fraction. However, in order to be fully representative of PM pollution, a comprehensive source apportionment analysis is needed by taking into account all major components of submicron aerosols, creating strengthened bonds between the organic components and pollution sources. We present here a novel two-step methodology to perform such an analysis, by taking advantage of high time resolution of monitoring instruments: the aerosol chemical speciation monitor (ACSM) and the multi-wavelength absorption measurements (Aethalometer AE31) in Paris, France. As a first step, organic aerosols (OA) were de-convolved to hydrocarbon-like OA (HOA), biomass burning OA (BBOA) and oxygenated OA (OOA) with positive matrix factorization (PMF), and black carbon was de-convolved into its wood burning and fossil fuel combustion fractions. A second PMF analysis was then carried out with organic factors, BC fractions and inorganic species (nitrate, sulfate, ammonium, chloride), leading to a four-factor solution allowing highly time-resolved characterization of the major sources of PM1. Outputs of this PMF2 include two dominant combustion sources (wood burning and traffic) as well as semi-volatile and low-volatile secondary aerosols. While HOA is found to be emitted by both wood burning and traffic, the latter sources occurred to significantly contribute also to OOA. (authors)

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

    Science.gov (United States)

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

    2013-12-01

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

  8. Airborne studies of submicron aerosol in the troposphere over West Siberia

    Energy Technology Data Exchange (ETDEWEB)

    Panchenko, M.V.; Zuev, V.E.; Belan, B.D.; Terpugova, S.A. [Institute of Atmospheric Optics, Tomsk (Russian Federation)

    1996-04-01

    Submicron fraction particles that have the longest lifespan and are included in almost all atmospheric processes are of special importance among the great variety of sizes of particles present in the atmosphere. Submicron particles mainly determine the opticle state of the atmosphere in the visible spectral range, essentially cause the absorption of infrared radiation and, since they are the products and participants in all aerosol-to-gas transformations, accumulate of a lot of various chemical compounds and transfer them to large distances. Investigation of the processes of the spatial-temporal variability of aerosol particles for different climatic zones of the earth is the experimental base for studying their effect on climatically and ecologically significant factors and estimating their unfavorable tendencies. The increasing anthropogenic loading of the earth`s atmosphere is creating an urgency for aerosol research. Regardless of how perfect the analytical and numerical methods of solving radiation problems may be, success in forecasting climatic change is mainly determined by the reliability of the experimental data on optical parameters of the atmosphere and of the description of their variability under the effect of external factors.

  9. Springtime variations of organic and inorganic constituents in submicron aerosols (PM1.0) from Cape Hedo, Okinawa

    Science.gov (United States)

    Kunwar, Bhagawati; Torii, K.; Zhu, Chunmao; Fu, Pingqing; Kawamura, Kimitaka

    2016-04-01

    During the spring season with enhanced Asian outflow, we collected submicron aerosol (PM1.0) samples at Cape Hedo, Okinawa Island in the western North Pacific Rim. We analyzed the filter samples for diacids, oxoacids, pyruvic acid, α-dicarbonyls and fatty acids to better understand the sources and atmospheric processes in the outflow regions of Asian pollutants. Molecular distributions of diacids show a predominance of oxalic acid (C2) followed by malonic (C3) and succinic (C4) acids. Total diacids strongly correlated with secondary source tracers such as SO42- (r = 0.87), NH4+ (0.90) and methanesulfonate (MSA-) (0.84), suggesting that diacids are secondarily formed from their precursor compounds. We also found good correlations among C2, organic carbon (OC) and elemental carbon (EC) in the Okinawa aerosols, suggesting that diacids are mainly derived from anthropogenic sources. However, a weak correlation of diacids with levoglucosan, a biomass burning tracer, suggests that biomass buring is not the main source of diacids, rather diacids are secondarily formed by photochemical oxidation of organic precursors derived from fossil fuel combustion. We found a strong correlation (r = 0.98) between inorganic nitrogen (NO3-N + NH4-N) and total nitrogen (TN), to which organic nitrogen (ON) contributed 23%. Fatty acids were characterized by even carbon number predominance, suggesting that they are derived from biogenic sources. The higher abundances of short chain fatty acids (C20) further suggest that fatty acids are largely derived from marine phytoplankton during spring bloom.

  10. Lung deposition of sub-micron aerosols calculated as a function of age and breathing rate

    International Nuclear Information System (INIS)

    James, A.C.

    1978-01-01

    Experimental measurements of lung deposition and especially of regional deposition, of aerosols in the sub-micron size range have been so few that it is worthwhile establishing a method of calculation. A computer routine has therefore been developed to calculate aerosol deposition in successive bronchial and bronchiolar generations of the Weibel 'A' model of human lung for the sub-micron size range where deposition occurs solely by diffusion. This model can be scaled to represent lungs at various ages and vital capacities. Some calculated results are presented here and compared with measurements of lung deposition made under carefully controlled conditions in humans. (author)

  11. Chemical compositions, sources and evolution processes of the submicron aerosols in Nanjing, China during wintertime

    Science.gov (United States)

    Wu, Y.; He, Y.; Ge, X.; Wang, J.; Yu, H.; Chen, M.

    2016-12-01

    Elevated atmospheric particulate matter pollution is one of the most significant environmental issues in the Yangtze River Delta (YRD), China. Thus it is important to unravel the characteristics, sources and evolution processes of the ambient aerosols in order to improve the air quality. In this study, we report the real-time monitoring results on submicron aerosol particles (PM1) in suburban Nanjing during wintertime of 2015, using an Aerodyne soot particle aerosol mass spectrometer (SP-AMS). This instrument allows the fast measurement of refractory black carbon simultaneously with other aerosol components. Results show that organics was on average the most abundant species of PM1 (25.9%), but other inorganic species, such as nitrate (23.7%) and sulfate (23.3%) also comprised large mass fractions. As the sampling site is heavily influenced by various sources including industrial, traffic and other anthropogenic emissions, etc., six organic aerosol (OA) factors were identified from Positive matrix factorization (PMF) analysis of the SP-AMS OA mass spectra. These factors include three primary OA factors - a hydrocarbon-like OA, an industry-related OA (IOA) and a cooking OA (COA), and three secondary OA factors, i.e., a local OOA (LSOA), a semi-volatile OOA (SV-OOA) and a low-volatility OOA (LV-OOA). Overall, the primary organic aerosol (POA) (HOA, IOA and COA) dominated the total OA mass. Behaviors and evolution processes of these OA factors will be discussed in combining with the other supporting data.

  12. Insights into Submicron Aerosol Composition and Sources from the WINTER Aircraft Campaign Over the Eastern US.

    Science.gov (United States)

    Schroder, J. C.; Campuzano Jost, P.; Day, D. A.; Fibiger, D. L.; McDuffie, E. E.; Blake, N. J.; Hills, A. J.; Hornbrook, R. S.; Apel, E. C.; Weinheimer, A. J.; Campos, T. L.; Brown, S. S.; Jimenez, J. L.

    2015-12-01

    The WINTER aircraft campaign was a recent field experiment to probe the sources and evolution of gas pollutants and aerosols in Northeast US urban and industrial plumes during the winter. A highly customized Aerodyne aerosol mass spectrometer (AMS) was flown on the NCAR C-130 to characterize submicron aerosol composition and evolution. Thirteen research flights were conducted covering a wide range of conditions, including rural, urban, and marine environments during day and night. Organic aerosol (OA) was a large component of the submicron aerosol in the boundary layer. The fraction of OA (fOA) was smaller (35-40%) than in recent US summer campaigns (~60-70%). Biomass burning was observed to be an important source of OA in the boundary layer, which is consistent with recent wintertime studies that show a substantial contribution of residential wood burning to the OA loadings. OA oxygenation (O/C ratio) shows a broad distribution with a substantial fraction of smaller O/C ratios when compared to previous summertime campaigns. Since measurements were rarely made very close to primary sources (i.e. directly above urban areas), this is consistent with oxidative chemistry being slower during winter. SOA formation and aging in the NYC plume was observed during several flights and compared with summertime results from LA (CalNex) and Mexico City (MILAGRO). Additionally, an oxidation flow reactor (OFR) capable of oxidizing ambient air up to several equivalent days of oxidation was deployed for the first time in an aircraft platform. The aerosol outflow of the OFR was sampled with the AMS to provide real-time snapshots of the potential for aerosol formation and aging. For example, a case study of a flight through the Ohio River valley showed evidence of oxidation of SO2 to sulfate. The measured sulfate enhancements were in good agreement with our OFR chemical model. OFR results for SOA will be discussed.

  13. On the contribution of organics to the North East Atlantic aerosol number concentration

    International Nuclear Information System (INIS)

    Bialek, Jakub; Dall’Osto, Manuel; Monahan, Ciaran; O’Dowd, Colin; Beddows, David

    2012-01-01

    k-means statistical-cluster analysis of submicron aerosol size distributions is combined with coincident humidity tandem differential mobility analyser data, leading to five unique aerosol categories for hygroscopic growth factors (HGFs): low sea-salt background marine, high sea-salt background marine, coastal nucleation, open ocean nucleation and anthropogenically influenced scenarios. When considering only marine conditions, and generic aerosol species associated with this environment (e.g. non-sea-salt sulfate, sea-salt, partly soluble organic matter and water insoluble organic matter), the two-year annual average contribution to aerosol number concentration from the different generic species was made up as follows: 46% (30–54%) of partially modified ammonium sulfate particles; 23% (11–40%) of partially modified sea-salt; and the remaining 31% (25–35%) contribution attributed to two distinct organic species as evidenced by different, but low, HGFs. The analysis reveals that on annual timescales, ∼30% of the submicron marine aerosol number concentration is sourced from predominantly organic aerosol while 60% of the anthropogenic aerosol number is predominantly organic. Coastal nucleation events show the highest contribution of the lowest HGF mode (1.19), although this contribution is more likely to be influenced by inorganic iodine oxides. While organic mass internally mixed with inorganic salts will lower the activation potential of these mixed aerosol types, thereby potentially reducing the concentration of cloud condensation nuclei (CCN), pure organic water soluble particles are still likely to be activated into cloud droplets, thereby increasing the concentration of CCN. A combination of dynamics and aerosol concentrations will determine which effect will prevail under given conditions. (letter)

  14. Submicron-sized aerosol and radon progeny measurements in an uranium mine

    International Nuclear Information System (INIS)

    Boulaud, D.; Chouard, J.C.

    1992-01-01

    Submicron-sized aerosol was studied in an uranium mine using an Electrical Aerosol Analyzer and a Differential Mobility Particle Sizer. In addition radon progeny particle size distributions were measured using a prototype instrument developed by us (SDI 2000). With cascade impactor the number weighted mean electrical mobility diameters and the geometric standard deviations ranged respectively from 0.05 to 0.1 μm and 1.8 to 2. The gross alpha activity weighted mean thermodynamic diameters ranged typically from 0.1 to 0.2 μm. 6 refs., 3 figs

  15. Seasonal characterization of submicron aerosol chemical composition and organic aerosol sources in the southeastern United States: Atlanta, Georgia,and Look Rock, Tennessee

    Directory of Open Access Journals (Sweden)

    S. H. Budisulistiorini

    2016-04-01

    Full Text Available A year-long near-real-time characterization of non-refractory submicron aerosol (NR-PM1 was conducted at an urban (Atlanta, Georgia, in 2012 and rural (Look Rock, Tennessee, in 2013 site in the southeastern US using the Aerodyne Aerosol Chemical Speciation Monitor (ACSM collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (up to 76 % and sulfate (up to 31 %. Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the 1 year of near-continuous measurements at each site: hydrocarbon-like OA (HOA, biomass burning OA (BBOA, semi-volatile oxygenated OA (SV-OOA, low-volatility oxygenated OA (LV-OOA, isoprene-derived epoxydiols (IEPOX OA (IEPOX-OA and 91Fac (a factor dominated by a distinct ion at m∕z 91 fragment ion previously observed in biogenic influenced areas. LV-OOA was observed throughout the year at both sites and contributed up to 66 % of total OA mass. HOA was observed during the entire year only at the urban site (on average 21 % of OA mass. BBOA (15–33 % of OA mass was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly ( ∼  27 %, it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27–41 % of OA at both sites, particularly in spring and summer. An ion fragment at m∕z 75 is well correlated with the m∕z 82 ion associated with the aerosol mass spectrum of IEPOX

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

    Science.gov (United States)

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

    2011-05-01

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

  17. Chemical Characterization of Submicron Aerosol Particles in São Paulo, Brazil

    Science.gov (United States)

    Ferreira De Brito, J.; Rizzo, L. V.; Godoy, J.; Godoy, M. L.; de Assunção, J. V.; Alves, N. D.; Artaxo, P.

    2013-12-01

    Megacities, large urban conglomerates with a population of 10 million or more inhabitants, are increasingly receiving attention as strong pollution hotspots with significant global impact. The emissions from such large centers in both the developed and developing parts of the world are strongly impacted by the transportation sector. The São Paulo Metropolitan Area (SPMA), located in the Southeast of Brazil, is a megacity with a population of 18 million people and 7 million vehicles, many of which fuelled by a considerably amount of anhydrous ethanol. Such fleet is considered a unique case of large scale biofuel usage worldwide. Despite the large impact on human health and atmospheric chemistry/dynamics, many uncertainties are found in terms of gas and particulate matter emissions from vehicles and their atmospheric reactivity, e.g. secondary organic aerosol formation. In order to better understand aerosol life cycle on such environment, a suite of instruments for gas and particulate matter characterization has been deployed in two sampling sites within the SPMA, including an Aerosol Chemical Speciation Monitor (ACSM). The instrumentation was deployed at the rooftop of a 45m high building in the University of São Paulo during winter/spring 2012. The site is located roughly 6km downwind of the city center with little influence from local sources. The second site is located in a downtown area, sampling at the top floor of the Public Health Faculty, approximately 10m above ground. The instrumentation was deployed at the Downtown site during summer/fall 2013. The average non-refractory submicron aerosol concentration at the University site was 6.7 μg m-3, being organics the most abundant specie (70%), followed by NO3 (12%), NH4 (8%), SO4 (8%) and Chl (2%). At the Downtown site, average aerosol concentration was 15.1 μg m-3, with Organics composing 65% of the mass, followed by NH4 (12%), NO3 (11%), SO4 (11%) and Chl (1%). The analysis of specific fragmentation

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

    Science.gov (United States)

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

    2011-09-01

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

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

    Directory of Open Access Journals (Sweden)

    G. R. McMeeking

    2011-09-01

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

  20. Relating hygroscopicity and composition of organic aerosol particulate matter

    CERN Document Server

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

    2011-01-01

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

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

    Science.gov (United States)

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

    2015-12-01

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

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

    Science.gov (United States)

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

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

    Directory of Open Access Journals (Sweden)

    L. Hildebrandt

    2010-05-01

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

  4. Chemical characteristics of submicron particles at the central Tibetan Plateau: insights from aerosol mass spectrometry

    Science.gov (United States)

    Xu, Jianzhong; Zhang, Qi; Shi, Jinsen; Ge, Xinlei; Xie, Conghui; Wang, Junfeng; Kang, Shichang; Zhang, Ruixiong; Wang, Yuhang

    2018-01-01

    Recent studies have revealed a significant influx of anthropogenic aerosol from South Asia to the Himalayas and Tibetan Plateau (TP) during pre-monsoon period. In order to characterize the chemical composition, sources, and transport processes of aerosol in this area, we carried out a field study during June 2015 by deploying a suite of online instruments including an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) and a multi-angle absorption photometer (MAAP) at Nam Co station (90°57' E, 30°46' N; 4730 m a.s.l.) at the central of the TP. The measurements were made at a period when the transition from pre-monsoon to monsoon occurred. The average ambient mass concentration of submicron particulate matter (PM1) over the whole campaign was ˜ 2.0 µg m-3, with organics accounting for 68 %, followed by sulfate (15 %), black carbon (8 %), ammonium (7 %), and nitrate (2 %). Relatively higher aerosol mass concentration episodes were observed during the pre-monsoon period, whereas persistently low aerosol concentrations were observed during the monsoon period. However, the chemical composition of aerosol during the higher aerosol concentration episodes in the pre-monsoon season was on a case-by-case basis, depending on the prevailing meteorological conditions and air mass transport routes. Most of the chemical species exhibited significant diurnal variations with higher values occurring during afternoon and lower values during early morning, whereas nitrate peaked during early morning in association with higher relative humidity and lower air temperature. Organic aerosol (OA), with an oxygen-to-carbon ratio (O / C) of 0.94, was more oxidized during the pre-monsoon period than during monsoon (average O / C ratio of 0.72), and an average O / C was 0.88 over the entire campaign period, suggesting overall highly oxygenated aerosol in the central TP. Positive matrix factorization of the high-resolution mass spectra of OA identified two oxygenated

  5. Sources and Characterization of Submicron Aerosols in a Rural Forest During the PROPHET-AMOS 2016 Campaign

    Science.gov (United States)

    Bui, A. T.; Wallace, H. W., IV; Alvarez, S. L.; Erickson, M.; Alwe, H. D.; May, N.; Cook, R.; Connor, M.; Slade, J. H., Jr.; Shi, Q.; Kavassalis, S.; Tyndall, G. S.; Shepson, P. B.; Pratt, K.; Ault, A. P.; Millet, D. B.; Murphy, J. G.; Usenko, S.; Sheesley, R. J.; Flynn, J. H., III; Griffin, R. J.; Wang, W.

    2017-12-01

    Forests are a rich source of biogenic volatile organic compounds (BVOCs). Oxidation of BVOCs can result in the formation of secondary organic aerosol (SOA) and in the presence of NOx (NO+NO2) produce organic nitrate-containing particles. However, the distribution of both BVOCs and oxidants can be dramatically altered by the physical barriers provided by a forest canopy. Global models currently neglect the effect of these canopies on SOA formation in forested regions. In this work, we characterize non-refractory submicron aerosol (NR-PM1) using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) during the 2016 Program on Oxidants: Photochemistry, Emissions, and Transport-Atmospheric Measurements of Oxidants in Summer (PROPHET-AMOS) campaign. This site is located in a rural forest in northern Michigan and features a tower that allowed for both above and below canopy measurements. Our results indicate that organic aerosols (OA) account for a substantial portion of the NR-PM1 measured at this site. Organic nitrate aerosol can contribute up to 18% of the total OA and an average of 75% of the total measured nitrate aerosol. Episodes of above- and below-canopy NR-PM1 concentration differences indicate that above-canopy OA concentrations can be up to 40% greater than below-canopy, which represents an increase of up to 1.5 µg/m3. Organic fragment ions such as CxHy, CxHyOz, and CxHyO1 contribute to enhanced above-canopy OA concentrations. Positive matrix factorization analysis of the high-resolution OA mass spectra identified three SOA factors: low volatility oxygenated OA (LVOOA), isoprene-derived OOA (ISOOA), and oxygenated organic aerosol. Analysis of air mass backward trajectories and correlations with external data indicate that LVOOA correlates well with sulfate and aged, urban-influenced air masses, whereas ISOOA correlates well with isoprene SOA tracers and air masses originating from semi-remote areas. Our results indicate that the OA at this

  6. Volatility measurement of atmospheric submicron aerosols in an urban atmosphere in southern China

    Science.gov (United States)

    Cao, Li-Ming; Huang, Xiao-Feng; Li, Yuan-Yuan; Hu, Min; He, Ling-Yan

    2018-02-01

    Aerosol pollution has been a very serious environmental problem in China for many years. The volatility of aerosols can affect the distribution of compounds in the gas and aerosol phases, the atmospheric fates of the corresponding components, and the measurement of the concentration of aerosols. Compared to the characterization of chemical composition, few studies have focused on the volatility of aerosols in China. In this study, a thermodenuder aerosol mass spectrometer (TD-AMS) system was deployed to study the volatility of non-refractory submicron particulate matter (PM1) species during winter in Shenzhen. To our knowledge, this paper is the first report of the volatilities of aerosol chemical components based on a TD-AMS system in China. The average PM1 mass concentration during the experiment was 42.7±20.1 µg m-3, with organic aerosol (OA) being the most abundant component (43.2 % of the total mass). The volatility of chemical species measured by the AMS varied, with nitrate showing the highest volatility, with a mass fraction remaining (MFR) of 0.57 at 50 °C. Organics showed semi-volatile characteristics (the MFR was 0.88 at 50 °C), and the volatility had a relatively linear correlation with the TD temperature (from the ambient temperature to 200 °C), with an evaporation rate of 0.45 % °C-1. Five subtypes of OA were resolved from total OA using positive matrix factorization (PMF) for data obtained under both ambient temperature and high temperatures through the TD, including a hydrocarbon-like OA (HOA, accounting for 13.5 %), a cooking OA (COA, 20.6 %), a biomass-burning OA (BBOA, 8.9 %), and two oxygenated OAs (OOAs): a less-oxidized OOA (LO-OOA, 39.1 %) and a more-oxidized OOA (MO-OOA, 17.9 %). Different OA factors presented different volatilities, and the volatility sequence of the OA factors at 50 °C was HOA (MFR of 0.56) > LO-OOA (0.70) > COA (0.85) ≈ BBOA (0.87) > MO-OOA (0.99), which was not completely consistent with the sequence of their O

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-06-01

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

  8. Sources and composition of submicron organic mass in marine aerosol particles

    Science.gov (United States)

    Frossard, Amanda A.; Russell, Lynn M.; Burrows, Susannah M.; Elliott, Scott M.; Bates, Timothy S.; Quinn, Patricia K.

    2014-11-01

    The sources and composition of atmospheric marine aerosol particles (aMA) have been investigated with a range of physical and chemical measurements from open-ocean research cruises. This study uses the characteristic functional group composition (from Fourier transform infrared spectroscopy) of aMA from five ocean regions to show the following: (i) The organic functional group composition of aMA that can be identified as mainly atmospheric primary marine (ocean derived) aerosol particles (aPMA) is 65 ± 12% hydroxyl, 21 ± 9% alkane, 6 ± 6% amine, and 7 ± 8% carboxylic acid functional groups. Contributions from photochemical reactions add carboxylic acid groups (15%-25%), shipping effluent in seawater and ship emissions add additional alkane groups (up to 70%), and coastal or continental emissions mix in alkane and carboxylic acid groups. (ii) The organic composition of aPMA is nearly identical to model-generated primary marine aerosol particles from bubbled seawater (gPMA, which has 55 ± 14% hydroxyl, 32 ± 14% alkane, and 13 ± 3% amine functional groups), indicating that its overall functional group composition is the direct consequence of the organic constituents of the seawater source. (iii) While the seawater organic functional group composition was nearly invariant across all three ocean regions studied and the ratio of organic carbon to sodium (OC/Na+) in the gPMA remained nearly constant over a broad range of chlorophyll a concentrations, the gPMA alkane group fraction appeared to increase with chlorophyll a concentrations (r = 0.66). gPMA from productive seawater had a larger fraction of alkane functional groups (42 ± 9%) compared to gPMA from nonproductive seawater (22 ± 10%), perhaps due to the presence of surfactants in productive seawater that stabilize the bubble film and lead to preferential drainage of the more soluble (lower alkane group fraction) organic components. gPMA has a hydroxyl group absorption peak location characteristic of

  9. Sources and atmospheric processing of organic aerosol in the Mediterranean: insights from aerosol mass spectrometer factor analysis

    Directory of Open Access Journals (Sweden)

    L. Hildebrandt

    2011-12-01

    Full Text Available Atmospheric particles were measured in the late winter (25 February–26 March 2009 at a remote coastal site on the island of Crete, Greece during the Finokalia Aerosol Measurement Experiment-2009. A quadrupole aerosol mass spectrometer (Q-AMS was employed to quantify the size-resolved chemical composition of non-refractory submicron aerosol, and a thermodenuder was used to analyze the organic aerosol (OA volatility. Complementary measurements included particle size distributions from a scanning mobility particle sizer, inorganic and organic particle composition from filter analysis, air ion concentrations, O3, NOx and NOy concentrations, and meteorological measurements. Factor analysis was performed on the OA mass spectra, and the variability in OA composition could best be explained with three OA components. The oxygenated organic aerosol (OOA was similar in composition and volatility to the summertime OA previously measured at this site and may represent an effective endpoint in particle-phase oxidation of organics. The two other OA components, one associated with amines (Amine-OA and the other probably associated with the burning of olive branches (OB-OA, had very low volatility but were less oxygenated. Hydrocarbon-like organic aerosol (HOA was not detected. The absence of OB-OA and Amine-OA in the summer data may be due to lower emissions and/or photochemical conversion of these components to OOA.

  10. Chemical characteristics of submicron particles at the central Tibetan Plateau: insights from aerosol mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. Xu

    2018-01-01

    Full Text Available Recent studies have revealed a significant influx of anthropogenic aerosol from South Asia to the Himalayas and Tibetan Plateau (TP during pre-monsoon period. In order to characterize the chemical composition, sources, and transport processes of aerosol in this area, we carried out a field study during June 2015 by deploying a suite of online instruments including an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS and a multi-angle absorption photometer (MAAP at Nam Co station (90°57′ E, 30°46′ N; 4730 m a.s.l. at the central of the TP. The measurements were made at a period when the transition from pre-monsoon to monsoon occurred. The average ambient mass concentration of submicron particulate matter (PM1 over the whole campaign was  ∼  2.0 µg m−3, with organics accounting for 68 %, followed by sulfate (15 %, black carbon (8 %, ammonium (7 %, and nitrate (2 %. Relatively higher aerosol mass concentration episodes were observed during the pre-monsoon period, whereas persistently low aerosol concentrations were observed during the monsoon period. However, the chemical composition of aerosol during the higher aerosol concentration episodes in the pre-monsoon season was on a case-by-case basis, depending on the prevailing meteorological conditions and air mass transport routes. Most of the chemical species exhibited significant diurnal variations with higher values occurring during afternoon and lower values during early morning, whereas nitrate peaked during early morning in association with higher relative humidity and lower air temperature. Organic aerosol (OA, with an oxygen-to-carbon ratio (O ∕ C of 0.94, was more oxidized during the pre-monsoon period than during monsoon (average O ∕ C ratio of 0.72, and an average O ∕ C was 0.88 over the entire campaign period, suggesting overall highly oxygenated aerosol in the central TP. Positive matrix factorization of the

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

    Directory of Open Access Journals (Sweden)

    N. Meskhidze

    2011-11-01

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

  12. Toward Quantifying the Mass-Based Hygroscopicity of Individual Submicron Atmospheric Aerosol Particles with STXM/NEXAFS and SEM/EDX

    Science.gov (United States)

    Yancey Piens, D.; Kelly, S. T.; OBrien, R. E.; Wang, B.; Petters, M. D.; Laskin, A.; Gilles, M. K.

    2014-12-01

    The hygroscopic behavior of atmospheric aerosols influences their optical and cloud-nucleation properties, and therefore affects climate. Although changes in particle size as a function of relative humidity have often been used to quantify the hygroscopic behavior of submicron aerosol particles, it has been noted that calculations of hygroscopicity based on size contain error due to particle porosity, non-ideal volume additivity and changes in surface tension. We will present a method to quantify the hygroscopic behavior of submicron aerosol particles based on changes in mass, rather than size, as a function of relative humidity. This method results from a novel experimental approach combining scanning transmission x-ray microscopy with near-edge x-ray absorption fine spectroscopy (STXM/NEXAFS), as well as scanning electron microscopy with energy dispersive x-ray spectroscopy (SEM/EDX) on the same individual particles. First, using STXM/NEXAFS, our methods are applied to aerosol particles of known composition ‒ for instance ammonium sulfate, sodium bromide and levoglucosan ‒ and validated by theory. Then, using STXM/NEXAFS and SEM/EDX, these methods are extended to mixed atmospheric aerosol particles collected in the field at the DOE Atmospheric Radiation Measurement (ARM) Climate Research Facility at the Southern Great Planes sampling site in Oklahoma, USA. We have observed and quantified a range of hygroscopic behaviors which are correlated to the composition and morphology of individual aerosol particles. These methods will have implications for parameterizing aerosol mixing state and cloud-nucleation activity in atmospheric models.

  13. A new physically-based quantification of marine isoprene and primary organic aerosol emissions

    Directory of Open Access Journals (Sweden)

    N. Meskhidze

    2009-07-01

    Full Text Available The global marine sources of organic carbon (OC are estimated here using a physically-based parameterization for the emission of marine isoprene and primary organic matter. The marine isoprene emission model incorporates new physical parameters such as light sensitivity of phytoplankton isoprene production and dynamic euphotic depth to simulate hourly marine isoprene emissions totaling 0.92 Tg C yr−1. Sensitivity studies using different schemes for the euphotic zone depth and ocean phytoplankton speciation produce the upper and the lower range of marine-isoprene emissions of 0.31 to 1.09 Tg C yr−1, respectively. Established relationships between sea spray fractionation of water-insoluble organic carbon (WIOC and chlorophyll-a concentration are used to estimate the total primary sources of marine sub- and super-micron OC of 2.9 and 19.4 Tg C yr−1, respectively. The consistent spatial and temporal resolution of the two emission types allow us, for the first time, to explore the relative contributions of sub- and super-micron organic matter and marine isoprene-derived secondary organic aerosol (SOA to the total OC fraction of marine aerosol. Using a fixed 3% mass yield for the conversion of isoprene to SOA, our emission simulations show minor (<0.2% contribution of marine isoprene to the total marine source of OC on a global scale. However, our model calculations also indicate that over the tropical oceanic regions (30° S to 30° N, marine isoprene SOA may contribute over 30% of the total monthly-averaged sub-micron OC fraction of marine aerosol. The estimated contribution of marine isoprene SOA to hourly-averaged sub-micron marine OC emission is even higher, approaching 50% over the vast regions of the oceans during the midday hours when isoprene emissions are highest. As it is widely believed that sub-micron OC has the potential to influence the cloud droplet activation of marine aerosols, our

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

    Directory of Open Access Journals (Sweden)

    C. J. Ebben

    2011-10-01

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

  15. Volatility measurement of atmospheric submicron aerosols in an urban atmosphere in southern China

    Directory of Open Access Journals (Sweden)

    L.-M. Cao

    2018-02-01

    Full Text Available Aerosol pollution has been a very serious environmental problem in China for many years. The volatility of aerosols can affect the distribution of compounds in the gas and aerosol phases, the atmospheric fates of the corresponding components, and the measurement of the concentration of aerosols. Compared to the characterization of chemical composition, few studies have focused on the volatility of aerosols in China. In this study, a thermodenuder aerosol mass spectrometer (TD-AMS system was deployed to study the volatility of non-refractory submicron particulate matter (PM1 species during winter in Shenzhen. To our knowledge, this paper is the first report of the volatilities of aerosol chemical components based on a TD-AMS system in China. The average PM1 mass concentration during the experiment was 42.7±20.1 µg m−3, with organic aerosol (OA being the most abundant component (43.2 % of the total mass. The volatility of chemical species measured by the AMS varied, with nitrate showing the highest volatility, with a mass fraction remaining (MFR of 0.57 at 50 °C. Organics showed semi-volatile characteristics (the MFR was 0.88 at 50 °C, and the volatility had a relatively linear correlation with the TD temperature (from the ambient temperature to 200 °C, with an evaporation rate of 0.45 % °C−1. Five subtypes of OA were resolved from total OA using positive matrix factorization (PMF for data obtained under both ambient temperature and high temperatures through the TD, including a hydrocarbon-like OA (HOA, accounting for 13.5 %, a cooking OA (COA, 20.6 %, a biomass-burning OA (BBOA, 8.9 %, and two oxygenated OAs (OOAs: a less-oxidized OOA (LO-OOA, 39.1 % and a more-oxidized OOA (MO-OOA, 17.9 %. Different OA factors presented different volatilities, and the volatility sequence of the OA factors at 50 °C was HOA (MFR of 0.56  >  LO-OOA (0.70  >  COA (0.85  ≈  BBOA (0.87

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

    DEFF Research Database (Denmark)

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

    2003-01-01

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

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

    DEFF Research Database (Denmark)

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

    2003-01-01

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

  18. High summertime aerosol organic functional group concentrations from marine and seabird sources at Ross Island, Antarctica, during AWARE

    Directory of Open Access Journals (Sweden)

    J. Liu

    2018-06-01

    Full Text Available Observations of the organic components of the natural aerosol are scarce in Antarctica, which limits our understanding of natural aerosols and their connection to seasonal and spatial patterns of cloud albedo in the region. From November 2015 to December 2016, the ARM West Antarctic Radiation Experiment (AWARE measured submicron aerosol properties near McMurdo Station at the southern tip of Ross Island. Submicron organic mass (OM, particle number, and cloud condensation nuclei concentrations were higher in summer than other seasons. The measurements included a range of compositions and concentrations that likely reflected both local anthropogenic emissions and natural background sources. We isolated the natural organic components by separating a natural factor and a local combustion factor. The natural OM was 150 times higher in summer than in winter. The local anthropogenic emissions were not hygroscopic and had little contribution to the CCN concentrations. Natural sources that included marine sea spray and seabird emissions contributed 56 % OM in summer but only 3 % in winter. The natural OM had high hydroxyl group fraction (55 %, 6 % alkane, and 6 % amine group mass, consistent with marine organic composition. In addition, the Fourier transform infrared (FTIR spectra showed the natural sources of organic aerosol were characterized by amide group absorption, which may be from seabird populations. Carboxylic acid group contributions were high in summer and associated with natural sources, likely forming by secondary reactions.

  19. Dry deposition of submicron atmospheric aerosol over water surfaces in motion

    International Nuclear Information System (INIS)

    Nevenick, Calec

    2013-01-01

    Whether by chronic or accidental releases, the impact of a nuclear installation on the environment mainly depends on atmospheric transfers; and as the accidents at Chernobyl and Fukushima show, affect the contamination of surfaces and impacts in the medium and long-term on the environment and the population. In this context, this work focuses on the characterization and modeling of dry deposition of submicron aerosols on liquid surfaces in motion such as rivers. Unlike wet deposition which is conditioned by washout and rainout (rain and clouds), dry deposition is a phenomenon that depends entirely on the characteristics of aerosols, receiving surfaces, and air flow. In practice, the evaluation of dry deposition is based on the estimation of flux modeling as the product of particle concentration and deposition velocity which can vary over several orders of magnitude depending on the receiving surfaces (forest, snow, urban, grassland...). This topic is motivated by the virtual non-existence of studies on the mechanisms of dry deposition on continental water systems such as rivers; and respect for submicron aerosols. They have the lowest deposition efficiencies and filtration and the longer residence time in the atmosphere. In addition, they are potentially the most dangerous to living beings because they can penetrate deeper into the airway. Due to the lack of data on the dry deposition of submicron aerosols on a liquid surface in motion, the approach was based on two axes: 1) the acquisition of experimental deposition velocities and 2) the analysis and interpretation of results through modeling. The experiments were performed with uranine aerosols released into the IOA wind tunnel (Interface Ocean Atmosphere) of the Institute for Research on Non Equilibrium Phenomena which is configured to study the coupling between the air flow and water. These experiments have given many dry deposition velocities for different configurations characterized according to wind

  20. Dry deposition of submicron atmospheric aerosol over water surfaces in motion

    International Nuclear Information System (INIS)

    Calec, Nevenick

    2013-01-01

    Whether by chronic or accidental releases, the impact of a nuclear installation on the environment mainly depends on atmospheric transfers; and as the accidents at Chernobyl and Fukushima show, affect the contamination of surfaces and impacts in the medium and long-term on the environment and the population. In this context, this work focuses on the characterization and modeling of dry deposition of submicron aerosols on liquid surfaces in motion such as rivers. Unlike wet deposition which is conditioned by washout and rainout (rain and clouds), dry deposition is a phenomenon that depends entirely on the characteristics of aerosols, receiving surfaces, and air flow. In practice, the evaluation of dry deposition is based on the estimation of flux modeling as the product of particle concentration and deposition velocity which can vary over several orders of magnitude depending on the receiving surfaces (forest, snow, urban, grassland..). This topic is motivated by the virtual non-existence of studies on the mechanisms of dry deposition on continental water systems such as rivers; and respect for submicron aerosols. They have the lowest deposition efficiencies and filtration and the longer residence time in the atmosphere. In addition, they are potentially the most dangerous to living beings because they can penetrate deeper into the airway. Due to the lack of data on the dry deposition of submicron aerosols on a liquid surface in motion, the approach was based on two axes: 1) the acquisition of experimental deposition velocities and 2) the analysis and interpretation of results through modeling. The experiments were performed with uranine aerosols released into the IOA wind tunnel (Interface Ocean Atmosphere) of the Institute for Research on Non Equilibrium Phenomena which is configured to study the coupling between the air flow and water. These experiments have given many dry deposition velocities for different configurations characterized according to wind

  1. Organic aerosols

    International Nuclear Information System (INIS)

    Penner, J.E.

    1994-01-01

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

  2. Fourteen months of on-line measurements of the non-refractory submicron aerosol at the Jungfraujoch (3580 m a.s.l.) - chemical composition, origins and organic aerosol sources

    Science.gov (United States)

    Fröhlich, R.; Cubison, M. J.; Slowik, J. G.; Bukowiecki, N.; Canonaco, F.; Croteau, P. L.; Gysel, M.; Henne, S.; Herrmann, E.; Jayne, J. T.; Steinbacher, M.; Worsnop, D. R.; Baltensperger, U.; Prévôt, A. S. H.

    2015-10-01

    Chemically resolved (organic, nitrate, sulfate, ammonium) data of non-refractory submicron (NR-PM1) aerosol from the first long-term deployment (27 July 2012 to 02 October 2013) of a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) at the Swiss high-altitude site Jungfraujoch (JFJ; 3580 m a.s.l.) are presented. Besides total mass loadings, diurnal variations and relative species contributions during the different meteorological seasons, geographical origin and sources of organic aerosol (OA) are discussed. Backward transport simulations show that the highest (especially sulfate) concentrations of NR-PM1 were measured in air masses advected to the station from regions south of the JFJ, while lowest concentrations were seen from western regions. OA source apportionment for each season was performed using the Source Finder (SoFi) interface for the multilinear engine (ME-2). OA was dominated in all seasons by oxygenated OA (OOA, 71-88 %), with lesser contributions from local tourism-related activities (7-12 %) and hydrocarbon-like OA related to regional vertical transport (3-9 %). In summer the OOA can be separated into a background low-volatility OA (LV-OOA I, possibly associated with long-range transport) and a slightly less oxidised low-volatility OA (LV-OOA II) associated with regional vertical transport. Wood burning-related OA associated with regional transport was detected during the whole winter 2012/2013 and during rare events in summer 2013, in the latter case attributed to small-scale transport for the surrounding valleys. Additionally, the data were divided into periods with free tropospheric (FT) conditions and periods with planetary boundary layer (PBL) influence, enabling the assessment of the composition for each. Most nitrate and part of the OA are injected from the regional PBL, while sulfate is mainly produced in the FT. The south/north gradient of sulfate is also pronounced in FT air masses (sulfate mass fraction from the south: 45

  3. Chemical composition and characteristics of ambient aerosols and rainwater residues during Indian summer monsoon: Insight from aerosol mass spectrometry

    Science.gov (United States)

    Chakraborty, Abhishek; Gupta, Tarun; Tripathi, Sachchida N.

    2016-07-01

    Real time composition of non-refractory submicron aerosol (NR-PM1) is measured via Aerosol mass spectrometer (AMS) for the first time during Indian summer monsoon at Kanpur, a polluted urban location located at the heart of Indo Gangetic Plain (IGP). Submicron aerosols are found to be dominated by organics followed by nitrate. Source apportionment of organic aerosols (OA) via positive matrix factorization (PMF) revealed several types of secondary/oxidized and primary organic aerosols. On average, OA are completely dominated by oxidized OA with a very little contribution from biomass burning OA. During rain events, PM1 concentration is decreased almost by 60%, but its composition remains nearly the same. Oxidized OA showed slightly more decrease than primary OAs, probably due to their higher hygroscopicity. The presence of organo nitrates (ON) is also detected in ambient aerosols. Apart from real-time sampling, collected fog and rainwater samples were also analyzed via AMS in offline mode and in the ICP-OES (Inductively coupled plasma - Optical emission spectrometry) for elements. The presence of sea salt, organo nitrates and sulfates has been observed. Rainwater residues are also dominated by organics but their O/C ratios are 15-20% lower than the observed values for ambient OA. Alkali metals such as Ca, Na, K are found to be most abundant in the rainwater followed by Zn. Rainwater residues are also found to be much less oxidized than the aerosols present inside the fog water, indicating presence of less oxidized organics. These findings indicate that rain can act as an effective scavenger of different types of pollutants even for submicron particle range. Rainwater residues also contain organo sulfates which indicate that some portion of the dissolved aerosols has undergone aqueous processing, possibly inside the cloud. Highly oxidized and possibly hygroscopic OA during monsoon period compared to other seasons (winter, post monsoon), indicates that they can act

  4. Highly time-resolved chemical characterization of atmospheric submicron particles during 2008 Beijing Olympic Games using an Aerodyne High-Resolution Aerosol Mass Spectrometer

    Directory of Open Access Journals (Sweden)

    X.-F. Huang

    2010-09-01

    Full Text Available As part of Campaigns of Air Quality Research in Beijing and Surrounding Region-2008 (CAREBeijing-2008, an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS was deployed in urban Beijing to characterize submicron aerosol particles during the time of 2008 Beijing Olympic Games and Paralympic Games (24 July to 20 September 2008. The campaign mean PM1 mass concentration was 63.1 ± 39.8 μg m−3; the mean composition consisted of organics (37.9%, sulfate (26.7%, ammonium (15.9%, nitrate (15.8%, black carbon (3.1%, and chloride (0.87%. The average size distributions of the species (except BC were all dominated by an accumulation mode peaking at about 600 nm in vacuum aerodynamic diameter, and organics was characterized by an additional smaller mode extending below 100 nm. Positive Matrix Factorization (PMF analysis of the high resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., hydrocarbon-like (HOA, cooking-related (COA, and two oxygenated organic aerosols (OOA-1 and OOA-2, which on average accounted for 18.1, 24.4, 33.7 and 23.7% of the total organic mass, respectively. The HOA was identified to be closely associated with primary combustion sources, while the COA mass spectrum and diurnal pattern showed similar characteristics to that measured for cooking emissions. The OOA components correspond to aged secondary organic aerosol. Although the two OOA components have similar elemental (O/C, H/C compositions, they display differences in mass spectra and time series which appear to correlate with the different source regions sampled during the campaign. Back trajectory clustering analysis indicated that the southerly air flows were associated with the highest PM1 pollution during the campaign. Aerosol particles in southern airmasses were especially rich in inorganic and oxidized organic species. Aerosol particles in northern airmasses

  5. Highly time-resolved chemical characterization of atmospheric submicron particles during 2008 Beijing Olympic Games using an Aerodyne High-Resolution Aerosol Mass Spectrometer

    Science.gov (United States)

    Huang, X.-F.; He, L.-Y.; Hu, M.; Canagaratna, M. R.; Sun, Y.; Zhang, Q.; Zhu, T.; Xue, L.; Zeng, L.-W.; Liu, X.-G.; Zhang, Y.-H.; Jayne, J. T.; Ng, N. L.; Worsnop, D. R.

    2010-09-01

    As part of Campaigns of Air Quality Research in Beijing and Surrounding Region-2008 (CAREBeijing-2008), an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in urban Beijing to characterize submicron aerosol particles during the time of 2008 Beijing Olympic Games and Paralympic Games (24 July to 20 September 2008). The campaign mean PM1 mass concentration was 63.1 ± 39.8 μg m-3; the mean composition consisted of organics (37.9%), sulfate (26.7%), ammonium (15.9%), nitrate (15.8%), black carbon (3.1%), and chloride (0.87%). The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at about 600 nm in vacuum aerodynamic diameter, and organics was characterized by an additional smaller mode extending below 100 nm. Positive Matrix Factorization (PMF) analysis of the high resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., hydrocarbon-like (HOA), cooking-related (COA), and two oxygenated organic aerosols (OOA-1 and OOA-2), which on average accounted for 18.1, 24.4, 33.7 and 23.7% of the total organic mass, respectively. The HOA was identified to be closely associated with primary combustion sources, while the COA mass spectrum and diurnal pattern showed similar characteristics to that measured for cooking emissions. The OOA components correspond to aged secondary organic aerosol. Although the two OOA components have similar elemental (O/C, H/C) compositions, they display differences in mass spectra and time series which appear to correlate with the different source regions sampled during the campaign. Back trajectory clustering analysis indicated that the southerly air flows were associated with the highest PM1 pollution during the campaign. Aerosol particles in southern airmasses were especially rich in inorganic and oxidized organic species. Aerosol particles in northern airmasses contained a large fraction of primary HOA

  6. Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

    Science.gov (United States)

    Jing, Bo; Wang, Zhen; Tan, Fang; Guo, Yucong; Tong, Shengrui; Wang, Weigang; Zhang, Yunhong; Ge, Maofa

    2018-04-01

    While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO3)2) and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA). The nitrate salt / organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH), the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

  7. Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

    Directory of Open Access Journals (Sweden)

    B. Jing

    2018-04-01

    Full Text Available While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO32 and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA. The nitrate salt ∕ organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH, the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

  8. Role of organic aerosols in CCN activation and closure over a rural background site in Western Ghats, India

    Science.gov (United States)

    Singla, V.; Mukherjee, S.; Safai, P. D.; Meena, G. S.; Dani, K. K.; Pandithurai, G.

    2017-06-01

    The cloud condensation nuclei (CCN) closure study was performed to exemplify the effect of aerosol chemical composition on the CCN activity of aerosols at Mahabaleshwar, a high altitude background site in the Western Ghats, India. For this, collocated aerosol, CCN, Elemental Carbon (EC), Organic Carbon (OC), sub-micron aerosol chemical speciation for the period from 3rd June to 19th June 2015 was used. The chemical composition of non-refractory particulate matter (theory on the basis of measured aerosol particle number size distribution, size independent NR-PM1 chemical composition and calculated hygroscopicity. The CCN closure study was evaluated for 3 scenarios, B-I (all soluble inorganics), B-IO (all soluble organics and inorganics) and B-IOOA (all soluble inorganic and soluble oxygenated organic aerosol, OOA). OOA component was derived from the positive matrix factorization (PMF) analysis of organic aerosol mass spectra. Considering the bulk composition as internal mixture, CCN closure study was underestimated by 16-39% for B-I and overestimated by 47-62% for B-IO. The CCN closure result was appreciably improved for B-IOOA where the knowledge of OOA fraction was introduced and uncertainty reduced to within 8-10%.

  9. Seasonal Variations of High Time-Resolved Chemical Compositions, Sources and Evolution for Atmospheric Submicron Aerosols in the Megacity of Beijing

    Science.gov (United States)

    Hu, Min; Hu, Wei; Hu, Weiwei; Zheng, Jing; Guo, Song; Wu, Yusheng; Lu, Sihua; Zeng, Limin

    2016-04-01

    This study aims to investigate aerosol secondary formation and aging process in the megacity of Beijing. Seasonal intensive campaigns were conducted from March 2012 to March 2013 at an urban site located at the campus of Peking University (116.31° E, 37.99° N). An Aerodyne high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) and other relevant instrumentations for gaseous and particulate pollutants were deployed. The average submicron aerosol (PM1) mass concentrations were 45.1 ± 45.8, 37.5 ± 31.0, 41.3 ± 42.7 and 81.7 ± 72.4 μg m-3 in spring, summer, autumn and winter, respectively. Organic matter was the most abundant component, accounting for 31%, 33%, 44% and 36% in PM1 correspondingly, followed by sulfate and nitrate. Distinct seasonal and diurnal patterns of the components of PM1 tracking primary sources (e.g., BC and HOA) and secondary formation (e.g., sulfate, nitrate, ammonium, LV-OOA and SV-OOA) were significantly influenced by primary emissions and mesoscale meteorology. Combining positive matrix factorization (PMF) analysis with the mass spectrometry of organics measured by AMS, the contributions of primary and secondary sources to submicron organic aerosols (OA) were apportioned. In spring and summer, the primary sources were hydrocarbon-like OA (HOA) and cooking OA (COA), and the secondary components were low volatility (LV-OOA) and semi-volatile oxygenated OA (SV-OOA). In winter biomass burning OA (BBOA) was also resolved. In autumn, four factors were resolved, that is, OOA, HOA, COA and BBOA. In general, OOA (sum of LV-OOA and SV-OOA) was important in OA in four seasons, accounting for about 63%, 70%, 47% and 50%, respectively. SV-OOA dominated OA in summer (44%) due to the fresh secondary formation from strong photochemical oxidations; whereas, LV-OOA was dominant in OA in winter (33%), maybe because the transported air masses were more aged in heavily polluted days. The POA (sum of HOA, COA and BBOA) in OA was dominant in

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

    Science.gov (United States)

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

    2017-06-01

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

  11. Occurrence of weak, sub-micron, tropospheric aerosol events at high Arctic latitudes

    Science.gov (United States)

    O'Neill, N. T.; Pancrati, O.; Baibakov, K.; Eloranta, E.; Batchelor, R. L.; Freemantle, J.; McArthur, L. J. B.; Strong, K.; Lindenmaier, R.

    2008-07-01

    Numerous fine mode (sub-micron) aerosol optical events were observed during the summer of 2007 at the High Arctic atmospheric observatory (PEARL) located at Eureka, Nunavut, Canada. Half of these events could be traced to forest fires in southern and eastern Russia and the Northwest Territories of Canada. The most notable findings were that (a) a combination of ground-based measurements (passive sunphotometry, high spectral resolution lidar) could be employed to determine that weak (near sub-visual) fine mode events had occurred, and (b) this data combined with remote sensing imagery products (MODIS, OMI-AI, FLAMBE fire sources), Fourier transform spectroscopy and back trajectories could be employed to identify the smoke events.

  12. Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modeling of complete high time-resolution aerosol mass spectra

    Science.gov (United States)

    McGuire, M. L.; Chang, R. Y.-W.; Slowik, J. G.; Jeong, C.-H.; Healy, R. M.; Lu, G.; Mihele, C.; Abbatt, J. P. D.; Brook, J. R.; Evans, G. J.

    2014-08-01

    Receptor modeling was performed on quadrupole unit mass resolution aerosol mass spectrometer (Q-AMS) sub-micron particulate matter (PM) chemical speciation measurements from Windsor, Ontario, an industrial city situated across the Detroit River from Detroit, Michigan. Aerosol and trace gas measurements were collected on board Environment Canada's Canadian Regional and Urban Investigation System for Environmental Research (CRUISER) mobile laboratory. Positive matrix factorization (PMF) was performed on the AMS full particle-phase mass spectrum (PMFFull MS) encompassing both organic and inorganic components. This approach compared to the more common method of analyzing only the organic mass spectra (PMFOrg MS). PMF of the full mass spectrum revealed that variability in the non-refractory sub-micron aerosol concentration and composition was best explained by six factors: an amine-containing factor (Amine); an ammonium sulfate- and oxygenated organic aerosol-containing factor (Sulfate-OA); an ammonium nitrate- and oxygenated organic aerosol-containing factor (Nitrate-OA); an ammonium chloride-containing factor (Chloride); a hydrocarbon-like organic aerosol (HOA) factor; and a moderately oxygenated organic aerosol factor (OOA). PMF of the organic mass spectrum revealed three factors of similar composition to some of those revealed through PMFFull MS: Amine, HOA and OOA. Including both the inorganic and organic mass proved to be a beneficial approach to analyzing the unit mass resolution AMS data for several reasons. First, it provided a method for potentially calculating more accurate sub-micron PM mass concentrations, particularly when unusual factors are present, in this case the Amine factor. As this method does not rely on a priori knowledge of chemical species, it circumvents the need for any adjustments to the traditional AMS species fragmentation patterns to account for atypical species, and can thus lead to more complete factor profiles. It is expected that this

  13. Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modelling of complete high time-resolution aerosol mass spectra

    Science.gov (United States)

    McGuire, M. L.; Chang, R. Y.-W.; Slowik, J. G.; Jeong, C.-H.; Healy, R. M.; Lu, G.; Mihele, C.; Abbatt, J. P. D.; Brook, J. R.; Evans, G. J.

    2014-02-01

    Receptor modelling was performed on quadrupole unit mass resolution aerosol mass spectrometer (Q-AMS) sub-micron particulate matter (PM) chemical speciation measurements from Windsor, Ontario, an industrial city situated across the Detroit River from Detroit, Michigan. Aerosol and trace gas measurements were collected on board Environment Canada's CRUISER mobile laboratory. Positive matrix factorization (PMF) was performed on the AMS full particle-phase mass spectrum (PMFFull MS) encompassing both organic and inorganic components. This approach was compared to the more common method of analysing only the organic mass spectra (PMFOrg MS). PMF of the full mass spectrum revealed that variability in the non-refractory sub-micron aerosol concentration and composition was best explained by six factors: an amine-containing factor (Amine); an ammonium sulphate and oxygenated organic aerosol containing factor (Sulphate-OA); an ammonium nitrate and oxygenated organic aerosol containing factor (Nitrate-OA); an ammonium chloride containing factor (Chloride); a hydrocarbon-like organic aerosol (HOA) factor; and a moderately oxygenated organic aerosol factor (OOA). PMF of the organic mass spectrum revealed three factors of similar composition to some of those revealed through PMFFull MS: Amine, HOA and OOA. Including both the inorganic and organic mass proved to be a beneficial approach to analysing the unit mass resolution AMS data for several reasons. First, it provided a method for potentially calculating more accurate sub-micron PM mass concentrations, particularly when unusual factors are present, in this case, an Amine factor. As this method does not rely on a priori knowledge of chemical species, it circumvents the need for any adjustments to the traditional AMS species fragmentation patterns to account for atypical species, and can thus lead to more complete factor profiles. It is expected that this method would be even more useful for HR-ToF-AMS data, due to the ability

  14. Submicron particulate organic matter in the urban atmosphere: a new method for real-time measurement, molecular-level characterization and source apportionment

    Science.gov (United States)

    Müller, Markus; Eichler, Philipp; D'Anna, Barbara; Tan, Wen; Wisthaler, Armin

    2017-04-01

    We used a novel chemical analytical method for measuring submicron particulate organic matter in the atmosphere of three European cities (Innsbruck, Lyon, Valencia). Proton-Transfer-Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) was used in combination with the "chemical analysis of aerosol online" (CHARON) inlet for detecting particulate organic compounds on-line (i.e. without filter pre-collection), in real-time (1-min time resolution), at ng m-3 concentrations, with molecular-level resolution (i.e. obtaining molecular weight and elemental composition information). The CHARON-PTR-ToF-MS system monitored molecular tracers associated with different particle sources including levoglucosan from biomass combustion, PAHs from vehicular traffic, nicotine from cigarette smoking, and monoterpene oxidation products secondarily formed from biogenic emissions. The tracer information was used for interpreting positive matrix factorization (PMF) data which allowed us to apportion the sources of submicron particulate organic matter in the different urban environments. This work was funded through the PIMMS ITN, which was supported by the European Commission's 7th Framework Programme under grant agreement number 287382.

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

    Directory of Open Access Journals (Sweden)

    Y. L. Sun

    2012-09-01

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

  16. A statistical analysis of North East Atlantic (submicron aerosol size distributions

    Directory of Open Access Journals (Sweden)

    M. Dall'Osto

    2011-12-01

    Full Text Available The Global Atmospheric Watch research station at Mace Head (Ireland offers the possibility to sample some of the cleanest air masses being imported into Europe as well as some of the most polluted being exported out of Europe. We present a statistical cluster analysis of the physical characteristics of aerosol size distributions in air ranging from the cleanest to the most polluted for the year 2008. Data coverage achieved was 75% throughout the year. By applying the Hartigan-Wong k-Means method, 12 clusters were identified as systematically occurring. These 12 clusters could be further combined into 4 categories with similar characteristics, namely: coastal nucleation category (occurring 21.3 % of the time, open ocean nucleation category (occurring 32.6% of the time, background clean marine category (occurring 26.1% of the time and anthropogenic category (occurring 20% of the time aerosol size distributions. The coastal nucleation category is characterised by a clear and dominant nucleation mode at sizes less than 10 nm while the open ocean nucleation category is characterised by a dominant Aitken mode between 15 nm and 50 nm. The background clean marine aerosol exhibited a clear bimodality in the sub-micron size distribution, with although it should be noted that either the Aitken mode or the accumulation mode may dominate the number concentration. However, peculiar background clean marine size distributions with coarser accumulation modes are also observed during winter months. By contrast, the continentally-influenced size distributions are generally more monomodal (accumulation, albeit with traces of bimodality. The open ocean category occurs more often during May, June and July, corresponding with the North East (NE Atlantic high biological period. Combined with the relatively high percentage frequency of occurrence (32.6%, this suggests that the marine biota is an important source of new nano aerosol particles in NE Atlantic Air.

  17. New characteristics of submicron aerosols and factor analysis of combined organic and inorganic aerosol mass spectra during winter in Beijing

    Science.gov (United States)

    Zhang, J. K.; Ji, D. S.; Liu, Z. R.; Hu, B.; Wang, L. L.; Huang, X. J.; Wang, Y. S.

    2015-07-01

    In recent years, an increasing amount of attention has been paid to heavy haze pollution in Beijing, China. In addition to Beijing's population of approximately 20 million and its 5 million vehicles, nearby cities and provinces are host to hundreds of heavily polluting industries. In this study, a comparison between observations in January 2013 and January 2014 showed that non-refractory PM1 (NR-PM1) pollution was weaker in January 2014, which was primarily caused by variations in meteorological conditions. For the first time, positive matrix factorization (PMF) was applied to the merged high-resolution mass spectra of organic and inorganic aerosols from aerosol mass spectrometer measurements in Beijing, and the sources and evolution of NR-PM1 in January 2014 were investigated. The two factors, NO3-OA1 and NO3-OA2, were primarily composed of ammonium nitrate, and each showed a different degree of oxidation and diurnal variation. The organic fraction of SO4-OA showed the highest degree of oxidation of all PMF factors. The hydrocarbon-like organic aerosol (OA) and cooking OA factors contained negligible amounts of inorganic species. The coal combustion OA factor contained a high contribution from chloride in its mass spectrum. The NR-PM1 composition showed significant variations in January 2014, in which the contribution of nitrate clearly increased during heavy pollution events. The most effective way to control fine particle pollution in Beijing is through joint prevention and control measures at the regional level, rather than a focus on an individual city, especially for severe haze events.

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

    Science.gov (United States)

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

    2014-12-01

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

  19. Investigating organic aerosol loading in the remote marine environment

    Directory of Open Access Journals (Sweden)

    K. Lapina

    2011-09-01

    Full Text Available Aerosol loading in the marine environment is investigated using aerosol composition measurements from several research ship campaigns (ICEALOT, MAP, RHaMBLe, VOCALS and OOMPH, observations of total AOD column from satellite (MODIS and ship-based instruments (Maritime Aerosol Network, MAN, and a global chemical transport model (GEOS-Chem. This work represents the most comprehensive evaluation of oceanic OM emission inventories to date, by employing aerosol composition measurements obtained from campaigns with wide spatial and temporal coverage. The model underestimates AOD over the remote ocean on average by 0.02 (21 %, compared to satellite observations, but provides an unbiased simulation of ground-based Maritime Aerosol Network (MAN observations. Comparison with cruise data demonstrates that the GEOS-Chem simulation of marine sulfate, with the mean observed values ranging between 0.22 μg m−3 and 1.34 μg m−3, is generally unbiased, however surface organic matter (OM concentrations, with the mean observed concentrations between 0.07 μg m−3 and 0.77 μg m−3, are underestimated by a factor of 2–5 for the standard model run. Addition of a sub-micron marine OM source of approximately 9 TgC yr−1 brings the model into agreement with the ship-based measurements, however this additional OM source does not explain the model underestimate of marine AOD. The model underestimate of marine AOD is therefore likely the result of a combination of satellite retrieval bias and a missing marine aerosol source (which exhibits a different spatial pattern than existing aerosol in the model.

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

    Directory of Open Access Journals (Sweden)

    N. H. Robinson

    2011-02-01

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

  1. Long-term real-time chemical characterization of submicron aerosols at Montsec (southern Pyrenees, 1570 m a.s.l.)

    Science.gov (United States)

    Ripoll, A.; Minguillón, M. C.; Pey, J.; Jimenez, J. L.; Day, D. A.; Sosedova, Y.; Canonaco, F.; Prévôt, A. S. H.; Querol, X.; Alastuey, A.

    2015-03-01

    Real-time measurements of inorganic (sulfate, nitrate, ammonium, chloride and black carbon (BC)) and organic submicron aerosols (particles with an aerodynamic diameter of less than 1 μm) from a continental background site (Montsec, MSC, 1570 m a.s.l.) in the western Mediterranean Basin (WMB) were conducted for 10 months (July 2011-April 2012). An aerosol chemical speciation monitor (ACSM) was co-located with other online and offline PM1 measurements. Analyses of the hourly, diurnal, and seasonal variations are presented here, for the first time, for this region. Seasonal trends in PM1 components are attributed to variations in evolution of the planetary boundary layer (PBL) height, air mass origin, and meteorological conditions. In summer, the higher temperature and solar radiation increases convection, enhancing the growth of the PBL and the transport of anthropogenic pollutants towards high altitude sites. Furthermore, the regional recirculation of air masses over the WMB creates a continuous increase in the background concentrations of PM1 components and causes the formation of reservoir layers at relatively high altitudes. The combination of all these atmospheric processes results in a high variability of PM1 components, with poorly defined daily patterns, except for the organic aerosols (OA). OA was mostly composed (up to 90%) of oxygenated organic aerosol (OOA), split in two types: semivolatile (SV-OOA) and low-volatility (LV-OOA), the rest being hydrocarbon-like OA (HOA). The marked diurnal cycles of OA components regardless of the air mass origin indicates that they are not only associated with anthropogenic and long-range-transported secondary OA (SOA) but also with recently produced biogenic SOA. Very different conditions drive the aerosol phenomenology in winter at MSC. The thermal inversions and the lower vertical development of the PBL leave MSC in the free troposphere most of the day, being affected by PBL air masses only after midday, when the

  2. Future aerosols of the southwest - Implications for fundamental aerosol research

    International Nuclear Information System (INIS)

    Friedlander, S.K.

    1980-01-01

    It is shown that substantial increases in the use of coal in the U.S. will lead to substantial increases in emissions of particulate matter, SO/sub x/, and NO/sub x/ in the part of the U.S. west of the Mississippi. A shift in the primary particulate emissions from coarse to submicron particles is predicted. Attention is given to the nature of the submicron aerosol in the southwest, the distribution of sulfur with respect to particle size, the formation of new particles in the atmosphere, and the ammonium nitrate equilibrium. It is concluded that increased coal use will result in a 50% increase in SO/sub x/ emissions and a doubling of NO/sub x/ emissions in the western U.S. by the year 2000, that ambient levels of aerosol sulfates and nitrates will increase, and that a large increase in submicron aerosol mass is likely

  3. Rural continental aerosol properties and processes observed during the Hohenpeissenberg Aerosol Characterization Experiment (HAZE2002

    Directory of Open Access Journals (Sweden)

    N. Hock

    2008-02-01

    Full Text Available Detailed investigations of the chemical and microphysical properties of rural continental aerosols were performed during the HAZE2002 experiment, which was conducted in May 2002 at the Meteorological Observatory Hohenpeissenberg (DWD in Southern Germany.

    Online measurements included: Size-resolved chemical composition of submicron particles; total particle number concentrations and size distributions over the diameter range of 3 nm to 9 μm; gas-phase concentration of monoterpenes, CO, O3, OH, and H2SO4. Filter sampling and offline analytical techniques were used to determine: Fine particle mass (PM2.5, organic, elemental and total carbon in PM2.5 (OC2.5, EC2.5, TC2.5, and selected organic compounds (dicarboxylic acids, polycyclic aromatic hydrocarbons, proteins.

    Overall, the non-refractory components of submicron particles detected by aerosol mass spectrometry (PM1, 6.6±5.4 μg m−3, arithmetic mean and standard deviation accounted for ~62% of PM2.5 determined by filter gravimetry (10.6±4.7 μg m−3. The relative proportions of non-refractory submicron particle components were: (23±39% ammonium nitrate, (27±23% ammonium sulfate, and (50±40% organics (OM1. OM1 was closely correlated with PM1 (r2=0.9 indicating a near-constant ratio of non-refractory organics and inorganics.

    The average ratio of OM1 to OC2.5 was 2.1±1.4, indicating a high proportion of heteroelements in the organic fraction of the sampled rural aerosol. This is consistent with the high ratio of oxygenated organic aerosol (OOA over hydrocarbon-like organic aerosol (HOA inferred from the AMS results (4:1, and also with the high abundance of proteins (~3% indicating a high proportion of primary biological material (~30% in PM2.5. This finding was confirmed by low abundance of PAHs (<1 ng m−3 and EC (<1 μg m−3 in PM2.5 and detection of several

  4. Aerosol volatility in a boreal forest environment

    Science.gov (United States)

    Häkkinen, S. A. K.; ńijälä, M.; Lehtipalo, K.; Junninen, H.; Virkkula, A.; Worsnop, D. R.; Kulmala, M.; Petäjä, T.; Riipinen, I.

    2012-04-01

    Climate and health effects of atmospheric aerosols are determined by their properties such as their chemical composition. Aerosol chemical composition can be studied indirectly by measuring volatility of aerosol particles. The volatility of submicron aerosol particles (20-500 nm) was studied in a boreal forest site at SMEAR II (Station for Measuring Ecosystem-Atmosphere Relations II) station (Vesala et al., 1998) in Hyytiälä, Finland, during 01/2008-05/2010. The instrument used for the measurements was VDMPS (Volatility Differential Mobility Particle Sizer), which consists of two separate instruments: DMPS (Differential Mobility Particle Sizer, Aalto et al., 2001) and TD (Thermodenuder, Wehner et al., 2002). Aerosol evaporation was examined by heating the aerosol and comparing the total aerosol mass before and after heating. In the VDMPS system ambient aerosol sample was heated up to temperatures ranging from 80 °C to 280 °C. The higher the heating temperature was the more aerosol material was evaporated. There was a non-volatile residual present in aerosol particles when heated up to 280 °C. This residual explained (20±8)% of the total aerosol mass. Aerosol non-volatile mass fraction was highest during winter and smallest during summer months. The role of black carbon in the observed non-volatile residual was determined. Black carbon explained 40 to 90% of the non-volatile mass. Especially during colder seasons noticeable amount of non-volatile material, something else than black carbon, was observed. According to Kalberer et al. (2004) some atmospheric organic species can form polymers that have high evaporation temperatures. Also low-volatile organic salts may contribute to the non-volatile aerosol (Smith et al., 2010). Aerosol mass composition measured directly with AMS (Aerosol Mass Spectrometer, Jayne et al., 2000) was analyzed in order to examine the properties of the non-volatile material (other than black carbon). The AMS measurements were performed

  5. Micron-sized and submicron-sized aerosol deposition in a new ex vivo preclinical model.

    Science.gov (United States)

    Perinel, Sophie; Leclerc, Lara; Prévôt, Nathalie; Deville, Agathe; Cottier, Michèle; Durand, Marc; Vergnon, Jean-Michel; Pourchez, Jérémie

    2016-07-07

    The knowledge of where particles deposit in the respiratory tract is crucial for understanding the health effects associated with inhaled drug particles. An ex vivo study was conducted to assess regional deposition patterns (thoracic vs. extrathoracic) of radioactive polydisperse aerosols with different size ranges [0.15 μm-0.5 μm], [0.25 μm-1 μm] and [1 μm-9 μm]. SPECT/CT analyses were performed complementary in order to assess more precisely the regional deposition of aerosols within the pulmonary tract. Experiments were set using an original respiratory tract model composed of a human plastinated head connected to an ex vivo porcine pulmonary tract. The model was ventilated by passive expansion, simulating pleural depressions. Aerosol was administered during nasal breathing. Planar scintigraphies allowed to calculate the deposited aerosol fractions for particles in the three size ranges from sub-micron to micron The deposited fractions obtained, for thoracic vs. extra-thoracic regions respectively, were 89 ± 4 % vs. 11 ± 4 % for [0.15 μm-0.5 μm], 78 ± 5 % vs. 22 ± 5 % for [0.25 μm-1 μm] and 35 ± 11 % vs.65 ± 11 % for [1 μm-9 μm]. Results obtained with this new ex vivo respiratory tract model are in good agreement with the in vivo data obtained in studies with baboons and humans.

  6. Aerosols in the tropical and subtropical UT/LS: in-situ measurements of submicron particle abundance and volatility

    Directory of Open Access Journals (Sweden)

    S. Borrmann

    2010-06-01

    Full Text Available Processes occurring in the tropical upper troposphere (UT, the Tropical Transition Layer (TTL, and the lower stratosphere (LS are of importance for the global climate, for stratospheric dynamics and air chemistry, and for their influence on the global distribution of water vapour, trace gases and aerosols. In this contribution we present aerosol and trace gas (in-situ measurements from the tropical UT/LS over Southern Brazil, Northern Australia, and West Africa. The instruments were operated on board of the Russian high altitude research aircraft M-55 "Geophysica" and the DLR Falcon-20 during the campaigns TROCCINOX (Araçatuba, Brazil, February 2005, SCOUT-O3 (Darwin, Australia, December 2005, and SCOUT-AMMA (Ouagadougou, Burkina Faso, August 2006. The data cover submicron particle number densities and volatility from the COndensation PArticle counting System (COPAS, as well as relevant trace gases like N2O, ozone, and CO. We use these trace gas measurements to place the aerosol data into a broader atmospheric context. Also a juxtaposition of the submicron particle data with previous measurements over Costa Rica and other tropical locations between 1999 and 2007 (NASA DC-8 and NASA WB-57F is provided. The submicron particle number densities, as a function of altitude, were found to be remarkably constant in the tropical UT/LS altitude band for the two decades after 1987. Thus, a parameterisation suitable for models can be extracted from these measurements. Compared to the average levels in the period between 1987 and 2007 a slight increase of particle abundances was found for 2005/2006 at altitudes with potential temperatures, Θ, above 430 K. The origins of this increase are unknown except for increases measured during SCOUT-AMMA. Here the eruption of the Soufrière Hills volcano in the Caribbean caused elevated particle mixing ratios. The vertical profiles from Northern hemispheric mid-latitudes between 1999 and 2006 also are

  7. OCEANFILMS-2: Representing coadsorption of saccharides in marine films and potential impacts on modeled marine aerosol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Burrows, Susannah M. [Atmospheric Science and Global Change Division, Pacific Northwest National Laboratory, Richland Washington USA; Gobrogge, Eric [Department of Chemistry and Biochemistry, Montana State University, Bozeman Montana USA; Fu, Li [Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland Washington USA; Link, Katie [Department of Chemistry and Biochemistry, Montana State University, Bozeman Montana USA; Elliott, Scott M. [Climate, Ocean, and Sea Ice Modelling Group, Los Alamos National Laboratory, Los Alamos New Mexico USA; Wang, Hongfei [Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland Washington USA; Walker, Rob [Department of Chemistry and Biochemistry, Montana State University, Bozeman Montana USA

    2016-08-10

    Here we show that the addition of chemical interactions of soluble polysaccharides with a surfactant monolayer improves agreement of modeled sea spray chemistry with observed marine aerosol chemistry. In particular, the fraction of hydroxyl functional groups in modeled sea spray organic matter is increased, improving agreement with FTIR observations of marine aerosol composition. The overall organic fraction of submicron sea spray also increases, allowing organic mass fractions in the range 0.5 – 0.7 for submicron sea spray particles over highly active phytoplankton blooms. We show results from Sum Frequency Generation (SFG) experiments that support the modeling approach, by demonstrating that soluble polysaccharides can strongly adsorb to a lipid monolayer via columbic interactions under appropriate conditions.

  8. Chemical characterization and source apportionment of submicron aerosols measured in Senegal during the 2015 SHADOW campaign

    Science.gov (United States)

    Rivellini, Laura-Hélèna; Chiapello, Isabelle; Tison, Emmanuel; Fourmentin, Marc; Féron, Anaïs; Diallo, Aboubacry; N'Diaye, Thierno; Goloub, Philippe; Canonaco, Francesco; Prévôt, André Stephan Henry; Riffault, Véronique

    2017-09-01

    The present study offers the first chemical characterization of the submicron (PM1) fraction in western Africa at a high time resolution, thanks to collocated measurements of nonrefractory (NR) species with an Aerosol Chemical Speciation Monitor (ACSM), black carbon and iron concentrations derived from absorption coefficient measurements with a 7-wavelength Aethalometer, and total PM1 determined by a TEOM-FDMS (tapered element oscillating microbalance-filtered dynamic measurement system) for mass closure. The field campaign was carried out over 3 months (March to June 2015) as part of the SHADOW (SaHAran Dust Over West Africa) project at a coastal site located in the outskirts of the city of Mbour, Senegal. With an averaged mass concentration of 5.4 µg m-3, levels of NR PM1 in Mbour were 3 to 10 times lower than those generally measured in urban and suburban polluted environments. Nonetheless the first half of the observation period was marked by intense but short pollution events (NR PM1 concentrations higher than 15 µg m-3), sea breeze phenomena and Saharan desert dust outbreaks (PM10 up to 900 µg m-3). During the second half of the campaign, the sampling site was mainly under the influence of marine air masses. The air masses on days under continental and sea breeze influences were dominated by organics (36-40 %), whereas sulfate particles were predominant (40 %) for days under oceanic influence. Overall, measurements showed that about three-quarters of the total PM1 were explained by NR PM1, BC (black carbon) and Fe (a proxy for dust) concentrations, leaving approximately one-quarter for other refractory species. A mean value of 4.6 % for the Fe / PM1 ratio was obtained. Source apportionment of the organic fraction, using positive matrix factorization (PMF), highlighted the impact of local combustion sources, such as traffic and residential activities, which contribute on average to 52 % of the total organic fraction. A new organic aerosol (OA) source

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

    Directory of Open Access Journals (Sweden)

    A. Hodzic

    2009-09-01

    Full Text Available The meso-scale chemistry-transport model CHIMERE is used to assess our understanding of major sources and formation processes leading to a fairly large amount of organic aerosols – OA, including primary OA (POA and secondary OA (SOA – observed in Mexico City during the MILAGRO field project (March 2006. Chemical analyses of submicron aerosols from aerosol mass spectrometers (AMS indicate that organic particles found in the Mexico City basin contain a large fraction of oxygenated organic species (OOA which have strong correspondence with SOA, and that their production actively continues downwind of the city. The SOA formation is modeled here by the one-step oxidation of anthropogenic (i.e. aromatics, alkanes, biogenic (i.e. monoterpenes and isoprene, and biomass-burning SOA precursors and their partitioning into both organic and aqueous phases. Conservative assumptions are made for uncertain parameters to maximize the amount of SOA produced by the model. The near-surface model evaluation shows that predicted OA correlates reasonably well with measurements during the campaign, however it remains a factor of 2 lower than the measured total OA. Fairly good agreement is found between predicted and observed POA within the city suggesting that anthropogenic and biomass burning emissions are reasonably captured. Consistent with previous studies in Mexico City, large discrepancies are encountered for SOA, with a factor of 2–10 model underestimate. When only anthropogenic SOA precursors were considered, the model was able to reproduce within a factor of two the sharp increase in OOA concentrations during the late morning at both urban and near-urban locations but the discrepancy increases rapidly later in the day, consistent with previous results, and is especially obvious when the column-integrated SOA mass is considered instead of the surface concentration. The increase in the missing SOA mass in the afternoon coincides with the sharp drop in POA

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

    Science.gov (United States)

    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

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

    Directory of Open Access Journals (Sweden)

    M. Crippa

    2013-01-01

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

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

  12. Modelling size and structure of nanoparticles formed from drying of submicron solution aerosols

    International Nuclear Information System (INIS)

    Bandyopadhyay, Arpan A.; Pawar, Amol A.; Venkataraman, Chandra; Mehra, Anurag

    2015-01-01

    Drying of submicron solution aerosols, under controlled conditions, has been explored to prepare nanoparticles for drug delivery applications. A computational model of solution drop evaporation is developed to study the evolution of solute gradients inside the drop and predict the size and shell thickness of precipitating nanoparticles. The model considers evaporation as a two-stage process involving droplet shrinkage and shell growth. It was corroborated that droplet evaporation rate controls the solute distribution within a droplet and the resulting particle structure (solid or shell type). At higher gas temperatures, rapid build-up of solute near drop surface from high evaporation rates results in early attainment of critical supersaturation solubility and a steeper solute gradient, which favours formation of larger, shell-type particles. At lower gas temperatures, formation of smaller, solid nanoparticles is indicated. The computed size and shell thickness are in good agreement with experimentally prepared lipid nanoparticles. This study indicates that solid or shell structure of precipitated nanoparticles is strongly affected by evaporation rate, while initial solute concentration in the precursor solution and atomized droplet size affect shell thickness. For the gas temperatures considered, evaporative cooling leads to droplet temperature below the melting point of the lipid solute. Thus, we conclude that control over nanoparticle size and structure, of thermolabile precursor materials suitable for drug delivery, can be achieved by controlling evaporation rates, through selection of aerosol processing conditions

  13. Modelling size and structure of nanoparticles formed from drying of submicron solution aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Bandyopadhyay, Arpan A.; Pawar, Amol A.; Venkataraman, Chandra; Mehra, Anurag, E-mail: mehra@iitb.ac.in [Indian Institute of Technology Bombay, Department of Chemical Engineering (India)

    2015-01-15

    Drying of submicron solution aerosols, under controlled conditions, has been explored to prepare nanoparticles for drug delivery applications. A computational model of solution drop evaporation is developed to study the evolution of solute gradients inside the drop and predict the size and shell thickness of precipitating nanoparticles. The model considers evaporation as a two-stage process involving droplet shrinkage and shell growth. It was corroborated that droplet evaporation rate controls the solute distribution within a droplet and the resulting particle structure (solid or shell type). At higher gas temperatures, rapid build-up of solute near drop surface from high evaporation rates results in early attainment of critical supersaturation solubility and a steeper solute gradient, which favours formation of larger, shell-type particles. At lower gas temperatures, formation of smaller, solid nanoparticles is indicated. The computed size and shell thickness are in good agreement with experimentally prepared lipid nanoparticles. This study indicates that solid or shell structure of precipitated nanoparticles is strongly affected by evaporation rate, while initial solute concentration in the precursor solution and atomized droplet size affect shell thickness. For the gas temperatures considered, evaporative cooling leads to droplet temperature below the melting point of the lipid solute. Thus, we conclude that control over nanoparticle size and structure, of thermolabile precursor materials suitable for drug delivery, can be achieved by controlling evaporation rates, through selection of aerosol processing conditions.

  14. Spatiotemporal Variation in Composition of Submicron Particles in Santiago Metropolitan Region, Chile

    Directory of Open Access Journals (Sweden)

    Matías Tagle

    2018-05-01

    Full Text Available The chemical composition of submicron particles (aerodynamic diameter Da < 1.0 μm was investigated at three locations in the Santiago Metropolitan Region (SMR, Chile. Measurements campaigns were conducted in winter and spring 2016, at representative sites of a rural, urban, and urban receptor environment. Instrumentation consisted of an optical analyzer to determine Black Carbon (BC and the Aerosol Chemical Speciation Monitor (ACSM to measure concentrations of particulate chloride (Cl−, nitrate (NO3-, sulfate (SO42-, ammonium (NH4+, and non-refractory carbonaceous species (organics. Complementary data, such as ozone concentration and meteorological parameters were obtained from the public air quality network. Results showed that in both the winter and spring seasons the organics predominated in the mass of submicron particles. This fraction was followed in decreasing order by NO3-, NH4+, BC, SO42-, and Cl−. The highest average organics concentrations were measured in winter at the urban (32.2 μg m−3 and urban receptor sites (20.1 μg m−3. In winter, average concentrations of both NO3- and NH4+ were higher at the urban receptor site (12.3 and 4.5 μg m−3, respectively when compared to the urban site (6.4 and 3.1 μg m−3, respectively. In general, all the measured species were present in higher concentrations during winter, excepting SO42-, which was the only one that increased during spring. The transition toward spring was also associated with an acidification of the aerosol at the rural and urban receptor site, while at the urban site the aerosol was observed alkaline. The highest average ozone concentration during both the winter and spring seasons were recorded at the urban receptor site (7.2 and 24.0 ppb, respectively. The study reports data showing that the atmosphere in the SMR has a considerable load of particulate organic compounds, NO3- and NH4+, which are in higher concentrations at urban sites during the winter season

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

    Science.gov (United States)

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

    2015-01-01

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

  16. Characterization and source apportionment of organic aerosol at 260 m on a meteorological tower in Beijing, China

    Science.gov (United States)

    Zhou, Wei; Wang, Qingqing; Zhao, Xiujuan; Xu, Weiqi; Chen, Chen; Du, Wei; Zhao, Jian; Canonaco, Francesco; Prévôt, André S. H.; Fu, Pingqing; Wang, Zifa; Worsnop, Douglas R.; Sun, Yele

    2018-03-01

    Despite extensive efforts toward the characterization of submicron aerosols at ground level in the megacity of Beijing, our understanding of aerosol sources and processes at high altitudes remains low. Here we conducted a 3-month real-time measurement of non-refractory submicron aerosol (NR-PM1) species at a height of 260 m from 10 October 2014 to 18 January 2015 using an aerosol chemical speciation monitor. Our results showed a significant change in aerosol composition from the non-heating period (NHP) to the heating period (HP). Organics and chloride showed clear increases during HP due to coal combustion emissions, while nitrate showed substantial decreases from 28 to 15-18 %. We also found that NR-PM1 species in the heating season can have average mass differences of 30-44 % under similar emission sources yet different meteorological conditions. Multi-linear engine 2 (ME-2) using three primary organic aerosol (OA) factors as constraints, i.e., fossil-fuel-related OA (FFOA) dominantly from coal combustion emissions, cooking OA (COA), and biomass burning OA (BBOA) resolved from ground high-resolution aerosol mass spectrometer measurements, was applied to OA mass spectra of ACSM. Two types of secondary OA (SOA) that were well correlated with nitrate and chloride-CO, respectively, were identified. SOA played a dominant role in OA during all periods at 260 m although the contributions were decreased from 72 % during NHP to 58-64 % during HP. The SOA composition also changed significantly from NHP to HP. While the contribution of oxygenated OA (OOA) was decreased from 56-63 to 32-40 %, less oxidized OOA (LO-OOA) showed a large increase from 9-16 to 24-26 %. COA contributed a considerable fraction of OA at high altitude, and the contribution was relatively similar across different periods (10-13 %). In contrast, FFOA showed a large increase during HP due to the influences of coal combustion emissions. We also observed very different OA composition between ground level

  17. Organic functional groups in the submicron aerosol at 82.5° N, 62.5° W from 2012 to 2014

    Science.gov (United States)

    Leaitch, W. Richard; Russell, Lynn M.; Liu, Jun; Kolonjari, Felicia; Toom, Desiree; Huang, Lin; Sharma, Sangeeta; Chivulescu, Alina; Veber, Dan; Zhang, Wendy

    2018-03-01

    The first multi-year contributions from organic functional groups to the Arctic submicron aerosol are documented using 126 weekly-integrated samples collected from April 2012 to October 2014 at the Alert Observatory (82.45° N, 62.51° W). Results from the particle transport model FLEXPART, linear regressions among the organic and inorganic components and positive matrix factorization (PMF) enable associations of organic aerosol components with source types and regions. Lower organic mass (OM) concentrations but higher ratios of OM to non-sea-salt sulfate mass concentrations (nss-SO4=) accompany smaller particles during the summer (JJA). Conversely, higher OM but lower OM / nss-SO4= accompany larger particles during winter-spring. OM ranges from 7 to 460 ng m-3, and the study average is 129 ng m-3. The monthly maximum in OM occurs during May, 1 month after the peak in nss-SO4= and 2 months after that of elemental carbon (EC). Winter (DJF), spring (MAM), summer and fall (SON) values of OM / nss-SO4= are 26, 28, 107 and 39 %, respectively, and overall about 40 % of the weekly variability in the OM is associated with nss-SO4=. Respective study-averaged concentrations of alkane, alcohol, acid, amine and carbonyl groups are 57, 24, 23, 15 and 11 ng m-3, representing 42, 22, 18, 14 and 5 % of the OM, respectively. Carbonyl groups, detected mostly during spring, may have a connection with snow chemistry. The seasonally highest O / C occurs during winter (0.85) and the lowest O / C is during spring (0.51); increases in O / C are largely due to increases in alcohol groups. During winter, more than 50 % of the alcohol groups are associated with primary marine emissions, consistent with Shaw et al. (2010) and Frossard et al. (2011). A secondary marine connection, rather than a primary source, is suggested for the highest and most persistent O / C observed during the coolest and cleanest summer (2013), when alcohol and acid groups made up 63 % of the OM. A secondary marine

  18. Insights into characteristics, sources, and evolution of submicron aerosols during harvest seasons in the Yangtze River delta region, China

    Science.gov (United States)

    Zhang, Y. J.; Tang, L. L.; Wang, Z.; Yu, H. X.; Sun, Y. L.; Liu, D.; Qin, W.; Canonaco, F.; Prévôt, A. S. H.; Zhang, H. L.; Zhou, H. C.

    2015-02-01

    Atmospheric submicron particulate matter (PM1) is one of the most significant pollution components in China. Despite its current popularity in the studies of aerosol chemistry, the characteristics, sources and evolution of atmospheric PM1 species are still poorly understood in China, particularly for the two harvest seasons, namely, the summer wheat harvest and autumn rice harvest. An Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was deployed for online monitoring of PM1 components during summer and autumn harvest seasons in urban Nanjing, in the Yangtze River delta (YRD) region of China. PM1 components were shown to be dominated by organic aerosol (OA, 39 and 41%) and nitrate (23 and 20%) during the harvest seasons (the summer and autumn harvest). Positive matrix factorization (PMF) analysis of the ACSM OA mass spectra resolved four OA factors: hydrocarbon-like mixed with cooking-related OA (HOA + COA), fresh biomass-burning OA (BBOA), oxidized biomass-burning-influenced OA (OOA-BB), and highly oxidized OA (OOA); in particular the oxidized BBOA contributes ~80% of the total BBOA loadings. Both fresh and oxidized BBOA exhibited apparent diurnal cycles with peak concentration at night, when the high ambient relative humidity and low temperature facilitated the partitioning of semi-volatile organic species into the particle phase. The fresh BBOA concentrations for the harvests are estimated as BBOA = 15.1 × (m/z 60-0.26% × OA), where m/z (mass-to-charge ratio) 60 is a marker for levoglucosan-like species. The (BBOA + OOA-BB)/ΔCO, (ΔCO is the CO minus background CO), decreases as a function of f44 (fraction of m/z 44 in OA signal), which might indicate that BBOA was oxidized to less volatile OOA, e.g., more aged and low volatility OOA (LV-OOA) during the aging process. Analysis of air mass back trajectories indicates that the high BB pollutant concentrations are linked to the air masses from the western (summer harvest) and southern (autumn harvest) areas.

  19. Aerosol Chemical Composition and its Effects on Cloud-Aerosol Interactions during the 2007 CHAPS Experiment

    Science.gov (United States)

    Lee, Y.; Alexander, L.; Newburn, M.; Jayne, J.; Hubbe, J.; Springston, S.; Senum, G.; Andrews, B.; Ogren, J.; Kleinman, L.; Daum, P.; Berg, L.; Berkowitz, C.

    2007-12-01

    Chemical composition of submicron aerosol particles was determined using an Aerodyne Time-of-Flight Aerosol Mass Spectrometer (AMS) outfitted on the DOE G-1 aircraft during the Cumulus Humilis Aerosol Processing Study (CHAPS) conducted in Oklahoma City area in June 2007. The primary objective of CHAPS was to investigate the effects of urban emissions on cloud aerosol interactions as a function of processing of the emissions. Aerosol composition was typically determined at three different altitudes: below, in, and above cloud, in both upwind and downwind regions of the urban area. Aerosols were sampled from an isokinetic inlet with an upper size cut-off of ~1.5 micrometer. During cloud passages, the AMS also sampled particles that were dried from cloud droplets collected using a counter-flow virtual impactor (CVI) sampler. The aerosol mass concentrations were typically below 10 microgram per cubic meter, and were dominated by organics and sulfate. Ammonium was often less than required for complete neutralization of sulfate. Aerosol nitrate levels were very low. We noted that nitrate levels were significantly enhanced in cloud droplets compared to aerosols, most likely resulting from dissolution of gaseous nitric acid. Organic to sulfate ratios appeared to be lower in cloud droplets than in aerosols, suggesting cloud condensation nuclei properties of aerosol particles might be affected by loading and nature of the organic components in aerosols. In-cloud formation of sulfate was considered unimportant because of the very low SO2 concentration in the region. A detailed examination of the sources of the aerosol organic components (based on hydrocarbons determined using a proton transfer reaction mass spectrometer) and their effects on cloud formation as a function of atmospheric processing (based on the degree of oxidation of the organic components) will be presented.

  20. One year online chemical speciation of submicron particulate matter (PM1) sampled at a French industrial and coastal site

    Science.gov (United States)

    Zhang, Shouwen; Riffault, Véronique; Dusanter, Sébastien; Augustin, Patrick; Fourmentin, Marc; Delbarre, Hervé

    2015-04-01

    The harbor of Dunkirk (Northern France) is surrounded by different industrial plants (metallurgy, petrochemistry, food processing, power plant, etc.), which emit gaseous and particulate pollutants such as Volatile Organic Compounds (VOCs), oxides of nitrogen (NOx) and sulfur (SO2), and submicron particles (PM1). These emissions are poorly characterized and their impact on neighboring urban areas has yet to be assessed. Studies are particularly needed in this type of complex environments to get a better understanding of PM1sources, especially from the industrial sector, their temporal variability, and their transformation. Several instruments, capable of real-time measurements (temporal resolution ≤ 30 min), were deployed at a site located downwind from the industrial area of Dunkirk for a one-year duration (July 2013-September 2014). An Aerosol Chemical Speciation Monitor (ACSM) and an Aethalometer monitored the main chemical species in the non-refractory submicron particles and black carbon, respectively. Concomitant measurements of trace gases and wind speed and direction were also performed. This dataset was analyzed considering four wind sectors, characteristics of marine, industrial, industrial-urban, and urban influences, and the different seasons. We will present a descriptive analysis of PM1, showing strong variations of ambient concentrations, as well as evidences of SO2 to SO4 gas-particle conversion when industrial plumes reached the monitoring site. The organic fraction measured by ACSM (37% of the total mass on average) was analyzed using a source-receptor model based on Positive Matrix Factorization (PMF) to identify chemical signatures of main emission sources and to quantify the contribution of each source to the PM1 budget given the wind sector. Four main factors were identified: hydrocarbon organic aerosol (HOA), oxygenated organic aerosol (OOA), biomass burning organic aerosol (BBOA) and cooking-like organic aerosol (COA). Overall, the total PM

  1. Online Chemical Characterization of Food-Cooking Organic Aerosols: Implications for Source Apportionment.

    Science.gov (United States)

    Reyes-Villegas, Ernesto; Bannan, Thomas; Le Breton, Michael; Mehra, Archit; Priestley, Michael; Percival, Carl; Coe, Hugh; Allan, James D

    2018-04-11

    Food-cooking organic aerosols (COA) are one of the primary sources of submicron particulate matter in urban environments. However, there are still many questions surrounding source apportionment related to instrumentation as well as semivolatile partitioning because COA evolve rapidly in the ambient air, making source apportionment more complex. Online measurements of emissions from cooking different types of food were performed in a laboratory to characterize particles and gases. Aerosol mass spectrometer (AMS) measurements showed that the relative ionization efficiency for OA was higher (1.56-3.06) relative to a typical value of 1.4, concluding that AMS is over-estimating COA and suggesting that previous studies likely over-estimated COA concentrations. Food-cooking mass spectra were generated using AMS, and gas and particle food markers were identified with filter inlets for gases and aerosols-chemical ionization mass spectrometer (CIMS) measurements to be used in future food cooking-source apportionment studies. However, there is a considerable variability in both gas and particle markers, and dilution plays an important role in the particle mass budget, showing the importance of using these markers with caution during receptor modeling. These findings can be used to better understand the chemical composition of COA, and they provides useful information to be used in future source-apportionment studies.

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

    Science.gov (United States)

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

    2017-12-01

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

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

    International Nuclear Information System (INIS)

    Liu Xiaohong; Wang Jian

    2010-01-01

    Organics are among the most abundant aerosol components in the atmosphere. However, there are still large uncertainties with emissions of primary organic aerosol (POA) and volatile organic compounds (VOCs) (precursor gases of secondary organic aerosol, SOA), formation of SOA, and chemical and physical properties (e.g., hygroscopicity) of POA and SOA. All these may have significant impacts on aerosol direct and indirect forcing estimated from global models. In this study a modal aerosol module (MAM) in the NCAR community atmospheric model (CAM) is used to examine sensitivities of aerosol indirect forcing to hygroscopicity (represented by a single parameter 'κ' ) of POA and SOA. Our model simulation indicates that in the present-day (PD) condition changing the 'κ' value of POA from 0 to 0.1 increases the number concentration of cloud condensational nuclei (CCN) at supersaturation S = 0.1% by 40-80% over the POA source regions, while changing the 'κ' value of SOA by ± 50% (from 0.14 to 0.07 and 0.21) changes the CCN concentration within 40%. There are disproportionally larger changes in CCN concentration in the pre-industrial (PI) condition. Due to the stronger impact of organics hygroscopicity on CCN and cloud droplet number concentration at PI condition, global annual mean anthropogenic aerosol indirect forcing (AIF) between PD and PI conditions reduces with the increase of the hygroscopicity of organics. Global annual mean AIF varies by 0.4 W m -2 in the sensitivity runs with the control run of - 1.3 W m -2 , highlighting the need for improved understanding of organics hygroscopicity and its representation in global models.

  4. Quantification of the carbonaceous matter origin in submicron marine aerosol particles by dual carbon isotope analysis

    Science.gov (United States)

    Ceburnis, D.; Garbaras, A.; Szidat, S.; Rinaldi, M.; Fahrni, S.; Perron, N.; Wacker, L.; Leinert, S.; Remeikis, V.; Facchini, M. C.; Prevot, A. S. H.; Jennings, S. G.; O'Dowd, C. D.

    2011-01-01

    Dual carbon isotope analysis has been performed for the first time demonstrating a potential in organic matter apportionment between three principal sources: marine, terrestrial (non-fossil) and fossil fuel due to unique isotopic signatures. The results presented here, utilising combinations of dual carbon isotope analysis, provides a conclusive evidence of a dominant biogenic organic fraction to organic aerosol over biologically active oceans. In particular, the NE Atlantic, which is also subjected to notable anthropogenic influences via pollution transport processes, was found to contain 80% organic aerosol matter of biogenic origin directly linked to plankton emissions. The remaining carbonaceous aerosol was of fossil-fuel origin. By contrast, for polluted air advecting out from Europe into the NE Atlantic, the source apportionment is 30% marine biogenic, 40% fossil fuel, and 30% continental non-fossil fuel. The dominant marine organic aerosol source in the atmosphere has significant implications for climate change feedback processes.

  5. Two years of near real-time chemical composition of submicron aerosols in the region of Paris using an Aerosol Chemical Speciation Monitor (ACSM) and a multi-wavelength Aethalometer

    Science.gov (United States)

    Petit, J.-E.; Favez, O.; Sciare, J.; Crenn, V.; Sarda-Estève, R.; Bonnaire, N.; Močnik, G.; Dupont, J.-C.; Haeffelin, M.; Leoz-Garziandia, E.

    2015-03-01

    Aerosol mass spectrometer (AMS) measurements have been successfully used towards a better understanding of non-refractory submicron (PM1) aerosol chemical properties based on short-term campaigns. The recently developed Aerosol Chemical Speciation Monitor (ACSM) has been designed to deliver quite similar artifact-free chemical information but for low cost, and to perform robust monitoring over long-term periods. When deployed in parallel with real-time black carbon (BC) measurements, the combined data set allows for a quasi-comprehensive description of the whole PM1 fraction in near real time. Here we present 2-year long ACSM and BC data sets, between mid-2011 and mid-2013, obtained at the French atmospheric SIRTA supersite that is representative of background PM levels of the region of Paris. This large data set shows intense and time-limited (a few hours) pollution events observed during wintertime in the region of Paris, pointing to local carbonaceous emissions (mainly combustion sources). A non-parametric wind regression analysis was performed on this 2-year data set for the major PM1 constituents (organic matter, nitrate, sulfate and source apportioned BC) and ammonia in order to better refine their geographical origins and assess local/regional/advected contributions whose information is mandatory for efficient mitigation strategies. While ammonium sulfate typically shows a clear advected pattern, ammonium nitrate partially displays a similar feature, but, less expectedly, it also exhibits a significant contribution of regional and local emissions. The contribution of regional background organic aerosols (OA) is significant in spring and summer, while a more pronounced local origin is evidenced during wintertime, whose pattern is also observed for BC originating from domestic wood burning. Using time-resolved ACSM and BC information, seasonally differentiated weekly diurnal profiles of these constituents were investigated and helped to identify the main

  6. Submicron particle mass concentrations and sources in the Amazonian wet season (AMAZE-08)

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Q.; Farmer, D. K.; Rizzo, L. V.; Pauliqueivis, T.; Kuwata, Mikinori; Karl, Thomas G.; Guenther, Alex B.; Allan, James D.; Coe, H.; Andreae, M. O.; Poeschl, U.; Jiminez, J. L.; Artaxo, Paulo; Martin, Scot T.

    2015-01-01

    Real-time mass spectra of non-refractory component of submicron aerosol particles were recorded in a tropical rainforest in the central Amazon basin during the wet season of 2008, as a part of the Amazonian Aerosol Characterization Experiment (AMAZE-08). Organic components accounted on average for more than 80% of the non-refractory submicron particle mass concentrations during the period of measurements. Ammonium was present in sufficient quantities to halfway neutralize sulfate. In this acidic, isoprene-dominated, low-NOx environment the high-resolution mass spectra as well as mass closures with ion chromatography measurements did not provide evidence for significant contributions of organosulfate species, at least at concentrations above uncertainty levels. Positive-matrix factorization of the time series of particle mass spectra identified four statistical factors to account for the variance of the signal intensities of the organic constituents: a factor HOA having a hydrocarbon-like signature and identified as regional emissions of primary organic material, a factor OOA-1 associated with fresh production of secondary organic material by a mechanism of BVOC oxidation followed by gas-to-particle conversion, a factor OOA-2 consistent with reactive uptake of isoprene oxidation products, especially epoxydiols by acidic particles, and a factor OOA-3 associated with long range transport and atmospheric aging. The OOA-1, -2, and -3 factors had progressively more oxidized signatures. Diameter-resolved mass spectral markers also suggested enhanced reactive uptake of isoprene oxidation products to the accumulation mode for the OOA-2 factor, and such size partitioning can be indicative of in-cloud process. The campaign-average factor loadings were in a ratio of 1.1:1.0 for the OOA-1 compared to the OOA-2 pathway, suggesting the comparable importance of gas-phase compared to particle-phase (including cloud waters) production pathways of secondary organic material during

  7. Combustion aerosols from potassium-containing fuels

    Energy Technology Data Exchange (ETDEWEB)

    Balzer Nielsen, Lars

    1999-12-31

    The scope of the work presented in this thesis is the formation and evolution of aerosol particles in the submicron range during combustion processes, in particular where biomass is used alone or co-fired with coal. An introduction to the formation processes of fly ash in general and submicron aerosol in particular during combustion is presented, along with some known problems related to combustion of biomass for power generation. The work falls in two parts. The first is the design of a laboratory setup for investigation of homogeneous nucleation and particle dynamics at high temperature. The central unit of the setup is a laminar flow aerosol condenser (LFAC), which essentially is a 173 cm long tubular furnace with an externally cooled wall. A mathematical model is presented which describes the formation and evolution of the aerosol in the LFAC, where the rate of formation of new nuclei is calculated using the so-called classical theory. The model includes mass and energy conservation equations and an expression for the description of particle growth by diffusion. The resulting set of nonlinear second-order partial differential equations are solved numerically using the method of orthogonal collocation. The model is implemented in the FORTRAN code MONAERO. The second part of this thesis describes a comprehensive investigation of submicron aerosol formation during co-firing of coal and straw carried out at a 380 MW{sub Th} pulverized coal unit at Studstrup Power Plant, Aarhus. Three types of coal are used, and total boiler load and straw input is varied systematically. Straw contains large amounts of potassium, which is released during combustion. Submicron aerosol is sampled between the two banks of the economizer at a flue gas temperature of 350 deg. C using a novel ejector probe. The aerosol is characterized using the SMPS system and a Berner-type low pressure impactor. The chemical composition of the particles collected in the impactor is determined using

  8. Combustion aerosols from potassium-containing fuels

    International Nuclear Information System (INIS)

    Balzer Nielsen, Lars

    1998-01-01

    The scope of the work presented in this thesis is the formation and evolution of aerosol particles in the submicron range during combustion processes, in particular where biomass is used alone or co-fired with coal. An introduction to the formation processes of fly ash in general and submicron aerosol in particular during combustion is presented, along with some known problems related to combustion of biomass for power generation. The work falls in two parts. The first is the design of a laboratory setup for investigation of homogeneous nucleation and particle dynamics at high temperature. The central unit of the setup is a laminar flow aerosol condenser (LFAC), which essentially is a 173 cm long tubular furnace with an externally cooled wall. A mathematical model is presented which describes the formation and evolution of the aerosol in the LFAC, where the rate of formation of new nuclei is calculated using the so-called classical theory. The model includes mass and energy conservation equations and an expression for the description of particle growth by diffusion. The resulting set of nonlinear second-order partial differential equations are solved numerically using the method of orthogonal collocation. The model is implemented in the FORTRAN code MONAERO. The second part of this thesis describes a comprehensive investigation of submicron aerosol formation during co-firing of coal and straw carried out at a 380 MW Th pulverized coal unit at Studstrup Power Plant, Aarhus. Three types of coal are used, and total boiler load and straw input is varied systematically. Straw contains large amounts of potassium, which is released during combustion. Submicron aerosol is sampled between the two banks of the economizer at a flue gas temperature of 350 deg. C using a novel ejector probe. The aerosol is characterized using the SMPS system and a Berner-type low pressure impactor. The chemical composition of the particles collected in the impactor is determined using chemical

  9. Combustion aerosols from potassium-containing fuels

    Energy Technology Data Exchange (ETDEWEB)

    Balzer Nielsen, Lars

    1998-12-31

    The scope of the work presented in this thesis is the formation and evolution of aerosol particles in the submicron range during combustion processes, in particular where biomass is used alone or co-fired with coal. An introduction to the formation processes of fly ash in general and submicron aerosol in particular during combustion is presented, along with some known problems related to combustion of biomass for power generation. The work falls in two parts. The first is the design of a laboratory setup for investigation of homogeneous nucleation and particle dynamics at high temperature. The central unit of the setup is a laminar flow aerosol condenser (LFAC), which essentially is a 173 cm long tubular furnace with an externally cooled wall. A mathematical model is presented which describes the formation and evolution of the aerosol in the LFAC, where the rate of formation of new nuclei is calculated using the so-called classical theory. The model includes mass and energy conservation equations and an expression for the description of particle growth by diffusion. The resulting set of nonlinear second-order partial differential equations are solved numerically using the method of orthogonal collocation. The model is implemented in the FORTRAN code MONAERO. The second part of this thesis describes a comprehensive investigation of submicron aerosol formation during co-firing of coal and straw carried out at a 380 MW{sub Th} pulverized coal unit at Studstrup Power Plant, Aarhus. Three types of coal are used, and total boiler load and straw input is varied systematically. Straw contains large amounts of potassium, which is released during combustion. Submicron aerosol is sampled between the two banks of the economizer at a flue gas temperature of 350 deg. C using a novel ejector probe. The aerosol is characterized using the SMPS system and a Berner-type low pressure impactor. The chemical composition of the particles collected in the impactor is determined using

  10. Secondary organic aerosols: Formation potential and ambient data

    DEFF Research Database (Denmark)

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

    1997-01-01

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

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

    Science.gov (United States)

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

    2017-08-01

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

  12. Characterization and source apportionment of organic aerosol at 260 m on a meteorological tower in Beijing, China

    Directory of Open Access Journals (Sweden)

    W. Zhou

    2018-03-01

    Full Text Available Despite extensive efforts toward the characterization of submicron aerosols at ground level in the megacity of Beijing, our understanding of aerosol sources and processes at high altitudes remains low. Here we conducted a 3-month real-time measurement of non-refractory submicron aerosol (NR-PM1 species at a height of 260 m from 10 October 2014 to 18 January 2015 using an aerosol chemical speciation monitor. Our results showed a significant change in aerosol composition from the non-heating period (NHP to the heating period (HP. Organics and chloride showed clear increases during HP due to coal combustion emissions, while nitrate showed substantial decreases from 28 to 15–18 %. We also found that NR-PM1 species in the heating season can have average mass differences of 30–44 % under similar emission sources yet different meteorological conditions. Multi-linear engine 2 (ME-2 using three primary organic aerosol (OA factors as constraints, i.e., fossil-fuel-related OA (FFOA dominantly from coal combustion emissions, cooking OA (COA, and biomass burning OA (BBOA resolved from ground high-resolution aerosol mass spectrometer measurements, was applied to OA mass spectra of ACSM. Two types of secondary OA (SOA that were well correlated with nitrate and chloride–CO, respectively, were identified. SOA played a dominant role in OA during all periods at 260 m although the contributions were decreased from 72 % during NHP to 58–64 % during HP. The SOA composition also changed significantly from NHP to HP. While the contribution of oxygenated OA (OOA was decreased from 56–63 to 32–40 %, less oxidized OOA (LO-OOA showed a large increase from 9–16 to 24–26 %. COA contributed a considerable fraction of OA at high altitude, and the contribution was relatively similar across different periods (10–13 %. In contrast, FFOA showed a large increase during HP due to the influences of coal combustion emissions. We also

  13. Evaluation of New and Proposed Organic Aerosol Sources and Mechanisms using the Aerosol Modeling Testbed. MILAGRO, CARES, CalNex, BEACHON, and GVAX

    Energy Technology Data Exchange (ETDEWEB)

    Hodzic, Alma [National Center for Atmospheric Research (NCAR), Boulder, CO (United States); Jimenez, Jose L. [Univ. of Colorado, Boulder, CO (United States)

    2015-04-09

    This work investigated the formation and evolution of organic aerosols (OA) arising from anthropogenic and biogenic sources in a framework that combined state-of-the-science process and regional modeling, and their evaluation against advanced and emerging field measurements. Although OA are the dominant constituents of submicron particles, our understanding of their atmospheric lifecycle is limited, and current models fail to describe the observed amounts and properties of chemically formed secondary organic aerosols (SOA), leaving large uncertainties on the effects of SOA on climate. Our work has provided novel modeling constraints on sources, formation, aging and removal of SOA by investigating in particular (i) the contribution of trash burning emissions to OA levels in a megacity, (ii) the contribution of glyoxal to SOA formation in aqueous particles in California during CARES/CalNex and over the continental U.S., (iii) SOA formation and regional growth over a pine forest in Colorado and its sensitivity to anthropogenic NOx levels during BEACHON, and the sensitivity of SOA to (iv) the sunlight exposure during its atmospheric lifetime, and to (v) changes in solubility and removal of organic vapors in the urban plume (MILAGRO, Mexico City), and over the continental U.S.. We have also developed a parameterization of water solubility for condensable organic gases produced from major anthropogenic and biogenic precursors based on explicit chemical modeling, and made it available to the wider community. This work used for the first time constraints from the explicit model GECKO-A to improve SOA representation in 3D regional models such as WRF-Chem.

  14. Quantification of the carbonaceous matter origin in submicron marine aerosol by 13C and 14C isotope analysis

    Directory of Open Access Journals (Sweden)

    M. Ramonet

    2011-08-01

    Full Text Available Dual carbon isotope analysis of marine aerosol samples has been performed for the first time demonstrating a potential in organic matter apportionment between three principal sources: marine, terrestrial (non-fossil and fossil fuel due to unique isotopic signatures. The results presented here, utilising combinations of dual carbon isotope analysis, provides conclusive evidence of a dominant biogenic organic fraction to organic aerosol over biologically active oceans. In particular, the NE Atlantic, which is also subjected to notable anthropogenic influences via pollution transport processes, was found to contain 80 % organic aerosol matter of biogenic origin directly linked to plankton emissions. The remaining carbonaceous aerosol was of terrestrial origin. By contrast, for polluted air advected out from Europe into the NE Atlantic, the source apportionment is 30 % marine biogenic, 40 % fossil fuel, and 30 % continental non-fossil fuel. The dominant marine organic aerosol source in the atmosphere has significant implications for climate change feedback processes.

  15. Quantification of the carbonaceous matter origin in submicron marine aerosol by 13C and 14C isotope analysis

    Science.gov (United States)

    Ceburnis, D.; Garbaras, A.; Szidat, S.; Rinaldi, M.; Fahrni, S.; Perron, N.; Wacker, L.; Leinert, S.; Remeikis, V.; Facchini, M. C.; Prevot, A. S. H.; Jennings, S. G.; Ramonet, M.; O'Dowd, C. D.

    2011-08-01

    Dual carbon isotope analysis of marine aerosol samples has been performed for the first time demonstrating a potential in organic matter apportionment between three principal sources: marine, terrestrial (non-fossil) and fossil fuel due to unique isotopic signatures. The results presented here, utilising combinations of dual carbon isotope analysis, provides conclusive evidence of a dominant biogenic organic fraction to organic aerosol over biologically active oceans. In particular, the NE Atlantic, which is also subjected to notable anthropogenic influences via pollution transport processes, was found to contain 80 % organic aerosol matter of biogenic origin directly linked to plankton emissions. The remaining carbonaceous aerosol was of terrestrial origin. By contrast, for polluted air advected out from Europe into the NE Atlantic, the source apportionment is 30 % marine biogenic, 40 % fossil fuel, and 30 % continental non-fossil fuel. The dominant marine organic aerosol source in the atmosphere has significant implications for climate change feedback processes.

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

    Science.gov (United States)

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

    2015-06-01

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

  17. Aerosol Chemical Speciation Monitor (ACSM) Instrument Handbook

    Energy Technology Data Exchange (ETDEWEB)

    Watson, Thomas B. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2017-08-15

    The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) measures particle mass loading and chemical composition in real time for non-refractory sub-micron aerosol particles. The ACSM is designed for long-term unattended deployment and routine monitoring applications.

  18. Number Size Distributions and Seasonality of Submicron Particles in Europe 2008–2009

    Czech Academy of Sciences Publication Activity Database

    Asmi, A.; Wiedensohler, A.; Laj, P.; Fjaeraa, A.-M.; Sellegri, K.; Birmili, W.; Weingartner, E.; Baltensperger, U.; Ždímal, Vladimír; Zíková, Naděžda; Putaud, J.-P.; Marioni, A.; Tunved, P.; Hansson, H.-C.; Fiebig, M.; Kivekäs, N.; Lihavainen, H.; Asmi, E.; Ulevicius, V.; Aalto, P.P.; Swietlicki, E.; Kristensson, E.; Mihalopoulos, N.; Kalivitis, N.; Kalapov, I.; Kiss, G.; de Leeuw, G.; Henzig, B.; Harrison, R. M.; Beddows, D.; O´Dowd, C.; Jennings, S.G.; Flentje, H.; Weinhold, K.; Meinhardt, F.; Ries, L.; Kulmala, M.

    2011-01-01

    Roč. 11, - (2011), s. 5505-5538 ISSN 1680-7316 EU Projects: European Commission(XE) RII3-CT-2006-026140; European Commission(XE) 36833; European Commission(IT) Ev-K2-CNR Grant - others:AFCE(FI) 1118615 Program:FP6 Institutional research plan: CEZ:AV0Z40720504 Keywords : aerosol particle number * aerosol concentrations * european submicron Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.520, year: 2011

  19. Aerosol optical properties relevant to regional remote sensing of CCN activity and links to their organic mass fraction: airborne observations over Central Mexico and the US West Coast during MILAGRO/INTEX-B

    Science.gov (United States)

    Shinozuka, Y.; Clarke, A. D.; Decarlo, P. F.; Jimenez, J. L.; Dunlea, E. J.; Roberts, G. C.; Tomlinson, J. M.; Collins, D. R.; Howell, S. G.; Kapustin, V. N.; McNaughton, C. S.; Zhou, J.

    2009-09-01

    Remote sensing of cloud condensation nuclei (CCN) would help evaluate the indirect effects of tropospheric aerosols on clouds and climate. To assess its feasibility, we examined relationships of submicron aerosol composition to CCN activity and optical properties observed during the MILAGRO/INTEX-B aircraft campaigns. An indicator of CCN activity, κ, was calculated from hygroscopicity measured under saturation. κ for dry 100 nm particles decreased with increasing organic fraction of non-refractory mass of submicron particles (OMF) as 0.34-0.20×OMF over Central Mexico and 0.47-0.43×OMF over the US West Coast. These fits represent the critical dry diameter, centered near 100 nm for 0.2% supersaturation but varied as κ(-1/3), within measurement uncertainty (~20%). The decreasing trends of CCN activity with the organic content, evident also in our direct CCN counts, were consistent with previous ground and laboratory observations of highly organic particles. The wider range of OMF, 0-0.8, for our research areas means that aerosol composition will be more critical for estimation of CCN concentration than at the fixed sites previously studied. Furthermore, the wavelength dependence of extinction was anti-correlated with OMF as -0.70×OMF+2.0 for Central Mexico's urban and industrial pollution air masses, for unclear reasons. The Angstrom exponent of absorption increased with OMF, more rapidly under higher single scattering albedo, as expected for the interplay between soot and colored weak absorbers (some organic species and dust). Because remote sensing products currently use the wavelength dependence of extinction albeit in the column integral form and may potentially include that of absorption, these regional spectral dependencies are expected to facilitate retrievals of aerosol bulk chemical composition and CCN activity over Central Mexico.

  20. Clouds and aerosols in Puerto Rico - a new evaluation

    Science.gov (United States)

    Allan, J. D.; Baumgardner, D.; Raga, G. B.; Mayol-Bracero, O. L.; Morales-García, F.; García-García, F.; Montero-Martínez, G.; Borrmann, S.; Schneider, J.; Mertes, S.; Walter, S.; Gysel, M.; Dusek, U.; Frank, G. P.; Krämer, M.

    2008-03-01

    The influence of aerosols, both natural and anthropogenic, remains a major area of uncertainty when predicting the properties and behaviour of clouds and their influence on climate. In an attempt to better understand warm cloud formation in a tropical marine environment, a period of intensive measurements took place in December 2004 in Puerto Rico, using some of the latest developments in online instrumentation such as aerosol mass spectrometers, cloud condensation nuclei counters and a hygroscopicity tandem differential mobility analyser. Simultaneous online measurements of aerosol size distributions, composition, hygroscopicity and optical properties were made near the lighthouse of Cape San Juan in the north-eastern corner of the island and at the top of East Peak mountain (1040 m a.s.l.), the two sites separated by 17 km. Additional measurements of the cloud droplet residual and interstitial aerosol properties were made at the mountain site, accompanied by measurements of cloud droplet size distributions, liquid water content and the chemical composition of cloud and rain water samples. Both aerosol composition and cloud properties were found to be sensitive to wind sector. Air from the east-northeast (ENE) was mostly free of anthropogenic influences, the submicron fraction being mainly composed of non-sea salt sulphate, while that from the east-southeast (ESE) was found to be moderately influenced by populated islands upwind, adding smaller (residual particles and concentrations of cloudwater nitrate, sulphate and insoluble material increased during polluted conditions. Previous studies in Puerto Rico had reported the presence of a significant non-anthropogenic organic fraction in the aerosols measured and concluded that this was a factor controlling the in situ cloud properties. However, this was not observed in our case. In contrast to the 1.00±0.14 μg m-3 of organic carbon measured in 1992 and 1995, the organic matter measured in the current study of 0

  1. Where and What Is Pristine Marine Aerosol?

    Science.gov (United States)

    Russell, L. M.; Frossard, A. A.; Long, M. S.; Burrows, S. M.; Elliott, S.; Bates, T. S.; Quinn, P.

    2014-12-01

    , 48:v-x, doi10.1080/02786826.2013.879979, 2014a. Frossard, A.A., L.M. Russell, M.S. Long, S.M. Burrows, S.M. Elliot, T.S. Bates, and P.K. Quinn, "Sources and Composition of Submicron Organic Mass in Marine Aerosol Particles," Journal of Geophysical Research - Atmospheres, submitted 2014b.

  2. AIP1OGREN: Aerosol Observing Station Intensive Properties Value-Added Product

    Energy Technology Data Exchange (ETDEWEB)

    Koontz, Annette [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Flynn, Connor [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2017-09-15

    The aip1ogren value-added product (VAP) computes several aerosol intensive properties. It requires as input calibrated, corrected, aerosol extensive properties (scattering and absorption coefficients, primarily) from the Aerosol Observing Station (AOS). Aerosol extensive properties depend on both the nature of the aerosol and the amount of the aerosol. We compute several properties as relationships between the various extensive properties. These intensive properties are independent of aerosol amount and instead relate to intrinsic properties of the aerosol itself. Along with the original extensive properties we report aerosol single-scattering albedo, hemispheric backscatter fraction, asymmetry parameter, and Ångström exponent for scattering and absorption with one-minute averaging. An hourly averaged file is produced from the 1-minute files that includes all extensive and intensive properties as well as submicron scattering and submicron absorption fractions. Finally, in both the minutely and hourly files the aerosol radiative forcing efficiency is provided.

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

    International Nuclear Information System (INIS)

    Galbally, Ian

    2007-01-01

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

  4. Aircraft-based Observations and Modeling of Wintertime Submicron Aerosol Composition over the Northeastern U.S.

    Science.gov (United States)

    Shah, V.; Jaegle, L.; Schroder, J. C.; Campuzano-Jost, P.; Jimenez, J. L.; Guo, H.; Sullivan, A.; Weber, R. J.; Green, J. R.; Fiddler, M.; Bililign, S.; Lopez-Hilfiker, F.; Lee, B. H.; Thornton, J. A.

    2017-12-01

    Submicron aerosol particles (PM1) remain a major air pollution concern in the urban areas of northeastern U.S. While SO2 and NOx emission controls have been effective at reducing summertime PM1 concentrations, this has not been the case for wintertime sulfate and nitrate concentrations, suggesting a nonlinear response during winter. During winter, organic aerosol (OA) is also an important contributor to PM1 mass despite low biogenic emissions, suggesting the presence of important urban sources. We use aircraft-based observations collected during the Wintertime INvestigation of Transport, Emissions and Reactivity (WINTER) campaign (Feb-March 2015), together with the GEOS-Chem chemical transport model, to investigate the sources and chemical processes governing wintertime PM1 over the northeastern U.S. The mean observed concentration of PM1 between the surface and 1 km was 4 μg m-3, about 30% of which was composed of sulfate, 20% nitrate, 10% ammonium, and 40% OA. The model reproduces the observed sulfate, nitrate and ammonium concentrations after updates to HNO3 production and loss, SO2 oxidation, and NH3 emissions. We find that 65% of the sulfate formation occurs in the aqueous phase, and 55% of nitrate formation through N2O5 hydrolysis, highlighting the importance of multiphase and heterogeneous processes during winter. Aqueous-phase sulfate production and the gas-particle partitioning of nitrate and ammonium are affected by atmospheric acidity, which in turn depends on the concentration of these species. We examine these couplings with GEOS-Chem, and assess the response of wintertime PM1 concentrations to further emission reductions based on the U.S. EPA projections for the year 2023. For OA, we find that the standard GEOS-Chem simulation underestimates the observed concentrations, but a simple parameterization developed from previous summer field campaigns is able to reproduce the observations and the contribution of primary and secondary OA. We find that

  5. Seasonal dependence of aerosol processing in urban Philadelphia

    Science.gov (United States)

    Avery, A. M.; Waring, M. S.; DeCarlo, P. F.

    2017-12-01

    Urban aerosols pose an important threat to human health due to the conflation of emissions and concentrated population exposed. Winter and summer aerosol and trace gas measurements were taken in downtown Philadelphia in 2016. Measurements included aerosol composition and size with an Aerodyne Aerosol Mass Spectrometer (AMS), particle size distributions with an SMPS, and an aethalometer. Trace gas measurements of O3, NO, CH4, CO, and CO2 were taken concurrently. Sampling in seasonal extremes provided contrast in aerosol and trace gas composition, aerosol processing, and emission factors. Inorganic aerosol components contributed approximately 60% of the submicron aerosol mass, while summertime aerosol composition was roughly 70% organic matter. Positive Matrix Factorization (PMF) on the organic aerosol (OA) matrix revealed three factors in common in each season, including an oxygenated organic aerosol (OOA) factor with different temporal behavior in each season. In summertime, OOA varied diurnally with ozone and daytime temperature, but in the wintertime, it was anti-correlated with ozone and temperature, and instead trended with calculated liquid water, indicating a seasonally-dependent processing of organic aerosol in Philadelphia's urban environment. Due to the inorganic dominant winter aerosol, liquid water much higher (2.65 μg/m3) in winter than in summer (1.54 μg/m3). Diurnally varying concentrations of background gas phase species (CH4, CO2) were higher in winter and varied less as a result of boundary layer conditions; ozone was also higher in background in winter than summer. Winter stagnation events with low windspeed showed large buildup of trace gases CH4, CO, CO2, and NO. Traffic related aerosol was also elevated with black carbon and hydrocarbon-like OA (HOA) plumes of each at 3-5 times higher than the winter the average value for each. Winter ratios of HOA to black carbon were significantly higher in the winter than the summer due to lower

  6. Aerosol characterization over the southeastern United States using high resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition, sources, and organic nitrates

    Science.gov (United States)

    Xu, L.; Suresh, S.; Guo, H.; Weber, R. J.; Ng, N. L.

    2015-04-01

    We deployed a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) to characterize the chemical composition of submicron non-refractory particles (NR-PM1) in the southeastern US. Measurements were performed in both rural and urban sites in the greater Atlanta area, GA and Centreville, AL for approximately one year, as part of Southeastern Center of Air Pollution and Epidemiology study (SCAPE) and Southern Oxidant and Aerosol Study (SOAS). Organic aerosol (OA) accounts for more than half of NR1 mass concentration regardless of sampling sites and seasons. Positive matrix factorization (PMF) analysis of HR-ToF-AMS measurements identified various OA sources, depending on location and season. Hydrocarbon-like OA (HOA) and cooking OA (COA) have important but not dominant contributions to total OA in urban sites. Biomass burning OA (BBOA) concentration shows a distinct seasonal variation with a larger enhancement in winter than summer. We find a good correlation between BBOA and brown carbon, indicating biomass burning is an important source for brown carbon, although an additional, unidentified brown carbon source is likely present at the rural Yorkville site. Isoprene-derived OA (Isoprene-OA) is only deconvolved in warmer months and contributes 18-36% of total OA. The presence of Isoprene-OA factor in urban sites is more likely from local production in the presence of NOx than transport from rural sites. More-oxidized and less-oxidized oxygenated organic aerosol (MO-OOA and LO-OOA, respectively) are dominant fractions (47-79%) of OA in all sites. MO-OOA correlates well with ozone in summer, but not in winter, indicating MO-OOA sources may vary with seasons. LO-OOA, which reaches a daily maximum at night, correlates better with estimated nitrate functionality from organic nitrates than total nitrates. Based on the HR-ToF-AMS measurements, we estimate that the nitrate functionality from organic nitrates

  7. The attachment of radon daughters to submicron aerosol particles

    International Nuclear Information System (INIS)

    Grenier, M.G.; Bigu, J.

    1984-04-01

    A study of the effects of aerosol concentration, aerosol size distribution and relative humidity on the Working Level and the radon daughter concentration was conducted in a 3000 L radon environmental chamber. Typical values of the aerosol concentration varied in the 1 x 10 3 particles/cm 3 to 4.5 x 10 5 particles/cm 3 range. Various size distributions of aerosols that have mean diffusional aerodynamic diameters of .025 μm, .045 μm and .090 μm were tested. A good correlation was found between the Working Level and the aerosol concentration as well as the relative humidity. Most of the activity seems to be associated with particles of diameter between .05 μm and .2 μm. The results presented here are in agreement with work done by other investigators in the health physics field

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-08-05

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

  9. Field and Laboratory Studies of Atmospheric Organic Aerosol

    Science.gov (United States)

    Coggon, Matthew Mitchell

    This thesis is the culmination of field and laboratory studies aimed at assessing processes that affect the composition and distribution of atmospheric organic aerosol. An emphasis is placed on measurements conducted using compact and high-resolution Aerodyne Aerosol Mass Spectrometers (AMS). The first three chapters summarize results from aircraft campaigns designed to evaluate anthropogenic and biogenic impacts on marine aerosol and clouds off the coast of California. Subsequent chapters describe laboratory studies intended to evaluate gas and particle-phase mechanisms of organic aerosol oxidation. The 2013 Nucleation in California Experiment (NiCE) was a campaign designed to study environments impacted by nucleated and/or freshly formed aerosol particles. Terrestrial biogenic aerosol with > 85% organic mass was observed to reside in the free troposphere above marine stratocumulus. This biogenic organic aerosol (BOA) originated from the Northwestern United States and was transported to the marine atmosphere during periodic cloud-clearing events. Spectra recorded by a cloud condensation nuclei counter demonstrated that BOA is CCN active. BOA enhancements at latitudes north of San Francisco, CA coincided with enhanced cloud water concentrations of organic species such as acetate and formate. Airborne measurements conducted during the 2011 Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) were aimed at evaluating the contribution of ship emissions to the properties of marine aerosol and clouds off the coast of central California. In one study, analysis of organic aerosol mass spectra during periods of enhanced shipping activity yielded unique tracers indicative of cloud-processed ship emissions (m/z 42 and 99). The variation of their organic fraction (f42 and f 99) was found to coincide with periods of heavy (f 42 > 0.15; f99 > 0.04), moderate (0.05 controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed

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

    Science.gov (United States)

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

    2017-01-01

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

  11. Aerosol filtration with metallic fibrous filters

    International Nuclear Information System (INIS)

    Klein, M.; Goossens, W.R.A.

    1983-01-01

    The filtration efficiency of stainless steel fibrous filters (BEKIPOR porous mats and sintered webs) is determined using submicronic monodisperse polystyrene aerosols. Lasers spectrometers are used for the aerosol measurements. The parameters varied are the fiber diameter, the number of layers, the aerosol diameter and the superficial velocity. Two selected types of filters are tested with polydisperse methylene blue aerosols to determine the effect of bed loading on the filter performance and to test washing techniques for the regeneration of the filter

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

    Directory of Open Access Journals (Sweden)

    D. K. Farmer

    2011-06-01

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

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

    Science.gov (United States)

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

    2017-12-01

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

  14. Aerosol characterization over the southeastern United States using high-resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition and sources with a focus on organic nitrates

    Science.gov (United States)

    Xu, L.; Suresh, S.; Guo, H.; Weber, R. J.; Ng, N. L.

    2015-07-01

    We deployed a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) to characterize the chemical composition of submicron non-refractory particulate matter (NR-PM1) in the southeastern USA. Measurements were performed in both rural and urban sites in the greater Atlanta area, Georgia (GA), and Centreville, Alabama (AL), for approximately 1 year as part of Southeastern Center for Air Pollution and Epidemiology study (SCAPE) and Southern Oxidant and Aerosol Study (SOAS). Organic aerosol (OA) accounts for more than half of NR-PM1 mass concentration regardless of sampling sites and seasons. Positive matrix factorization (PMF) analysis of HR-ToF-AMS measurements identified various OA sources, depending on location and season. Hydrocarbon-like OA (HOA) and cooking OA (COA) have important, but not dominant, contributions to total OA in urban sites (i.e., 21-38 % of total OA depending on site and season). Biomass burning OA (BBOA) concentration shows a distinct seasonal variation with a larger enhancement in winter than summer. We find a good correlation between BBOA and brown carbon, indicating biomass burning is an important source for brown carbon, although an additional, unidentified brown carbon source is likely present at the rural Yorkville site. Isoprene-derived OA factor (isoprene-OA) is only deconvolved in warmer months and contributes 18-36 % of total OA. The presence of isoprene-OA factor in urban sites is more likely from local production in the presence of NOx than transport from rural sites. More-oxidized and less-oxidized oxygenated organic aerosol (MO-OOA and LO-OOA, respectively) are dominant fractions (47-79 %) of OA in all sites. MO-OOA correlates well with ozone in summer but not in winter, indicating MO-OOA sources may vary with seasons. LO-OOA, which reaches a daily maximum at night, correlates better with estimated nitrate functionality from organic nitrates than total nitrates. Based

  15. Airborne measurement of submicron aerosol number concentration and CCN activity in and around the Korean Peninsula and their comparison to ground measurement in Seoul

    Science.gov (United States)

    Park, M.; Kim, N.; Yum, S. S.

    2016-12-01

    Aerosols exert impact not only on human health and visibility but also on climate change directly by scattering or absorbing solar radiation and indirectly by acting as cloud condensation nuclei (CCN) and thus altering cloud radiative and microphysical properties. Aerosol indirect effects on climate has been known to have large uncertainty because of insufficient measurement data on aerosol and CCN activity distribution. Submicron aerosol number concentration (NCN, TSI CPC) and CCN number concentration (NCCN, DMT CCNC) were measured on board the NASA DC-8 research aircraft and at a ground site at Olympic Park in Seoul from May 2nd to June 10th, 2016. CCNC on the airborne platform was operated with the fixed internal supersaturation of 0.6% and CCNC at the ground site was operated with the five different supersaturations (0.2%, 0.4%, 0.6%, 0.8%, and 1.0%). The NASA DC-8 conducted 20 research flights (about 150 hours) in and around the Korean Peninsula and the ground measurement at Olympic Park was continuously made during the measurement period. Both airborne and ground measurements showed spatially and temporally varied aerosol number concentration and CCN activity. Aerosol number concentration in the boundary layer measured on airborne platform was highly affected by pollution sources on the ground. The average diurnal distribution of ground aerosol number concentration showed distinct peaks are located at about 0800, 1500, and 2000. The middle peak indicates that new particle formation events frequently occurred during the measurement period. CCN activation ratio at 0.6% supersaturation (NCCN/NCN) of the airborne measurement ranged from 0.1 to 0.9, indicating that aerosol properties in and around the Korean Peninsula varied so much (e. g. size, hygroscopicity). Comprehensive analysis results will be shown at the conference.

  16. Ambient Aerosol in Southeast Asia: High Resolution Aerosol Mass Spectrometer Measurements Over Oil Palm (Elaeis guineensis)

    Science.gov (United States)

    Phillips, G.; Dimarco, C.; Misztal, P.; Nemitz, E.; Farmer, D.; Kimmel, J.; Jimenez, J.

    2008-12-01

    The emission of organic compounds in the troposphere is important factor in the formation of secondary organic aerosol (SOA). A very large proportion of organic material emitted globally is estimated to arise from biogenic sources, with almost half coming from tropical and sub-tropical forests. Preliminary analyses of leave cuvette emission studies suggest that oil palm (Elaeis guineensis) is a significantly larger source of isoprene than tropical forest. Much larger sources of isoprene over oil palm allied with a larger anthropogenic component of local emissions contrast greatly with the remote tropical forest environment and therefore the character of SOA formed may differ significantly. These issues, allied with the high price of palm oil on international markets leading to increased use of land for oil palm production, could give rise to rapidly changing chemical and aerosol regimes in the tropics. It is therefore important to understand the current emissions and composition of organic aerosol over all important land-uses in the tropical environment. This in turn will lead to a greater understanding of the present, and to an improvement in predictive capacity for the future system. To help address these issues, a high resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) was deployed in the Sabahmas (PPB OIL) oil palm plantation near Lahad Datu, in Eastern Sabah, as part of the field component of the Aerosol Coupling in the Earth System (ACES) project, part of the UK NERC APPRAISE program. This project was allied closely with measurements made of similar chemical species and aerosol components at a forest site in the Danum Valley as part of the UK Oxidant and Particle Photochemical Processes above a Southeast Asian tropical rainforest (OP3) project. Measurements of submicron non- refractory aerosol composition are presented along with some preliminary analysis of chemically resolved aerosol fluxes made with a new eddy covariance system, based on the

  17. a Study of the Origin of Atmospheric Organic Aerosols

    Science.gov (United States)

    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

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

    Science.gov (United States)

    Jathar, Shantanu Hemant

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

  19. Seasonal variations in high time-resolved chemical compositions, sources, and evolution of atmospheric submicron aerosols in the megacity Beijing

    Science.gov (United States)

    Hu, Wei; Hu, Min; Hu, Wei-Wei; Zheng, Jing; Chen, Chen; Wu, Yusheng; Guo, Song

    2017-08-01

    A severe regional haze problem in the megacity Beijing and surrounding areas, caused by fast formation and growth of fine particles, has attracted much attention in recent years. In order to investigate the secondary formation and aging process of urban aerosols, four intensive campaigns were conducted in four seasons between March 2012 and March 2013 at an urban site in Beijing (116.31° E, 37.99° N). An Aerodyne high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) was deployed to measure non-refractory chemical components of submicron particulate matter (NR-PM1). The average mass concentrations of PM1 (NR-PM1+black carbon) were 45.1 ± 45.8, 37.5 ± 31.0, 41.3 ± 42.7, and 81.7 ± 72.4 µg m-3 in spring, summer, autumn, and winter, respectively. Organic aerosol (OA) was the most abundant component in PM1, accounting for 31, 33, 44, and 36 % seasonally, and secondary inorganic aerosol (SNA, sum of sulfate, nitrate, and ammonium) accounted for 59, 57, 43, and 55 % of PM1 correspondingly. Based on the application of positive matrix factorization (PMF), the sources of OA were obtained, including the primary ones of hydrocarbon-like (HOA), cooking (COA), biomass burning OA (BBOA) and coal combustion OA (CCOA), and secondary component oxygenated OA (OOA). OOA, which can be split into more-oxidized (MO-OOA) and less-oxidized OOA (LO-OOA), accounted for 49, 69, 47, and 50 % in four seasons, respectively. Totally, the fraction of secondary components (OOA+SNA) contributed about 60-80 % to PM1, suggesting that secondary formation played an important role in the PM pollution in Beijing, and primary sources were also non-negligible. The evolution process of OA in different seasons was investigated with multiple metrics and tools. The average carbon oxidation states and other metrics show that the oxidation state of OA was the highest in summer, probably due to both strong photochemical and aqueous-phase oxidations. It was indicated by the good correlations

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

    Science.gov (United States)

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

    2016-07-01

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

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

    Directory of Open Access Journals (Sweden)

    Y. Sun

    2016-07-01

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

  2. Processing of Unsaturated Organic Acid Aerosols by Ozone

    Science.gov (United States)

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

    2002-05-01

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

  3. The Pasadena Aerosol Characterization Observatory (PACO: chemical and physical analysis of the Western Los Angeles basin aerosol

    Directory of Open Access Journals (Sweden)

    S. P. Hersey

    2011-08-01

    Full Text Available The Pasadena Aerosol Characterization Observatory (PACO represents the first major aerosol characterization experiment centered in the Western/Central Los Angeles Basin. The sampling site, located on the campus of the California Institute of Technology in Pasadena, was positioned to sample a continuous afternoon influx of transported urban aerosol with a photochemical age of 1–2 h and generally free from major local contributions. Sampling spanned 5 months during the summer of 2009, which were broken into 3 regimes on the basis of distinct meteorological conditions. Regime I was characterized by a series of low pressure systems, resulting in high humidity and rainy periods with clean conditions. Regime II typified early summer meteorology, with significant morning marine layers and warm, sunny afternoons. Regime III was characterized by hot, dry conditions with little marine layer influence. Regardless of regime, organic aerosol (OA is the most significant constituent of nonrefractory submicron Los Angeles aerosol (42, 43, and 55 % of total submicron mass in regimes I, II, and III, respectively. The overall oxidation state remains relatively constant on timescales of days to weeks (O:C = 0.44 ± 0.08, 0.55 ± 0.05, and 0.48 ± 0.08 during regimes I, II, and III, respectively, with no difference in O:C between morning and afternoon periods. Periods characterized by significant morning marine layer influence followed by photochemically favorable afternoons displayed significantly higher aerosol mass and O:C ratio, suggesting that aqueous processes may be important in the generation of secondary aerosol and oxidized organic aerosol (OOA in Los Angeles. Online analysis of water soluble organic carbon (WSOC indicates that water soluble organic mass (WSOM reaches maxima near 14:00–15:00 local time (LT, but the percentage of AMS organic mass contributed by WSOM remains relatively constant throughout the day. Sulfate and nitrate reside predominantly

  4. Ground-based aerosol characterization during the South American Biomass Burning Analysis (SAMBBA field experiment

    Directory of Open Access Journals (Sweden)

    J. Brito

    2014-11-01

    Full Text Available This paper investigates the physical and chemical characteristics of aerosols at ground level at a site heavily impacted by biomass burning. The site is located near Porto Velho, Rondônia, in the southwestern part of the Brazilian Amazon rainforest, and was selected for the deployment of a large suite of instruments, among them an Aerosol Chemical Speciation Monitor. Our measurements were made during the South American Biomass Burning Analysis (SAMBBA field experiment, which consisted of a combination of aircraft and ground-based measurements over Brazil, aimed to investigate the impacts of biomass burning emissions on climate, air quality, and numerical weather prediction over South America. The campaign took place during the dry season and the transition to the wet season in September/October 2012. During most of the campaign, the site was impacted by regional biomass burning pollution (average CO mixing ratio of 0.6 ppm, occasionally superimposed by intense (up to 2 ppm of CO, freshly emitted biomass burning plumes. Aerosol number concentrations ranged from ~1000 cm−3 to peaks of up to 35 000 cm−3 (during biomass burning (BB events, corresponding to an average submicron mass mean concentrations of 13.7 μg m−3 and peak concentrations close to 100 μg m−3. Organic aerosol strongly dominated the submicron non-refractory composition, with an average concentration of 11.4 μg m−3. The inorganic species, NH4, SO4, NO3, and Cl, were observed, on average, at concentrations of 0.44, 0.34, 0.19, and 0.01 μg m−3, respectively. Equivalent black carbon (BCe ranged from 0.2 to 5.5 μg m−3, with an average concentration of 1.3 μg m−3. During BB peaks, organics accounted for over 90% of total mass (submicron non-refractory plus BCe, among the highest values described in the literature. We examined the ageing of biomass burning organic aerosol (BBOA using the changes in the H : C and O : C ratios, and found that throughout most of the

  5. Physical properties of aerosols at Maitri, Antarctica

    Indian Academy of Sciences (India)

    Measurements of the submicron aerosol size distribution made at the Indian Antarctic station, Maitri (70° 45′S, 11° 44′E) from January 10th to February 24th, 1997, are reported. Total aerosol concentrations normally range from 800 to 1200 particles cm-3 which are typical values for the coastal stations at Antarctica in ...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-08-23

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

  7. Characterization of organic aerosols in Beirut, Lebanon

    International Nuclear Information System (INIS)

    Waked, Antoine

    2012-01-01

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

  8. Theoretical studies on aerosol agglomeration processes

    Energy Technology Data Exchange (ETDEWEB)

    Lehtinen, K.E.J. [VTT Energy, Espoo (Finland). Energy Use

    1997-12-31

    In this thesis, theoretical modeling of certain aerosol systems has been presented. At first, the aerosol general dynamic equation is introduced, along with a discretization routine for its numerical solution. Of the various possible phenomena affecting aerosol behaviour, this work is mostly focused on aerosol agglomeration. The fundamentals of aerosol agglomeration theory are thus briefly reviewed. The two practical applications of agglomeration studied in this thesis are flue gas cleaning using an electrical agglomerator and nanomaterial synthesis with a free jet reactor. In an electrical agglomerator the aerosol particles are charged and brought into an alternating electric field. The aim is to remove submicron particles from flue gases by collisions with larger particles before conventional gas cleaning devices that have a clear penetration window in the problematic 0.1-1{mu}m size range. A mathematical model was constructed to find out the effects of the different system parameters on the agglomerator`s performance. A crucial part of this task was finding out the collision efficiencies of particles of varying size and charge. The original idea was to use unipolar charging of the particles, and a laboratory scale apparatus was constructed for this purpose. Both theory and experiments clearly show that significant removal of submicron particles can not be achieved by such an arrangement. The theoretical analysis further shows that if the submicron particles and the large collector particles were charged with opposite polarity, significant removal of the submicron particles could be obtained. The second application of agglomeration considered in this thesis is predicting/controlling nanoparticle size in the gas-to-particle aerosol route to material synthesis. In a typical material reactor, a precursor vapor reacts to form molecules of the desired material. In a cooling environment, a particulate phase forms, the dynamics of which are determined by the rates of

  9. Theoretical studies on aerosol agglomeration processes

    Energy Technology Data Exchange (ETDEWEB)

    Lehtinen, K E.J. [VTT Energy, Espoo (Finland). Energy Use

    1998-12-31

    In this thesis, theoretical modeling of certain aerosol systems has been presented. At first, the aerosol general dynamic equation is introduced, along with a discretization routine for its numerical solution. Of the various possible phenomena affecting aerosol behaviour, this work is mostly focused on aerosol agglomeration. The fundamentals of aerosol agglomeration theory are thus briefly reviewed. The two practical applications of agglomeration studied in this thesis are flue gas cleaning using an electrical agglomerator and nanomaterial synthesis with a free jet reactor. In an electrical agglomerator the aerosol particles are charged and brought into an alternating electric field. The aim is to remove submicron particles from flue gases by collisions with larger particles before conventional gas cleaning devices that have a clear penetration window in the problematic 0.1-1{mu}m size range. A mathematical model was constructed to find out the effects of the different system parameters on the agglomerator`s performance. A crucial part of this task was finding out the collision efficiencies of particles of varying size and charge. The original idea was to use unipolar charging of the particles, and a laboratory scale apparatus was constructed for this purpose. Both theory and experiments clearly show that significant removal of submicron particles can not be achieved by such an arrangement. The theoretical analysis further shows that if the submicron particles and the large collector particles were charged with opposite polarity, significant removal of the submicron particles could be obtained. The second application of agglomeration considered in this thesis is predicting/controlling nanoparticle size in the gas-to-particle aerosol route to material synthesis. In a typical material reactor, a precursor vapor reacts to form molecules of the desired material. In a cooling environment, a particulate phase forms, the dynamics of which are determined by the rates of

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

    Science.gov (United States)

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

    2014-10-07

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

  11. Evolution of Asian aerosols during transpacific transport in INTEX-B

    Energy Technology Data Exchange (ETDEWEB)

    Dunlea, E. J.; DeCarlo, Peter; Aiken, Allison; Kimmel, Joel; Peltier, R. E.; Weber, R. J.; Tomlinson, Jason M.; Collins, Donald R.; Shinozuka, Yohei; McNaughton, C. S.; Howell, S. G.; Clarke, A. D.; Emmons, L.; Apel, Eric; Pfister, G. G.; van Donkelaar, A.; Martin, R. V.; Millet, D. B.; Heald, C. L.; Jimenez, J. L.

    2009-10-01

    Measurements of aerosol composition were made with an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) on board the NSF/NCAR C-130 aircraft as part of the Intercontinental Chemical Transport Experiment Phase B 5 (INTEX-B) field campaign over the Eastern Pacific Ocean. The HR-ToF-AMS measurements of non-refractory submicron aerosol mass are shown to compare well with other aerosol instrumentation in the INTEX-B field study. Two case studies are described for pollution layers transported across the Pacific from the Asian continent, intercepted 3–4 days and 7–10 days downwind of Asia, respectively. Aerosol chemistry is shown to 10 be a robust tracer for air masses originating in Asia, specifically the presence of sulfate dominated aerosol is a distinguishing feature of Asian pollution layers that have been transported to the Eastern Pacific. We examine the time scales of processing for sulfate and organic aerosol in the atmosphere and show that our observations confirm a conceptual model for transpacific transport from Asia proposed by Brock et al. (2004). 15 Our observations of both sulfate and organic aerosol in aged Asian pollution layers are consistent with fast formation near the Asian continent, followed by washout during lofting and subsequent transformation during transport across the Pacific. Our observations are the first atmospheric measurements to indicate that although secondary organic aerosol (SOA) formation from pollution happens on the timescale of one day, 20 the oxidation of organic aerosol continues at longer timescales in the atmosphere. Comparisons with chemical transport models of data from the entire campaign reveal an under-prediction of SOA mass in the MOZART model, but much smaller discrepancies with the GEOS-Chem model than found in previous studies over the Western Pacific. No evidence is found to support a previous hypothesis for significant secondary 25 organic aerosol formation in the free troposphere.

  12. Seasonal variations of ultra-fine and submicron aerosols in Taipei, Taiwan: implications for particle formation processes in a subtropical urban area

    Directory of Open Access Journals (Sweden)

    H. C. Cheung

    2016-02-01

    Full Text Available The aim of this study is to investigate the seasonal variations in the physicochemical properties of atmospheric ultra-fine particles (UFPs, d ≤ 100 nm and submicron particles (PM1, d ≤ 1 µm in an east Asian urban area, which are hypothesized to be affected by the interchange of summer and winter monsoons. An observation experiment was conducted at TARO (Taipei Aerosol and Radiation Observatory, an urban aerosol station in Taipei, Taiwan, from October 2012 to August 2013. The measurements included the mass concentration and chemical composition of UFPs and PM1, as well as the particle number concentration (PNC and the particle number size distribution (PSD with size range of 4–736 nm. The results indicated that the mass concentration of PM1 was elevated during cold seasons with a peak level of 18.5 µg m−3 in spring, whereas the highest concentration of UFPs was measured in summertime with a mean of 1.64 µg m−3. Moreover, chemical analysis revealed that the UFPs and PM1 were characterized by distinct composition; UFPs were composed mostly of organics, whereas ammonium and sulfate were the major constituents of PM1. The seasonal median of total PNCs ranged from 13.9  ×  103 cm−3 in autumn to 19.4  ×  103 cm−3 in spring. Median concentrations for respective size distribution modes peaked in different seasons. The nucleation-mode PNC (N4 − 25 peaked at 11.6  ×  103 cm−3 in winter, whereas the Aitken-mode (N25 − 100 and accumulation-mode (N100 − 736 PNC exhibited summer maxima at 6.0  ×  103 and 3.1  ×  103 cm−3, respectively. The change in PSD during summertime was attributed to the enhancement in the photochemical production of condensable organic matter that, in turn, contributed to the growth of aerosol particles in the atmosphere. In addition, clear photochemical production of particles was observed, mostly in the summer season

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-06-30

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

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

    Directory of Open Access Journals (Sweden)

    J. G. Slowik

    2012-10-01

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

  15. Seasonal variations in high time-resolved chemical compositions, sources, and evolution of atmospheric submicron aerosols in the megacity Beijing

    Directory of Open Access Journals (Sweden)

    W. Hu

    2017-08-01

    Full Text Available A severe regional haze problem in the megacity Beijing and surrounding areas, caused by fast formation and growth of fine particles, has attracted much attention in recent years. In order to investigate the secondary formation and aging process of urban aerosols, four intensive campaigns were conducted in four seasons between March 2012 and March 2013 at an urban site in Beijing (116.31° E, 37.99° N. An Aerodyne high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS was deployed to measure non-refractory chemical components of submicron particulate matter (NR-PM1. The average mass concentrations of PM1 (NR-PM1+black carbon were 45.1 ± 45.8, 37.5 ± 31.0, 41.3 ± 42.7, and 81.7 ± 72.4 µg m−3 in spring, summer, autumn, and winter, respectively. Organic aerosol (OA was the most abundant component in PM1, accounting for 31, 33, 44, and 36 % seasonally, and secondary inorganic aerosol (SNA, sum of sulfate, nitrate, and ammonium accounted for 59, 57, 43, and 55 % of PM1 correspondingly. Based on the application of positive matrix factorization (PMF, the sources of OA were obtained, including the primary ones of hydrocarbon-like (HOA, cooking (COA, biomass burning OA (BBOA and coal combustion OA (CCOA, and secondary component oxygenated OA (OOA. OOA, which can be split into more-oxidized (MO-OOA and less-oxidized OOA (LO-OOA, accounted for 49, 69, 47, and 50 % in four seasons, respectively. Totally, the fraction of secondary components (OOA+SNA contributed about 60–80 % to PM1, suggesting that secondary formation played an important role in the PM pollution in Beijing, and primary sources were also non-negligible. The evolution process of OA in different seasons was investigated with multiple metrics and tools. The average carbon oxidation states and other metrics show that the oxidation state of OA was the highest in summer, probably due to both strong photochemical and aqueous-phase oxidations

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

    Science.gov (United States)

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

    2001-04-01

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

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

    Science.gov (United States)

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

    2005-12-01

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

  18. Complementary online aerosol mass spectrometry and offline FT-IR spectroscopy measurements: Prospects and challenges for the analysis of anthropogenic aerosol particle emissions

    Science.gov (United States)

    Faber, Peter; Drewnick, Frank; Bierl, Reinhard; Borrmann, Stephan

    2017-10-01

    The aerosol mass spectrometer (AMS) is well established in investigating highly time-resolved dynamics of submicron aerosol chemical composition including organic aerosol (OA). However, interpretation of mass spectra on molecular level is limited due to strong fragmentation of organic substances and potential reactions inside the AMS ion chamber. Results from complementary filter-based FT-IR absorption measurements were used to explain features in high-resolution AMS mass spectra of different types of OA (e.g. cooking OA, cigarette smoking OA, wood burning OA). Using this approach some AMS fragment ions were validated in this study as appropriate and rather specific markers for a certain class of organic compounds for all particle types under investigation. These markers can therefore be used to get deeper insights in the chemical composition of OA based on AMS mass spectra in upcoming studies. However, the specificity of other fragment ions such as C2H4O2+ (m/z 60.02114) remains ambiguous. In such cases, complementary FT-IR measurements allow the interpretation of highly time-resolved AMS mass spectra at the level of molecular functional groups. Furthermore, this study discusses the challenges in reducing inorganic interferences (e.g. from water and ammonium salts) in FT-IR spectra of atmospheric aerosols to decrease spectral uncertainties for better comparisons and, thus, to get more robust results.

  19. The uptake of HO2 radicals to organic aerosols

    Science.gov (United States)

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

    2014-05-01

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

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

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset contains data presented in the figures of the paper "On the implications of aerosol liquid water and phase separation for organic aerosol mass"...

  1. Characteristics and direct radiative effect of mid-latitude continental aerosols: the ARM case

    Directory of Open Access Journals (Sweden)

    M. G. Iziomon

    2003-01-01

    Full Text Available A multi-year field measurement analysis of the characteristics and direct radiative effect of aerosols at the Southern Great Plains (SGP central facility of the Atmospheric Radiation Measurement (ARM Program is presented. Inter-annual mean and standard deviation of submicrometer scattering fraction (at 550 nm and Ångström exponent å (450 nm, 700 nm at the mid-latitude continental site are indicative of the scattering dominance of fine mode aerosol particles, being 0.84±0.03 and 2.25±0.09, respectively. We attribute the diurnal variation of submicron aerosol concentration to coagulation, photochemistry and the evolution of the boundary layer. Precipitation does not seem to play a role in the observed afternoon maximum in aerosol concentration. Submicron aerosol mass at the site peaks in the summer (12.1±6.7mg m-3, with the summer value being twice that in the winter. Of the chemically analyzed ionic components (which exclude carbonaceous aerosols, SO4= and NH4+ constitute the dominant species at the SGP seasonally, contributing 23-30% and 9-12% of the submicron aerosol mass, respectively. Although a minor species, there is a notable rise in NO3- mass fraction in winter. We contrast the optical properties of dust and smoke haze. The single scattering albedo w0 shows the most remarkable distinction between the two aerosol constituents. We also present aircraft measurements of vertical profiles of aerosol optical properties at the site. Annually, the lowest 1.2 km contributes 70% to the column total light scattering coefficient. Column-averaged and surface annual mean values of hemispheric backscatter fraction (at 550 nm, w0 (at 550 nm and å (450 nm, 700 nm agree to within 5% in 2001. Aerosols produce a net cooling (most pronounced in the spring at the ARM site

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-08-31

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

  3. Overview and preliminary results of the Surface Ocean Aerosol Production (SOAP campaign

    Directory of Open Access Journals (Sweden)

    C. S. Law

    2017-11-01

    , contaminant markers and a common aerosol inlet facilitated multi-sensor measurement of uncontaminated air. Aerosol characterization identified variable Aitken mode and consistent submicron-sized accumulation and coarse modes. Submicron aerosol mass was dominated by secondary particles containing ammonium sulfate/bisulfate under light winds, with an increase in sea salt under higher wind speeds. MBL measurements and chamber experiments identified a significant organic component in primary and secondary aerosols. Comparison of SOAP aerosol number and size distributions reveals an underprediction in GLOMAP (GLObal Model of Aerosol Processes-mode aerosol number in clean marine air masses, suggesting a missing marine aerosol source in the model. The SOAP data will be further examined for evidence of nucleation events and also to identify relationships between MBL composition and surface ocean biogeochemistry that may provide potential proxies for aerosol precursors and production.

  4. Continuous measurements at the urban roadside in an Asian megacity by Aerosol Chemical Speciation Monitor (ACSM): particulate matter characteristics during fall and winter seasons in Hong Kong

    Science.gov (United States)

    Sun, C.; Lee, B. P.; Huang, D.; Jie Li, Y.; Schurman, M. I.; Louie, P. K. K.; Luk, C.; Chan, C. K.

    2016-02-01

    Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM) in the fall and winter seasons of 2013 on the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA), characterized by application of Positive Matrix Factorization (PMF), and sulfate are found to be dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear mealtime concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during mealtimes, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and the influence of continental air masses.

  5. Continuous measurements at the urban roadside in an Asian megacity by Aerosol Chemical Speciation Monitor (ACSM: particulate matter characteristics during fall and winter seasons in Hong Kong

    Directory of Open Access Journals (Sweden)

    C. Sun

    2016-02-01

    Full Text Available Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM in the fall and winter seasons of 2013 on the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA, characterized by application of Positive Matrix Factorization (PMF, and sulfate are found to be dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear mealtime concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during mealtimes, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and the influence of continental air masses.

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

    Directory of Open Access Journals (Sweden)

    M. R. Beaver

    2006-01-01

    Full Text Available Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C3 to C10 and ketones (C3 and C9 on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point were found to play a dominant role in determining the inferred mode of nucleation (homogenous or heterogeneous and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C4-C7, (of intermediate solubility and melting temperatures nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.

  7. Insights on organic aerosol aging and the influence of coal combustion at a regional receptor site of central eastern China

    Directory of Open Access Journals (Sweden)

    W. W. Hu

    2013-10-01

    Full Text Available In order to understand the aging and processing of organic aerosols (OA, an intensive field campaign (Campaign of Air Pollution at Typical Coastal Areas IN Eastern China, CAPTAIN was conducted March–April at a receptor site (a Changdao island in central eastern China. Multiple fast aerosol and gas measurement instruments were used during the campaign, including a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS that was applied to measure mass concentrations and non-refractory chemical components of submicron particles (PM1nr. The average mass concentration of PM1(PM1nr+black carbon was 47 ± 36 μg m−3 during the campaign and showed distinct variation, depending on back trajectories and their overlap with source regions. Organic aerosol (OA is the largest component of PM1 (30%, followed by nitrate (28%, sulfate (19%, ammonium (15%, black carbon (6%, and chloride (3%. Four OA components were resolved by positive matrix factorization (PMF of the high-resolution spectra, including low-volatility oxygenated organic aerosol (LV-OOA, semi-volatile oxygenated OA (SV-OOA, hydrocarbon-like OA (HOA and a coal combustion OA (CCOA. The mass spectrum of CCOA had high abundance of fragments from polycyclic aromatic hydrocarbons (PAHs (m/z 128, 152, 178, etc.. The average atomic ratio of oxygen to carbon in OA (O / C at Changdao was 0.59, which is comparable to other field studies reported at locations downwind of large pollution sources, indicating the oxidized nature of most OA during the campaign. The evolution of OA elemental composition in the van Krevelen diagram (H / C vs. O / C showed a slope of −0.63; however, the OA influenced by coal combustion exhibits a completely different evolution that appears dominated by physical mixing. The aging of organic aerosols vs. photochemical age was investigated. It was shown that OA / ΔCO, as well as LV-OOA / ΔCO and SV-OOA / ΔCO, positively correlated with photochemical age. LV

  8. Aerosol chemical composition at Cabauw, the Netherlands as observed in two intensive periods in May 2008 and March 2009

    NARCIS (Netherlands)

    Mensah, A.A.; Holzinger, R.; Otjes, R.; Trimborn, A.; Mentel, T.F.; Brink, H. ten; Henzing, B.; Kiendler-Scharr, A.

    2012-01-01

    Observations of aerosol chemical composition in Cabauw, the Netherlands, are presented for two intensive measurement periods in May 2008 and March 2009. Sub-micron aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and is compared to observations from aerosol

  9. Aerosol composition and sources in the central Arctic Ocean during ASCOS

    Science.gov (United States)

    Chang, R. Y.-W.; Leck, C.; Graus, M.; Müller, M.; Paatero, J.; Burkhart, J. F.; Stohl, A.; Orr, L. H.; Hayden, K.; Li, S.-M.; Hansel, A.; Tjernström, M.; Leaitch, W. R.; Abbatt, J. P. D.

    2011-10-01

    Measurements of submicron aerosol chemical composition were made over the central Arctic Ocean from 5 August to 8 September 2008 as a part of the Arctic Summer Cloud Ocean Study (ASCOS) using an aerosol mass spectrometer (AMS). The median levels of sulphate and organics for the entire study were 0.051 and 0.055 μ g m-3, respectively. Positive matrix factorisation was performed on the entire mass spectral time series and this enabled marine biogenic and continental sources of particles to be separated. These factors accounted for 33% and 36% of the sampled ambient aerosol mass, respectively, and they were both predominantly composed of sulphate, with 47% of the sulphate apportioned to marine biogenic sources and 48% to continental sources, by mass. Within the marine biogenic factor, the ratio of methane sulphonate to sulphate was 0.25 ± 0.02, consistent with values reported in the literature. The organic component of the continental factor was more oxidised than that of the marine biogenic factor, suggesting that it had a longer photochemical lifetime than the organics in the marine biogenic factor. The remaining ambient aerosol mass was apportioned to an organic-rich factor that could have arisen from a combination of marine and continental sources. In particular, given that the factor does not correlate with common tracers of continental influence, we cannot rule out that the organic factor arises from a primary marine source.

  10. Biomass burning and its effects on fine aerosol acidity, water content and nitrogen partitioning

    Science.gov (United States)

    Bougiatioti, Aikaterini; Nenes, Athanasios; Paraskevopoulou, Despina; Fourtziou, Luciana; Stavroulas, Iasonas; Liakakou, Eleni; Myriokefalitakis, Stelios; Daskalakis, Nikos; Weber, Rodney; Kanakidou, Maria; Gerasopoulos, Evangelos; Mihalopoulos, Nikolaos

    2017-04-01

    Aerosol acidity is an important property that drives the partitioning of semi-volatile species, the formation of secondary particulate matter and metal and nutrient solubility. Aerosol acidity varies considerably between aerosol types, RH, temperature, the degree of atmospheric chemical aging and may also change during transport. Among aerosol different sources, sea salt and dust have been well studied and their impact on aerosol acidity and water uptake is more or less understood. Biomass burning (BB) on the other hand, despite its significance as a source in a regional and global scale, is much less understood. Currently, there is no practical and accurate enough method, to directly measure the pH of in-situ aerosol. The combination of thermodynamic models, with targeted experimental observations can provide reliable predictions of aerosol particle water and pH, using as input the concentration of gas/aerosol species, temperature (T), and relative humidity (RH). As such an example, ISORROPIA-II (Fountoukis and Nenes, 2007) has been used for the thermodynamic analysis of measurements conducted in downtown Athens during winter 2013, in order to evaluate the effect of BB on aerosol water and acidity. Biomass burning, especially during night time, was found to contribute significantly to the increased organics concentrations, but as well to the BC component associated with wood burning, particulate nitrates, chloride, and potassium. These increased concentrations were found to impact on fine aerosol water, with Winorg having an average concentration of 11±14 μg m-3 and Worg 12±19 μg m-3 with the organic component constituting almost 38% of the total calculated submicron water. When investigating the fine aerosol acidity it was derived that aerosol was generally acidic, with average pH during strong BB influence of 2.8±0.5, value similar to the pH observed for regional aerosol influenced by important biomass burning episodes at the remote background site of

  11. The effect of changes in humidity on the size of submicron aerosols

    International Nuclear Information System (INIS)

    Phillips, C.R.; Khan, A.

    1987-06-01

    The effect of humidity on inhaled aerosols in the respiratory tract is to cause an increase in particle size of up to several times if the aerosol particle is hygroscopic. The presence of ionizing radiation and air ions (for example, from uranium and radon/thoron) increases the tendency of water vapour to nucleate. The desposition of particles in the lung is enhanced by high charge density (>10 charges/particle). Radon has been reported to play an important role in the formation of sulphate and nitrate particles in the atmosphere. A detailed overview of the effect of humidity on aerosols is presented in the present work. Results of experimental measurements made on NaCl (hygroscopic) and kerosene combustion (hydrophobic) aerosols under ambient and humid conditions are reported. Initial aerosol conditions were 20 degrees C and 35% R.H. Final aerosol conditions were maintained at 37 degrees C and 100% R.H. in order to simulate the conditions inside the respiratory tract. An average growth factor of 1.9 ± 0.4 (standard deviation) was observed for the NaCl aerosol and 1.3 ± 0.2 (standard deviation) for the kerosene aerosol. For the activity size distribution, however, the NaCl aerosols were observed to grow by an average factor of only 1.2 ± 0.1 (standard deviation) whereas the kerosene aerosols grew by a factor of 1.3 ± 0.2 (standard deviation)

  12. The relative importance of competing pathways for the formation of high-molecular-weight peroxides in the ozonolysis of organic aerosol particles

    Directory of Open Access Journals (Sweden)

    M. Mochida

    2006-01-01

    Full Text Available High-molecular-weight (HMW organic compounds are an important component of atmospheric particles, although their origins, possibly including in situ formation pathways, remain incompletely understood. This study investigates the formation of HMW organic peroxides through reactions involving stabilized Criegee intermediates (SCI's. The model system is methyl oleate (MO mixed with dioctyl adipate (DOA and myristic acid (MA in submicron aerosol particles, and Criegee intermediates are formed by the ozonolysis of the double bond in methyl oleate. An aerosol flow tube coupled to a quadrupole aerosol mass spectrometer (AMS is employed to determine the relative importance of different HMW organic peroxides following the ozonolysis of different mixing mole fractions of MO in DOA and MA. Possible peroxide products include secondary ozonides (SOZ's, α-acyloxyalkyl hydroperoxides and α-acyloxyalkyl alkyl peroxides (αAAHP-type compounds, diperoxides, and monoperoxide oligomers. Of these, the AMS data identify two SOZ's as major HMW products in the ozonolysis of pure methyl oleate as well as in an inert matrix of DOA to as low as 0.04 mole fraction MO. In comparison, in mixed particles of MO and MA, αAAHP-type compounds form in high yields for MO mole fractions of 0.5 or less, suggesting that SCI's efficiently attack the carboxylic acid group of myristic acid. The reactions of SCI's with carboxylic acid groups to form αAAHP-type compounds therefore compete with those of SCI's with aldehydes to form SOZ's, provided that both types of functionalities are present at significant concentrations. The results therefore suggest that SCI's in atmospheric particles contribute to the transformation of carboxylic acids and other protic groups into HMW organic peroxides.

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

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    I. S. A. Isaksen

    2007-11-01

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

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

    Directory of Open Access Journals (Sweden)

    B. H. Lee

    2010-12-01

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

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

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

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

    Science.gov (United States)

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

    2016-03-25

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

  16. Clouds and aerosols in Puerto Rico ─ a new evaluation

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    U. Dusek

    2008-03-01

    shifted from the ENE to ESE. Larger numbers of interstitial particles were recorded, most notably at sizes greater than 100 nm, which were absent during clean conditions. The average size of the residual particles and concentrations of cloudwater nitrate, sulphate and insoluble material increased during polluted conditions. Previous studies in Puerto Rico had reported the presence of a significant non-anthropogenic organic fraction in the aerosols measured and concluded that this was a factor controlling the in situ cloud properties. However, this was not observed in our case. In contrast to the 1.00±0.14 μg m−3 of organic carbon measured in 1992 and 1995, the organic matter measured in the current study of 0.17±0.35 μg m−3 is many times lower, most of which can be attributed to anthropogenic sources. During clean conditions, the submicron aerosol was observed to be almost entirely inorganic, an observation supported by the hygroscopicity measurements. This suggests that organic aerosols from marine sources may not be completely ubiquitous (either spatially or temporally in this environment and requires further investigation to quantify their true extent and implications, with more extensive, longer-term sampling in conjunction with wind field analyses.

  17. Real-Time Measurement of Electronic Cigarette Aerosol Size Distribution and Metals Content Analysis.

    Science.gov (United States)

    Mikheev, Vladimir B; Brinkman, Marielle C; Granville, Courtney A; Gordon, Sydney M; Clark, Pamela I

    2016-09-01

    Electronic cigarette (e-cigarette) use is increasing worldwide and is highest among both daily and nondaily smokers. E-cigarettes are perceived as a healthier alternative to combustible tobacco products, but their health risk factors have not yet been established, and one of them is lack of data on aerosol size generated by e-cigarettes. We applied a real-time, high-resolution aerosol differential mobility spectrometer to monitor the evolution of aerosol size and concentration during puff development. Particles generated by e-cigarettes were immediately delivered for analysis with minimal dilution and therefore with minimal sample distortion, which is critically important given the highly dynamic aerosol/vapor mixture inherent to e-cigarette emissions. E-cigarette aerosols normally exhibit a bimodal particle size distribution: nanoparticles (11-25nm count median diameter) and submicron particles (96-175nm count median diameter). Each mode has comparable number concentrations (10(7)-10(8) particles/cm(3)). "Dry puff" tests conducted with no e-cigarette liquid (e-liquid) present in the e-cigarette tank demonstrated that under these conditions only nanoparticles were generated. Analysis of the bulk aerosol collected on the filter showed that e-cigarette emissions contained a variety of metals. E-cigarette aerosol size distribution is different from that of combustible tobacco smoke. E-cigarettes generate high concentrations of nanoparticles and their chemical content requires further investigation. Despite the small mass of nanoparticles, their toxicological impact could be significant. Toxic chemicals that are attached to the small nanoparticles may have greater adverse health effects than when attached to larger submicron particles. The e-cigarette aerosol size distribution is different from that of combustible tobacco smoke and typically exhibits a bimodal behavior with comparable number concentrations of nanoparticles and submicron particles. While vaping the e

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-08-23

    Significantly improved returns in their aerosol chemistry data can be achieved via the development of a value-added product (VAP) of deriving OA components, called Organic Aerosol Components (OACOMP). OACOMP is primarily based on multivariate analysis of the measured organic mass spectral matrix. The key outputs of OACOMP are the concentration time series and the mass spectra of OA factors that are associated with distinct sources, formation and evolution processes, and physicochemical properties.

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

    Directory of Open Access Journals (Sweden)

    H.-P. Dorn

    2009-02-01

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

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

    Science.gov (United States)

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

    2011-02-01

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

  1. Overview of aerosol properties associated with air masses sampled by the ATR-42 during the EUCAARI campaign (2008

    Directory of Open Access Journals (Sweden)

    S. Crumeyrolle

    2013-05-01

    Full Text Available Within the frame of the European Aerosol Cloud Climate and Air Quality Interactions (EUCAARI project, the Météo-France aircraft ATR-42 performed 22 research flights over central Europe and the North Sea during the intensive observation period in May 2008. For the campaign, the ATR-42 was equipped to study the aerosol physical, chemical, hygroscopic and optical properties, as well as cloud microphysics. For the 22 research flights, retroplume analyses along the flight tracks were performed with FLEXPART in order to classify air masses into five sectors of origin, allowing for a qualitative evaluation of emission influence on the respective air parcel. This study shows that the extensive aerosol parameters (aerosol mass and number concentrations show vertical decreasing gradients and in some air masses maximum mass concentrations (mainly organics in an intermediate layer (1–3 km. The observed mass concentrations (in the boundary layer (BL: between 10 and 30 μg m−3; lower free troposphere (LFT: 0.8 and 14 μg m−3 are high especially in comparison with the 2015 European norms for PM2.5 (25 μg m−3 and with previous airborne studies performed over England (Morgan et al., 2009; McMeeking et al., 2012. Particle number size distributions show a larger fraction of particles in the accumulation size range in the LFT compared to BL. The chemical composition of submicron aerosol particles is dominated by organics in the BL, while ammonium sulphate dominates the submicron aerosols in the LFT, especially in the aerosol particles originated from north-eastern Europe (~ 80%, also experiencing nucleation events along the transport. As a consequence, first the particle CCN acting ability, shown by the CCN/CN ratio, and second the average values of the scattering cross sections of optically active particles (i.e. scattering coefficient divided by the optical active particle concentration are increased in the LFT compared to BL.

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

    Directory of Open Access Journals (Sweden)

    P. Q. Fu

    2013-02-01

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

  3. Characterization of aerosol chemical composition with aerosol mass spectrometry in Central Europe: an overview

    Directory of Open Access Journals (Sweden)

    V. A. Lanz

    2010-11-01

    Full Text Available Real-time measurements of non-refractory submicron aerosols (NR-PM1 were conducted within the greater Alpine region (Switzerland, Germany, Austria, France and Liechtenstein during several week-long field campaigns in 2002–2009. This region represents one of the most important economic and recreational spaces in Europe. A large variety of sites was covered including urban backgrounds, motorways, rural, remote, and high-alpine stations, and also mobile on-road measurements were performed. Inorganic and organic aerosol (OA fractions were determined by means of aerosol mass spectrometry (AMS. The data originating from 13 different field campaigns and the combined data have been utilized for providing an improved temporal and spatial data coverage.

    The average mass concentration of NR-PM1 for the different campaigns typically ranged between 10 and 30 μg m−3. Overall, the organic portion was most abundant, ranging from 36% to 81% of NR-PM1. Other main constituents comprised ammonium (5–15%, nitrate (8–36%, sulfate (3–26%, and chloride (0–5%. These latter anions were, on average, fully neutralized by ammonium. As a major result, time of the year (winter vs. summer and location of the site (Alpine valleys vs. Plateau could largely explain the variability in aerosol chemical composition for the different campaigns and were found to be better descriptors for aerosol composition than the type of site (urban, rural etc.. Thus, a reassessment of classifications of measurements sites might be considered in the future, possibly also for other regions of the world.

    The OA data was further analyzed using positive matrix factorization (PMF and the multi-linear engine ME (factor analysis separating the total OA into its underlying components, such as oxygenated (mostly secondary organic aerosol (OOA, hydrocarbon-like and freshly emitted organic aerosol (HOA, as well as OA from biomass

  4. Chemical composition, sources and evolution processes of aerosol at an urban site in Yangtze River Delta, China during wintertime

    Science.gov (United States)

    Zhang, Yunjiang; Tang, Lili; Yu, Hongxia; Wang, Zhuang; Sun, Yele; Qin, Wei; Chen, Wentai; Chen, Changhong; Ding, Aijun; Wu, Jing; Ge, Shun; Chen, Cheng; Zhou, Hong-cang

    2015-12-01

    To investigate the composition, sources and evolution processes of submicron aerosol during wintertime, a field experiment was conducted during December 1-31, 2013 in urban Nanjing, a megacity in Yangtze River Delta of China. Non-refractory submicron aerosol (NR-PM1) species were measured with an Aerodyne Aerosol Chemical Speciation Monitor. NR-PM1 is dominated by secondary inorganic aerosol (55%) and organic aerosol (OA, 42%) during haze periods. Six OA components were identified by positive matrix factorization of the OA mass spectra. The hydrocarbon-like OA and cooking-related OA represent the local traffic and cooking sources, respectively. A highly oxidized factor related to biomass burning OA accounted for 15% of the total OA mass during haze periods. Three types of oxygenated OA (OOA), i.e., a less-oxidized OOA (LO-OOA), a more-oxidized OOA (MO-OOA), and a low-volatility OOA (LV-OOA), were identified. LO-OOA is likely associated with fresh urban secondary OA. MO-OOA likely represents photochemical products showing a similar diurnal cycle to nitrate with a pronounced noon peak. LV-OOA appears to be a more oxidized factor with a pronounced noon peak. The OA composition is dominated by secondary species, especially during haze events. LO-OOA, MO-OOA and LV-OOA on average account for 11%, (18%), 24% (21%) and 23% (18%) of the total OA mass for the haze (clean) periods respectively. Analysis of meteorological influence suggested that regional transport from the northern and southeastern areas of the city is responsible for large secondary and low-volatility aerosol formation.

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

    Science.gov (United States)

    Glotfelty, Timothy; He, Jian; Zhang, Yang

    2017-06-01

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

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

    Science.gov (United States)

    Fu, P.; Kawamura, K.

    2017-12-01

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

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

    Directory of Open Access Journals (Sweden)

    L. D. Yee

    2013-08-01

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

  8. Real-Time Characterization of Aerosol Particle Composition above the Urban Canopy in Beijing: Insights into the Interactions between the Atmospheric Boundary Layer and Aerosol Chemistry.

    Science.gov (United States)

    Sun, Yele; Du, Wei; Wang, Qingqing; Zhang, Qi; Chen, Chen; Chen, Yong; Chen, Zhenyi; Fu, Pingqing; Wang, Zifa; Gao, Zhiqiu; Worsnop, Douglas R

    2015-10-06

    Despite extensive efforts into the characterization of air pollution during the past decade, real-time characterization of aerosol particle composition above the urban canopy in the megacity Beijing has never been performed to date. Here we conducted the first simultaneous real-time measurements of aerosol composition at two different heights at the same location in urban Beijing from December 19, 2013 to January 2, 2014. The nonrefractory submicron aerosol (NR-PM1) species were measured in situ by a high-resolution aerosol mass spectrometer at near-ground level and an aerosol chemical speciation monitor at 260 m on a 325 m meteorological tower in Beijing. Secondary aerosol showed similar temporal variations between ground level and 260 m, whereas much weaker correlations were found for the primary aerosol. The diurnal evolution of the ratios and correlations of aerosol species between 260 m and the ground level further illustrated a complex interaction between vertical mixing processes and local source emissions on aerosol chemistry in the atmospheric boundary layer. As a result, the aerosol compositions at the two heights were substantially different. Organic aerosol (OA), mainly composed of primary OA (62%), at the ground level showed a higher contribution to NR-PM1 (65%) than at 260 m (54%), whereas a higher concentration and contribution (15%) of nitrate was observed at 260 m, probably due to the favorable gas-particle partitioning under lower temperature conditions. In addition, two different boundary layer structures were observed, each interacting differently with the evolution processes of aerosol chemistry.

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

    Science.gov (United States)

    Russell, L. M.

    2017-12-01

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

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

    Science.gov (United States)

    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

  11. Dynamic-chemistry-aerosol modelling interaction: the ESCOMPTE 2001 experiment; Modelisation de l'interaction dynamique- chimie - aerosol: campagne ESCOMPTE 2001

    Energy Technology Data Exchange (ETDEWEB)

    Cousin, F

    2004-09-01

    After most pollution studies independently devoted to gases and aerosols, there now appears an urgent need to consider their interactions. In this view, an aerosol module has been implemented in the Meso-NH-C model to simulate two IOPs documented during the ESCOMPTE campaign which took place in the Marseille/Fos-Berre region in June-July 2001. First, modelled dynamic parameters (winds, temperatures, boundary layer thickness) and gaseous chemistry have been validated with measurements issued from the exhaustive ESCOMPTE database. Sensitivity analysis have also been performed using different gaseous emission inventories at various resolution. These simulations have illustrated the deep impact of both synoptic and local dynamics on observed ozone concentrations on June 24 (IOP2b) in the ESCOMPTE domain. Afterwards, the ORISAM aerosol module has been introduced into the Meso-NH-C model. Dynamics, gaseous chemistry and aerosol processes have thus been coupled on-line. The particulate pollution episode on June 24 (IOP2b) has been characterised through a satisfactory comparison, specially from sub-micron particles, between modelling and measurements at different representative stations in the domain. This study, with validation of the particulate emission inventory has also highlighted the need for future improvements, such as further characterisation of organic and inorganic aerosol species and consideration of coarse particles. Aerosol impact on gaseous chemistry has been preliminary approached in view of future development and modification to be given to the Meso-NH-C model. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-12-02

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

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

    Science.gov (United States)

    Glotfelty, Timothy; He, Jian

    2017-01-01

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

  14. Ambient Aerosols in the Southern Hemisphere on Ascension Island during the LASIC Campaign: Biomass Burning Season versus Near Pristine Background Conditions

    Science.gov (United States)

    Aiken, A. C.; Springston, S. R.; Watson, T. B.; Sedlacek, A. J., III; Zuidema, P.; Adebiyi, A. A.; Uin, J.; Kuang, C.; Flynn, C. J.

    2017-12-01

    Ascension Island is located 8 degrees South of the Equator and 15 degrees West Longitude in the middle of the South Atlantic Ocean, at least 1000 miles from any major shoreline and closest to the continent of Africa. While low Southern Hemisphere background aerosol and trace gas measurements are observed most of the year, that picture changes during the South African Biomass Burning (BB) season. BB emissions are a large source of carbon to the atmosphere via particles and gas phase species and with a potential rise in drought and extreme events in the future, these numbers are expected to increase. From approximately June-October every year, the plume of South African BB emissions, the largest BB source in the world, are advected West and are known to impact both the boundary layer and free troposphere at Ascension Island (Zuidema et al., 2016). During the U.S. DOE ARM field campaign, Layered Atlantic Smoke Interactions with Clouds (LASIC), aerosol and trace gas measurements were collected continuously from June 2016 through October 2017 over a 1.5 year period. Two BB seasons are contrasted with the near pristine background conditions during the campaign from the ARM Aerosol Mobile Facility 1 (AMF1) and Mobile Aerosol Observing System (MAOS). Numerous direct in situ aerosol and trace gas measurements are presented, e.g. black carbon (BC), carbon monoxide (CO), PM1 and PM10 aerosol absorption and scattering, submicron non-refractory chemical composition (Organics, Sulfate, Nitrate, Ammonium, Chloride), etc. Aerosol and trace gas signatures are investigated along with backtrajectories to identify sources. Carbonaceous aerosols emitted with gas-phase CO are used to determine particulate emission ratios along with intrinsic and extrinsic aerosol properties. BC mass concentrations reach 1 µg m-3 during multiday plumes and exceed 25% of the total aerosol submicron mass concentration. Organic Aerosol (OA) to BC Ratios of 2.4 in the plume are much higher than previously

  15. A global perspective on aerosol from low-volatility organic compounds

    Directory of Open Access Journals (Sweden)

    H. O. T. Pye

    2010-05-01

    Full Text Available Global production of organic aerosol from primary emissions of semivolatile (SVOCs and intermediate (IVOCs volatility organic compounds is estimated using the global chemical transport model, GEOS-Chem. SVOC oxidation is predicted to be a larger global source of net aerosol production than oxidation of traditional parent hydrocarbons (terpenes, isoprene, and aromatics. Using a prescribed rate constant and reduction in volatility for atmospheric oxidation, the yield of aerosol from SVOCs is predicted to be about 75% on a global, annually-averaged basis. For IVOCs, the use of a naphthalene-like surrogate with different high-NOx and low-NOx parameterizations produces a global aerosol yield of about 30%, or roughly 5 Tg/yr of aerosol. Estimates of the total global organic aerosol source presented here range between 60 and 100 Tg/yr. This range reflects uncertainty in the parameters for SVOC volatility, SVOC oxidation, SVOC emissions, and IVOC emissions, as well as wet deposition. The highest estimates result if SVOC emissions are significantly underestimated (by more than a factor of 2 or if wet deposition of the gas-phase semivolatile species is less effective than previous estimates. A significant increase in SVOC emissions, a reduction of the volatility of the SVOC emissions, or an increase in the enthalpy of vaporization of the organic aerosol all lead to an appreciable reduction of prediction/measurement discrepancy. In addition, if current primary organic aerosol (POA inventories capture only about one-half of the SVOC emission and the Henrys Law coefficient for oxidized semivolatiles is on the order of 103 M/atm, a global estimate of OA production is not inconsistent with the top-down estimate of 140 Tg/yr by (Goldstein and Galbally, 2007. Additional information is needed to constrain the emissions and treatment of SVOCs and IVOCs, which have traditionally not been included in models.

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

    OpenAIRE

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

    2018-01-01

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

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

    Science.gov (United States)

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

    2018-03-01

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

  18. Secondary organic aerosol formation from road vehicle emissions

    Science.gov (United States)

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

    2014-05-01

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

  19. Emissions of Black Carbon, Organic, and Inorganic Aerosols From Biomass Burning in North America and Asia in 2008

    Science.gov (United States)

    Kondo, Y.; Matsui, H.; Moteki, N.; Sahu, L.; Takegawa, N.; Kajino, M.; Zhao, Y.; Cubison, M. J.; Jimenez, J. L.; Vay, S.; hide

    2011-01-01

    Reliable assessment of the impact of aerosols emitted from boreal forest fires on the Arctic climate necessitates improved understanding of emissions and the microphysical properties of carbonaceous (black carbon (BC) and organic aerosols (OA)) and inorganic aerosols. The size distributions of BC were measured by an SP2 based on the laser-induced incandescence technique on board the DC-8 aircraft during the NASA ARCTAS campaign. Aircraft sampling was made in fresh plumes strongly impacted by wildfires in North America (Canada and California) in summer 2008 and in those transported from Asia (Siberia in Russia and Kazakhstan) in spring 2008. We extracted biomass burning plumes using particle and tracer (CO, CH3CN, and CH2Cl2) data. OA constituted the dominant fraction of aerosols mass in the submicron range. The large majority of the emitted particles did not contain BC. We related the combustion phase of the fire as represented by the modified combustion efficiency (MCE) to the emission ratios between BC and other species. In particular, we derived the average emission ratios of BC/CO = 2.3 +/- 2.2 and 8.5 +/- 5.4 ng/cu m/ppbv for BB in North America and Asia, respectively. The difference in the BC/CO emission ratios is likely due to the difference in MCE. The count median diameters and geometric standard deviations of the lognormal size distribution of BC in the BB plumes were 136-141 nm and 1.32-1.36, respectively, and depended little on MCE. These BC particles were thickly coated, with shell/core ratios of 1.3-1.6. These parameters can be used directly for improving model estimates of the impact of BB in the Arctic.

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

    Directory of Open Access Journals (Sweden)

    N. Sareen

    2010-02-01

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

  1. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-19

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

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

    Science.gov (United States)

    Hutchings, James W., III

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

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

    Directory of Open Access Journals (Sweden)

    C. Zhu

    2016-06-01

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

  4. Effect of phytoplackton-derived organic matter on the behavior of marine aerosols

    Science.gov (United States)

    Fuentes, E.; Coe, H.; McFiggans, G.; Green, D.

    2009-04-01

    The presence of significant concentrations of organic material in marine aerosols has been appreciated for several decades; however, only recently has significant progress been made towards demonstrating that this organic content is biogenically formed. Biogenic organics of placktonic life origin are incorporated in marine aerosol composition as a result of bubble bursting/breaking waves mechanisms that occur at the ocean surface. The presence of organic surfactants in the marine aerosol composition might have a significant impact on the properties of the generated aerosols by affecting the particles surface tension and solution balance properties. Nevertheless, it remains uncertain the role of such organics on the physical-chemical behavior of marine aerosols. In this work an experimental study was performed in order to determine the influence of biogenic marine organic compounds on the size distribution, hygroscopicity and cloud-nucleating properties of marine aerosols. For the experimental study a laboratory water recirculation system (bubble tank), designed for the simulation of bubble-burst aerosol formation, was used as marine aerosol generator. The bubble spectra produced by such system was characterized by means of an optical bubble measuring device (BMS) and it was found to be consistent with oceanic bubble spectra properties. Seawater proxy solutions were prepared from laboratory biologically-synthesized exudates produced by oceanic representative algal species and introduced in the tank for the generation of marine aerosol by bubble bursting. Two experimental methods were employed for seawater proxies preparation: the formation of surface monolayers from the biogenic surfactants extracted by a solid phase extraction technique (monolayer method) and the mixing of the exudates in the sea salt water bulk (bulk mixing method). Particle size distribution, hygroscopicity and cloud condensation nuclei experiments for different monolayers, and exudate mixtures

  5. Annual cycle of size-resolved organic aerosol characterization in an urbanized desert environment

    Science.gov (United States)

    Cahill, Thomas M.

    2013-06-01

    Studies of size-resolved organic speciation of aerosols are still relatively rare and are generally only conducted over short durations. However, size-resolved organic data can both suggest possible sources of the aerosols and identify the human exposure to the chemicals since different aerosol sizes have different lung capture efficiencies. The objective of this study was to conduct size-resolved organic aerosol speciation for a calendar year in Phoenix, Arizona to determine the seasonal variations in both chemical concentrations and size profiles. The results showed large seasonal differences in combustion pollutants where the highest concentrations were observed in winter. Summertime aerosols have a greater proportion of biological compounds (e.g. sugars and fatty acids) and the biological compounds represent the largest fraction of the organic compounds detected. These results suggest that standard organic carbon (OC) measurements might be heavily influenced by primary biological compounds particularly if the samples are PM10 and TSP samples. Several large dust storms did not significantly alter the organic aerosol profile since Phoenix resides in a dusty desert environment, so the soil and plant tracer of trehalose was almost always present. The aerosol size profiles showed that PAHs were generally most abundant in the smallest aerosol size fractions, which are most likely to be captured by the lung, while the biological compounds were almost exclusively found in the coarse size fraction.

  6. Organic Aerosols as Cloud Condensation Nuclei

    Science.gov (United States)

    Hudson, J. G.

    2002-05-01

    The large organic component of the atmospheric aerosol contributes to both natural and anthropogenic cloud condensation nuclei (CCN). Moreover, some organic substances may reduce droplet surface tension (Facchini et al. 1999), while others may be partially soluble (Laaksonen et al. 1998), and others may inhibit water condensation. The interaction of organics with water need to be understood in order to better understand the indirect aerosol effect. Therefore, laboratory CCN spectral measurements of organic aerosols are presented. These are measurements of the critical supersaturation (Sc), the supersaturation needed to produce an activated cloud droplet, as a function of the size of the organic particles. Substances include sodium lauryl (dodecyl) sulfate, oxalic, adipic, pinonic, hexadecanedioic, glutaric, stearic, succinic, phthalic, and benzoic acids. These size-Sc relationships are compared with theoretical and measured size-Sc relationships of common inorganic compounds (e.g., NaCl, KI, ammonium and calcium sulfate). Unlike most inorganics some organics display variations in solubility per unit mass as a function of particle size. Those showing relatively greater solubility at smaller sizes may be attributable to surface tension reduction, which is greater for less water dilution, as is the case for smaller particles, which are less diluted at the critical sizes. This was the case for sodium dodecyl sulfate, which does reduce surface tension. Relatively greater solubility for larger particles may be caused by greater dissolution at the higher dilutions that occur with larger particles; this is partial solubility. Measurements are also presented of internal mixtures of various organic and inorganic substances. These measurements were done with two CCN spectrometers (Hudson 1989) operating simultaneously. These two instruments usually displayed similar results in spite of the fact that they have different flow rates and supersaturation profiles. The degree of

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

    Science.gov (United States)

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

    2004-01-01

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

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

    Directory of Open Access Journals (Sweden)

    J. Ofner

    2012-07-01

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

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

  9. Aerosol source apportionment from 1-year measurements at the CESAR tower in Cabauw, the Netherlands

    Directory of Open Access Journals (Sweden)

    P. Schlag

    2016-07-01

    Full Text Available Intensive measurements of submicron aerosol particles and their chemical composition were performed with an Aerosol Chemical Speciation Monitor (ACSM at the Cabauw Experimental Site for Atmospheric Research (CESAR in Cabauw, the Netherlands, sampling at 5 m height above ground. The campaign lasted nearly 1 year from July 2012 to June 2013 as part of the EU-FP7-ACTRIS project (Q-ACSM Network. Including equivalent black carbon an average particulate mass concentration of 9.50 µg m−3 was obtained during the whole campaign with dominant contributions from ammonium nitrate (45 %, organic aerosol (OA, 29 %, and ammonium sulfate (19 %. There were 12 exceedances of the World Health Organization (WHO PM2.5 daily mean limit (25 µg m−3 observed at this rural site using PM1 instrumentation only. Ammonium nitrate and OA represented the largest contributors to total particulate matter during periods of exceedance. Source apportionment of OA was performed season-wise by positive matrix factorization (PMF using the multilinear engine 2 (ME-2 controlled via the source finder (SoFi. Primary organic aerosols were attributed mainly to traffic (8–16 % contribution to total OA, averaged season-wise and biomass burning (0–23 %. Secondary organic aerosols (SOAs, 61–84 % dominated the organic fraction during the whole campaign, particularly on days with high mass loadings. A SOA factor which is attributed to humic-like substances (HULIS was identified as a highly oxidized background aerosol in Cabauw. This shows the importance of atmospheric aging processes for aerosol concentration at this rural site. Due to the large secondary fraction, the reduction of particulate mass at this rural site is challenging on a local scale.

  10. Aerosol chemical composition at Cabauw, The Netherlands as observed in two intensive periods in May 2008 and March 2009

    Science.gov (United States)

    Mensah, A. A.; Holzinger, R.; Otjes, R.; Trimborn, A.; Mentel, Th. F.; ten Brink, H.; Henzing, B.; Kiendler-Scharr, A.

    2012-05-01

    Observations of aerosol chemical composition in Cabauw, the Netherlands, are presented for two intensive measurement periods in May 2008 and March 2009. Sub-micron aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and is compared to observations from aerosol size distribution measurements as well as composition measurements with a Monitor for AeRosol and GAses (MARGA) based instrument and a Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometer (TD-PTR-MS). An overview of the data is presented and the data quality is discussed. In May 2008 enhanced pollution was observed with organics contributing 40% to the PM1 mass. In contrast the observed average mass loading was lower in March 2009 and a dominance of ammonium nitrate (42%) was observed. The semi-volatile nature of ammonium nitrate is evident in the diurnal cycles with maximum concentrations observed in the morning hours in May 2008 and little diurnal variation observed in March 2009. Size dependent composition data from AMS measurements are presented and show a dominance of organics in the size range below 200 nm. A higher O:C ratio of the organics is observed for May 2008 than for March 2009. Together with the time series of individual tracer ions this shows the dominance of OOA over HOA in May 2008.

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

    Science.gov (United States)

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

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

  12. Observations of gas- and aerosol-phase organic nitrates at BEACHON-RoMBAS 2011

    Directory of Open Access Journals (Sweden)

    J. L. Fry

    2013-09-01

    Full Text Available At the Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS field campaign in the Colorado front range, July–August 2011, measurements of gas- and aerosol-phase organic nitrates enabled a study of the role of NOx (NOx = NO + NO2 in oxidation of forest-emitted volatile organic compounds (VOCs and subsequent aerosol formation. Substantial formation of peroxy- and alkyl-nitrates is observed every morning, with an apparent 2.9% yield of alkyl nitrates from daytime RO2 + NO reactions. Aerosol-phase organic nitrates, however, peak in concentration during the night, with concentrations up to 140 ppt as measured by both optical spectroscopic and mass spectrometric instruments. The diurnal cycle in aerosol fraction of organic nitrates shows an equilibrium-like response to the diurnal temperature cycle, suggesting some reversible absorptive partitioning, but the full dynamic range cannot be reproduced by thermodynamic repartitioning alone. Nighttime aerosol organic nitrate is observed to be positively correlated with [NO2] × [O3] but not with [O3]. These observations support the role of nighttime NO3-initiated oxidation of monoterpenes as a significant source of nighttime aerosol. Nighttime production of organic nitrates is comparable in magnitude to daytime photochemical production at this site, which we postulate to be representative of the Colorado front range forests.

  13. Organic aerosol formation in citronella candle plumes

    OpenAIRE

    Bothe, Melanie; Donahue, Neil McPherson

    2010-01-01

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

  14. Lipid organics in background aerosols, cloudwater, and snow and implication for organic scavenging

    International Nuclear Information System (INIS)

    Groellert, C.

    1998-01-01

    During three years free tropospheric snow, aerosol, and cloudwater samples were collected at Mount Sonnblick, Austria, at an elevation of 3106 m a.s.l. The samples were analyzed for their lipid organic trace components using extraction with n-hexane as sample pretreatment and gas chromatography-mass spectrometry-flame ionization detection for identification and quantification of the substances. The main components identified in all the samples were the phthalic acid esters which are of anthropogenic origin. Of further interest were aliphatic alcohols (not detected in aerosols) and phenols. They are of biogenic origin. The concentrations were found to be higher in spring than in the fall season. To compare the concentrations of aerosol, cloudwater and snow samples scavenging ratios (aerosol to snow), scavenging efficiencies (aerosol to cloud) and cloud to snow ratios were calculated for the first time for organic compounds. Scavenging ratios were 10 to 100 times lower, scavenging efficiencies 2 to 10 times lower than sulfate. This can result from the poor watersolubility of the compounds or from gas phase sorptions on the filter surface (overestimation of aerosol concentrations). The cloud to snow ratios were generally higher than for sulfate. However, a few components exhibited very low cloud to snow ratios which might be due to additional sources in snow for these substances (alcohols). (author)

  15. Causes and consequences of decreasing atmospheric organic aerosol in the United States

    Science.gov (United States)

    Ridley, D. A.; Heald, C. L.; Ridley, K. J.; Kroll, J. H.

    2018-01-01

    Exposure to atmospheric particulate matter (PM) exacerbates respiratory and cardiovascular conditions and is a leading source of premature mortality globally. Organic aerosol contributes a significant fraction of PM in the United States. Here, using surface observations between 1990 and 2012, we show that organic carbon has declined dramatically across the entire United States by 25–50%; accounting for more than 30% of the US-wide decline in PM. The decline is in contrast with the increasing organic aerosol due to wildfires and no clear trend in biogenic emissions. By developing a carbonaceous emissions database for the United States, we show that at least two-thirds of the decline in organic aerosol can be explained by changes in anthropogenic emissions, primarily from vehicle emissions and residential fuel burning. We estimate that the decrease in anthropogenic organic aerosol is responsible for averting 180,000 (117,000–389,000) premature deaths between 1990 and 2012. The unexpected decrease in organic aerosol, likely a consequence of the implementation of Clean Air Act Amendments, results in 84,000 (30,000–164,000) more lives saved than anticipated by the EPA between 2000 and 2010.

  16. Predicting Thermal Behavior of Secondary Organic Aerosols

    Data.gov (United States)

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

  17. Dynamic-chemistry-aerosol modelling interaction: the ESCOMPTE 2001 experiment

    International Nuclear Information System (INIS)

    Cousin, F.

    2004-09-01

    After most pollution studies independently devoted to gases and aerosols, there now appears an urgent need to consider their interactions. In this view, an aerosol module has been implemented in the Meso-NH-C model to simulate two IOPs documented during the ESCOMPTE campaign which took place in the Marseille/Fos-Berre region in June-July 2001. First, modelled dynamic parameters (winds, temperatures, boundary layer thickness) and gaseous chemistry have been validated with measurements issued from the exhaustive ESCOMPTE database. Sensitivity analysis have also been performed using different gaseous emission inventories at various resolution. These simulations have illustrated the deep impact of both synoptic and local dynamics on observed ozone concentrations on June 24 (IOP2b) in the ESCOMPTE domain. Afterwards, the ORISAM aerosol module has been introduced into the Meso-NH-C model. Dynamics, gaseous chemistry and aerosol processes have thus been coupled on-line. The particulate pollution episode on June 24 (IOP2b) has been characterised through a satisfactory comparison, specially from sub-micron particles, between modelling and measurements at different representative stations in the domain. This study, with validation of the particulate emission inventory has also highlighted the need for future improvements, such as further characterisation of organic and inorganic aerosol species and consideration of coarse particles. Aerosol impact on gaseous chemistry has been preliminary approached in view of future development and modification to be given to the Meso-NH-C model. (author)

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

    Science.gov (United States)

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

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

    Science.gov (United States)

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

    2017-06-01

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

  20. Scalable Sub-micron Patterning of Organic Materials Toward High Density Soft Electronics.

    Science.gov (United States)

    Kim, Jaekyun; Kim, Myung-Gil; Kim, Jaehyun; Jo, Sangho; Kang, Jingu; Jo, Jeong-Wan; Lee, Woobin; Hwang, Chahwan; Moon, Juhyuk; Yang, Lin; Kim, Yun-Hi; Noh, Yong-Young; Jaung, Jae Yun; Kim, Yong-Hoon; Park, Sung Kyu

    2015-09-28

    The success of silicon based high density integrated circuits ignited explosive expansion of microelectronics. Although the inorganic semiconductors have shown superior carrier mobilities for conventional high speed switching devices, the emergence of unconventional applications, such as flexible electronics, highly sensitive photosensors, large area sensor array, and tailored optoelectronics, brought intensive research on next generation electronic materials. The rationally designed multifunctional soft electronic materials, organic and carbon-based semiconductors, are demonstrated with low-cost solution process, exceptional mechanical stability, and on-demand optoelectronic properties. Unfortunately, the industrial implementation of the soft electronic materials has been hindered due to lack of scalable fine-patterning methods. In this report, we demonstrated facile general route for high throughput sub-micron patterning of soft materials, using spatially selective deep-ultraviolet irradiation. For organic and carbon-based materials, the highly energetic photons (e.g. deep-ultraviolet rays) enable direct photo-conversion from conducting/semiconducting to insulating state through molecular dissociation and disordering with spatial resolution down to a sub-μm-scale. The successful demonstration of organic semiconductor circuitry promise our result proliferate industrial adoption of soft materials for next generation electronics.

  1. Properties of submicron particles in Atmospheric Brown Clouds

    Science.gov (United States)

    Adushkin, V. V.; Chen, B. B.; Dubovskoi, A. N.; Friedrich, F.; Pernik, L. M.; Popel, S. I.; Weidler, P. G.

    2010-05-01

    The Atmospheric Brown Clouds (ABC) is an important problem of this century. Investigations of last years and satellite data show that the ABC (or brown gas, smog, fog) cover extensive territories including the whole continents and oceans. The brown gas consists of a mixture of particles of anthropogenic sulfates, nitrates, organic origin, black carbon, dust, ashes, and also natural aerosols such as sea salt and mineral dust. The brown color is a result of absorption and scattering of solar radiation by the anthropogenic black carbon, ashes, the particles of salt dust, and nitrogen dioxide. The investigation of the ABC is a fundamental problem for prevention of degradation of the environment. At present in the CIS in-situ investigations of the ABC are carried out on Lidar Station Teplokluchenka (Kyrgyz Republic). Here, we present the results of experimental investigation of submicron (nanoscale) particles originating from the ABC and the properties of the particles. Samples of dust precipitating from the ABC were obtained at the area of Lidar Station Teplokluchenka as well as scientific station of the Russian Academy of Sciences near Bishkek. The data for determination of the grain composition were obtained with the aid of the scanning electron microscopes JEOL 6460 LV and Philips XL 30 FEG. Analysis of the properties of the particles was performed by means of the X-ray diffraction using diffractometer Siemens D5000. The images of the grains were mapped. The investigation allows us to get (after the image processing) the grain composition within the dust particle size range of 60 nm to 700 μm. Distributions of nano- and microscale particles in sizes were constructed using Rozin-Rammler coordinates. Analysis of the distributions shows that the ABC contain submicron (nanoscale) particles; 2) at higher altitudes the concentration of the submicron (nanoscale) particles in the ABC is higher than at lower altitudes. The chemical compositions of the particles are shown to

  2. Submicron superconducting structures

    International Nuclear Information System (INIS)

    Golovashkin, A.I.; Lykov, A.N.

    1986-01-01

    An overview of works concerning superconducting structures of submicron dimensions and a system of such structures is given. It is noted that usage of the above structures in superconducting microelectronics permits, first, to increase the element packing density, to decrease the signal transmission time, capacity, power dissipated in high-frequency applications. Secondly, negligible coherence length in transition metals, their alloys and high-temperature compounds also restrict the dimensions of superconducting weak couplings when the 'classical' Josephson effect is displayed. The most effective methods for production of submicron superconducting structures are the following: lithography, double scribering. Recently the systems of superconducting submicron elements are extensively studied. It is shown that such systems can be phased by magnetic field

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

    Directory of Open Access Journals (Sweden)

    G. J. Roelofs

    2008-02-01

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

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

    Science.gov (United States)

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

    2018-03-01

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

  7. Characteristics of Aerosol Transport from Asia to the West Coast of North America

    Science.gov (United States)

    Brock, C. A.; Bahreini, R.; Middlebrook, A. M.; Atlas, E. L.; Blake, D. R.; Brioude, J.; Cooper, O. R.; de Gouw, J. A.; Holloway, J. S.; Lack, D. A.; Langridge, J. M.; Meinardi, S.; Nowak, J. B.; Peischl, J.; Perring, A.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Schwarz, J. P.; Spackman, J. R.; Trainer, M.; Trytko, J.; Warneke, C.

    2010-12-01

    During the CalNex field program of May and June 2010, the NOAA WP-3D aircraft observed several layers of enhanced trace gas mixing ratios and aerosol concentrations at altitudes ranging from 1 to 4 km over southern and central California. The submicron aerosol composition within these layers was dominated by partially neutralized sulfate, while nitrate, organic matter and black carbon were only minor constituents. The particle layers were associated with trace gases, such as benzene and sulfur dioxide, consistent with anthropogenic fossil fuel emissions, and were not associated with enhancements of the biomass burning tracer acetonitrile. The particle size distribution was dominated by a single accumulation mode that is characteristic of a well aged aerosol. Transport modeling indicates an Asian source for these layers of pollution. Dew point temperatures within the layers were less than -15 degrees Celsius, indicating desiccation by precipitation during transport. Taken together, these observations are consistent with those from earlier studies in which was diagnosed the removal of primary and organic particles by precipitation scavenging during uplift from the polluted Asian boundary layer into the free troposphere. Oxidation of residual sulfur dioxide that remained following transport through the cloud system may have resulted in the observed sulfate-rich aerosol. The repeated observation of such layers suggests that wet scavenging frequently modifies the chemical and optical characteristics of aerosols emitted in urban regions in Asia and transported in the free troposphere across the Pacific.

  8. Organics, Meteoritic Material, and other Elements in High Altitude Aerosols

    Science.gov (United States)

    Mahoney, M.; Murphy, D. M.; Thomson, D. S.

    1998-01-01

    Recent in situ measurements of the chemical composition of single aerosol particles at altitudes up to 19 km have revealed a number of surprising features about ambient particles. Upper tropospheric aerosols in the study region often contained more organic material than sulfate.

  9. Characterization of the sources and processes of organic and inorganic aerosols in New York city with a high-resolution time-of-flight aerosol mass apectrometer

    Directory of Open Access Journals (Sweden)

    Y.-L. Sun

    2011-02-01

    Full Text Available Submicron aerosol particles (PM1 were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer during the summer 2009 Field Intensive Study at Queens College in New York, NY. Organic aerosol (OA and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of the total PM1 mass. The average mass-based size distribution of OA presents a small mode peaking at ~150 nm (Dva and an accumulation mode (~550 nm that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of both sulfate and OA peak between 01:00–02:00 p.m. EST due to photochemical production. The average (±σ oxygen-to-carbon (O/C, hydrogen-to-carbon (H/C, and nitrogen-to-carbon (N/C ratios of OA in NYC are 0.36 (±0.09, 1.49 (±0.08, and 0.012 (±0.005, respectively, corresponding to an average organic mass-to-carbon (OM/OC ratio of 1.62 (±0.11. Positive matrix factorization (PMF of the high resolution mass spectra identified two primary OA (POA sources, traffic and cooking, and three secondary OA (SOA components including a highly oxidized, regional low-volatility oxygenated OA (LV-OOA; O/C = 0.63, a less oxidized, semi-volatile SV-OOA (O/C = 0.38 and a unique nitrogen-enriched OA (NOA; N/C = 0.053 characterized with prominent CxH2x + 2N+ peaks likely from amino compounds. Our results indicate that cooking and traffic are two distinct and mass-equivalent POA sources in NYC, together contributing ~30% of the total OA mass during this study. The OA composition is dominated by secondary species, especially during high PM events. SV-OOA and LV-OOA on average account for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC appears to progress with a continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed

  10. Aerosol chemical composition at Cabauw, The Netherlands as observed in two intensive periods in May 2008 and March 2009

    Directory of Open Access Journals (Sweden)

    A. A. Mensah

    2012-05-01

    Full Text Available Observations of aerosol chemical composition in Cabauw, the Netherlands, are presented for two intensive measurement periods in May 2008 and March 2009. Sub-micron aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS and is compared to observations from aerosol size distribution measurements as well as composition measurements with a Monitor for AeRosol and GAses (MARGA based instrument and a Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometer (TD-PTR-MS. An overview of the data is presented and the data quality is discussed. In May 2008 enhanced pollution was observed with organics contributing 40% to the PM1 mass. In contrast the observed average mass loading was lower in March 2009 and a dominance of ammonium nitrate (42% was observed. The semi-volatile nature of ammonium nitrate is evident in the diurnal cycles with maximum concentrations observed in the morning hours in May 2008 and little diurnal variation observed in March 2009. Size dependent composition data from AMS measurements are presented and show a dominance of organics in the size range below 200 nm. A higher O:C ratio of the organics is observed for May 2008 than for March 2009. Together with the time series of individual tracer ions this shows the dominance of OOA over HOA in May 2008.

  11. Effect of Heterogeneous Chemical Reactions on the Köhler Activation of Aqueous Organic Aerosols.

    Science.gov (United States)

    Djikaev, Yuri S; Ruckenstein, Eli

    2018-05-03

    We study some thermodynamic aspects of the activation of aqueous organic aerosols into cloud droplets considering the aerosols to consist of liquid solution of water and hydrophilic and hydrophobic organic compounds, taking into account the presence of reactive species in the air. The hydrophobic (surfactant) organic molecules on the surface of such an aerosol can be processed by chemical reactions with some atmospheric species; this affects the hygroscopicity of the aerosol and hence its ability to become a cloud droplet either via nucleation or via Köhler activation. The most probable pathway of such processing involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic organic molecules located on the aerosol surface (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). These two reactions play a crucial role in the enhancement of the Köhler activation of the aerosol and its evolution into a cloud droplet. Taking them and a third reaction (next in the multistep chain of relevant heterogeneous reactions) into account, one can derive an explicit expression for the free energy of formation of a four-component aqueous droplet on a ternary aqueous organic aerosol as a function of four independent variables of state of a droplet. The results of numerical calculations suggest that the formation of cloud droplets on such (aqueous hydrophilic/hydrophobic organic) aerosols is most likely to occur as a Köhler activation-like process rather than via nucleation. The model allows one to determine the threshold parameters of the system necessary for the Köhler activation of such aerosols, which are predicted to be very sensitive to the equilibrium constant of the chain of three heterogeneous reactions involved in the chemical aging of aerosols.

  12. Hygroscopic properties of organic and inorganic aerosols[Dissertation 17260

    Energy Technology Data Exchange (ETDEWEB)

    Sjoegren, N O Staffan

    2007-07-01

    The atmosphere contains gases and particulate matter (aerosol). Organic material is present both in the gas phase and in the aerosol phase. Biogenic sources such as vegetation and anthropogenic sources such as biomass burning, fossil fuel use and various industries contribute to their emissions. The study of organic compounds in aerosol particles is of importance because they affect the water uptake (hygroscopicity) of inorganic aerosol, and hence the radiation budget of the Earth through the direct and indirect aerosol effects. The hygroscopicity of mixed organic/inorganic aerosol particles produced in the laboratory was characterized. This work reports on the following substances, and mixtures of them with ammonium sulfate (AS): adipic acid (AA), citric acid (CA), glutaric acid (GA) and humic acid sodium salt (NaHA). The AA and NaHA mixtures with AS were found to require up to tens of seconds for equilibrium water content to be reached. Therefore, measurements carried out on timescales shorter than a few seconds underestimate the hygroscopic growth factor (GF) with up to 10%, for samples containing a solid phase. Conversely, the GA and CA mixtures with AS were found to take up water readily and were well described by the Zdanovskii-Stokes-Robinson (ZSR) mixing rule. The distinct deliquescence and efflorescence points of AS could be seen to gradually disappear as the CA content was increased. Furthermore mineral dust (standard Arizona test dust) was investigated, as well as the influence of nitric acid (HNO{sub 3}) uptake thereon. Mineral dust is hydrophobic, but after processing with HNO{sub 3} turns slightly hygroscopic. Large amounts of dust are injected to the atmosphere (largely from the Sahara and the Gobi deserts, but also from human land-use). Mineral dust is important as ice nuclei, and due to its larger sizes it can also contribute as cloud condensation nuclei. Mineral dust also offers surface for heterogeneous chemistry, and can play an important role

  13. Predicting Thermal Behavior of Secondary Organic Aerosols

    Science.gov (United States)

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

  14. Chemical and physical drivers of the evolution of organic aerosols over forests

    NARCIS (Netherlands)

    Janssen, R.H.H.

    2013-01-01

    Diurnal evolution of organic aerosol over boreal and tropical forests

    The first research question of this thesis is: how do local surface forcings and large-scale meteorological forcings shape the evolution of organic aerosol over the boreal and tropical forest? This

  15. Two year-long continuous monitoring of PM1 aerosol chemical composition at the Cyprus Atmospheric Observatory. Source apportionment of the Organic content and geographic origins.

    Science.gov (United States)

    Stavroulas, Iasonas; Pikridas, Michael; Oikonomou, Kostantina; Vasiliadou, Emily; Savvides, Chrysanthos; Vrekoussis, Mihalis; Mihalopoulos, Nikolaos; Gros, Valerie; Sciare, Jean

    2017-04-01

    Particulate matter with diameter smaller than 1{μ}m (PM1) induces direct and indirect effects on local and regional pollution, global climate and health. As of the beginning of 2015, the chemical composition of submicron aerosols, is continuously being monitored at the newly established Cyprus Atmospheric Observatory (CAO, http://www.cyi.ac.cy/index.php/cao.html), a national facility of the ACTRIS Research Infrastructure operated by The Cyprus Institute. Cyprus, an island located in the Eastern Mediterranean Middle East region and influenced by diverse air masses throughout the year, is ideal for monitoring photochemically aged aerosols and gaseous pollutants of both natural and anthropogenic origin. Furthermore this is a unique dataset for this area in such proximity to the Middle East, a poorly documented area in terms of atmospheric aerosol observations. An Aerodyne Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) is currently deployed at the CAO premises (35.04N - 33.06E) situated at the rural area of Agia Marina Xyliatou on the foothill of mount Troodos at an elevation of 532m above sea level (asl). The ACSM delivers chemical composition of the major non-refractory aerosol (PM1) chemical constituents (organics, sulfate, nitrate, ammonium, chloride) with an effective (close to 100{%}) collection efficiency for particles in the diameter range of 65-700 nm at a 30 minute temporal resolution. Black Carbon (BC) was also monitored using both Magee Scientific AE-31 and AE-33 aethalometers. Quality control of the PM chemical dataset was conducted by comparison with chemical analysis performed on collocated 24-h filter samples (PM1) and comparison with 1-h PM2.5 derived from a Thermo Scientific TEOM (1400a) Monitor. Positive Matrix Factorization (PMF) was conducted and different organic aerosol factors were distinguished using the Igor based SoFi toolkit utilizing the ME-2 multilinear engine. Air mass origin was investigated for each measurement day using the

  16. Natural and Anthropogenic Influences on Atmospheric Aerosol Variability

    Energy Technology Data Exchange (ETDEWEB)

    Asmi, A.

    2012-07-01

    Aerosol particles are everywhere in the atmosphere. They are a key factor in many important processes in the atmosphere, including cloud formation, scattering of incoming solar radiation and air chemistry. The aerosol particles have relatively short lifetimes in lower atmosphere, typically from days to weeks, and thus they have a high spatial and temporal variability. This thesis concentrates on the extent and reasons of sub-micron aerosol particle variability in the lower atmosphere, using both global atmospheric models and analysis of observational data. Aerosol number size distributions in the lower atmosphere are affected strongly by the new particle formation. Perhaps more importantly, a strong influence new particle formation is also evident in the cloud condensation nuclei (CCN) concentrations, suggesting a major role of the sulphuric acid driven new particle formation in the climate system. In this thesis, the sub-micron aerosol number size distributions in the European regional background air were characterized for the first time from consistent, homogenized and comparable datasets. Some recent studies have suggested that differences in aerosol emissions between weekdays could also affect the weather via aerosol-cloud interactions. In this thesis, the weekday-to-weekday variation of CCN sized aerosol number concentrations in Europe were found to be much smaller than expected from earlier studies, based on particle mass measurements. This result suggests that a lack of week-day variability in meteorology is not necessarily a sign of weak aerosol-cloud interactions. An analysis of statistically significant trends in past decades of measured aerosol number concentrations from Europe, North America, Pacific islands and Antarctica generally show decreases in concentrations. The analysis of these changes show that a potential explanation for the decreasing trends is the general reduction of anthropogenic emissions, especially SO{sub 2}, although a combination of

  17. Aerosol particle measurements at three stationary sites in the megacity of Paris during summer 2009: meteorology and air mass origin dominate aerosol particle composition and size distribution

    Directory of Open Access Journals (Sweden)

    F. Freutel

    2013-01-01

    Full Text Available During July 2009, a one-month measurement campaign was performed in the megacity of Paris. Amongst other measurement platforms, three stationary sites distributed over an area of 40 km in diameter in the greater Paris region enabled a detailed characterization of the aerosol particle and gas phase. Simulation results from the FLEXPART dispersion model were used to distinguish between different types of air masses sampled. It was found that the origin of air masses had a large influence on measured mass concentrations of the secondary species particulate sulphate, nitrate, ammonium, and oxygenated organic aerosol measured with the Aerodyne aerosol mass spectrometer in the submicron particle size range: particularly high concentrations of these species (about 4 μg m−3, 2 μg m−3, 2 μg m−3, and 7 μg m−3, respectively were measured when aged material was advected from continental Europe, while for air masses originating from the Atlantic, much lower mass concentrations of these species were observed (about 1 μg m−3, 0.2 μg m−3, 0.4 μg m−3, and 1–3 μg m−3, respectively. For the primary emission tracers hydrocarbon-like organic aerosol, black carbon, and NOx it was found that apart from diurnal source strength variations and proximity to emission sources, local meteorology had the largest influence on measured concentrations, with higher wind speeds leading to larger dilution and therefore smaller measured concentrations. Also the shape of particle size distributions was affected by wind speed and air mass origin. Quasi-Lagrangian measurements performed under connected flow conditions between the three stationary sites were used to estimate the influence of the Paris emission plume onto its surroundings, which was found to be rather small. Rough estimates for the impact of the Paris emission plume on the suburban areas can be

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-01

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

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

    Directory of Open Access Journals (Sweden)

    W. Hu

    2016-09-01

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

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

    Science.gov (United States)

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

    2010-03-01

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

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

    Science.gov (United States)

    Li, Xinghua; Chen, Yanju; Bond, Tami C.

    2016-11-01

    Organic aerosol (OA) can absorb solar radiation in the low-visible and ultra-violet wavelengths thereby modifying radiative forcing. Agricultural waste burning emits a large quantity of organic carbon in many developing countries. In this work, we improved the extraction and analysis method developed by Chen and Bond, and extended the spectral range of OC absorption. We examined light absorbing properties of primary OA from pyrolysis of corn stalk, which is a major type of agricultural wastes. Light absorption of bulk liquid extracts of OA was measured using a UV-vis recording spectrophotometer. OA can be extracted by methanol at 95%, close to full extent, and shows polar character. Light absorption of organic aerosol has strong spectral dependence (Absorption Ångström exponent = 7.7) and is not negligible at ultra-violet and low-visible regions. Higher pyrolysis temperature produced OA with higher absorption. Imaginary refractive index of organic aerosol (kOA) is 0.041 at 400 nm wavelength and 0.005 at 550 nm wavelength, respectively.

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

    Science.gov (United States)

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

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

    Science.gov (United States)

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

    2010-12-01

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

  4. Diurnal cycling of urban aerosols under different weather regimes

    Science.gov (United States)

    Gregorič, Asta; Drinovec, Luka; Močnik, Griša; Remškar, Maja; Vaupotič, Janja; Stanič, Samo

    2016-04-01

    A one month measurement campaign was performed in summer 2014 in Ljubljana, the capital of Slovenia (population 280,000), aiming to study temporal and spatial distribution of urban aerosols and the mixing state of primary and secondary aerosols. Two background locations were chosen for this purpose, the first one in the city center (urban background - KIS) and the second one in the suburban background (Brezovica). Simultaneous measurements of black carbon (BC) and particle number size distribution of submicron aerosols (PM1) were conducted at both locations. In the summer season emission from traffic related sources is expected to be the main local contribution to BC concentration. Concentrations of aerosol species and gaseous pollutants within the planetary boundary layer are controlled by the balance between emission sources of primary aerosols and gases, production of secondary aerosols, chemical reactions of precursor gases under solar radiation and the rate of dilution by mixing within the planetary boundary layer (PBL) as well as with tropospheric air. Only local emission sources contribute to BC concentration during the stable PBL with low mixing layer height, whereas during the time of fully mixed PBL, regionally transported BC and other aerosols can contribute to the surface measurements. The study describes the diurnal behaviour of the submicron aerosol at the urban and suburban background location under different weather regimes. Particles in three size modes - nucleation (humidity, wind speed and direction), diurnal profile differs for sunny, cloudy and rainy days. Nucleation mode particles were found to be subjected to lower daily variation and only slightly influenced by weather, as opposed to Aitken and accumulation mode particles. The highest correlation between BC and particle number concentration is observed during stable atmospheric conditions in the night and morning hours and is attributed to different particle size modes, depending on the

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

    Science.gov (United States)

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

    2016-05-12

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

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

    Directory of Open Access Journals (Sweden)

    Y. Zhang

    2018-06-01

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

  7. Chemical composition of free tropospheric aerosol for PM1 and coarse mode at the high alpine site Jungfraujoch

    Directory of Open Access Journals (Sweden)

    J. Cozic

    2008-01-01

    Full Text Available The chemical composition of submicron (fine mode and supermicron (coarse mode aerosol particles has been investigated at the Jungfraujoch high alpine research station (3580 m a.s.l., Switzerland as part of the GAW aerosol monitoring program since 1999. A clear seasonality was observed for all major components throughout the period with low concentrations in winter (predominantly free tropospheric aerosol and higher concentrations in summer (enhanced vertical transport of boundary layer pollutants. In addition, mass closure was attempted during intensive campaigns in March 2004, February–March 2005 and August 2005. Ionic, carbonaceous and non-refractory components of the aerosol were quantified as well as the PM1 and coarse mode total aerosol mass concentrations. A relatively low conversion factor of 1.8 for organic carbon (OC to particulate organic matter (OM was found in winter (February–March 2005. Organics, sulfate, ammonium, and nitrate were the major components of the fine aerosol fraction that were identified, while calcium and nitrate were the only two measured components contributing to the coarse mode. The aerosol mass concentrations for fine and coarse mode aerosol measured during the intensive campaigns were not typical of the long-term seasonality due largely to dynamical differences. Average fine and coarse mode concentrations during the intensive field campaigns were 1.7 μg m−3 and 2.4 μg m−3 in winter and 2.5 μg m−3 and 2.0 μg m−3 in summer, respectively. The mass balance of aerosols showed higher contributions of calcium and nitrate in the coarse mode during Saharan dust events (SDE than without SDE.

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

    Science.gov (United States)

    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

  9. Highly time-resolved urban aerosol characteristics during springtime in Yangtze River Delta, China: insights from soot particle aerosol mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. Wang

    2016-07-01

    Full Text Available In this work, the Aerodyne soot particle – aerosol mass spectrometer (SP-AMS was deployed for the first time during the spring of 2015 in urban Nanjing, a megacity in the Yangtze River Delta (YRD of China, for online characterization of the submicron aerosols (PM1. The SP-AMS enables real-time and fast quantification of refractory black carbon (rBC simultaneously with other non-refractory species (ammonium, sulfate, nitrate, chloride, and organics. The average PM1 concentration was found to be 28.2 µg m−3, with organics (45 % as the most abundant component, following by sulfate (19.3 %, nitrate (13.6 %, ammonium (11.1 %, rBC (9.7 %, and chloride (1.3 %. These PM1 species together can reconstruct ∼ 44 % of the light extinction during this campaign based on the IMPROVE method. Chemically resolved mass-based size distributions revealed that small particles especially ultrafine ones (< 100 nm vacuum aerodynamic diameter were dominated by organics and rBC, while large particles had significant contributions from secondary inorganic species. Source apportionment of organic aerosols (OA yielded four OA subcomponents, including hydrocarbon-like OA (HOA, cooking-related OA (COA, semi-volatile oxygenated OA (SV-OOA, and low-volatility oxygenated OA (LV-OOA. Overall, secondary organic aerosol (SOA, equal to the sum of SV-OOA and LV-OOA dominated the total OA mass (55.5 %, but primary organic aerosol (POA, equal to the sum of HOA and COA can outweigh SOA in the early morning and evening due to enhanced human activities. High OA concentrations were often associated with high mass fractions of POA and rBC, indicating the important role of anthropogenic emissions during heavy pollution events. The diurnal cycles of nitrate, chloride, and SV-OOA both showed good anti-correlations with air temperatures, suggesting their variations were likely driven by thermodynamic equilibria and gas-to-particle partitioning. On the other hand

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-01

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

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

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

    Science.gov (United States)

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

    2017-12-01

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

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

    Science.gov (United States)

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

    2013-01-01

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

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

    Science.gov (United States)

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

    2013-07-16

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

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

    Directory of Open Access Journals (Sweden)

    P. J. Gallimore

    2011-12-01

    Full Text Available Many important atmospheric aerosol processes depend on the chemical composition of the aerosol, e.g. water uptake and particle cloud interactions. Atmospheric ageing processes, such as oxidation reactions, significantly and continuously change the chemical composition of aerosol particles throughout their lifetime. These ageing processes are often poorly understood. In this study we utilize an aerosol flow tube set up and an ultra-high resolution mass spectrometer to explore the effect of relative humidity (RH in the range of <5–90% on the ozonolysis of maleic acid aerosol which is employed as model organic aerosol system. Due to the slow reaction kinetics relatively high ozone concentrations of 160–200 ppm were used to achieve an appreciable degree of oxidation of maleic acid. The effect of oxidative ageing on the hygroscopicity of maleic acid particles is also investigated using an electrodynamic balance and thermodynamic modelling. RH has a profound effect on the oxidation of maleic acid particles. Very little oxidation is observed at RH < 50% and the only observed reaction products are glyoxylic acid and formic acid. In comparison, when RH > 50% there are about 15 oxidation products identified. This increased oxidation was observed even when the particles were exposed to high humidities long after a low RH ozonolysis reaction. This result might have negative implications for the use of water as an extraction solvent for the analysis of oxidized organic aerosols. These humidity-dependent differences in the composition of the ozonolyzed aerosol demonstrate that water is both a key reactant in the oxidation scheme and a determinant of particle phase and hence diffusivity. The measured chemical composition of the processed aerosol is used to model the hygroscopic growth, which compares favourably with water uptake results from the electrodynamic balance measurements. A reaction mechanism is presented which takes into account the RH dependent

  15. Organic aerosol formation in citronella candle plumes.

    Science.gov (United States)

    Bothe, Melanie; Donahue, Neil McPherson

    2010-09-01

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

  16. Submicron X-ray diffraction

    International Nuclear Information System (INIS)

    MacDowell, Alastair; Celestre, Richard; Tamura, Nobumichi; Spolenak, Ralph; Valek, Bryan; Brown, Walter; Bravman, John; Padmore, Howard; Batterman, Boris; Patel, Jamshed

    2000-01-01

    At the Advanced Light Source in Berkeley the authors have instrumented a beam line that is devoted exclusively to x-ray micro diffraction problems. By micro diffraction they mean those classes of problems in Physics and Materials Science that require x-ray beam sizes in the sub-micron range. The instrument is for instance, capable of probing a sub-micron size volume inside micron sized aluminum metal grains buried under a silicon dioxide insulating layer. The resulting Laue pattern is collected on a large area CCD detector and automatically indexed to yield the grain orientation and deviatoric (distortional) strain tensor of this sub-micron volume. A four-crystal monochromator is then inserted into the beam, which allows monochromatic light to illuminate the same part of the sample. Measurement of diffracted photon energy allows for the determination of d spacings. The combination of white and monochromatic beam measurements allow for the determination of the total strain/stress tensor (6 components) inside each sub-micron sized illuminated volume of the sample

  17. Organic condensation: A vital link connecting aerosol formation to climate forcing (Invited)

    Science.gov (United States)

    Riipinen, I.; Pierce, J. R.; Yli-Juuti, T.; Nieminen, T.; Häkkinen, S.; Ehn, M.; Junninen, H.; Lehtipalo, K.; Petdjd, T. T.; Slowik, J. G.; Chang, R. Y.; Shantz, N. C.; Abbatt, J.; Leaitch, W. R.; Kerminen, V.; Worsnop, D. R.; Pandis, S. N.; Donahue, N. M.; Kulmala, M. T.

    2010-12-01

    Aerosol-cloud interactions represent the largest uncertainty in calculations of Earth’s radiative forcing. Number concentrations of atmospheric aerosol particles are in the core of this uncertainty, as they govern the numbers of cloud condensation nuclei (CCN) and influence the albedo and lifetime of clouds. Aerosols also impair air quality through their adverse effects on atmospheric visibility and human health. The ultrafine fraction ( 100 nm) and enhance the loss of ultrafine particles. Primary organic aerosol (POA) contributes to the large end of the aerosol size distribution, enhancing the scavenging of the ultrafine particles.

  18. Real-time analysis of ambient organic aerosols using aerosol flowing atmospheric-pressure afterglow mass spectrometry (AeroFAPA-MS)

    Science.gov (United States)

    Brüggemann, Martin; Karu, Einar; Stelzer, Torsten; Hoffmann, Thorsten

    2015-04-01

    Organic aerosol accounts for a major fraction of atmospheric aerosols and has implications on the earth's climate and human health. However, due to the chemical complexity its measurement remains a major challenge for analytical instrumentation.1 Here, we present the development, characterization and application of a new soft ionization technique that allows mass spectrometric real-time detection of organic compounds in ambient aerosols. The aerosol flowing atmospheric-pressure afterglow (AeroFAPA) ion source utilizes a helium glow discharge plasma to produce excited helium species and primary reagent ions. Ionization of the analytes occurs in the afterglow region after thermal desorption and results mainly in intact molecular ions, facilitating the interpretation of the acquired mass spectra. In the past, similar approaches were used to detect pesticides, explosives or illicit drugs on a variety of surfaces.2,3 In contrast, the AeroFAPA source operates 'online' and allows the detection of organic compounds in aerosols without a prior precipitation or sampling step. To our knowledge, this is the first application of an atmospheric-pressure glow discharge ionization technique to ambient aerosol samples. We illustrate that changes in aerosol composition and concentration are detected on the time scale of seconds and in the ng-m-3 range. Additionally, the successful application of AeroFAPA-MS during a field study in a mixed forest region in Central Europe is presented. Several oxidation products of monoterpenes were clearly identified using the possibility to perform tandem MS experiments. The acquired data are in agreement with previous studies and demonstrate that AeroFAPA-MS is a suitable tool for organic aerosol analysis. Furthermore, these results reveal the potential of this technique to enable new insights into aerosol formation, growth and transformation in the atmosphere. References: 1) IPCC, 2013: Summary for Policymakers. In: Climate Change 2013: The

  19. Elemental composition and oxidation of chamber organic aerosol

    Directory of Open Access Journals (Sweden)

    P. S. Chhabra

    2011-09-01

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

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

    Directory of Open Access Journals (Sweden)

    K. Tsigaridis

    2003-01-01

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

  1. Chemical composition, microstructure, and hygroscopic properties of aerosol particles at the Zotino Tall Tower Observatory (ZOTTO), Siberia, during a summer campaign

    Science.gov (United States)

    Mikhailov, E. F.; Mironov, G. N.; Pöhlker, C.; Chi, X.; Krüger, M. L.; Shiraiwa, M.; Förster, J.-D.; Pöschl, U.; Vlasenko, S. S.; Ryshkevich, T. I.; Weigand, M.; Kilcoyne, A. L. D.; Andreae, M. O.

    2015-08-01

    In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in central Siberia (61° N, 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical compositions of aerosol particles were analyzed by x-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38 % of particulate matter (PM) in the accumulation mode and coarse mode, respectively. The water-soluble fraction of organic matter was estimated to be 52 and 8 % of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ~ 34 % in the accumulation mode vs. ~ 47 % in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5-99.4 % RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same relative humidity (RH), starting at ~ 70 %, while efflorescence occurred at different humidities, i.e., at ~ 35 % RH for submicron particles vs. ~ 50 % RH for supermicron particles. This ~ 15 % RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5-99.4 % RH range. Based on KIM, the volume-based hygroscopicity parameter, κv, was calculated. The κv,ws value related to the water-soluble (ws

  2. Biogenic oxidized organic functional groups in aerosol particles from a mountain forest site and their similarities to laboratory chamber products

    Directory of Open Access Journals (Sweden)

    R. E. Schwartz

    2010-06-01

    Full Text Available Submicron particles collected at Whistler, British Columbia, at 1020 m a.s.l. during May and June 2008 on Teflon filters were analyzed by Fourier transform infrared (FTIR and X-ray fluorescence (XRF techniques for organic functional groups (OFG and elemental composition. Organic mass (OM concentrations ranged from less than 0.5 to 3.1 μg m−3, with a project mean and standard deviation of 1.3±1.0 μg m−3 and 0.21±0.16 μg m−3 for OM and sulfate, respectively. On average, organic hydroxyl, alkane, and carboxylic acid groups represented 34%, 33%, and 23% of OM, respectively. Ketone, amine and organosulfate groups constituted 6%, 5%, and <1% of the average organic aerosol composition, respectively. Measurements of volatile organic compounds (VOC, including isoprene and monoterpenes from biogenic VOC (BVOC emissions and their oxidation products (methyl-vinylketone / methacrolein, MVK/MACR, were made using co-located proton transfer reaction mass spectrometry (PTR-MS. We present chemically-specific evidence of OFG associated with BVOC emissions. Positive matrix factorization (PMF analysis attributed 65% of the campaign OM to biogenic sources, based on the correlations of one factor to monoterpenes and MVK/MACR. The remaining fraction was attributed to anthropogenic sources based on a correlation to sulfate. The functional group composition of the biogenic factor (consisting of 32% alkane, 25% carboxylic acid, 21% organic hydroxyl, 16% ketone, and 6% amine groups was similar to that of secondary organic aerosol (SOA reported from the oxidation of BVOCs in laboratory chamber studies, providing evidence that the magnitude and chemical composition of biogenic SOA simulated in the laboratory is similar to that found in actual atmospheric conditions. The biogenic factor OM is also correlated to dust elements, indicating that dust may act as a non-acidic SOA sink. This role is supported by the organic functional

  3. Evidence of a reduction in cloud condensation nuclei activity of water-soluble aerosols caused by biogenic emissions in a cool-temperate forest.

    Science.gov (United States)

    Müller, Astrid; Miyazaki, Yuzo; Tachibana, Eri; Kawamura, Kimitaka; Hiura, Tsutom

    2017-08-16

    Biogenic organic aerosols can affect cloud condensation nuclei (CCN) properties, and subsequently impact climate change. Large uncertainties exist in how the difference in the types of terrestrial biogenic sources and the abundance of organics relative to sulfate affect CCN properties. For the submicron water-soluble aerosols collected for two years in a cool-temperate forest in northern Japan, we show that the hygroscopicity parameter κ CCN (0.44 ± 0.07) exhibited a distinct seasonal trend with a minimum in autumn (κ CCN  = 0.32-0.37); these κ CCN values were generally larger than that of ambient particles, including water-insoluble fractions. The temporal variability of κ CCN was controlled by the water-soluble organic matter (WSOM)-to-sulfate ratio (R 2  > 0.60), where the significant reduction of κ CCN in autumn was linked to the increased WSOM/sulfate ratio. Positive matrix factorization analysis indicates that α-pinene-derived secondary organic aerosol (SOA) substantially contributed to the WSOM mass (~75%) in autumn, the majority of which was attributable to emissions from litter/soil microbial activity near the forest floor. These findings suggest that WSOM, most likely α-pinene SOA, originated from the forest floor can significantly suppress the aerosol CCN activity in cool-temperate forests, which have implications for predicting climate effects by changes in biogenic emissions in future.

  4. Chemical composition of aerosol measurements in the air pollution plume during KORUS-AQ

    Science.gov (United States)

    Park, T.; Lee, J. B.; Lim, Y. J.; Ahn, J.; Park, J. S.; Soo, C. J.; Kim, J.; Park, S.; Lee, Y.; Desyaterik, Y.; Collett, J. L., Jr.; Lee, T.

    2017-12-01

    The Korean peninsula is a great place to study different sources of the aerosols: urban, rural and marine. In addition, Seoul is one of the large metropolitan areas in the world and has a variety of sources because half of the Korean population lives in Seoul, which comprises only 12% of the country's area. To understand the chemical composition of aerosol form long-range transport and local sources better, an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed on an airborne platform (NASA DC-8 aircraft). The HR-ToF-AMS is capable of measuring non-refractory size resolved chemical composition of submicron particle(NR-PM1) in the air pollution plume, including mass concentration of organic carbon, nitrate, sulfate, and ammonium with 10 seconds time resolution. The measurements were performed twenty times research flight for understanding characteristic of the air pollution from May to June, 2016 on the South Korean peninsula during KORUS-AQ 2016 campaign. The scientific goal of this study is to characterize aerosol chemical properties and mass concentration in order to understand the role of the long-range transport from northeast Asia to South Korea, and influence of the local sources. To brief, organics dominated during all of flights. Also, organics and nitrate were dominant around energy industrial complex near by Taean, South Korea. The presentation will provide an overview of the composition of NR-PM1 measured in air pollution plumes, and deliver detail information about width, depth and spatial distribution of the pollutant in the air pollution plumes. The results of this study will provide high temporal and spatial resolved details on the air pollution plumes, which are valuable input parameters of aerosol properties for the current air quality models.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-12-15

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

  6. Aerosol Indirect effect on Stratocumulus Organization

    Science.gov (United States)

    Zhou, X.; Heus, T.; Kollias, P.

    2015-12-01

    Large-eddy simulations are used to investigate the role of aerosol loading on organized Stratocumulus. We prescribed the cloud droplet number concentration (Nc) and considered it as the proxy for different aerosol loading. While the presence of drizzle amplifies the mesoscale variability as is in Savic-Jovcic and Stevens (JAS, 2008), two noticeable findings are discussed here: First, the scale of marine boundary layer circulation appears to be independent of aerosol loading, suggesting a major role of the turbulence. The precise role of the turbulence in stratocumulus organization is studied by modifying the large scale fluctuations from the LES domain. Second, while it is commonly thought that the whole circulation needs to be represented for robust cloud development, we find that stratocumulus dynamics, including variables like w'w' and w'w'w', are remarkably robust even if large scales are ignored by simply reducing the domain sizes. The only variable that is sensitive to the change of the scale is the amount of cloudiness. Despite their smaller cloud thickness and inhomogeneous macroscopic structure for low Nc, individual drizzling clouds have sizes that are commensurate with circulation scale. We observe an Nc threshold below which stratocumulus is thin enough so that a little decrease of Nc would lead to great change of cloud fraction. The simulated cloud albedo is more sensitive to in-cloud liquid water content than to the amount of cloudiness since the former decreases at least three times faster than the latter due to drizzle. The main impact of drizzle evaporation is observed to keep the sub-cloud layer moist and as a result to extend the lifetime of stratocumulus by a couple of hours.

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

    Science.gov (United States)

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

    2003-01-01

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

  8. Production and characterization of submicron hematite (α−Fe{sub 2}O{sub 3}) particles by ultrasonic spray pyrolysis method

    Energy Technology Data Exchange (ETDEWEB)

    Kırcı, Burak; Ebin, Burçak; Gürmen, Sebahattin [Department of Metallurgical and Materials Engineering, Istanbul Technical University Istanbul (Turkey)

    2013-12-16

    The ultrasonic spray pyrolysis (USP) method has been used to prepare submicron hematite (α−Fe{sub 2}O{sub 3}) particles using two different industrial pickling solutions of iron chloride (41 g/L FeCl{sub 2} and 54 g/L FeCl{sub 3}) Particles were obtained by thermal decomposition of generated aerosols from precursor solutions using 1.7 MHz ultrasonic atomizer. Reaction temperature was set up at 800 °C and aerosol droplets were carried into the heated zone by 0.7 L/min air flow rate. X-Ray Diffraction (XRD) studies were used to determine the crystal structure and crystallite size of the particles. Results indicate that patterns correspond to hematite phase with rhombohedral crystal structure (space group: R3c). The crystallite sizes of particles prepared from FeCl{sub 2} and FeCl{sub 3} solutions that were calculated from Scherrer equation are 59 and 33 nm, respectively. Scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) investigations give detailed information about particle size, morphology and composition. SEM micrographs show that hematite nanoparticles aggregate and formed spherical secondary particles in submicron range.

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

    Science.gov (United States)

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

    2012-06-01

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

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

    Directory of Open Access Journals (Sweden)

    A. T. Lambe

    2011-09-01

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

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

    Science.gov (United States)

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

    2017-12-01

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

  12. Organic condensation - a vital link connecting aerosol formation to climate forcing

    Science.gov (United States)

    Riipinen, I.; Pierce, J. R.; Yli-Juuti, T.; Nieminen, T.; Häkkinen, S.; Ehn, M.; Junninen, H.; Lehtipalo, K.; Petäjä, T.; Slowik, J.; Chang, R.; Shantz, N. C.; Abbatt, J.; Leaitch, W. R.; Kerminen, V.-M.; Worsnop, D. R.; Pandis, S. N.; Donahue, N. M.; Kulmala, M.

    2011-01-01

    Atmospheric aerosol particles influence global climate as well as impair air quality through their effects on atmospheric visibility and human health. Ultrafine (<100 nm) particles often dominate aerosol numbers, and nucleation of atmospheric vapors is an important source of these particles. To have climatic relevance, however, the freshly-nucleated particles need to grow in size. We combine observations from two continental sites (Egbert, Canada and Hyytiälä, Finland) to show that condensation of organic vapors is a crucial factor governing the lifetimes and climatic importance of the smallest atmospheric particles. We demonstrate that state-of-the-science organic gas-particle partitioning models fail to reproduce the observations, and propose a modeling approach that is consistent with the measurements. We demonstrate the large sensitivity of climatic forcing of atmospheric aerosols to these interactions between organic vapors and the smallest atmospheric nanoparticles - highlighting the need for representing this process in global climate models.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  14. On the sources of submicron aerosol particles in savannah: implications for climate and air quality

    Energy Technology Data Exchange (ETDEWEB)

    Vakkari, V.

    2013-11-01

    Aerosol is defined as solid or liquid particles suspended in a gas lighter than the particles, which means that the atmosphere we live in is an aerosol in itself. Although aerosol particles are only a trace component of the atmosphere they affect our lives in several ways. The aerosol particles can cause adverse health effects and deteriorate visibility, but they affect also the Earth s climate directly by scattering and absorbing solar radiation and indirectly by modulating the properties of the clouds. Anthropogenic aerosol particles have a net cooling effect on the climate, but the uncertainty in the amount of cooling is presently as large as the heating effect of carbon dioxide. To reduce the uncertainty in the aerosol climate effects, spatially representative reference data of high quality are needed for the global climate models. To be able to capture the diurnal and seasonal variability the data have to be collected continuously over time periods that cover at least one full seasonal cycle. Until recently such data have been nearly non-existing for continental Africa and hence one aim of this work was to establish a permanent measurement station measuring the key aerosol particle properties in a continental location in southern Africa. In close collaboration with the North-West University in South Africa this aim has now been achieved at the Welgegund measurement station. The other aims of this work were to determine the aerosol particle concentrations including their seasonal and diurnal variation and to study the most important aerosol particle sources in continental southern Africa. In this thesis the aerosol size distribution and its seasonal and diurnal variation is reported for different environments ranging from a clean rural background to an anthropogenically heavily influenced mining region in continental southern Africa. Atmospheric regional scale new particle formation has been observed at a world record high frequency and it dominates the diurnal

  15. Physico-Chemical Evolution of Organic Aerosol from Wildfire Emissions

    Science.gov (United States)

    Croteau, P.; Jathar, S.; Akherati, A.; Galang, A.; Tarun, S.; Onasch, T. B.; Lewane, L.; Herndon, S. C.; Roscioli, J. R.; Yacovitch, T. I.; Fortner, E.; Xu, W.; Daube, C.; Knighton, W. B.; Werden, B.; Wood, E.

    2017-12-01

    Wildfires are the largest combustion-related source of carbonaceous emissions to the atmosphere; these include direct emissions of black carbon (BC), primary organic aerosol (POA) and semi-volatile, intermediate-volatility, and volatile organic compounds (SVOCs, IVOCs, and VOCs). However, there are large uncertainties surrounding the evolution of these carbonaceous emissions as they are physically and chemically transformed in the atmosphere. To understand these transformations, we performed sixteen experiments using an environmental chamber to simulate day- and night-time chemistry of gas- and aerosol-phase emissions from 6 different fuels at the Fire Laboratory in Missoula, MT. Across the test matrix, the experiments simulated 2 to 8 hours of equivalent day-time aging (with the hydroxyl radical and ozone) or several hours of night-time aging (with the nitrate radical). Aging resulted in an average organic aerosol (OA) mass enhancement of 28% although the full range of OA mass enhancements varied between -10% and 254%. These enhancement findings were consistent with chamber and flow reactor experiments performed at the Fire Laboratory in 2010 and 2012 but, similar to previous studies, offered no evidence to link the OA mass enhancement to fuel type or oxidant exposure. Experiments simulating night-time aging resulted in an average OA mass enhancement of 10% and subsequent day-time aging resulted in a decrease in OA mass of 8%. While small, for the first time, these experiments highlighted the continuous nature of the OA evolution as the wildfire smoke cycled through night- and day-time processes. Ongoing work is focussed on (i) quantifying bulk compositional changes in OA, (ii) comparing the near-field aging simulated in this work with far-field aging simulated during the same campaign (via a mini chamber and flow tube) and (iii) integrating wildfire smoke aging datasets over the past decade to examine the relationship between OA mass enhancement ratios, modified

  16. Aerosol composition, oxidation properties, and sources in Beijing: results from the 2014 Asia-Pacific Economic Cooperation summit study

    Science.gov (United States)

    Xu, W. Q.; Sun, Y. L.; Chen, C.; Du, W.; Han, T. T.; Wang, Q. Q.; Fu, P. Q.; Wang, Z. F.; Zhao, X. J.; Zhou, L. B.; Ji, D. S.; Wang, P. C.; Worsnop, D. R.

    2015-12-01

    The mitigation of air pollution in megacities remains a great challenge because of the complex sources and formation mechanisms of aerosol particles. The 2014 Asia-Pacific Economic Cooperation (APEC) summit in Beijing serves as a unique experiment to study the impacts of emission controls on aerosol composition, size distributions, and oxidation properties. Herein, a high-resolution time-of-flight aerosol mass spectrometer was deployed in urban Beijing for real-time measurements of size-resolved non-refractory submicron aerosol (NR-PM1) species from 14 October to 12 November 2014, along with a range of collocated measurements. The average (±σ) PM1 was 41.6 (±38.9) μg m-3 during APEC, which was decreased by 53 % compared with that before APEC. The aerosol composition showed substantial changes owing to emission controls during APEC. Secondary inorganic aerosol (SIA: sulfate + nitrate + ammonium) showed significant reductions of 62-69 %, whereas organics presented much smaller decreases (35 %). The results from the positive matrix factorization of organic aerosol (OA) indicated that highly oxidized secondary organic aerosol (SOA) showed decreases similar to those of SIA during APEC. However, primary organic aerosol (POA) from cooking, traffic, and biomass-burning sources were comparable to those before APEC, indicating the presence of strong local source emissions. The oxidation properties showed corresponding changes in response to OA composition. The average oxygen-to-carbon level during APEC was 0.36 (±0.10), which is lower than the 0.43 (±0.13) measured before APEC, demonstrating a decrease in the OA oxidation degree. The changes in size distributions of primary and secondary species varied during APEC. SIA and SOA showed significant reductions in large accumulation modes with peak diameters shifting from ~ 650 to 400 nm during APEC, whereas those of POA remained relatively unchanged. The changes in aerosol composition, size distributions, and oxidation

  17. Hygroscopic properties of smoke-generated organic aerosol particles emitted in the marine atmosphere

    Directory of Open Access Journals (Sweden)

    A. Wonaschütz

    2013-10-01

    Full Text Available During the Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE, a plume of organic aerosol was produced by a smoke generator and emitted into the marine atmosphere from aboard the R/V Point Sur. In this study, the hygroscopic properties and the chemical composition of the plume were studied at plume ages between 0 and 4 h in different meteorological conditions. In sunny conditions, the plume particles had very low hygroscopic growth factors (GFs: between 1.05 and 1.09 for 30 nm and between 1.02 and 1.1 for 150 nm dry size at a relative humidity (RH of 92%, contrasted by an average marine background GF of 1.6. New particles were produced in large quantities (several 10 000 cm−3, which lead to substantially increased cloud condensation nuclei (CCN concentrations at supersaturations between 0.07 and 0.88%. Ratios of oxygen to carbon (O : C and water-soluble organic mass (WSOM increased with plume age: from −3, respectively, while organic mass fractions decreased slightly (~ 0.97 to ~ 0.94. High-resolution aerosol mass spectrometer (AMS spectra show that the organic fragment m/z 43 was dominated by C2H3O+ in the small, new particle mode and by C3H7+ in the large particle mode. In the marine background aerosol, GFs for 150 nm particles at 40% RH were found to be enhanced at higher organic mass fractions: an average GF of 1.06 was observed for aerosols with an organic mass fraction of 0.53, and a GF of 1.04 for an organic mass fraction of 0.35.

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

    Science.gov (United States)

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

    2010-07-15

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

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

    Directory of Open Access Journals (Sweden)

    M. I. García

    2017-07-01

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

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

    Directory of Open Access Journals (Sweden)

    Matteo Rinaldi

    2010-01-01

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

  1. The capture of submicron particles by collector plates - Wind-tunnel investigations

    International Nuclear Information System (INIS)

    Gauthier, Daniel

    1971-01-01

    The deposition of submicron particles on collector plates parallel to the flow was studied experimentally in a wind-tunnel. The validity of a theoretical model based on brownian diffusion was investigated and its Inadequacies tested. The aerosol sample consisted of uranine particles (mean geometrical radius: about 0. 1 μm). The average flow speeds varied from 1 to 10 m/s and the length of the collector plates between 1 and 10 cm. Results showed that capture was mainly due to diffusion and was in good agreement with the theoretical model; however a noticeable deposit of particles on the front part of the collector edge was observed. Sedimentation was insignificant in almost all the cases. (author) [fr

  2. Seasonal variations in aerosol particle composition at the puy-de-Dôme research station in France

    Directory of Open Access Journals (Sweden)

    E. J. Freney

    2011-12-01

    Full Text Available Detailed investigations of the chemical and microphysical properties of atmospheric aerosol particles were performed at the puy-de-Dôme (pdD research station (1465 m in autumn (September and October 2008, winter (February and March 2009, and summer (June 2010 using a compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS. Over the three campaigns, the average mass concentrations of the non-refractory submicron particles ranged from 10 μg m−3 up to 27 μg m−3. Highest nitrate and ammonium mass concentrations were measured during the winter and during periods when marine modified airmasses were arriving at the site, whereas highest concentrations of organic particles were measured during the summer and during periods when continental airmasses arrived at the site. The measurements reported in this paper show that atmospheric particle composition is strongly influenced by both the season and the origin of the airmass. The total organic mass spectra were analysed using positive matrix factorisation to separate individual organic components contributing to the overall organic particle mass concentrations. These organic components include a low volatility oxygenated organic aerosol particle (LV-OOA and a semi-volatile organic aerosol particle (SV-OOA. Correlations of the LV-OOA components with fragments of m/z 60 and m/z 73 (mass spectral markers of wood burning during the winter campaign suggest that wintertime LV-OOA are related to aged biomass burning emissions, whereas organic aerosol particles measured during the summer are likely linked to biogenic sources. Equivalent potential temperature calculations, gas-phase, and LIDAR measurements define whether the research site is in the planetary boundary layer (PBL or in the free troposphere (FT/residual layer (RL. We observe that SV-OOA and nitrate particles are associated with air masses arriving from the PBL where as particle composition measured from RL

  3. Fine aerosol bulk composition measured on WP-3D research aircraft in vicinity of the Northeastern United States – results from NEAQS

    Directory of Open Access Journals (Sweden)

    C. Warneke

    2007-06-01

    Full Text Available During the New England Air Quality Study (NEAQS in the summer of 2004, airborne measurements were made of the major inorganic ions and the water-soluble organic carbon (WSOC of the submicron (PM1.0 aerosol. These and ancillary data are used to describe the overall aerosol chemical characteristics encountered during the study. Fine particle mass was estimated from particle volume and a calculated density based on measured particle composition. Fine particle organic matter (OM was estimated from WSOC and a mass balance analysis. The aerosol over the northeastern United States (U.S. and Canada was predominantly sulfate and associated ammonium, and organic components, although in unique plumes additional ionic components were also periodically above detection limits. In power generation regions, and especially in the Ohio River Valley region, the aerosol tended to be predominantly sulfate (~60% μg μg−1 and apparently acidic, based on an excess of measured anions compared to cations. In all other regions where sulfate concentrations were lower and a smaller fraction of overall mass, the cations and anions were balanced suggesting a more neutral aerosol. In contrast, the WSOC and estimated OM were more spatially uniform and the fraction of OM relative to PM mass was largely influenced by sources of sulfate. The study median OM mass fraction was 40%. Throughout the study region, sulfate and organic aerosol mass were highest near the surface and decreased rapidly with increasing altitude. The relative fraction of organic mass to sulfate was similar throughout all altitudes within the boundary layer (altitude less than 2.5 km, but was significantly higher at altitude layers in the free troposphere (above 2.5 km. A number of distinct biomass burning plumes from fires in Alaska and the Yukon were periodically intercepted, mostly at altitudes between 3 and 4 km. These plumes were associated with highest aerosol concentrations of the study and were

  4. Highly time-resolved urban aerosol characteristics during springtime in Yangtze River Delta, China: insights from soot particle aerosol mass spectrometry

    Science.gov (United States)

    Wang, Junfeng; Ge, Xinlei; Chen, Yanfang; Shen, Yafei; Zhang, Qi; Sun, Yele; Xu, Jianzhong; Ge, Shun; Yu, Huan; Chen, Mindong

    2016-07-01

    In this work, the Aerodyne soot particle - aerosol mass spectrometer (SP-AMS) was deployed for the first time during the spring of 2015 in urban Nanjing, a megacity in the Yangtze River Delta (YRD) of China, for online characterization of the submicron aerosols (PM1). The SP-AMS enables real-time and fast quantification of refractory black carbon (rBC) simultaneously with other non-refractory species (ammonium, sulfate, nitrate, chloride, and organics). The average PM1 concentration was found to be 28.2 µg m-3, with organics (45 %) as the most abundant component, following by sulfate (19.3 %), nitrate (13.6 %), ammonium (11.1 %), rBC (9.7 %), and chloride (1.3 %). These PM1 species together can reconstruct ˜ 44 % of the light extinction during this campaign based on the IMPROVE method. Chemically resolved mass-based size distributions revealed that small particles especially ultrafine ones (cooking-related OA (COA), semi-volatile oxygenated OA (SV-OOA), and low-volatility oxygenated OA (LV-OOA). Overall, secondary organic aerosol (SOA, equal to the sum of SV-OOA and LV-OOA) dominated the total OA mass (55.5 %), but primary organic aerosol (POA, equal to the sum of HOA and COA) can outweigh SOA in the early morning and evening due to enhanced human activities. High OA concentrations were often associated with high mass fractions of POA and rBC, indicating the important role of anthropogenic emissions during heavy pollution events. The diurnal cycles of nitrate, chloride, and SV-OOA both showed good anti-correlations with air temperatures, suggesting their variations were likely driven by thermodynamic equilibria and gas-to-particle partitioning. On the other hand, in contrast to other species, sulfate, and LV-OOA concentrations increased in the afternoon, and showed no positive correlations with relative humidity (RH), likely indicating the contribution from photochemical oxidation is dominant over that of aqueous-phase processing for their formations. The

  5. The hygroscopicity parameter (κ) of ambient organic aerosol at a field site subject to biogenic and anthropogenic influences: relationship to degree of aerosol oxidation

    Science.gov (United States)

    Chang, R. Y.-W.; Slowik, J. G.; Shantz, N. C.; Vlasenko, A.; Liggio, J.; Sjostedt, S. J.; Leaitch, W. R.; Abbatt, J. P. D.

    2010-06-01

    Cloud condensation nuclei (CCN) concentrations were measured at Egbert, a rural site in Ontario, Canada during the spring of 2007. The CCN concentrations were compared to values predicted from the aerosol chemical composition and size distribution using κ-Köhler theory, with the specific goal of this work being to determine the hygroscopic parameter (κ) of the oxygenated organic component of the aerosol, assuming that oxygenation drives the hygroscopicity for the entire organic fraction of the aerosol. The hygroscopicity of the oxygenated fraction of the organic component, as determined by an Aerodyne aerosol mass spectrometer (AMS), was characterised by two methods. First, positive matrix factorization (PMF) was used to separate oxygenated and unoxygenated organic aerosol factors. By assuming that the unoxygenated factor is completely non-hygroscopic and by varying κ of the oxygenated factor so that the predicted and measured CCN concentrations are internally consistent and in good agreement, κ of the oxygenated organic factor was found to be 0.22±0.04 for the suite of measurements made during this five-week campaign. In a second, equivalent approach, we continue to assume that the unoxygenated component of the aerosol, with a mole ratio of atomic oxygen to atomic carbon (O/C) ≈ 0, is completely non-hygroscopic, and we postulate a simple linear relationship between κorg and O/C. Under these assumptions, the κ of the entire organic component for bulk aerosols measured by the AMS can be parameterised as κorg=(0.29±0.05)·(O/C), for the range of O/C observed in this study (0.3 to 0.6). These results are averaged over our five-week study at one location using only the AMS for composition analysis. Empirically, our measurements are consistent with κorg generally increasing with increasing particle oxygenation, but high uncertainties preclude us from testing this hypothesis. Lastly, we examine select periods of different aerosol composition, corresponding

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

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

    Directory of Open Access Journals (Sweden)

    J. Dron

    2010-08-01

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

  8. Enhancement of the aerosol direct radiative effect by semi-volatile aerosol components: airborne measurements in North-Western Europe

    Directory of Open Access Journals (Sweden)

    W. T. Morgan

    2010-09-01

    Full Text Available A case study of atmospheric aerosol measurements exploring the impact of the vertical distribution of aerosol chemical composition upon the radiative budget in North-Western Europe is presented. Sub-micron aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS on both an airborne platform and a ground-based site at Cabauw in the Netherlands. The examined period in May 2008 was characterised by enhanced pollution loadings in North-Western Europe and was dominated by ammonium nitrate and Organic Matter (OM. Both ammonium nitrate and OM were observed to increase with altitude in the atmospheric boundary layer. This is primarily attributed to partitioning of semi-volatile gas phase species to the particle phase at reduced temperature and enhanced relative humidity. Increased ammonium nitrate concentrations in particular were found to strongly increase the ambient scattering potential of the aerosol burden, which was a consequence of the large amount of associated water as well as the enhanced mass. During particularly polluted conditions, increases in aerosol optical depth of 50–100% were estimated to occur due to the observed increase in secondary aerosol mass and associated water uptake. Furthermore, the single scattering albedo was also shown to increase with height in the boundary layer. These enhancements combined to increase the negative direct aerosol radiative forcing by close to a factor of two at the median percentile level. Such increases have major ramifications for regional climate predictions as semi-volatile components are often not included in aerosol models.

    The results presented here provide an ideal opportunity to test regional and global representations of both the aerosol vertical distribution and subsequent impacts in North-Western Europe. North-Western Europe can be viewed as an analogue for the possible future air quality over other polluted regions of the Northern Hemisphere, where

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

    Science.gov (United States)

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

    2013-01-01

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

  10. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  11. Laser direct writing using submicron-diameter fibers.

    Science.gov (United States)

    Tian, Feng; Yang, Guoguang; Bai, Jian; Xu, Jianfeng; Hou, Changlun; Liang, Yiyong; Wang, Kaiwei

    2009-10-26

    In this paper, a novel direct writing technique using submicron-diameter fibers is presented. The submicron-diameter fiber probe serves as a tightly confined point source and it adopts micro touch mode in the process of writing. The energy distribution of direct writing model is analyzed by Three-Dimension Finite-Difference Time-Domain method. Experiments demonstrate that submicron-diameter fiber direct writing has some advantages: simple process, 350-nm-resolution (lower than 442-nm-wavelength), large writing area, and controllable width of lines. In addition, by altering writing direction of lines, complex submicron patterns can be fabricated.

  12. Aerosol effects in radiation transfer

    International Nuclear Information System (INIS)

    Binenko, V.I.; Harshvardhan, H.

    1993-01-01

    The radiative properties and effects of aerosols are assessed for the following aerosol sources: relatively clean background aerosol, dust storms and dust outbreaks, anthropogenic pollution, and polluted cloud layers. Studies show it is the submicron aerosol fraction that plays a dominant radiative role in the atmosphere. The radiative effect of the aerosol depends not only on its loading but also on the underlying surface albedo and on solar zenith angle. It is only with highly reflecting surfaces such as Arctic ice that aerosols have a warming effect. Radiometric, microphysical, mineral composition, and refractive index measurements are presented for dust and in particular for the Saharan aerosol layer (SAL). Short-wave radiative heating of the atmosphere is caused by the SAL and is due mainly to absorption. However, the SAL does not contribute significantly to the long-wave thermal radiation budget. Field program studies of the radiative effects of aerosols are described. Anthropogenic aerosols deplete the incoming solar radiation. A case field study for a regional Ukrainian center is discussed. The urban aerosol causes a cooling of metropolitan centers, compared with outlying areas, during the day, which is followed by a warming trend at night. In another study, an increase in turbidity by a factor of 3 due to increased industrialization for Mexico City is noted, together with a drop in atmospheric transmission by 10% over a 50-year period. Numerous studies are cited that demonstrate that anthropogenic aerosols affect both the microphysical and radiative properties of clouds, which in turn affect regional climate. Particles acting as cloud nuclei are considered to have the greatest indirect effect on cloud absorptivity of short-wave radiation. Satellite observations show that low-level stratus clouds contaminated by ship exhaust at sea lead to an increase in cloud albedo

  13. Field characterization of the PM2.5 Aerosol Chemical Speciation Monitor: insights into the composition, sources, and processes of fine particles in eastern China

    Science.gov (United States)

    Zhang, Yunjiang; Tang, Lili; Croteau, Philip L.; Favez, Olivier; Sun, Yele; Canagaratna, Manjula R.; Wang, Zhuang; Couvidat, Florian; Albinet, Alexandre; Zhang, Hongliang; Sciare, Jean; Prévôt, André S. H.; Jayne, John T.; Worsnop, Douglas R.

    2017-12-01

    A PM2.5-capable aerosol chemical speciation monitor (Q-ACSM) was deployed in urban Nanjing, China, for the first time to measure in situ non-refractory fine particle (NR-PM2.5) composition from 20 October to 19 November 2015, along with parallel measurements of submicron aerosol (PM1) species by a standard Q-ACSM. Our results show that the NR-PM2.5 species (organics, sulfate, nitrate, and ammonium) measured by the PM2.5-Q-ACSM are highly correlated (r2 > 0.9) with those measured by a Sunset Lab OC  /  EC analyzer and a Monitor for AeRosols and GAses (MARGA). The comparisons between the two Q-ACSMs illustrated similar temporal variations in all NR species between PM1 and PM2.5, yet substantial mass fractions of aerosol species were observed in the size range of 1-2.5 µm. On average, NR-PM1-2.5 contributed 53 % of the total NR-PM2.5, with sulfate and secondary organic aerosols (SOAs) being the two largest contributors (26 and 27 %, respectively). Positive matrix factorization of organic aerosol showed similar temporal variations in both primary and secondary OAs between PM1 and PM2.5, although the mass spectra were slightly different due to more thermal decomposition on the capture vaporizer of the PM2.5-Q-ACSM. We observed an enhancement of SOA under high relative humidity conditions, which is associated with simultaneous increases in aerosol pH, gas-phase species (NO2, SO2, and NH3) concentrations and aerosol water content driven by secondary inorganic aerosols. These results likely indicate an enhanced reactive uptake of SOA precursors upon aqueous particles. Therefore, reducing anthropogenic NOx, SO2, and NH3 emissions might not only reduce secondary inorganic aerosols but also the SOA burden during haze episodes in China.

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

    NARCIS (Netherlands)

    Roelofs, G.J.H.

    2007-01-01

    With the global aerosol-climate model ECHAM5-HAM we investigate the potential influence of organic aerosol originating from the ocean on aerosol mass and chemical composition and the droplet concentration and size of marine clouds. We present sensitivity simulations in which the uptake of organic

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

    Science.gov (United States)

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

    2017-06-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-23

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

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

    Directory of Open Access Journals (Sweden)

    T. Liu

    2017-06-01

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

  18. Quantitative characterization of urban sources of organic aerosol by high-resolution gas chromatography

    International Nuclear Information System (INIS)

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

    1991-01-01

    Fine aerosol emissions have been collected from a variety of urban combustion sources, including an industrial boiler, a fireplace, automobiles, diesel trucks, gas-fired home appliances, and meat cooking operations, by use of a dilution sampling system. Other sampling techniques have been utilized to collect fine aerosol samples of paved road dust, brake wear, tire wear, cigarette smoke, tar pot emissions, and vegetative detritus. The organic matter contained in each of these samples has been analyzed via high-resolution gas chromatography. By use of a simple computational approach, a quantitative, 50-parameter characterization of the elutable fine organic aerosol emitted from each source type has been determined. The organic mass distribution fingerprints obtained by this approach are shown to differ significantly from each other for most of the source types tested, using hierarchical cluster analysis

  19. Sub-Antarctic marine aerosol: dominant contributions from biogenic sources

    Directory of Open Access Journals (Sweden)

    J. Schmale

    2013-09-01

    Full Text Available Biogenic influences on the composition and characteristics of aerosol were investigated on Bird Island (54°00' S, 38°03' W in the South Atlantic during November and December 2010. This remote marine environment is characterised by large seabird and seal colonies. The chemical composition of the submicron particles, measured by an aerosol mass spectrometer (AMS, was 21% non-sea-salt sulfate, 2% nitrate, 8% ammonium, 22% organics and 47% sea salt including sea salt sulfate. A new method to isolate the sea spray signature from the high-resolution AMS data was applied. Generally, the aerosol was found to be less acidic than in other marine environments due to the high availability of ammonia, from local fauna emissions. By positive matrix factorisation five different organic aerosol (OA profiles could be isolated: an amino acid/amine factor (AA-OA, 18% of OA mass, a methanesulfonic acid OA factor (MSA-OA, 25%, a marine oxygenated OA factor (M-OOA, 41%, a sea spray OA fraction (SS-OA, 7% and locally produced hydrocarbon-like OA (HOA, 9%. The AA-OA was dominant during the first two weeks of November and found to be related with the hatching of penguins in a nearby colony. This factor, rich in nitrogen (N : C ratio = 0.13, has implications for the biogeochemical cycling of nitrogen in the area as particulate matter is often transported over longer distances than gaseous N-rich compounds. The MSA-OA was mainly transported from more southerly latitudes where phytoplankton bloomed. The bloom was identified as one of three sources for particulate sulfate on Bird Island, next to sea salt sulfate and sulfate transported from South America. M-OOA was the dominant organic factor and found to be similar to marine OA observed at Mace Head, Ireland. An additional OA factor highly correlated with sea spray aerosol was identified (SS-OA. However, based on the available data the type of mixture, internal or external, could not be determined. Potassium was not

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

    Directory of Open Access Journals (Sweden)

    E. M. Knipping

    2011-02-01

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

  1. Influence of organic films on the evaporation and condensation of water in aerosol.

    Science.gov (United States)

    Davies, James F; Miles, Rachael E H; Haddrell, Allen E; Reid, Jonathan P

    2013-05-28

    Uncertainties in quantifying the kinetics of evaporation and condensation of water from atmospheric aerosol are a significant contributor to the uncertainty in predicting cloud droplet number and the indirect effect of aerosols on climate. The influence of aerosol particle surface composition, particularly the impact of surface active organic films, on the condensation and evaporation coefficients remains ambiguous. Here, we report measurements of the influence of organic films on the evaporation and condensation of water from aerosol particles. Significant reductions in the evaporation coefficient are shown to result when condensed films are formed by monolayers of long-chain alcohols [C(n)H(2n+1)OH], with the value decreasing from 2.4 × 10(-3) to 1.7 × 10(-5) as n increases from 12 to 17. Temperature-dependent measurements confirm that a condensed film of long-range order must be formed to suppress the evaporation coefficient below 0.05. The condensation of water on a droplet coated in a condensed film is shown to be fast, with strong coherence of the long-chain alcohol molecules leading to islanding as the water droplet grows, opening up broad areas of uncoated surface on which water can condense rapidly. We conclude that multicomponent composition of organic films on the surface of atmospheric aerosol particles is likely to preclude the formation of condensed films and that the kinetics of water condensation during the activation of aerosol to form cloud droplets is likely to remain rapid.

  2. Influence of organic films on the evaporation and condensation of water in aerosol

    Science.gov (United States)

    Davies, James F.; Miles, Rachael E. H.; Haddrell, Allen E.; Reid, Jonathan P.

    2013-01-01

    Uncertainties in quantifying the kinetics of evaporation and condensation of water from atmospheric aerosol are a significant contributor to the uncertainty in predicting cloud droplet number and the indirect effect of aerosols on climate. The influence of aerosol particle surface composition, particularly the impact of surface active organic films, on the condensation and evaporation coefficients remains ambiguous. Here, we report measurements of the influence of organic films on the evaporation and condensation of water from aerosol particles. Significant reductions in the evaporation coefficient are shown to result when condensed films are formed by monolayers of long-chain alcohols [CnH(2n+1)OH], with the value decreasing from 2.4 × 10−3 to 1.7 × 10−5 as n increases from 12 to 17. Temperature-dependent measurements confirm that a condensed film of long-range order must be formed to suppress the evaporation coefficient below 0.05. The condensation of water on a droplet coated in a condensed film is shown to be fast, with strong coherence of the long-chain alcohol molecules leading to islanding as the water droplet grows, opening up broad areas of uncoated surface on which water can condense rapidly. We conclude that multicomponent composition of organic films on the surface of atmospheric aerosol particles is likely to preclude the formation of condensed films and that the kinetics of water condensation during the activation of aerosol to form cloud droplets is likely to remain rapid. PMID:23674675

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

    Directory of Open Access Journals (Sweden)

    E. Finessi

    2012-01-01

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

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

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

    Science.gov (United States)

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

    2017-12-01

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

  5. Some aspects of the control and management of air pollution by beryllium aerosols

    International Nuclear Information System (INIS)

    Noor, B.

    2000-01-01

    The concentration of beryllium aerosols in air of rooms and environment is determined by technological operations which are carried out on ITER and can be rather various. It determines differentiated the approaches to means and methods of the air pollution control. It is expedient to classify concentration Be, arising in air. Criterion of classification can be concentration of an impurity and its exposition. In tests of various duration are determined different on value of concentration Be in air of a working zone. At non-stationary processes of allocation the short-term tests have significant dispersion and allow to reveal both low and high meanings of concentration. This difference in conditions of astable allocation Be in air of a working zone can make the order and more. The long test in many respects smooths possible bursts of concentration, that does not allow to estimate real danger of technological operation or process. The high concentration Be can render decisive toxic astion on a human organism at high levels of pollution. The presence of submicronal particles Be, formed at work ITER presumably should strengthen effect of influence on organism. It is possible to explain it to that alongside with traditional toxic effect of aerosols Be, in addition can impose the mechanism action of a submicronal dust. With the purpose of increase information of tests and opportunity of the forecast of the air pollution levels the mathematical model of logarithmic normal distribution can be used. Submitting data of sampling in logarithmic probable grid, it is possible to carry out the analysis on two parameters: the median and the logarithmic standard. The existing standards and rules of the contents Be with reference to conditions ITER are expedient for differentiating with the account toxicity, exposition, affection on a human organism. The distinctions in allowable concentration Be in air on different sites in rooms allow to create more effective and economic methods

  6. Characterization of urban aerosol in Cork city (Ireland) using aerosol mass spectrometry

    Science.gov (United States)

    Dall'Osto, M.; Ovadnevaite, J.; Ceburnis, D.; Martin, D.; Healy, R. M.; O'Connor, I. P.; Kourtchev, I.; Sodeau, J. R.; Wenger, J. C.; O'Dowd, C.

    2013-05-01

    Ambient wintertime background urban aerosol in Cork city, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the ca. 1 350 000 single particles characterized by an Aerosol Time-of-Flight Mass Spectrometer (TSI ATOFMS) were classified into five organic-rich particle types, internally mixed to different proportions with elemental carbon (EC), sulphate and nitrate, while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was characterized using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS) and was also found to comprise organic aerosol as the most abundant species (62%), followed by nitrate (15%), sulphate (9%) and ammonium (9%), and chloride (5%). Positive matrix factorization (PMF) was applied to the HR-ToF-AMS organic matrix, and a five-factor solution was found to describe the variance in the data well. Specifically, "hydrocarbon-like" organic aerosol (HOA) comprised 20% of the mass, "low-volatility" oxygenated organic aerosol (LV-OOA) comprised 18%, "biomass burning" organic aerosol (BBOA) comprised 23%, non-wood solid-fuel combustion "peat and coal" organic aerosol (PCOA) comprised 21%, and finally a species type characterized by primary {m/z} peaks at 41 and 55, similar to previously reported "cooking" organic aerosol (COA), but possessing different diurnal variations to what would be expected for cooking activities, contributed 18%. Correlations between the different particle types obtained by the two aerosol mass spectrometers are also discussed. Despite wood, coal and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosol mass and non-refractory total PM1, respectively).

  7. Characterization of urban aerosol in Cork city (Ireland using aerosol mass spectrometry

    Directory of Open Access Journals (Sweden)

    M. Dall'Osto

    2013-05-01

    Full Text Available Ambient wintertime background urban aerosol in Cork city, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the ca. 1 350 000 single particles characterized by an Aerosol Time-of-Flight Mass Spectrometer (TSI ATOFMS were classified into five organic-rich particle types, internally mixed to different proportions with elemental carbon (EC, sulphate and nitrate, while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was characterized using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS and was also found to comprise organic aerosol as the most abundant species (62%, followed by nitrate (15%, sulphate (9% and ammonium (9%, and chloride (5%. Positive matrix factorization (PMF was applied to the HR-ToF-AMS organic matrix, and a five-factor solution was found to describe the variance in the data well. Specifically, "hydrocarbon-like" organic aerosol (HOA comprised 20% of the mass, "low-volatility" oxygenated organic aerosol (LV-OOA comprised 18%, "biomass burning" organic aerosol (BBOA comprised 23%, non-wood solid-fuel combustion "peat and coal" organic aerosol (PCOA comprised 21%, and finally a species type characterized by primary extit{m/z}~peaks at 41 and 55, similar to previously reported "cooking" organic aerosol (COA, but possessing different diurnal variations to what would be expected for cooking activities, contributed 18%. Correlations between the different particle types obtained by the two aerosol mass spectrometers are also discussed. Despite wood, coal and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosol mass and non-refractory total PM1, respectively.

  8. Polar and non-polar organic aerosols from large-scale agricultural-waste burning emissions in Northern India: Implications to organic mass-to-organic carbon ratio.

    Science.gov (United States)

    Rajput, Prashant; Sarin, M M

    2014-05-01

    This study focuses on characteristics of organic aerosols (polar and non-polar) and total organic mass-to-organic carbon ratio (OM/OC) from post-harvest agricultural-waste (paddy- and wheat-residue) burning emissions in Northern India. Aerosol samples from an upwind location (Patiala: 30.2°N, 76.3°E) in the Indo-Gangetic Plain were analyzed for non-polar and polar fractions of organic carbon (OC1 and OC2) and their respective mass (OM1 and OM2). On average, polar organic aerosols (OM2) contribute nearly 85% of the total organic mass (OM) from the paddy- and wheat-residue burning emissions. The water-soluble-OC (WSOC) to OC2 ratio, within the analytical uncertainty, is close to 1 from both paddy- and wheat-residue burning emissions. However, temporal variability and relatively low WSOC/OC2 ratio (Av: 0.67±0.06) is attributed to high moisture content and poor combustion efficiency during paddy-residue burning, indicating significant contribution (∼30%) of aromatic carbon to OC2. The OM/OC ratio for non-polar (OM1/OC1∼1.2) and polar organic aerosols (OM2/OC2∼2.2), hitherto unknown for open agricultural-waste burning emissions, is documented in this study. The total OM/OC ratio is nearly identical, 1.9±0.2 and 1.8±0.2, from paddy- and wheat-residue burning emissions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Photothermal spectroscopy of aerosols

    International Nuclear Information System (INIS)

    Campillo, A.J.; Lin, H.B.

    1981-04-01

    In situ aerosol absorption spectroscopy was performed using two novel photothermal detection schemes. The first, based on a photorefractive effect and coherent detection, called phase fluctuation optical heterodyne (PFLOH) spectroscopy, could, depending on the geometry employed, yield particle specific or particle and gas absorption data. Single particles of graphite as small as 1 μm were detected in the particle specific mode. In another geometrical configuration, the total absorption (both gas and particle) of submicron sized aerosols of ammonium sulfate particles in equilibrium with gaseous ammonia and water vapor were measured at varying CO 2 laser frequencies. The specific absorption coefficient for the sulfate ion was measured to be 0.5 m 2 /g at 1087 cm -1 . The absorption coefficient sensitivity of this scheme was less than or equal to 10 -8 cm -1 . The second scheme is a hybrid visible Mie scattering scheme incorporating photothermal modulation. Particle specific data on ammonium sulfate droplets were obtained. For chemically identical species, the relative absorption spectrum versus laser frequency can be obtained for polydisperse aerosol distributions directly from the data without the need for complex inverse scattering calculations

  10. Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

    Science.gov (United States)

    Pfrang, C.; Shiraiwa, M.; Pöschl, U.

    2011-07-01

    Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

  11. Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

    Directory of Open Access Journals (Sweden)

    C. Pfrang

    2011-07-01

    Full Text Available Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

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

    Science.gov (United States)

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

  13. Microphysical and chemical characteristics of near-water aerosol over White and Kara Seas

    Science.gov (United States)

    Terpugova, S. A.; Polkin, V. V.; Panchenko, M. V.; Golobokova, L. P.; Kozlov, V. S.; Shmargunov, V. P.; Shevchenko, V. P.; Lisitzin, A. P.

    2009-04-01

    The results are presented of five-year-long (2003-2007) study of the spatial - temporal variability of the near-water aerosol in the water area of White and Kara Seas (55, 64, 71 and 80-th cruises of RV "Professor Shtockman"; 53 and 54-th cruises of RV "Akademik Mstislav Keldysh"). Measurements of aerosol microphysical characteristics were carried out by means of the automated mobile aerosol complex consisting of nephelometer, photoelectric counter and aethalometer. The aerosol disperse composition was studied with photoelectric counter in 256 size intervals from 0.4 to 10 m. About 1500 series of measurements were carried out in White Sea, and about 1400 series in Kara Sea. Chemical characteristics of aerosol were determined from samples collected on aerosol filters (92 samples were collected in White Sea and 48 in Kara Sea). The ion composition was determined under laboratory conditions. The H+, Na+, K+, Ca2+, Mg2+, NH4+, Cl-, NO3-, HCO3-, SO42- ions were under examination. Comparing aerosol characteristics of two seas, one can note that the mean values of the aerosol content parameters in Kara Sea are less than in White Sea. The ratio of the aerosol mass concentration are from 2 (Yamal Peninsula, northern part of Novaya Zemlya) to 9 times (Blagopoluchia Bay, Ob' Gulf). The differences in the concentration of black carbon vary from 3 (Yamal Peninsula) to 17 times (Blagopoluchia Bay). The differences in the aerosol number concentration NA are not so big. The values NA near Kara Gate, Yamal Peninsula and northern part of Novaya Zemlya are practically the same as in White Sea. The concentration NA at Ob' gulf is one order of magnitude less than in White sea. The obtained aerosol volume size distributions were approximated by the sums of two fractions, submicron and coarse, with lognormal size distributions. The mean volume size distribution of submicron fraction in White Sea is approximated by the distribution with the variance of the radius logarithm s=0.6 and modal

  14. An advanced technique for speciation of organic nitrogen in atmospheric aerosols

    Science.gov (United States)

    Samy, S.; Robinson, J.; Hays, M. D.

    2011-12-01

    The chemical composition of organic nitrogen (ON) in the environment is a research topic of broad significance. The topic intersects the branches of atmospheric, aquatic, and ecological science; thus, a variety of instrumentation, analytical methods, and data interpretation tools have evolved for determination of ON. Recent studies that focus on atmospheric particulate nitrogen (N) suggest a significant fraction (20-80%) of total N is bound in organic compounds. The sources, bioavailability and transport mechanisms of these N-containing compounds can differ, producing a variety of environmental consequences. Amino acids (AA) are a key class of atmospheric ON compounds that can contribute to secondary organic aerosol (SOA) formation and potentially influence water cycles, air pollutant scavenging, and the radiation balance. AA are water-soluble organic compounds (WSOC) that can significantly alter the acid-base chemistry of aerosols, and may explain the buffering capacity that impacts heterogeneous atmospheric chemistry. The chemical transformations that N-containing organic compounds (including AA) undergo can increase the light-absorbing capacity of atmospheric carbon via formation of 'brown carbon'. Suggested sources of atmospheric AA include: marine surface layer transport from bursting sea bubbles, the suspension of bacteria, fungi, algae, pollen, spores, or biomass burning. Methodology for detection of native (underivatized) amino acids (AA) in atmospheric aerosols has been developed and validated (Samy et al., 2011). This presentation describes the use of LC-MS (Q-TOF) and microwave-assisted gas phase hydrolysis for detection of free and combined amino acids in aerosols collected in a Southeastern U.S. forest environment. Accurate mass detection and the addition of isotopically labeled surrogates prior to sample preparation allows for sensitive quantitation of target AA in a complex aerosol matrix. A total of 16 native AA were detected above the reporting

  15. Heterogeneous Uptake of HO2 Radicals onto Atmospheric Aerosols

    Science.gov (United States)

    George, I. J.; Matthews, P. S.; Brooks, B.; Goddard, A.; Whalley, L. K.; Baeza-Romero, M. T.; Heard, D. E.

    2011-12-01

    The hydroxyl (OH) and hydroperoxyl (HO2) radicals, together known as HOx, play a vital role in atmospheric chemistry by controlling the oxidative capacity of the troposphere. The atmospheric lifetime and concentrations of many trace reactive species, such as volatile organic compounds (VOCs), are determined by HOx radical levels. Therefore, the ability to accurately predict atmospheric HOx concentrations from a detailed knowledge of their sources and sinks is a very useful diagnostic tool to assess our current understanding of atmospheric chemistry. Several recent field studies have observed significantly lower concentrations of HO2 radicals than predicted using box models, where HO2 loss onto aerosols was suggested as a possible missing sink [1, 2]. However, the mechanism on HO2 uptake onto aerosols and its impact on ambient HOx levels are currently not well understood. To improve our understanding of this process, we have conducted laboratory experiments to measure HO2 uptake coefficients onto submicron aerosol particles. The FAGE (Fluorescence Assay by Gas Expansion) technique, a highly sensitive laser induced fluorescence based detection method, was used to monitor HO2 uptake kinetics onto aerosol particles in an aerosol flow tube. The application of the FAGE technique allowed for kinetic experiments to be performed under low HO2 concentrations, i.e. [HO2] atomizing dilute salt solutions or by homogeneous nucleation. HO2 uptake coefficients (γ) have been measured for single-component solid and aqueous inorganic salt and organic aerosol particles with a wide range of hygroscopicities. HO2 uptake coefficients on solid particles were below the detection limit (γ < 0.001), whereas on aqueous aerosols uptake coefficients were somewhat larger (γ = 0.001 - 0.008). HO2 uptake coefficients were highest on aerosols containing metal ions, such as Cu and Fe. Humidity and aerosol pH did not significantly impact the reactive HO2 uptake. Preliminary experiments have also

  16. 99mTc-DTPA aerosol for same-day post-perfusion ventilation imaging: Results of a multicentre study

    International Nuclear Information System (INIS)

    Koehn, H.; Koenig, B.; Bachmayr, S.; Markt, B.; Eber, O.; Lind, P.; Galvan, G.; Rettenbacher, L.; Holm, C.; Ogris, E.

    1993-01-01

    A multicentre study was performed in an attempt to evaluate a submicronic technetium-99m diethylene triamine penta-acetic acid aerosol generated by a newly developed delivery system, the aerosol production equipment (APE nebulizer), for same-day post-perfusion ventilation imaging in patients with clinically suspected pulmonary embolism. Quantitative comparison between the DTPA aerosol and krypton gas demonstrated a close correlation with respect to regional pulmonary distribution of activity and peripheral lung penetration (n=14, r=0.94, P 99m Tc-labelled DTPA aerosol is well suited for fast same-day post-perfusion ventilation imaging in patients with clinical suspicion of pulmonary embolism. (orig.)

  17. Submicron aerosol distributions and CCN activity measured in and around the Korean Peninsula during KORUS-AQ

    Science.gov (United States)

    Park, M.; Kim, N.; Yum, S. S.; Thornhill, K. L., II; Anderson, B. E.; Kim, D. S.; Kim, H. J.; Jeon, H. E.; Park, Y. S.; Lee, S. B.

    2017-12-01

    KORUS-AQ is a field campaign aimed at investigating formation of ozone and aerosol and interactions between chemistry, transport and various sources in the Korean Peninsula which is the region affected both by long-range transport and local emission. Aerosol number concentration and size distribution, and CCN number concentration were measured on board the NASA DC-8 research aircraft and at a ground site at Olympic Park in Seoul, capital city of Korea during the KORUS-AQ campaign (May 2nd to June 10th, 2017). There were 20 flights during the KORUS-AQ campaign and total flight time was about 150 hours. CCN counter (CCNC) on the airborne platform was operated at the fixed internal supersaturation of 0.6% and CCNC at the ground site was operated at five different supersaturations (0.2%, 0.4%, 0.6%, 0.8%, and 1.0%). Aerosol hygroscopic parameter κ was also estimated from CCN number concentration and aerosol size distribution. Airborne measurements showed a large spatio-temporal variation of aerosol number concentration and CCN activity in and around the Korean peninsula, and the ground measurements also showed a large temporal variation. The campaign period can be classified into long-range transport dominant cases, local emission dominant cases due to stagnant air mass, and others. Aerosol number concentration in the Korean Peninsula measured in stagnant air mass period was higher than those in long-range transport period, but CCN number concentration showed an opposite tendency. Both aerosol and CCN number concentrations over the Yellow Sea in local emission period were slightly higher than those in long-range transport period. Since CCN activity is different depending on time and space, our focus is on understanding how CCN activity and aerosol hygroscopicity vary with the source of aerosol. Comprehensive analysis results will be shown at the conference.

  18. Organic aerosols from biomass burning in Amazonian rain forest and their impact onto the environment

    International Nuclear Information System (INIS)

    Cecinato, A.; Mabilia, R.; De Castro Vasconcellos, P.

    2001-01-01

    A field campaign performed in Southern Brazilian Amazonia in 1993 has proved that this region is subjected to fallout of particulated exhausts released by fires of forestal biomass. In fact, organic content of aerosols collected at urban sites located on the border of pluvial forest, about 50 km from fires, was similar to that of biomass burning exhausts. Aerosol composition is indicative of dolous origin of fires. However, organic contents seems to be influenced by two additional sources, i. e. motor vehicle and high vegetation emission. Chemical pattern of organic aerosols released by biomass burning of forest seems to promote occurrence of photochemical smog episodes in that region [it

  19. Sensitivity of depositions to the size and hygroscopicity of Cs-bearing aerosols released by the Fukushima Nuclear Accident

    Energy Technology Data Exchange (ETDEWEB)

    Kajino, Mizuo [Meteorological Research Institute, 1-1 Nagamine, Tsukuba, Ibaraki 305-0052 (Japan); RIKEN Advanced Institute for Computational Science, 7-1-26 Minatojima-minamimachi, Chuo-ku, Kobe, Hyogo 650-0047 (Japan); Adachi, Kouji; Sekiyama, Tsuyoshi T.; Zaizen, Yuji; Igarashi, Yasuhito [Meteorological Research Institute, 1-1 Nagamine, Tsukuba, Ibaraki 305-0052 (Japan)

    2014-07-01

    We recently revealed that the micro-physical properties of aerosols carrying the radioactive Cs released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) at an early stage (March 14-15, 2011) of the accident could be very different from what we assumed previously: super-micron and non-hygroscopic at the early stage, whereas sub-micron and hygroscopic afterwards (at least later than March 20-22). In the study, two sensitivity simulations with the two different aerosol micro-physical properties were conducted using a regional scale meteorology- chemical transport model (NHM-Chem). The impact of the difference was quite significant. 17% (10-3%) of the radioactive Cs fell onto the ground by dry (wet) deposition processes, and the rest was deposited into the ocean or was transported out of the model domain, which is central and northern part of the main land of Japan under the assumption that Cs-bearing aerosols are non-hygroscopic and super-micron. On the other hand, 5.7% (11.3%) fell onto the ground by dry (wet) deposition, for the cases under the assumption that the Cs-bearing aerosols are hygroscopic and sub-micron. For the accurate simulation of the deposition of radionuclides, knowledge of the aerosol micro-physical properties is essential as well as the accuracy of the simulated wind fields and precipitation patterns. (authors)

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

    Science.gov (United States)

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

    2018-03-01

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

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

    Directory of Open Access Journals (Sweden)

    D. O'Donnell

    2011-08-01

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

  2. Small molecules as tracers in atmospheric secondary organic aerosol

    Science.gov (United States)

    Yu, Ge

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

  3. Fossil and non-fossil source contributions to atmospheric carbonaceous aerosols during extreme spring grassland fires in Eastern Europe

    Science.gov (United States)

    Ulevicius, Vidmantas; Byčenkienė, Steigvilė; Bozzetti, Carlo; Vlachou, Athanasia; Plauškaitė, Kristina; Mordas, Genrik; Dudoitis, Vadimas; Abbaszade, Gülcin; Remeikis, Vidmantas; Garbaras, Andrius; Masalaite, Agne; Blees, Jan; Fröhlich, Roman; Dällenbach, Kaspar R.; Canonaco, Francesco; Slowik, Jay G.; Dommen, Josef; Zimmermann, Ralf; Schnelle-Kreis, Jürgen; Salazar, Gary A.; Agrios, Konstantinos; Szidat, Sönke; El Haddad, Imad; Prévôt, André S. H.

    2016-05-01

    In early spring the Baltic region is frequently affected by high-pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB) on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1) was measured by an Aerodyne aerosol chemical speciation monitor (ACSM) and a source apportionment with the multilinear engine (ME-2) running the positive matrix factorization (PMF) model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ng m-3 and black carbon (BC) up to 17 µg m-3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C) measurements of the elemental (EC) and organic (OC) carbon fractions. Non-fossil organic carbon (OCnf) was the dominant fraction of PM1, with the primary (POCnf) and secondary (SOCnf) fractions contributing 26-44 % and 13-23 % to the total carbon (TC), respectively. 5-8 % of the TC had a primary fossil origin (POCf), whereas the contribution of fossil secondary organic carbon (SOCf) was 4-13 %. Non-fossil EC (ECnf) and fossil EC (ECf) ranged from 13-24 and 7-13 %, respectively. Isotope ratios of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning.

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

    Directory of Open Access Journals (Sweden)

    S. Bastelberger

    2017-07-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-10-28

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

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

    Directory of Open Access Journals (Sweden)

    Y. P. Li

    2013-07-01

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

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

    NARCIS (Netherlands)

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

    2017-01-01

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

  8. Variability of aerosol, gaseous pollutants and meteorological characteristics associated with continental, urban and marine air masses at the SW Atlantic coast of Iberia

    Science.gov (United States)

    Diesch, J.-M.; Drewnick, F.; Zorn, S. R.; von der Weiden-Reinmüller, S.-L.; Martinez, M.; Borrmann, S.

    2011-12-01

    Measurements of the ambient aerosol were performed at the Southern coast of Spain, within the framework of the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) project. The field campaign took place from 20 November until 9 December 2008 at the atmospheric research station "El Arenosillo" (37°5'47.76" N, 6°44'6.94" W). As the monitoring station is located at the interface between a natural park, industrial cities (Huelva, Seville) and the Atlantic Ocean a variety of physical and chemical parameters of aerosols and gas phase could be characterized in dependency on the origin of air masses. Backwards trajectories were examined and compared with local meteorology to classify characteristic air mass types for several source regions. Aerosol number and mass as well as polycyclic aromatic hydrocarbons and black carbon concentrations were measured in PM1 and size distributions were registered covering a size range from 7 nm up to 32 μm. The chemical composition of the non-refractory submicron aerosol was measured by means of an Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS). Gas phase analyzers monitored various trace gases (O3, SO2, NO, NO2, CO2) and a weather station provided meteorological parameters. Lowest average submicron particle mass and number concentrations were found in air masses arriving from the Atlantic Ocean with values around 2 μg m-3 and 1000 cm-3. These mass concentrations were about two to four times lower than the values recorded in air masses of continental and urban origins. For some species PM1-fractions in marine air were significantly larger than in air masses originating from Huelva, a closely located city with extensive industrial activities. The largest fraction of sulfate (54%) was detected in marine air masses and was to a high degree not neutralized. In addition small concentrations of methanesulfonic acid (MSA), a product of biogenic dimethyl sulfate (DMS) emissions could be identified in the particle phase. In all

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

    Science.gov (United States)

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

    2017-12-01

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

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

    Science.gov (United States)

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

    2012-04-01

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

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

    Directory of Open Access Journals (Sweden)

    P. S. Chhabra

    2010-05-01

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

  12. Rapid Measurements of Aerosol Size Distribution and Hygroscopic Growth via Image Processing with a Fast Integrated Mobility Spectrometer (FIMS)

    Science.gov (United States)

    Wang, Y.; Pinterich, T.; Spielman, S. R.; Hering, S. V.; Wang, J.

    2017-12-01

    Aerosol size distribution and hygroscopicity are among key parameters in determining the impact of atmospheric aerosols on global radiation and climate change. In situ submicron aerosol size distribution measurements commonly involve a scanning mobility particle sizer (SMPS). The SMPS scanning time is in the scale of minutes, which is often too slow to capture the variation of aerosol size distribution, such as for aerosols formed via nucleation processes or measurements onboard research aircraft. To solve this problem, a Fast Integrated Mobility Spectrometer (FIMS) based on image processing was developed for rapid measurements of aerosol size distributions from 10 to 500 nm. The FIMS consists of a parallel plate classifier, a condenser, and a CCD detector array. Inside the classifier an electric field separates charged aerosols based on electrical mobilities. Upon exiting the classifier, the aerosols pass through a three stage growth channel (Pinterich et al. 2017; Spielman et al. 2017), where aerosols as small as 7 nm are enlarged to above 1 μm through water or heptanol condensation. Finally, the grown aerosols are illuminated by a laser sheet and imaged onto a CCD array. The images provide both aerosol concentration and position, which directly relate to the aerosol size distribution. By this simultaneous measurement of aerosols with different sizes, the FIMS provides aerosol size spectra nearly 100 times faster than the SMPS. Recent deployment onboard research aircraft demonstrated that the FIMS is capable of measuring aerosol size distributions in 1s (Figure), thereby offering a great advantage in applications requiring high time resolution (Wang et al. 2016). In addition, the coupling of the FIMS with other conventional aerosol instruments provides orders of magnitude more rapid characterization of aerosol optical and microphysical properties. For example, the combination of a differential mobility analyzer, a relative humidity control unit, and a FIMS was

  13. Evaluation of traffic exhaust contributions to ambient carbonaceous submicron particulate matter in an urban roadside environment in Hong Kong

    Science.gov (United States)

    Lee, Berto Paul; Kwok Keung Louie, Peter; Luk, Connie; Keung Chan, Chak

    2017-12-01

    Road traffic has significant impacts on air quality particularly in densely urbanized and populated areas where vehicle emissions are a major local source of ambient particulate matter. Engine type (i.e., fuel use) significantly impacts the chemical characteristics of tailpipe emission, and thus the distribution of engine types in traffic impacts measured ambient concentrations. This study provides an estimation of the contribution of vehicles powered by different fuels (gasoline, diesel, LPG) to carbonaceous submicron aerosol mass (PM1) based on ambient aerosol mass spectrometer (AMS) and elemental carbon (EC) measurements and vehicle count data in an urban inner city environment in Hong Kong with the aim to gauge the importance of different engine types to particulate matter burdens in a typical urban street canyon. On an average per-vehicle basis, gasoline vehicles emitted 75 and 93 % more organics than diesel and LPG vehicles, respectively, while EC emissions from diesel vehicles were 45 % higher than those from gasoline vehicles. LPG vehicles showed no appreciable contributions to EC and thus overall represented a small contributor to traffic-related primary ambient PM1 despite their high abundance (˜ 30 %) in the traffic mix. Total carbonaceous particle mass contributions to ambient PM1 from diesel engines were only marginally higher (˜ 4 %) than those from gasoline engines, which is likely an effect of recently introduced control strategies targeted at commercial vehicles and buses. Overall, gasoline vehicles contributed 1.2 µg m-3 of EC and 1.1 µ m-3 of organics, LPG vehicles 0.6 µg m-3 of organics and diesel vehicles 2.0 µg m-3 of EC and 0.7 µg m-3 of organics to ambient carbonaceous PM1.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-15

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

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

    Science.gov (United States)

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

    2016-07-01

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

  16. Aircraft-Based measurement of the physico-chemical evolution of atmospheric aerosols in the air pollution plume over a megacity and a remote area

    Science.gov (United States)

    Park, J. S.; Lee, T.; Park, T.; Lee, J. B.; Lim, Y. J.; Ahn, J.; Kim, J.; Park, S.; Collett, J. L., Jr.

    2017-12-01

    Aerosols influence climate change directly (scattering and absorption) and indirectly (cloud condensation nuclei), also adverse health effects. The Korean peninsula is a great place to study different sources of the aerosols: urban, rural and marine. In addition, Seoul is one of the large metropolitan areas in the world and has a variety of sources because half of the Korean population lives in Seoul, which comprises only 12% of the country's area. To understand the physico-chemical evolution of atmospheric aerosols in the air pollution plume over a megacity and a remote area, an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed on an airborne platform (NASA DC-8 and Beechcraft King Air) in June, 2015 and May-June, 2016 during MAPS-Seoul and KORUS-AQ campaigns, respectively, in Korea. The HR-ToF-AMS is capable of measuring non-refractory size resolved chemical composition of submicron particle (NR-PM1). NR-PM1 includes mass concentration of organics, nitrate, sulfate, and ammonium with 10 seconds time resolution. Organics was dominated species in aerosol during all of flights. Organics and nitrate were dominant around energy industrial complex near by Taean, South Korea. The presentation will provide an overview of the composition of NR-PM1 measured in air pollution plumes, and deliver detail information about width, depth and spatial distribution of the pollutant in the air pollution plumes. The results of this study will provide high temporal and spatial resolved details on the air pollution plumes, which are valuable input parameters of aerosol properties for the current air quality models.

  17. Water soluble organic aerosols in the Colorado Rocky Mountains, USA: composition, sources and optical properties

    OpenAIRE

    Xie, Mingjie; Mladenov, Natalie; Williams, Mark W.; Neff, Jason C.; Wasswa, Joseph; Hannigan, Michael P.

    2016-01-01

    Atmospheric aerosols have been shown to be an important input of organic carbon and nutrients to alpine watersheds and influence biogeochemical processes in these remote settings. For many remote, high elevation watersheds, direct evidence of the sources of water soluble organic aerosols and their chemical and optical characteristics is lacking. Here, we show that the concentration of water soluble organic carbon (WSOC) in the total suspended particulate (TSP) load at a high elevation site in...

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

    Science.gov (United States)

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

    2005-12-01

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

  19. CCN Properties of Organic Aerosol Collected Below and within Marine Stratocumulus Clouds near Monterey, California

    Directory of Open Access Journals (Sweden)

    Akua Asa-Awuku

    2015-10-01

    Full Text Available The composition of aerosol from cloud droplets differs from that below cloud. Its implications for the Cloud Condensation Nuclei (CCN activity are the focus of this study. Water-soluble organic matter from below cloud, and cloud droplet residuals off the coast of Monterey, California were collected; offline chemical composition, CCN activity and surface tension measurements coupled with Köhler Theory Analysis are used to infer the molar volume and surfactant characteristics of organics in both samples. Based on the surface tension depression of the samples, it is unlikely that the aerosol contains strong surfactants. The activation kinetics for all samples examined are consistent with rapid (NH42SO4 calibration aerosol. This is consistent with our current understanding of droplet kinetics for ambient CCN. However, the carbonaceous material in cloud drop residuals is far more hygroscopic than in sub-cloud aerosol, suggestive of the impact of cloud chemistry on the hygroscopic properties of organic matter.

  20. Photoacoustics of single laser-trapped nanodroplets for the direct observation of nanofocusing in aerosol photokinetics

    Science.gov (United States)

    Cremer, Johannes W.; Thaler, Klemens M.; Haisch, Christoph; Signorell, Ruth

    2016-03-01

    Photochemistry taking place in atmospheric aerosol droplets has a significant impact on the Earth's climate. Nanofocusing of electromagnetic radiation inside aerosols plays a crucial role in their absorption behaviour, since the radiation flux inside the droplet strongly affects the activation rate of photochemically active species. However, size-dependent nanofocusing effects in the photokinetics of small aerosols have escaped direct observation due to the inability to measure absorption signatures from single droplets. Here we show that photoacoustic measurements on optically trapped single nanodroplets provide a direct, broadly applicable method to measure absorption with attolitre sensitivity. We demonstrate for a model aerosol that the photolysis is accelerated by an order of magnitude in the sub-micron to micron size range, compared with larger droplets. The versatility of our technique promises broad applicability to absorption studies of aerosol particles, such as atmospheric aerosols where quantitative photokinetic data are critical for climate predictions.

  1. Ultrahigh-strength submicron-sized metallic glass wires

    International Nuclear Information System (INIS)

    Wang, Y.B.; Lee, C.C.; Yi, J.; An, X.H.; Pan, M.X.; Xie, K.Y.; Liao, X.Z.; Cairney, J.M.; Ringer, S.P.; Wang, W.H.

    2014-01-01

    In situ deformation experiments were performed in a transmission electron microscope to investigate the mechanical properties of submicron-sized Pd 40 Cu 30 Ni 10 P 20 metallic glass (MG) wires. Results show that the submicron-sized MG wires exhibit intrinsic ultrahigh tensile strength of ∼2.8 GPa, which is nearly twice as high as that in their bulk counterpart, and ∼5% elastic strain approaching the elastic limits. The tensile strength, engineering strain at failure and deformation mode of the submicron-sized MG wires depend on the diameter of the wires

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-09

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

  3. Enhancement in electrical conductivity of pastes containing submicron Ag-coated Cu filler with palmitic acid surface modification

    Science.gov (United States)

    Choi, Eun Byeol; Lee, Jong-Hyun

    2017-09-01

    The fabrication and applied use of submicron Ag-coated Cu (Cu@Ag) particles as a filler material for epoxy-based conductive pastes having the advantages of a lower material cost and antioxidation behavior were studied. Submicron Cu@Ag particles were successfully prepared and surface-modified using palmitic acid. Diffuse reflectance infrared Fourier transform spectroscopy and thermogravimetric differential scanning calorimetry results indicated the formation of an organic layer by the chemical interaction between the Cu@Ag surface and palmitic acid and the survival of the organic layer after treatment at 160 °C for 3 h in air. The printed pastes containing both commercial micron Cu@Ag flakes and the fabricated submicron Cu@Ag particles showed a greatly reduced electrical resistivity (4.68 × 10-4 Ω cm) after surface modification compared to an initial value of 1.85 × 10-3 Ω cm when cured.

  4. Organic compounds in aerosols from selected European sites - Biogenic versus anthropogenic sources

    Science.gov (United States)

    Alves, Célia; Vicente, Ana; Pio, Casimiro; Kiss, Gyula; Hoffer, Andras; Decesari, Stefano; Prevôt, André S. H.; Minguillón, María Cruz; Querol, Xavier; Hillamo, Risto; Spindler, Gerald; Swietlicki, Erik

    2012-11-01

    Atmospheric aerosol samples from a boreal forest (Hyytiälä, April 2007), a rural site in Hungary (K-puszta, summer 2008), a polluted rural area in Italy (San Pietro Capofiume, Po Valley, April 2008), a moderately polluted rural site in Germany located on a meadow (Melpitz, May 2008), a natural park in Spain (Montseny, March 2009) and two urban background locations (Zurich, December 2008, and Barcelona, February/March 2009) were collected. Aliphatics, polycyclic aromatic hydrocarbons, carbonyls, sterols, n-alkanols, acids, phenolic compounds and anhydrosugars in aerosols were chemically characterised by gas chromatography-mass spectrometry, along with source attribution based on the carbon preference index (CPI), the ratios between the unresolved and the chromatographically resolved aliphatics, the contribution of wax n-alkanes, n-alkanols and n-alkanoic acids from plants, diagnostic ratios of individual target compounds and source-specific markers to organic carbon ratios. In spite of transboundary pollution episodes, Hyytiälä registered the lowest levels among all locations. CPI values close to 1 for the aliphatic fraction of the Montseny aerosol suggest that the anthropogenic input may be associated with the transport of aged air masses from the surrounding industrial/urban areas, which superimpose the locally originated hydrocarbons with biogenic origin. Aliphatic and aromatic hydrocarbons in samples from San Pietro Capofiume reveal that fossil fuel combustion is a major source influencing the diel pattern of concentrations. This source contributed to 25-45% of the ambient organic carbon (OC) at the Po Valley site. Aerosols from the German meadow presented variable contributions from both biogenic and anthropogenic sources. The highest levels of vegetation wax components and biogenic secondary organic aerosol (SOA) products were observed at K-puszta, while anthropogenic SOA compounds predominated in Barcelona. The primary vehicular emissions in the Spanish

  5. A novel tandem differential mobility analyzer with organic vapor treatment of aerosol particles

    Directory of Open Access Journals (Sweden)

    J. Joutsensaari

    2001-01-01

    Full Text Available A novel method to characterize the organic composition of aerosol particles has been developed. The method is based on organic vapor interaction with aerosol particles and it has been named an Organic Tandem Differential Mobility Analyzer (OTDMA. The OTDMA method has been tested for inorganic (sodium chloride and ammonium sulfate and organic (citric acid and adipic acid particles. Growth curves of the particles have been measured in ethanol vapor and as a comparison in water vapor as a function of saturation ratio. Measurements in water vapor show that sodium chloride and ammonium sulfate as well as citric acid particles grow at water saturation ratios (S of 0.8 and above, whereas adipic acid particles do not grow at S S = 0.75 and S = 0.79, respectively. Citric acid particles grow monotonously with increasing saturation ratios already at low saturation ratios and no clear deliquescence point is found. For sodium chloride and ammonium sulfate particles, no growth can be seen in ethanol vapor at saturation ratios below 0.93. In contrast, for adipic acid particles, the deliquescence takes place at around S = 0.95 in the ethanol vapor. The recrystallization of adipic acid takes place at S The results show that the working principles of the OTDMA are operational for single-component aerosols. Furthermore, the results indicate that the OTDMA method may prove useful in determining whether aerosol particles contain organic substances, especially if the OTDMA is operated in parallel with a hygroscopicity TDMA, as the growth of many substances is different in ethanol and water vapors.

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

    Science.gov (United States)

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

    2014-12-01

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

  7. Secondary organic aerosol formation through fog processing of VOCs

    Science.gov (United States)

    Herckes, P.; Hutchings, J. W.

    2010-07-01

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

  8. Organic condensation: a vital link connecting aerosol formation to cloud condensation nuclei (CCN) concentrations

    Science.gov (United States)

    Riipinen, I.; Pierce, J. R.; Yli-Juuti, T.; Nieminen, T.; Häkkinen, S.; Ehn, M.; Junninen, H.; Lehtipalo, K.; Petäjä, T.; Slowik, J.; Chang, R.; Shantz, N. C.; Abbatt, J.; Leaitch, W. R.; Kerminen, V.-M.; Worsnop, D. R.; Pandis, S. N.; Donahue, N. M.; Kulmala, M.

    2011-04-01

    Atmospheric aerosol particles influence global climate as well as impair air quality through their effects on atmospheric visibility and human health. Ultrafine (<100 nm) particles often dominate aerosol numbers, and nucleation of atmospheric vapors is an important source of these particles. To have climatic relevance, however, the freshly nucleated particles need to grow in size. We combine observations from two continental sites (Egbert, Canada and Hyytiälä, Finland) to show that condensation of organic vapors is a crucial factor governing the lifetimes and climatic importance of the smallest atmospheric particles. We model the observed ultrafine aerosol growth with a simplified scheme approximating the condensing species as a mixture of effectively non-volatile and semi-volatile species, demonstrate that state-of-the-art organic gas-particle partitioning models fail to reproduce the observations, and propose a modeling approach that is consistent with the measurements. We find that roughly half of the mass of the condensing mass needs to be distributed proportional to the aerosol surface area (thus implying that the condensation is governed by gas-phase concentration rather than the equilibrium vapour pressure) to explain the observed aerosol growth. We demonstrate the large sensitivity of predicted number concentrations of cloud condensation nuclei (CCN) to these interactions between organic vapors and the smallest atmospheric nanoparticles - highlighting the need for representing this process in global climate models.

  9. Submicron Emulsions and Their Applications in Oral Delivery.

    Science.gov (United States)

    Mundada, Veenu; Patel, Mitali; Sawant, Krutika

    2016-01-01

    A "submicron emulsion" is an isotropic mixture of drug, lipids, and surfactants, usually with hydrophilic cosolvents and with droplet diameters ranging from 10 to 500 nm. Submicron emulsions are of increasing interest in medicine due to their kinetic stability, high solubilizing capacity, and tiny globule size. Because of these properties, they have been applied in various fields, such as personal care, cosmetics, health care, pharmaceuticals, and agrochemicals. Submicron emulsions are by far the most advanced nanoparticulate systems for the systemic delivery of biologically active agents for controlled drug delivery and targeting. They are designed mainly for pharmaceutical formulations suitable for various routes of administration like parenteral, ocular, transdermal, and oral. This review article describes the marked potential of submicron emulsions for oral drug delivery owing to their numerous advantages like reduced first pass metabolism, inhibition of P-glycoprotein efflux system, and enhanced absorption via intestinal lymphatic pathway. To overcome the limitations of liquid dosage forms, submicron emulsions can be formulated into solid dosage forms such as solid self-emulsifying systems. This article covers various types of submicron emulsions like microemulsion, nanoemulsion, and self-emulsifying drug delivery system (SEDDS), and their potential pharmaceutical applications in oral delivery with emphasis on their advantages, limitations, and advancements.

  10. Photoacoustic measurements of photokinetics in single optically trapped aerosol droplets

    Science.gov (United States)

    Covert, Paul; Cremer, Johannes; Signorell, Ruth; Thaler, Klemens; Haisch, Christoph

    2017-04-01

    It is well established that interaction of light with atmospheric aerosols has a large impact on the Earth's climate. However, uncertainties in the magnitude of this impact remain large, due in part to broad distributions of aerosol size, composition, and chemical reactivity. In this context, photoacoustic spectroscopy is commonly used to measure light absorption by aerosols. Here, we present photoacoustic measurements of single, optically-trapped nanodroplets to reveal droplet size-depencies of photochemical and physical processes. Theoretical considerations have pointed to a size-dependence in the magnitude and phase of the photoacoustic response from aerosol droplets. This dependence is thought to originate from heat transfer processes that are slow compared to the acoustic excitation frequency. In the case of a model aerosol, our measurements of single particle absorption cross-section versus droplet size confirm these theoretical predictions. In a related study, using the same model aerosol, we also demonstrate a droplet size-dependence of photochemical reaction rates [1]. Within sub-micron sized particles, photolysis rates were observed to be an order of magnitude greater than those observed in larger droplets. [1] J. W. Cremer, K. M. Thaler, C. Haisch, and R. Signorell. Photoacoustics of single laser-trapped nanodroplets for the direct observation of nanofocusing in aerosol photokinetics. Nat. Commun., 7:10941, 2016.

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

    Directory of Open Access Journals (Sweden)

    Y.-L. Zhang

    2018-03-01

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

  12. Fog and Cloud Induced Aerosol Modification Observed by AERONET

    Science.gov (United States)

    Eck, T. F.; Holben, B. N.; Reid, J. S.; Giles, D. M.; Rivas, M. A.; Singh, R. P.; Tripathi, S. N.; Bruegge, C. J.; Platnick, S. E.; Arnold, G. T.; hide

    2011-01-01

    Large fine mode (sub-micron radius) dominated aerosols in size distributions retrieved from AERONET have been observed after fog or low-altitude cloud dissipation events. These column-integrated size distributions have been obtained at several sites in many regions of the world, typically after evaporation of low altitude cloud such as stratocumulus or fog. Retrievals with cloud processed aerosol are sometimes bimodal in the accumulation mode with the larger size mode often approx.0.4 - 0.5 microns radius (volume distribution); the smaller mode typically approx.0.12 to aprrox.0.20 microns may be interstitial aerosol that were not modified by incorporation in droplets and/or aerosol that are less hygroscopic in nature. Bimodal accumulation mode size distributions have often been observed from in situ measurements of aerosols that have interacted with clouds, and AERONET size distribution retrievals made after dissipation of cloud or fog are in good agreement with particle sizes measured by in situ techniques for cloud-processed aerosols. Aerosols of this type and large size range (in lower concentrations) may also be formed by cloud processing in partly cloudy conditions and may contribute to the shoulder of larger size particles in the accumulation mode retrievals, especially in regions where sulfate and other soluble aerosol are a significant component of the total aerosol composition. Observed trends of increasing aerosol optical depth (AOD) as fine mode radius increased suggests higher AOD in the near cloud environment and therefore greater aerosol direct radiative forcing than typically obtained from remote sensing, due to bias towards sampling at low cloud fraction.

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

    Directory of Open Access Journals (Sweden)

    P. J. Ziemann

    2009-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-12-01

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

  15. Simultaneous aerosol size distribution and turbidity measurements over St. Louis during METROMEX 1975

    International Nuclear Information System (INIS)

    Laulainen, N.S.; Alkezweeny, A.J.; Thorp, J.M.

    1978-01-01

    An experiment designed to measure aerosol size distributions and turbidity simultaneously over a metropolitan area is described. The particle volume size distributions measured in the city plume are found to be bimodal, with the total particle volume in the fine or submicron mode decreasing dramatically above the inversion. Aerosol extinction coefficients derived from sunphotometer optical depth measurements at four wavelengths are compared to those calculated from the measured size distributions using Mie theory with several different particle refractive indices. The accuracy of the experimental method for determining the aerosol extinction coefficient prevented any meaningful choice of the real part of particle refractive index between 1.5--1.6 and an imaginary part between 0 and -0.1i. Improvements to this type of experiment are discussed

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

    OpenAIRE

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

    2009-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Buchholz, Angela

    2011-07-06

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

  18. Characteristics of aerosol particles and trace gases in ship exhaust plumes

    Science.gov (United States)

    Drewnick, F.; Diesch, J.; Borrmann, S.

    2011-12-01

    -sulfur fuel, the chemical submicron aerosol fraction is mainly composed of hydrocarbon-like organic aerosol (HOA) species. These include PAHs that are adsorbed onto the high number of ultrafine particles. Nevertheless, the chemical composition, typical particle sizes as well as emitted gaseous components vary substantially dependent on the engine or ship type, engine operation condition and fuel mixture. This results in cargo vessels compared to tankers, passenger ships and river boats being the largest polluters influencing the Elbe shipping lane areas by high amounts of NOx, SO2, CO2, PAH, BC and ultrafine particulate matter. The tropospheric ozone chemistry in this area is also substantially affected particularly due to the increasing number of Elbe-passing ships. As onshore regions can be influenced by aged shipping plumes, trajectory pathways and transportation times were examined. As a consequence of the plumes' aging, variations of the organic fraction of the mass spectral fingerprints were found. Eyring, V. et al. (2010), Atmospheric Environment, 44, 4735-4771.

  19. Characterizing the Sources and Processing of Submicron Aerosols at a Coastal Site near Houston, TX, with a Specific Focus on the Impact of Regional Shipping Emissions

    Science.gov (United States)

    Schulze, B.; Wallace, H. W., IV; Bui, A.; Flynn, J. H., III; Erickson, M. H.; Griffin, R. J.

    2017-12-01

    The Texas Gulf Coast region historically has been influenced heavily by regional shipping emissions. However, the effects of the recent establishment of the North American Emissions Control Area (ECA) on aerosol properties in this region are presently unknown. In order to understand better the current sources and processing mechanisms influencing coastal aerosol near Houston, a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed for three weeks at a coastal location during May-June 2016. Total mass loadings of organic and inorganic non-refractory aerosol components during onshore flow periods were similar to those published before establishment of the regulations. Using estimated methanesulfonic acid (MSA) mass loadings and published biogenic MSA:non-sea-salt-sulfate (nss-SO4) ratios, we determined that over 70% of nss-SO4 over the Gulf was from anthropogenic sources, predominantly shipping emissions. Mass spectral analysis indicated that for periods with similar backward-trajectory-averaged meteorological conditions, air masses influenced by shipping emissions have an increased mass fraction of ions related to carboxylic acids and a significantly larger oxygen-to-carbon (O:C) ratio than air masses that stay within the ECA boundary, suggesting that shipping emissions impact marine organic aerosol (OA) oxidation state. Amine fragment mass loadings were positively correlated with anthropogenic nss-SO4 during onshore flow, implying anthropogenic-biogenic interaction in marine OA production. Five OA factors were resolved by positive matrix factorization, corresponding to a hydrocarbon-like OA, a semi-volatile OA, and three different oxygenated organic aerosols ranked by their O:C ratio (OOA-1, OOA-2, and OOA-3). OOA-1 constituted the majority of OA mass during a period likely influenced by aqueous-phase processing and may be linked to local glyoxal/methylglyoxal-related sources. OOA-2 was produced within the Houston urban region and was

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

    Directory of Open Access Journals (Sweden)

    K. P. Wyche

    2009-01-01

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

  1. A VUV photoionization organic aerosol mass spectrometric study with synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Fang Wenzheng; Lei Gong; Shan Xiaobin; Liu Fuyi [School of Nuclear Science and Technology, National Synchrotron Radiation Laboratory, University of Science and Technology of China, Anhui, Hefei 230029 (China); Wang Zhenya [Laboratory of Environmental Spectroscopy, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031 (China); Sheng Liusi, E-mail: lssheng@ustc.edu.cn [School of Nuclear Science and Technology, National Synchrotron Radiation Laboratory, University of Science and Technology of China, Anhui, Hefei 230029 (China)

    2011-04-15

    Research highlights: {yields} A photoionization aerosol time-of-flight mass spectrometer (ATOFMS) has been developed for on-line analysis of organic compounds in aerosol particles using tunable vacuum ultraviolet (VUV) synchrotron radiation. {yields} The degree of fragmentation of molecule can be controlled either by the heater temperature or by the photon energy. {yields} The direct determination of the IEs of benzopheneone (9.07 eV), salicylic acid (8.72 eV), and urea (9.85 eV) are measured from the photoionization efficiency spectra. {yields} The species can be identified by their molecular and fragment ions weights as well as by the comparisions between their theoretical and experimental ionization energies. - Abstract: A photoionization aerosol time-of-flight mass spectrometer (ATOFMS) has been developed for on-line analysis of organic compounds in aerosol particles using tunable vacuum ultraviolet (VUV) synchrotron radiation. Aerosol particles can be sampled directly from atmospheric pressure and are focused through an aerodynamic lens assembly into the mass spectrometer. The particles are vaporized when they impact on a heater, and then the nascent vapor is softly photoionized by synchrotron radiation. The degree of fragmentation of molecule can be controlled either by the heater temperature or by the photon energy. Thus, fragment-free tunable VUV mass spectra are obtained by tuning the photon energy close to the ionization energies (IEs) of the sample molecules. The direct determination of the IEs of benzophenone (9.07 eV), salicylic acid (8.72 eV), and urea (9.85 eV) are measured from the photoionization efficiency spectra with uncertainties of {+-}50 meV. Ab initio calculations have been employed to predict the theoretical ionization energy.

  2. Fossil and non-fossil source contributions to atmospheric carbonaceous aerosols during extreme spring grassland fires in Eastern Europe

    Directory of Open Access Journals (Sweden)

    V. Ulevicius

    2016-05-01

    Full Text Available In early spring the Baltic region is frequently affected by high-pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1 was measured by an Aerodyne aerosol chemical speciation monitor (ACSM and a source apportionment with the multilinear engine (ME-2 running the positive matrix factorization (PMF model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ng m−3 and black carbon (BC up to 17 µg m−3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C measurements of the elemental (EC and organic (OC carbon fractions. Non-fossil organic carbon (OCnf was the dominant fraction of PM1, with the primary (POCnf and secondary (SOCnf fractions contributing 26–44 % and 13–23 % to the total carbon (TC, respectively. 5–8 % of the TC had a primary fossil origin (POCf, whereas the contribution of fossil secondary organic carbon (SOCf was 4–13 %. Non-fossil EC (ECnf and fossil EC (ECf ranged from 13–24 and 7–13 %, respectively. Isotope ratios of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning.

  3. A case study of highly time-resolved evolution of aerosol chemical composition and optical properties during severe haze pollution in Shanghai, China

    Science.gov (United States)

    Zhu, W.; Cheng, Z.; Lou, S.

    2017-12-01

    Despite of extensive efforts into characterization of the sources in severe haze pollution periods in the megacity of Shanghai, the study of aerosol composition, mass-size distribution and optical properties to PM1 in the pollution periods remain poorly understood. Here we conducted a 47days real-time measurement of submicron aerosol (PM1) composition and size distribution by a High-Resolution Time-of-Flight Aerosol Mass spectrometer (HR-TOF-AMS), particle light scattering by a Cavity Attenuated Phase Shift ALBedo monitor (CAPS-ALB) and Photoacoustic Extinctionmeter (PAX) in Shanghai, China, from November 28, 2016 to January 12, 2017. The average PM1 concentration was 85.9(±14.7) μg/m3 during the pollution period, which was nearly 4 times higher than that of clean period. Increased scattering coefficient during EP was associated with higher secondary inorganic aerosols and organics. We also observed organics mass size distribution for different pollution extents showing different distribution characteristics. There were no obvious differences for ammonium nitrate and ammonium sulfate among the pollution periods, which represented single peak distributions, and peaks ranged at 650-700nm and 700nm, respectively. A strong relationship can be expected between PM1 compounds mass concentration size distribution and scattering coefficient, suggesting that chemical composition, size distribution of the particles and their variations could also contribute to the extinction coefficients. Organics and secondary inorganic species to particle light scattering were quantified. The results showed that organics and ammonium nitrate were the largest contribution to scattering coefficients of PM1. The contribution of (NH4)2SO4 to the light scattering exceeded that of NH4NO3 during clean period due to the enhanced sulfate concentrations. Our results elucidate substantial changes of aerosol composition, formation mechanisms, size distribution and optical properties due to local

  4. Mixing of secondary organic aerosols versus relative humidity

    Science.gov (United States)

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

    2016-01-01

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

  5. Mixing of secondary organic aerosols versus relative humidity.

    Science.gov (United States)

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

    2016-10-24

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Spindler, Christian

    2010-07-01

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

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

    Science.gov (United States)

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

    2012-07-01

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

  8. Ultrasonic-resonator-combined apparatus for purifying nuclear aerosol particles

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Suxia; Zhang, Quanhu; Li, Sufen; Chen, Chen; Su, Xianghua [Xi' an Hi-Tech Institute, Xi' an (China)

    2017-12-15

    The radiation hazards of radionuclides in the air arising from the storage room of nuclear devices to the operators cannot be ignored. A new ultrasonic-resonator-combined method for purifying nuclear aerosol particles is introduced. To remove particles with diameters smaller than 0.3 μm, an ultrasonic chamber is induced to agglomerate these submicron particles. An apparatus which is used to purify the nuclear aerosol particles is described in the article. The apparatus consists of four main parts: two filtering systems, an ultrasonic chamber and a high-pressure electrostatic precipitator system. Finally, experimental results demonstrated the effectiveness of the implementation of the ultrasonic resonators. The feasibility of the method is proven by its application to the data analysis of the experiments.

  9. Field characterization of the PM2.5 Aerosol Chemical Speciation Monitor: insights into the composition, sources, and processes of fine particles in eastern China

    Directory of Open Access Journals (Sweden)

    Y. Zhang

    2017-12-01

    Full Text Available A PM2.5-capable aerosol chemical speciation monitor (Q-ACSM was deployed in urban Nanjing, China, for the first time to measure in situ non-refractory fine particle (NR-PM2.5 composition from 20 October to 19 November 2015, along with parallel measurements of submicron aerosol (PM1 species by a standard Q-ACSM. Our results show that the NR-PM2.5 species (organics, sulfate, nitrate, and ammonium measured by the PM2.5-Q-ACSM are highly correlated (r2 > 0.9 with those measured by a Sunset Lab OC  /  EC analyzer and a Monitor for AeRosols and GAses (MARGA. The comparisons between the two Q-ACSMs illustrated similar temporal variations in all NR species between PM1 and PM2.5, yet substantial mass fractions of aerosol species were observed in the size range of 1–2.5 µm. On average, NR-PM1−2.5 contributed 53 % of the total NR-PM2.5, with sulfate and secondary organic aerosols (SOAs being the two largest contributors (26 and 27 %, respectively. Positive matrix factorization of organic aerosol showed similar temporal variations in both primary and secondary OAs between PM1 and PM2.5, although the mass spectra were slightly different due to more thermal decomposition on the capture vaporizer of the PM2.5-Q-ACSM. We observed an enhancement of SOA under high relative humidity conditions, which is associated with simultaneous increases in aerosol pH, gas-phase species (NO2, SO2, and NH3 concentrations and aerosol water content driven by secondary inorganic aerosols. These results likely indicate an enhanced reactive uptake of SOA precursors upon aqueous particles. Therefore, reducing anthropogenic NOx, SO2, and NH3 emissions might not only reduce secondary inorganic aerosols but also the SOA burden during haze episodes in China.

  10. Aerosol comparisons between sunphotometry / sky radiometry and the GEOS-Chem model

    Science.gov (United States)

    Chaubey, J. P.; Hesaraki, S.; O'Neill, N. T.; Saha, A.; Martin, R.; Lesins, G. B.; Abboud, I.

    2014-12-01

    Comparisons of aerosol optical depth (AOD), spectral AOD parameters and microphysical parameters derived from AEROCAN / AERONET sunphotometer / sky radiometer data acquired over Canada were compared with GEOS-Chem (Geos5,v9-01-03) estimations. The Canadian sites were selected so as to encompass a representative variety of different aerosol types ranging from fine mode (submicron) pollution and smoke aerosols, coarse mode (supermicron) dust, fine and coarse mode marine aerosols, volcanic (fine mode) sulfates and volcanic (coarse mode) ash, etc). A particular focus was placed on comparisons at remote Canadian sites with a further focus on Arctic sites. The analysis included meteorological-scale event comparisons as well as seasonal and yearly comparisons on a climatological scale. The investigations were given a further aerosol type context by comparing optical retrievals of fine and coarse mode AOD with the AODs of the different aerosol types predicted by GEOS-Chem. The effects of temporal and spectral cloud screening of the sunphotometer data on the quality and robustness of these comparisons was the object of an important supporting investigation. The results of this study will be presented for a 3 year period from 2009 to 2011.

  11. Gas-particle partitioning of semi-volatile organics on organic aerosols using a predictive activity coefficient model: analysis of the effects of parameter choices on model performance

    Science.gov (United States)

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

    The partitioning of a diverse set of semivolatile organic compounds (SOCs) on a variety of organic aerosols was studied using smog chamber experimental data. Existing data on the partitioning of SOCs on aerosols from wood combustion, diesel combustion, and the α-pinene-O 3 reaction was augmented by carrying out smog chamber partitioning experiments on aerosols from meat cooking, and catalyzed and uncatalyzed gasoline engine exhaust. Model compositions for aerosols from meat cooking and gasoline combustion emissions were used to calculate activity coefficients for the SOCs in the organic aerosols and the Pankow absorptive gas/particle partitioning model was used to calculate the partitioning coefficient Kp and quantitate the predictive improvements of using the activity coefficient. The slope of the log K p vs. log p L0 correlation for partitioning on aerosols from meat cooking improved from -0.81 to -0.94 after incorporation of activity coefficients iγ om. A stepwise regression analysis of the partitioning model revealed that for the data set used in this study, partitioning predictions on α-pinene-O 3 secondary aerosol and wood combustion aerosol showed statistically significant improvement after incorporation of iγ om, which can be attributed to their overall polarity. The partitioning model was sensitive to changes in aerosol composition when updated compositions for α-pinene-O 3 aerosol and wood combustion aerosol were used. The octanol-air partitioning coefficient's ( KOA) effectiveness as a partitioning correlator over a variety of aerosol types was evaluated. The slope of the log K p- log K OA correlation was not constant over the aerosol types and SOCs used in the study and the use of KOA for partitioning correlations can potentially lead to significant deviations, especially for polar aerosols.

  12. Evolution of multispectral aerosol optical properties in a biogenically-influenced urban environment during the CARES campaign

    Science.gov (United States)

    Gyawali, M.; Arnott, W. P.; Zaveri, R. A.; Song, C.; Pekour, M.; Flowers, B.; Dubey, M. K.; Setyan, A.; Zhang, Q.; Harworth, J. W.; Radney, J. G.; Atkinson, D. B.; China, S.; Mazzoleni, C.; Gorkowski, K.; Subramanian, R.; Jobson, B. T.; Moosmüller, H.

    2013-03-01

    Ground-based aerosol measurements made in June 2010 within Sacramento urban area (site T0) and at a 40-km downwind location (site T1) in the forested Sierra Nevada foothills area are used to investigate the evolution of multispectral optical properties as the urban aerosols aged and interacted with biogenic emissions. Along with black carbon and non-refractory aerosol mass and composition observations, spectral absorptio (βabs), scattering (βsca), and extinction (βext) coefficients for wavelengths ranging from 355 to 1064 nm were measured at both sites using photoacoustic (PA) instruments with integrating nephelometers and using cavity ring-down (CRD) instruments. The daytime average Ångström exponent of absorption (AEA) was ~1.6 for the wavelength pair 405 and 870 nm at T0, while it was ~1.8 for the wavelength pair 355 and 870 nm at T1, indicating a modest wavelength-dependent enhancement of absorption at both sites throughout the study. The measured and Mie theory calculations of multispectral βsca showed good correlation (R2=0.85-0.94). The average contribution of supermicron aerosol (mainly composed of sea salt particles advected in from the Pacific Ocean) to the total scattering coefficient ranged from less than 20% at 405 nm to greater than 80% at 1064 nm. From 22 to 28 June, secondary organic aerosol mass increased significantly at both sites due to increased biogenic emissions coupled with intense photochemical activity and air mass recirculation in the area. During this period, the short wavelength scattering coefficients at both sites gradually increased due to increase in the size of submicron aerosols. At the same time, BC mass-normalized absorption cross-section (MAC) values for ultraviolet wavelengths at T1 increased by ~60% compared to the relatively less aged urban emissions at the T0 site. In contrast, the average MAC values for 870 nm wavelength were identical at both sites. These results suggest formation of moderately brown secondary

  13. Measurements of aerosol fluxes to Speulder forest using a micrometeorological technique

    DEFF Research Database (Denmark)

    Gallagher, M.W.; Beswick, K.M.; Duyzer, J.

    1997-01-01

    It has often been stated that micrometeorological and throughfall measurements of dry deposition differ by an order of magnitude with the results being highly variable and difficult to interpret or reconcile. We present measurements by the eddy correlation method of sub-micron aerosol deposition...... to a forest and show that they are large, typically 1 cm s(-1) or more. We compare the measurements with literature values obtained by throughfall and related techniques. The results, rather than being irreconcilable, show a clear and consistent behaviour in deposition velocity across the aerosol size...... spectrum, despite the very different techniques involved. There would appear to be a contradiction with previously assumed model predictions of aerosol deposition Velocity to forests and rough vegetated surfaces particularly for particles in the size range 0.1-1.0 mu m where collection efficiencies appear...

  14. Quantitative estimates of the volatility of ambient organic aerosol

    Science.gov (United States)

    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

  15. The Hygroscopicity Parameter of Marine Organics in Sea Spray Aerosols

    Science.gov (United States)

    Boyer, M.; Chang, R. Y. W.

    2015-12-01

    The effects of aerosols on climate are poorly understood, specifically with respect to their influence on cloud properties. Since oceans cover >70% of Earth's surface, sea spray aerosols (SSA), which act efficiently as cloud condensation nuclei (CCN), may have important implications on Earth's radiation budget. Surface active organic species readily accumulate in the sea surface microlayer (SML), located at the ocean-atmosphere interface, and transfer onto nascent SSA. While it is understood that SSA are commonly enriched with organics, the resulting effect of the organic content on CCN activation remains unresolved. The hygroscopicity parameter, kappa (k), allows for the cloud nucleating properties of individual components to be predicted in particles of mixed composition; however, most studies typically infer k from ambient measurements without assessing the contribution of the individual components to the overall k. In this study, a method for quantifying the cloud nucleating properties of the organic species in surface seawater using k-Kohler theory is proposed. Ambient SML and bulk water samples will be collected and atomized to generate particles such that the overall k can be inferred from CCN measurements. The inorganic and organic components will be quantified, and the organic component will be separated so that the hygroscopicity of only the organic constituents can be determined. By comparing the inferred k values for the samples before and after removal of the inorganic component, the hygroscopicity of the organic constituents alone can be calculated, providing insight on the effect of organic species on CCN activation in SSA.

  16. Electron beam fabrication of a microfluidic device for studying submicron-scale bacteria

    Science.gov (United States)

    2013-01-01

    Background Controlled restriction of cellular movement using microfluidics allows one to study individual cells to gain insight into aspects of their physiology and behaviour. For example, the use of micron-sized growth channels that confine individual Escherichia coli has yielded novel insights into cell growth and death. To extend this approach to other species of bacteria, many of whom have dimensions in the sub-micron range, or to a larger range of growth conditions, a readily-fabricated device containing sub-micron features is required. Results Here we detail the fabrication of a versatile device with growth channels whose widths range from 0.3 μm to 0.8 μm. The device is fabricated using electron beam lithography, which provides excellent control over the shape and size of different growth channels and facilitates the rapid-prototyping of new designs. Features are successfully transferred first into silicon, and subsequently into the polydimethylsiloxane that forms the basis of the working microfluidic device. We demonstrate that the growth of sub-micron scale bacteria such as Lactococcus lactis or Escherichia coli cultured in minimal medium can be followed in such a device over several generations. Conclusions We have presented a detailed protocol based on electron beam fabrication together with specific dry etching procedures for the fabrication of a microfluidic device suited to study submicron-sized bacteria. We have demonstrated that both Gram-positive and Gram-negative bacteria can be successfully loaded and imaged over a number of generations in this device. Similar devices could potentially be used to study other submicron-sized organisms under conditions in which the height and shape of the growth channels are crucial to the experimental design. PMID:23575419

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

    Science.gov (United States)

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

    2011-09-01

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

  18. Flight-based chemical characterization of biomass burning aerosols within two prescribed burn smoke plumes

    Directory of Open Access Journals (Sweden)

    K. A. Pratt

    2011-12-01

    Full Text Available Biomass burning represents a major global source of aerosols impacting direct radiative forcing and cloud properties. Thus, the goal of a number of current studies involves developing a better understanding of how the chemical composition and mixing state of biomass burning aerosols evolve during atmospheric aging processes. During the Ice in Clouds Experiment-Layer Clouds (ICE-L in the fall of 2007, smoke plumes from two small Wyoming Bureau of Land Management prescribed burns were measured by on-line aerosol instrumentation aboard a C-130 aircraft, providing a detailed chemical characterization of the particles. After ~2–4 min of aging, submicron smoke particles, produced primarily from sagebrush combustion, consisted predominantly of organics by mass, but were comprised primarily of internal mixtures of organic carbon, elemental carbon, potassium chloride, and potassium sulfate. Significantly, the fresh biomass burning particles contained minor mass fractions of nitrate and sulfate, suggesting that hygroscopic material is incorporated very near or at the point of emission. The mass fractions of ammonium, sulfate, and nitrate increased with aging up to ~81–88 min and resulted in acidic particles. Decreasing black carbon mass concentrations occurred due to dilution of the plume. Increases in the fraction of oxygenated organic carbon and the presence of dicarboxylic acids, in particular, were observed with aging. Cloud condensation nuclei measurements suggested all particles >100 nm were active at 0.5% water supersaturation in the smoke plumes, confirming the relatively high hygroscopicity of the freshly emitted particles. For immersion/condensation freezing, ice nuclei measurements at −32 °C suggested activation of ~0.03–0.07% of the particles with diameters greater than 500 nm.

  19. Aerosol spectral optical depths and size characteristics at a coastal industriallocation in India - effect of synoptic and mesoscale weather

    Directory of Open Access Journals (Sweden)

    K. Niranjan

    2004-06-01

    Full Text Available The aerosol spectral optical depths at ten discrete channels in the visible and near IR bands, obtained from a ground-based passive multi-wavelength solar radiometer at a coastal industrial location, Visakhapatnam, on the east coast of India, are used to study the response of the aerosol optical properties and size distributions to the changes in atmospheric humidity, wind speed and direction. It is observed that during high humidity conditions, the spectral optical depths show about 30% higher growth factors, and the size distributions show the generation of a typical new mode around 0.4 microns. The surface wind speed and direction also indicate the formation of new particles when the humid marine air mass interacts with the industrial air mass. This is interpreted in terms of new particle formation and subsequent particle growth by condensation and self-coagulation. The results obtained on the surface-size segregated aerosol mass distribution from a co-located Quartz Crystal Microbalance during different humidity conditions also show a large mass increase in the sub-micron size range with an increase in atmospheric humidity, indicating new particle formation at the sub-micron size range.

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

    Science.gov (United States)

    Kim, H.; Zhang, Q.

    2016-12-01

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

  1. Entrapment of dye molecules within submicron silver particles

    Energy Technology Data Exchange (ETDEWEB)

    Yosef, Itzik; Avnir, David, E-mail: david@chem.ch.huji.ac.il [Hebrew University of Jerusalem, Institute of Chemistry (Israel)

    2011-09-15

    We describe a method for the preparation of metal-organic composites submicron particles. Specifically, the preparation of silver particle-clusters 150-200 nm in size, doped with an organic dye Congo-red, is reported. The use of sodium citrate coupled with sodium hypophosphite facilitated the formation of these particle-clusters, which were fully characterized by TEM analysis, Zeta potential and size measurements, scanning electron microscopy, UV-Vis measurements, and thermogravimetric analysis. The latter reveals a catalytic action of the metal on the thermal oxidative decomposition of the entrapped dye. The use of these particles to obtain dense thin metallic films was demonstrated by the coating of ITO glass.

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

    Science.gov (United States)

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

    2018-01-01

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

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

    OpenAIRE

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

    2016-01-01

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

  4. Aerosol emissions from prescribed fires in the United States: A synthesis of laboratory and aircraft measurements

    Science.gov (United States)

    A. A. May; G. R. McMeeking; T. Lee; J. W. Taylor; J. S. Craven; I. Burling; A. P. Sullivan; S. Akagi; J. L. Collett; M. Flynn; H. Coe; S. P. Urbanski; J. H. Seinfeld; R. J. Yokelson; S. M. Kreidenweis

    2014-01-01

    Aerosol emissions from prescribed fires can affect air quality on regional scales. Accurate representation of these emissions in models requires information regarding the amount and composition of the emitted species. We measured a suite of submicron particulate matter species in young plumes emitted from prescribed fires (chaparral and montane ecosystems in California...

  5. Variability of aerosol, gaseous pollutants and meteorological characteristics associated with changes in air mass origin at the SW Atlantic coast of Iberia

    Directory of Open Access Journals (Sweden)

    J.-M. Diesch

    2012-04-01

    Full Text Available Measurements of the ambient aerosol were performed at the Southern coast of Spain, within the framework of the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides project. The field campaign took place from 20 November until 9 December 2008 at the atmospheric research station "El Arenosillo" (37°5'47.76" N, 6°44'6.94" W. As the monitoring station is located at the interface between a natural park, industrial cities (Huelva, Seville and the Atlantic Ocean, a variety of physical and chemical parameters of aerosols and gas phase could be characterized in dependency on the origin of air masses. Backwards trajectories were examined and compared with local meteorology to classify characteristic air mass types for several source regions. Aerosol number and mass as well as polycyclic aromatic hydrocarbons and black carbon concentrations were measured in PM1 and size distributions were registered covering a size range from 7 nm up to 32 μm. The chemical composition of the non-refractory submicron aerosol (NR-PM1 was measured by means of an Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS. Gas phase analyzers monitored various trace gases (O3, SO2, NO, NO2, CO2 and a weather station provided meteorological parameters.

    Lowest average submicron particle mass and number concentrations were found in air masses arriving from the Atlantic Ocean with values around 2 μg m−3 and 1000 cm−3. These mass concentrations were about two to four times lower than the values recorded in air masses of continental and urban origins. For some species PM1-fractions in marine air were significantly larger than in air masses originating from Huelva, a closely located city with extensive industrial activities. The largest fraction of sulfate (54% was detected in marine air masses and was to a high degree not neutralized. In addition, small concentrations of

  6. Variability of aerosol, gaseous pollutants and meteorological characteristics associated with changes in air mass origin at the SW Atlantic coast of Iberia

    Science.gov (United States)

    Diesch, J.-M.; Drewnick, F.; Zorn, S. R.; von der Weiden-Reinmüller, S.-L.; Martinez, M.; Borrmann, S.

    2012-04-01

    Measurements of the ambient aerosol were performed at the Southern coast of Spain, within the framework of the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) project. The field campaign took place from 20 November until 9 December 2008 at the atmospheric research station "El Arenosillo" (37°5'47.76" N, 6°44'6.94" W). As the monitoring station is located at the interface between a natural park, industrial cities (Huelva, Seville) and the Atlantic Ocean, a variety of physical and chemical parameters of aerosols and gas phase could be characterized in dependency on the origin of air masses. Backwards trajectories were examined and compared with local meteorology to classify characteristic air mass types for several source regions. Aerosol number and mass as well as polycyclic aromatic hydrocarbons and black carbon concentrations were measured in PM1 and size distributions were registered covering a size range from 7 nm up to 32 μm. The chemical composition of the non-refractory submicron aerosol (NR-PM1) was measured by means of an Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS). Gas phase analyzers monitored various trace gases (O3, SO2, NO, NO2, CO2) and a weather station provided meteorological parameters. Lowest average submicron particle mass and number concentrations were found in air masses arriving from the Atlantic Ocean with values around 2 μg m-3 and 1000 cm-3. These mass concentrations were about two to four times lower than the values recorded in air masses of continental and urban origins. For some species PM1-fractions in marine air were significantly larger than in air masses originating from Huelva, a closely located city with extensive industrial activities. The largest fraction of sulfate (54%) was detected in marine air masses and was to a high degree not neutralized. In addition, small concentrations of methanesulfonic acid (MSA), a product of biogenic dimethyl sulfate (DMS) emissions, could be identified in the particle phase

  7. Sources and atmospheric processing of winter aerosols in Seoul, Korea: insights from real-time measurements using a high-resolution aerosol mass spectrometer

    Science.gov (United States)

    Kim, Hwajin; Zhang, Qi; Bae, Gwi-Nam; Kim, Jin Young; Bok Lee, Seung

    2017-02-01

    Highly time-resolved chemical characterization of nonrefractory submicrometer particulate matter (NR-PM1) was conducted in Seoul, the capital and largest metropolis of Korea, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The measurements were performed during winter, when elevated particulate matter (PM) pollution events are often observed. This is the first time that detailed real-time aerosol measurement results have been reported from Seoul, Korea, and they reveal valuable insights into the sources and atmospheric processes that contribute to PM pollution in this region. The average concentration of submicron aerosol (PM1 = NR-PM1+ black carbon (BC)) was 27.5 µg m-3, and the total mass was dominated by organics (44 %), followed by nitrate (24 %) and sulfate (10 %). The average atomic ratios of oxygen to carbon (O / C), hydrogen to carbon (H / C), and nitrogen to carbon (N / C) of organic aerosols (OA) were 0.37, 1.79, and 0.018, respectively, which result in an average organic mass-to-carbon (OM / OC) ratio of 1.67. The concentrations (2.6-90.7 µg m-3) and composition of PM1 varied dynamically during the measurement period due to the influences of different meteorological conditions, emission sources, and air mass origins. Five distinct sources of OA were identified via positive matrix factorization (PMF) analysis of the HR-ToF-AMS data: vehicle emissions represented by a hydrocarbon-like OA factor (HOA, O / C = 0.06), cooking activities represented by a cooking OA factor (COA, O / C = 0.14), wood combustion represented by a biomass burning OA factor (BBOA, O / C = 0.34), and secondary organic aerosol (SOA) represented by a semivolatile oxygenated OA factor (SV-OOA, O / C = 0.56) and a low-volatility oxygenated OA factor (LV-OOA, O / C = 0.68). On average, primary OA (POA = HOA + COA + BBOA) accounted for 59 % the OA mass, whereas SV-OOA and LV-OOA contributed 15 and 26 %, respectively. Our results indicate that air

  8. Characterizing Organic Aerosol Processes and Climatically Relevant Properties via Advanced and Integrated Analyses of Aerosol Mass Spectrometry Datasets from DOE Campaigns and ACRF Measurements. Final report for DE-SC0007178

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Qi [Univ. of California, Davis, CA (United States)

    2017-05-21

    Organic aerosols (OA) are an important but poorly characterized component of the earth’s climate system. Enormous complexities commonly associated with OA composition and life cycle processes have significantly complicated the simulation and quantification of aerosol effects. To unravel these complexities and improve understanding of the properties, sources, formation, evolution processes, and radiative properties of atmospheric OA, we propose to perform advanced and integrated analyses of multiple DOE aerosol mass spectrometry datasets, including two high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) datasets from intensive field campaigns on the aerosol life cycle and the Aerosol Chemical Speciation Monitor (ACSM) datasets from long-term routine measurement programs at ACRF sites. In this project, we will focus on 1) characterizing the chemical (i.e., composition, organic elemental ratios), physical (i.e., size distribution and volatility), and radiative (i.e., sub- and super-saturated growth) properties of organic aerosols, 2) examining the correlations of these properties with different source and process regimes (e.g., primary, secondary, urban, biogenic, biomass burning, marine, or mixtures), 3) quantifying the evolutions of these properties as a function of photochemical processing, 4) identifying and characterizing special cases for important processes such as SOA formation and new particle formation and growth, and 5) correlating size-resolved aerosol chemistry with measurements of radiative properties of aerosols to determine the climatically relevant properties of OA and characterize the relationship between these properties and processes of atmospheric aerosol organics. Our primary goal is to improve a process-level understanding of the life cycle of organic aerosols in the Earth’s atmosphere. We will also aim at bridging between observations and models via synthesizing and translating the results and insights generated from this

  9. Monitoring of organic and elemental carbon (OC/EC) in the atmospheric aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Hannemann, A.; Fuchs, J.; Jaeschke, W.; Weingartner, E.; Baltensperger, U.

    2003-03-01

    A new instrument for the measurement of ambient carbonaceous aerosol concentrations is described, which enables discrimination between organic and elemental carbon on a semi-continuous basis. (author)

  10. Design, characterization, and aerosolization of organic solution advanced spray-dried moxifloxacin and ofloxacin dipalmitoylphosphatidylcholine (DPPC) microparticulate/nanoparticulate powders for pulmonary inhalation aerosol delivery

    Science.gov (United States)

    Duan, Jinghua; Vogt, Frederick G; Li, Xiaojian; Hayes, Don; Mansour, Heidi M

    2013-01-01

    The aim of this study was to design and develop respirable antibiotics moxifloxacin (MOXI) hydrochloride and ofloxacin (OFLX) microparticles and nanoparticles, and multifunctional antibiotics particles with or without lung surfactant 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) for targeted dry powder inhalation delivery as a pulmonary nanomedicine. Particles were rationally designed and produced by advanced spray-drying particle engineering from an organic solution in closed mode (no water) from dilute solution. Scanning electron microscopy indicated that these particles had both optimal particle morphology and surface morphology, and the particle size distributions were suitable for pulmonary delivery. Comprehensive and systematic physicochemical characterization and in vitro aerosol dispersion performance revealed significant differences between these two fluoroquinolone antibiotics following spray drying as drug aerosols and as cospray-dried antibiotic drug: DPPC aerosols. Fourier transform infrared spectroscopy and confocal Raman microspectroscopy were employed to probe composition and interactions in the solid state. Spray-dried MOXI was rendered noncrystalline (amorphous) following organic solution advanced spray drying. This was in contrast to spray-dried OFLX, which retained partial crystallinity, as did OFLX:DPPC powders at certain compositions. Aerosol dispersion performance was conducted using inertial impaction with a dry powder inhaler device approved for human use. The present study demonstrates that the use of DPPC offers improved aerosol delivery of MOXI as cospray-dried microparticulate/nanoparticulate powders, whereas residual partial crystallinity influenced aerosol dispersion of OFLX and most of the compositions of OFLX:DPPC inhalation powders. PMID:24092972

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

    Science.gov (United States)

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

    2010-01-01

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

  12. Phenomenological study of aerosol dry deposition in urban area: surface properties, turbulence and local meteorology influences

    International Nuclear Information System (INIS)

    Roupsard, P.

    2013-01-01

    Aerosol dry deposition is not much known for urban areas due to the lack of data. Knowledge on this phenomenon is necessary to understand pollutant fluxes in cities and to estimate inhabitant exposition to ionizing radiation of radioactive aerosols. A data providing could enable to enhance dry deposition models for these areas. An original experimental approach is performed to study submicron aerosol dry deposition on urban surfaces. Wind tunnel coupled to in situ experiments give results to study different physical phenomenon governing dry deposition. Dry deposition velocities are measured using aerosol tracers. These data are associated to turbulent and meteorological measured conditions. This database permits to classify the principal physical phenomenon for each experiment type. Finally, different phenomenon must be considered for chronic and acute exposition of urban surfaces to atmospheric particles. (author)

  13. Secondary organic aerosol importance in the future atmosphere

    International Nuclear Information System (INIS)

    Tsigaridis, K.; Kanakidou, M.

    2007-01-01

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

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

    Science.gov (United States)

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

    2016-04-01

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

  15. Aerosol processing: a wind of innovation in the field of advanced heterogeneous catalysts.

    Science.gov (United States)

    Debecker, Damien P; Le Bras, Solène; Boissière, Cédric; Chaumonnot, Alexandra; Sanchez, Clément

    2018-04-16

    Aerosol processing is long known and implemented industrially to obtain various types of divided materials and nanomaterials. The atomisation of a liquid solution or suspension produces a mist of aerosol droplets which can then be transformed via a diversity of processes including spray-drying, spray pyrolysis, flame spray pyrolysis, thermal decomposition, micronisation, gas atomisation, etc. The attractive technical features of these aerosol processes make them highly interesting for the continuous, large scale, and tailored production of heterogeneous catalysts. Indeed, during aerosol processing, each liquid droplet undergoes well-controlled physical and chemical transformations, allowing for example to dry and aggregate pre-existing solid particles or to synthesise new micro- or nanoparticles from mixtures of molecular or colloidal precursors. In the last two decades, more advanced reactive aerosol processes have emerged as innovative means to synthesise tailored-made nanomaterials with tunable surface properties, textures, compositions, etc. In particular, the "aerosol-assisted sol-gel" process (AASG) has demonstrated tremendous potential for the preparation of high-performance heterogeneous catalysts. The method is mainly based on the low-cost, scalable, and environmentally benign sol-gel chemistry process, often coupled with the evaporation-induced self-assembly (EISA) concept. It allows producing micronic or submicronic, inorganic or hybrid organic-inorganic particles bearing tuneable and calibrated porous structures at different scales. In addition, pre-formed nanoparticles can be easily incorporated or formed in a "one-pot" bottom-up approach within the porous inorganic or hybrid spheres produced by such spray drying method. Thus, multifunctional catalysts with tailored catalytic activities can be prepared in a relatively simple way. This account is an overview of aerosol processed heterogeneous catalysts which demonstrated interesting performance in

  16. Nanocrystalline functional materials and nanocomposites synthesis through aerosol routes

    Directory of Open Access Journals (Sweden)

    Milošević Olivera B.

    2003-01-01

    Full Text Available This paper represents the results of the design of functional nanocrystalline powders and nanocomposites using chemical reactions in aerosols. The process involves ultrasonic aerosol formation (mist generators with the resonant frequencies of 800 kHz, 1.7 and 2.5 MHz from precursor salt solutions and control over the aerosol decomposition in a high-temperature tubular flow reactor. During decomposition, the aerosol droplets undergo evaporation/drying, precipitation and thermolysis in a single-step process. Consequently, spherical, solid, agglomerate-free submicronic particles are obtained. The particle morphology, revealed as a composite structure consisting of primary crystallites smaller than 20 nm was analysed by several methods (XRD, DSC/DTA, SEM, TEM and discussed in terms of precursor chemistry and process parameters. Following the initial attempts, a more detailed aspect of nanocrystalline particle synthesis was demonstrated for the case of nanocomposites based on ZnO-MeO (MeO=Bi Cr+, suitable for electronic applications, as well as an yttrium-aluminum base complex system, suitable for phosphorus applications. The results imply that parts of the material structure responsible for different functional behaviour appear through in situ aerosol synthesis by processes of intraparticle agglomeration, reaction and sintering in the last synthesis stage.

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

    Science.gov (United States)

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

    2017-07-01

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

  18. Influences of in-cloud aerosol scavenging parameterizations on aerosol concentrations and wet deposition in ECHAM5-HAM

    Directory of Open Access Journals (Sweden)

    B. Croft

    2010-02-01

    , mid-troposphere 210Pb vertical profiles, and the geographic distribution of aerosol optical depth is found for the new diagnostic scavenging scheme compared to the prescribed scavenging fraction scheme of the standard ECHAM5-HAM. The diagnostic and prognostic schemes represent the variability of scavenged fractions particularly for submicron size aerosols, and for mixed and ice phase clouds, and are recommended in preference to the prescribed scavenging fractions method.

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

    Science.gov (United States)

    2013-01-01

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

  20. Modeling organic aerosol from the oxidation of α-pinene in a Potential Aerosol Mass (PAM chamber

    Directory of Open Access Journals (Sweden)

    S. Chen

    2013-05-01

    Full Text Available A model has been developed to simulate the formation and evolution of secondary organic aerosol (SOA and was tested against data produced in a Potential Aerosol Mass (PAM flow reactor and a large environmental chamber. The model framework is based on the two-dimensional volatility basis set approach (2D-VBS, in which SOA oxidation products in the model are distributed on the 2-D space of effective saturation concentration (Ci* and oxygen-to-carbon ratio (O : C. The modeled organic aerosol mass concentrations (COA and O : C agree with laboratory measurements within estimated uncertainties. However, while both measured and modeled O : C increase with increasing OH exposure as expected, the increase of modeled O : C is rapid at low OH exposure and then slows as OH exposure increases while the increase of measured O : C is initially slow and then accelerates as OH exposure increases. A global sensitivity analysis indicates that modeled COA values are most sensitive to the assumed values for the number of Ci* bins, the heterogeneous OH reaction rate coefficient, and the yield of first-generation products. Modeled SOA O : C values are most sensitive to the assumed O : C of first-generation oxidation products, the number of Ci* bins, the heterogeneous OH reaction rate coefficient, and the number of O : C bins. All these sensitivities vary as a function of OH exposure. The sensitivity analysis indicates that the 2D-VBS model framework may require modifications to resolve discrepancies between modeled and measured O : C as a function of OH exposure.

  1. Oxygenated organic functional groups and their sources in single and submicron organic particles in MILAGRO 2006 campaign

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    S. Liu

    2009-09-01

    Full Text Available Fourier Transform Infrared (FTIR and X-ray Fluorescence (XRF were used to measure organic functional groups and elements of submicron particles collected during MILAGRO in March 2006 on three platforms: the Mexico City urban area (SIMAT, the high altitude site at 4010 m (Altzomoni, and the NCAR C130 aircraft. Scanning Transmission X-ray Microscopy (STXM and Near-Edge X-ray Absorption Fine Structure (NEXAFS were applied to single particle organic functional group abundance analysis of particles simultaneously collected at SIMAT and C130. Correlations of elemental concentrations showed different groups of source-related elements at SIMAT, Altzomoni, and C130, suggesting different processes affecting the air masses sampled at the three platforms. Cluster analysis resulted in seven distinct clusters of FTIR spectra, with the last three clusters consisting of spectra collected almost exclusively on the C130 platform, reflecting the variety of sources contributing to C130 samples. Positive Matrix Factorization (PMF of STXM-NEXAFS spectra identified three main factors representing soot, secondary, and biomass burning type spectra. PMF of FTIR spectra resulted in two fossil fuel combustion factors and one biomass burning factor, the former representative of source regions to the northeast and southwest of SIMAT. Alkane, carboxylic acid, amine, and alcohol functional groups were mainly associated with combustion related sources, while non-acid carbonyl groups were likely from biomass burning events. The majority of OM and O/C was attributed to combustion sources, although no distinction between direct emissions and atmospherically processed OM could be identified.

  2. Modelling organic aerosol concentrations and properties during ChArMEx summer campaigns of 2012 and 2013 in the western Mediterranean region

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    M. Chrit

    2017-10-01

    Full Text Available In the framework of the Chemistry-Aerosol Mediterranean Experiment, a measurement site was set up at a remote site (Ersa on Corsica Island in the northwestern Mediterranean Sea. Measurement campaigns performed during the summers of 2012 and 2013 showed high organic aerosol concentrations, mostly from biogenic origin. This work aims to represent the organic aerosol concentrations and properties (oxidation state and hydrophilicity using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA formation. Biogenic precursors are isoprene, monoterpenes and sesquiterpenes. In this work, the following model oxidation products of monoterpenes are added: (i a carboxylic acid (MBTCA to represent multi-generation oxidation products in the low-NOx regime, (ii organic nitrate chemistry and (iii extremely low-volatility organic compounds (ELVOCs formed by ozonolysis. The model shows good agreement of measurements of organic concentrations for both 2012 and 2013 summer campaigns. The modelled oxidation property and hydrophilic organic carbon properties of the organic aerosols also agree reasonably well with the measurements. The influence of the different chemical processes added to the model on the oxidation level of organics is studied. Measured and simulated water-soluble organic carbon (WSOC concentrations show that even at a remote site next to the sea, about 64 % of the organic carbon is soluble. The concentrations of WSOC vary with the origins of the air masses and the composition of organic aerosols. The marine organic emissions only contribute to a few percent of the organic mass in PM1, with maxima above the sea.

  3. Modelling organic aerosol concentrations and properties during ChArMEx summer campaigns of 2012 and 2013 in the western Mediterranean region

    Science.gov (United States)

    Chrit, Mounir; Sartelet, Karine; Sciare, Jean; Pey, Jorge; Marchand, Nicolas; Couvidat, Florian; Sellegri, Karine; Beekmann, Matthias

    2017-10-01

    In the framework of the Chemistry-Aerosol Mediterranean Experiment, a measurement site was set up at a remote site (Ersa) on Corsica Island in the northwestern Mediterranean Sea. Measurement campaigns performed during the summers of 2012 and 2013 showed high organic aerosol concentrations, mostly from biogenic origin. This work aims to represent the organic aerosol concentrations and properties (oxidation state and hydrophilicity) using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA) formation. Biogenic precursors are isoprene, monoterpenes and sesquiterpenes. In this work, the following model oxidation products of monoterpenes are added: (i) a carboxylic acid (MBTCA) to represent multi-generation oxidation products in the low-NOx regime, (ii) organic nitrate chemistry and (iii) extremely low-volatility organic compounds (ELVOCs) formed by ozonolysis. The model shows good agreement of measurements of organic concentrations for both 2012 and 2013 summer campaigns. The modelled oxidation property and hydrophilic organic carbon properties of the organic aerosols also agree reasonably well with the measurements. The influence of the different chemical processes added to the model on the oxidation level of organics is studied. Measured and simulated water-soluble organic carbon (WSOC) concentrations show that even at a remote site next to the sea, about 64 % of the organic carbon is soluble. The concentrations of WSOC vary with the origins of the air masses and the composition of organic aerosols. The marine organic emissions only contribute to a few percent of the organic mass in PM1, with maxima above the sea.

  4. Distinct high molecular weight organic compound (HMW-OC) types in aerosol particles collected at a coastal urban site

    Science.gov (United States)

    Dall'Osto, M.; Healy, R. M.; Wenger, J. C.; O'Dowd, C.; Ovadnevaite, J.; Ceburnis, D.; Harrison, Roy M.; Beddows, D. C. S.

    2017-12-01

    Organic oligomers were discovered in laboratory-generated atmospheric aerosol over a decade ago. However, evidence for the presence of oligomers in ambient aerosols is scarce and mechanisms for their formation have yet to be fully elucidated. In this work, three unique aerosol particle types internally mixed with High molecular weight organic compounds (HMW-OC) species - likely oligomers - were detected in ambient air using single particle Aerosol Time-Of-Flight Mass Spectrometry (ATOFMS) in Cork (Ireland) during winter 2009. These particle types can be described as follows: (1) HMW-OCs rich in organic nitrogen - possibly containing nitrocatechols and nitroguaiacols - originating from primary emissions of biomass burning particles during evening times; (2) HMW-OCs internally mixed with nitric acid, occurring in stagnant conditions during night time; and (3) HMW-OCs internally mixed with sea salt, likely formed via photochemical reactions during day time. The study exemplifies the power of methodologies capable of monitoring the simultaneous formation of organic and inorganic particle-phase reaction products. Primary emissions and atmospheric aging of different types of HMW-OC contributes to aerosol with a range of acidity, hygroscopic and optical properties, which can have different impacts on climate and health.

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

    Science.gov (United States)

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

    2009-03-01

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

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

    Directory of Open Access Journals (Sweden)

    P. J. Silva

    2009-03-01

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

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

    Directory of Open Access Journals (Sweden)

    R. C. Flagan

    2007-10-01

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

  8. Hygroscopic Behavior of Multicomponent Aerosols Involving NaCl and Dicarboxylic Acids.

    Science.gov (United States)

    Peng, Chao; Jing, Bo; Guo, Yu-Cong; Zhang, Yun-Hong; Ge, Mao-Fa

    2016-02-25

    Atmospheric aerosols are usually complex mixtures of inorganic and organic compounds. The hygroscopicity of mixed particles is closely related to their chemical composition and interactions between components, which is still poorly understood. In this study, the hygroscopic properties of submicron particles composed of NaCl and dicarboxylic acids including oxalic acid (OA), malonic acid (MA), and succinic acid (SA) with various mass ratios are investigated with a hygroscopicity tandem differential mobility analyzer (HTDMA) system. Both the Zdanovskii-Stokes-Robinson (ZSR) method and extended aerosol inorganics model (E-AIM) are applied to predict the water uptake behaviors of sodium chloride/dicarboxylic acid mixtures. For NaCl/OA mixed particles, the measured growth factors were significantly lower than predictions from the model methods, indicating a change in particle composition caused by chloride depletion. The hygroscopic growth of NaCl/MA particles was well described by E-AIM, and that of NaCl/SA particles was dependent upon mixing ratio. Compared with model predictions, it was determined that water uptake of the NaCl/OA mixture could be enhanced and could be closer to the predictions by addition of levoglucosan or malonic acid, which retained water even at low relative humidity (RH), leading to inhibition of HCl evaporation during dehydration. These results demonstrate that the coexisting hygroscopic species have a strong influence on the phase state of particles, thus affecting chemical interactions between inorganic and organic compounds as well as the overall hygroscopicity of mixed particles.

  9. Characterization of fresh and aged organic aerosol emissions from meat charbroiling

    Directory of Open Access Journals (Sweden)

    C. Kaltsonoudis

    2017-06-01

    Full Text Available Cooking emissions can be a significant source of fine particulate matter in urban areas. In this study the aerosol- and gas-phase emissions from meat charbroiling were characterized. Greek souvlakia with pork were cooked using a commercial charbroiler and a fraction of the emissions were introduced into a smog chamber where after a characterization phase they were exposed to UV illumination and oxidants. The particulate and gas phases were characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS and a proton-transfer-reaction mass spectrometer (PTR-MS correspondingly. More than 99 % of the aerosol emitted was composed of organic compounds, while black carbon (BC contributed 0.3 % and the inorganic species less than 0.5 % of the total aerosol mass. The initial O  :  C ratio was approximately 0.09 and increased up to 0.30 after a few hours of chemical aging (exposures of 1010 molecules cm−3 s for OH and 100 ppb h for ozone. The initial and aged AMS spectra differed considerably (θ =  27°. Ambient measurements were also conducted during Fat Thursday in Patras, Greece, when traditionally meat is charbroiled everywhere in the city. Positive matrix factorization (PMF revealed that cooking organic aerosol (COA reached up to 85 % of the total OA from 10:00 to 12:00 LST that day. The ambient COA factor in two major Greek cities had a mass spectrum during spring and summer similar to the aged meat charbroiling emissions. In contrast, the ambient COA factor during winter resembled strongly the fresh laboratory meat charbroiling emissions.

  10. Modeling regional air quality and climate: improving organic aerosol and aerosol activation processes in WRF/Chem version 3.7.1

    Science.gov (United States)

    Yahya, Khairunnisa; Glotfelty, Timothy; Wang, Kai; Zhang, Yang; Nenes, Athanasios

    2017-06-01

    Air quality and climate influence each other through the uncertain processes of aerosol formation and cloud droplet activation. In this study, both processes are improved in the Weather, Research and Forecasting model with Chemistry (WRF/Chem) version 3.7.1. The existing Volatility Basis Set (VBS) treatments for organic aerosol (OA) formation in WRF/Chem are improved by considering the following: the secondary OA (SOA) formation from semi-volatile primary organic aerosol (POA), a semi-empirical formulation for the enthalpy of vaporization of SOA, and functionalization and fragmentation reactions for multiple generations of products from the oxidation of VOCs. Over the continental US, 2-month-long simulations (May to June 2010) are conducted and results are evaluated against surface and aircraft observations during the Nexus of Air Quality and Climate Change (CalNex) campaign. Among all the configurations considered, the best performance is found for the simulation with the 2005 Carbon Bond mechanism (CB05) and the VBS SOA module with semivolatile POA treatment, 25 % fragmentation, and the emissions of semi-volatile and intermediate volatile organic compounds being 3 times the original POA emissions. Among the three gas-phase mechanisms (CB05, CB6, and SAPRC07) used, CB05 gives the best performance for surface ozone and PM2. 5 concentrations. Differences in SOA predictions are larger for the simulations with different VBS treatments (e.g., nonvolatile POA versus semivolatile POA) compared to the simulations with different gas-phase mechanisms. Compared to the simulation with CB05 and the default SOA module, the simulations with the VBS treatment improve cloud droplet number concentration (CDNC) predictions (normalized mean biases from -40.8 % to a range of -34.6 to -27.7 %), with large differences between CB05-CB6 and SAPRC07 due to large differences in their OH and HO2 predictions. An advanced aerosol activation parameterization based on the Fountoukis and Nenes

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

    Directory of Open Access Journals (Sweden)

    Y. Gómez-González

    2012-01-01

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

  12. Long-range transport biomass burning emissions to the Himalayas: insights from high-resolution aerosol mass spectrometer

    Science.gov (United States)

    Xu, J.; Zhang, X.; Liu, Y.; Shichang, K.; Ma, Y.

    2017-12-01

    An intensive measurement was conducted at a remote, background, and high-altitude site (Qomolangma station, QOMS, 4276 m a.s.l.) in the northern Himalayas, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) along with other collocated instruments. The field measurement was performed from April 12 to May 12, 2016 to chemically characterize high time-resolved submicron particulate matter (PM1) and obtain the influence of biomass burning emissions to the Himalayas, frequently transported from south Asia during pre-monsoon season. Two high aerosol loading periods were observed during the study. Overall, the average (± 1σ) PM1 mass concentration was 4.44 (± 4.54) µg m-3 for the entire study, comparable with those observed at other remote sites worldwide. Organic aerosols (OA) was the dominant PM1 species (accounting for 54.3% of total PM1 mass on average) and its contribution increased with the increase of total PM1 mass loading. The average size distributions of PM1 species all peaked at an overlapping accumulation mode ( 500 nm), suggesting that aerosol particles were internally well-mixed and aged during long-range transportations. Positive matrix factorization (PMF) analysis on the high-resolution organic mass spectra identified three distinct OA factors, including a biomass burning related OA (BBOA, 43.7%) and two oxygenated OA (Local-OOA and LRT-OOA; 13.9% and 42.4%) represented sources from local emissions and long-range transportations, respectively. Two polluted air mass origins (generally from the west and southwest of QOMS) and two polluted episodes with enhanced PM1 mass loadings and elevated BBOA contributions were observed, respectively, suggesting the important sources of wildfires from south Asia. One of polluted aerosol plumes was investigated in detail to illustrate the evolution of aerosol characteristics at QOMS driving by different impacts of wildfires, air mass origins, meteorological conditions and

  13. Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

    Science.gov (United States)

    Pindado, Oscar; Pérez, Rosa M. a.; García, Susana; Sánchez, Miguel; Galán, Pilar; Fernández, Marta

    The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σ n-alkane and ΣPAHs ranged from 3 to 81 ng m -3 and 0.1 to 6 ng m -3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m -3 and 39 to 733 ng m -3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.

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

    Directory of Open Access Journals (Sweden)

    J. Wildt

    2009-07-01

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

  15. Effects of continental anthropogenic sources on organic aerosols in the coastal atmosphere of East China

    International Nuclear Information System (INIS)

    Shang, Dongjie; Hu, Min; Guo, Qingfeng; Zou, Qi; Zheng, Jing; Guo, Song

    2017-01-01

    Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM 2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM 2.5 samples from the marine and Changdao Island atmospheres were 5.5 ± 3.1 μgC/m 3 and 6.9 ± 2.4 μgC/m 3 , respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM 2.5 samples was 17.0 ± 20.2 ng/m 3 , indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the “North China” marine atmospheric samples. The “Northeast China” marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM 2.5 without considering high spatial resolution

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  17. Biogenic oxidized organic functional groups in aerosol particles from a mountain forest site and their similarities to laboratory chamber products

    Science.gov (United States)

    Schwartz, R. E.; Russell, L. M.; Sjostedt, S. J.; Vlasenko, A.; Slowik, J. G.; Abbatt, J. P. D.; MacDonald, A. M.; Li, S. M.; Liggio, J.; Toom-Sauntry, D.; Leaitch, W. R.

    2010-06-01

    Submicron particles collected at Whistler, British Columbia, at 1020 m a.s.l. during May and June 2008 on Teflon filters were analyzed by Fourier transform infrared (FTIR) and X-ray fluorescence (XRF) techniques for organic functional groups (OFG) and elemental composition. Organic mass (OM) concentrations ranged from less than 0.5 to 3.1 μg m-3, with a project mean and standard deviation of 1.3±1.0 μg m-3 and 0.21±0.16 μg m-3 for OM and sulfate, respectively. On average, organic hydroxyl, alkane, and carboxylic acid groups represented 34%, 33%, and 23% of OM, respectively. Ketone, amine and organosulfate groups constituted 6%, 5%, and volatile organic compounds (VOC), including isoprene and monoterpenes from biogenic VOC (BVOC) emissions and their oxidation products (methyl-vinylketone / methacrolein, MVK/MACR), were made using co-located proton transfer reaction mass spectrometry (PTR-MS). We present chemically-specific evidence of OFG associated with BVOC emissions. Positive matrix factorization (PMF) analysis attributed 65% of the campaign OM to biogenic sources, based on the correlations of one factor to monoterpenes and MVK/MACR. The remaining fraction was attributed to anthropogenic sources based on a correlation to sulfate. The functional group composition of the biogenic factor (consisting of 32% alkane, 25% carboxylic acid, 21% organic hydroxyl, 16% ketone, and 6% amine groups) was similar to that of secondary organic aerosol (SOA) reported from the oxidation of BVOCs in laboratory chamber studies, providing evidence that the magnitude and chemical composition of biogenic SOA simulated in the laboratory is similar to that found in actual atmospheric conditions. The biogenic factor OM is also correlated to dust elements, indicating that dust may act as a non-acidic SOA sink. This role is supported by the organic functional group composition and morphology of single particles, which were analyzed by scanning transmission X-ray microscopy near edge X

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

    Science.gov (United States)

    Solomon, Danielle; Dutcher, Dabrina; Raymond, Timothy

    2013-11-01

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

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

    Directory of Open Access Journals (Sweden)

    A. P. Tsimpidi

    2010-01-01

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

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

    International Nuclear Information System (INIS)

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

    1990-10-01

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

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

    Directory of Open Access Journals (Sweden)

    N. Sareen

    2016-11-01

    Full Text Available Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols, leading to the formation of secondary organic aerosol (SOAAQ. Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS. Hydroxyl (OH⚫ radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS. Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS spectra and tandem MS (MS–MS fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and

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

    Science.gov (United States)

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

    2012-03-01

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

  3. Aerosol composition, oxidative properties, and sources in Beijing: results from the 2014 Asia-Pacific Economic Cooperation Summit study

    Science.gov (United States)

    Xu, W. Q.; Sun, Y. L.; Chen, C.; Du, W.; Han, T. T.; Wang, Q. Q.; Fu, P. Q.; Wang, Z. F.; Zhao, X. J.; Zhou, L. B.; Ji, D. S.; Wang, P. C.; Worsnop, D. R.

    2015-08-01

    The mitigation of air pollution in megacities remains a great challenge because of the complex sources and formation mechanisms of aerosol particles. The 2014 Asia- Pacific Economic Cooperation (APEC) summit in Beijing serves as a unique experiment to study the impacts of emission controls on aerosol composition, size distributions, and oxidative properties. Herein, a high-resolution time-of-flight aerosol mass spectrometer was deployed in urban Beijing for real-time measurements of size-resolved non-refractory submicron aerosol (NR-PM1) species from 14 October to 12 November 2014, along with a range of collocated measurements. The average (±σ) PM1 was 41.6 (±38.9) μg m-3 during APEC, which was decreased by 53 % compared with that before APEC. The aerosol composition showed substantial changes owing to emission controls during APEC. Secondary inorganic aerosols (SIA = sulfate + nitrate + ammonium) showed significant reductions of 62-69 %, whereas organics presented much smaller decreases (35 %). The results from the positive matrix factorization of organic aerosols (OA) indicated that highly oxidized secondary OA (SOA) showed decreases similar to those of SIA during APEC. However, primary OA (POA) from cooking, traffic, and biomass burning sources were comparable to those before APEC, indicating the presence of strong local source emissions. The oxidation properties showed corresponding changes in response to OA composition. The average oxygen-to-carbon level during APEC was 0.36 (±0.10), which is lower than the 0.43 (±0.13) measured before APEC, demonstrating a decrease in the OA oxidation degree. The changes in size distributions of primary and secondary species varied during APEC. SIA and SOA showed significant reductions in large accumulation modes with peak diameters shifting from ~ 650 to 400 nm during APEC, whereas those of POA remained relatively unchanged. The changes in aerosol composition, size distributions, and oxidation degrees during the aging

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

    OpenAIRE

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

    2013-01-01

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

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

    Science.gov (United States)

    Guo, T.; Guo, Z.

    2017-12-01

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

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

    Science.gov (United States)

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

    2014-12-01

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

  7. Characterization of aerosol particles at the forested site in Lithuania

    Science.gov (United States)

    Rimselyte, I.; Garbaras, A.; Kvietkus, K.; Remeikis, V.

    2009-04-01

    monitoring station (55˚ 26'26"N; 26˚ 03'60"E) in the eastern part of Lithuania in the Aukštaitija national park during 2-24 July, 2008. The Rugšteliškis station is located in a remote relatively clean forested area. An aerosol mass spectrometer (AMS), developed at Aerodyne Research, was used to obtain real-time quantitative information on particle size-resolved mass loadings for volatile and semi-volatile chemical components present in/on ambient aerosol. The AMS inlet system allows 100 % transmission efficiency for particles with size diameter between 60 to 600 nm and partial transmission down to 20 nm and up to 2000 nm. The aerosol sampling was also carried out using a Micro-Orifice Uniform Deposit Impactor (MOUDI) model 110. The flow rate was 30 l/min, and the 50% aerodynamic cutoff diameters of the 10 stages were 18, 10, 5.6, 3.2, 1.8, 1.0, 0.56, 0.32, 0.18, 0.10 and 0.056 m. Aluminum foil was used as the impaction surface. The aerosol samples were analyzed for total carbon using the elemental analyzer (Flash EA1112). Besides, samples were analyzed for ^13C/12C ratio by the isotopic ratio mass spectrometer (Thermo Finnigan Delta Plus Advantage) (Norman et al., 1999; Garbaras et al., 2008). During campaign the dynamic behavior of aerosols was measured and quantitatively compared with meteorological conditions and air mass transport. The submicron aerosol was predominately sulphate and organic material. The AMS was able to discriminate and quantify mixed organic/inorganic accumulation mode particles (300 - 400 nm), which appeared to be dominated by regional sources and were of the origin similar to those seen in the more remote areas. The particulate organic fraction was also investigated in detail using the mass spectral data. By combining the organic matter size distribution (measured with AMS) with the total carbon (TC) size distribution (measured with MOUDI) we were able to report organic carbon to total carbon (OC/TC) ratio in different size particles

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

    Science.gov (United States)

    Li, Lijie; Cocker, David R.

    2018-05-01

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

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

    Science.gov (United States)

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

    2003-09-15

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

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

    Science.gov (United States)

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

    2011-09-01

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

  11. Chemical signatures of urban, open burning and dust transportation in an urban environment- megacity in South Asia

    Science.gov (United States)

    Priyadharshini, B.; Verma, S.

    2016-12-01

    A sub-micron aerosol sampler (SAS) consisting of two parallel stacked filter units (SFU) was deployed at an urban location (Kolkata) to study the sub-micron aerosols (water soluble inorganic ions (WSII) and carbonaceous aerosols (elemental carbon (EC) and organic carbon (OC)) collected over a year (September 2010 to August 2011). Quantification of 10 WSII species using Ion Chromatograph (IC) indicated alkaline nature of aerosols with calcium (Ca2+) being the major neutralizing factor of acidity at the study site. In terms of WSII percentage contribution, the most abundant were crustal species (Ca2+, magnesium (Mg2+) and marine species (chloride (Cl-)), followed by the secondary species sulphate (SO42-), nitrate (NO3-) and ammonium (NH4+) . Ca2+ (fugitive and transported dust) was dominant throughout the study period with K+ concentrations exhibiting seasonality with agricultural residue burning. Further, results of carbonaceous aerosols analyzed using the OC-EC aerosol analyzer following Interagency Monitoring of Protected Visual Environment (IMPROVE) protocol exhibited pronounced seasonality in OC than EC with the overall mean concentration of OC being three folds than EC. Primary organic carbon (POC) and secondary organic carbon concentrations (SOC) estimated using EC tracer method showed 57% (43%) of POC (SOC) from various emission sources. Investigation of OC/EC ratio along with non-sea salt potassium (nss-K+) values revealed influence of season specific anthropogenic activities on both OC and EC concentrations (viz. Open burning (OB)) besides fossil fuel (FF) and biofuel (BF) usage for cooking and heating prevalent over the region. Source apportionment was discerned using positive matrix factorization (PMF) with four major factors (crustal, agricultural, anthropogenic sources and mixed source (crustal + agriculture + anthropogenic) as the primary contributors to the sub-micron aerosols at the study site.

  12. Estimation of the volatility distribution of organic aerosol combining thermodenuder and isothermal dilution measurements

    Directory of Open Access Journals (Sweden)

    E. E. Louvaris

    2017-10-01

    Full Text Available A method is developed following the work of Grieshop et al. (2009 for the determination of the organic aerosol (OA volatility distribution combining thermodenuder (TD and isothermal dilution measurements. The approach was tested in experiments that were conducted in a smog chamber using organic aerosol (OA produced during meat charbroiling. A TD was operated at temperatures ranging from 25 to 250 °C with a 14 s centerline residence time coupled to a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS and a scanning mobility particle sizer (SMPS. In parallel, a dilution chamber filled with clean air was used to dilute isothermally the aerosol of the larger chamber by approximately a factor of 10. The OA mass fraction remaining was measured as a function of temperature in the TD and as a function of time in the isothermal dilution chamber. These two sets of measurements were used together to estimate the volatility distribution of the OA and its effective vaporization enthalpy and accommodation coefficient. In the isothermal dilution experiments approximately 20 % of the OA evaporated within 15 min. Almost all the OA evaporated in the TD at approximately 200 °C. The resulting volatility distributions suggested that around 60–75 % of the cooking OA (COA at concentrations around 500 µg m−3 consisted of low-volatility organic compounds (LVOCs, 20–30 % of semivolatile organic compounds (SVOCs, and around 10 % of intermediate-volatility organic compounds (IVOCs. The estimated effective vaporization enthalpy of COA was 100 ± 20 kJ mol−1 and the effective accommodation coefficient was 0.06–0.07. Addition of the dilution measurements to the TD data results in a lower uncertainty of the estimated vaporization enthalpy as well as the SVOC content of the OA.

  13. Estimation of the volatility distribution of organic aerosol combining thermodenuder and isothermal dilution measurements

    Science.gov (United States)

    Louvaris, Evangelos E.; Karnezi, Eleni; Kostenidou, Evangelia; Kaltsonoudis, Christos; Pandis, Spyros N.

    2017-10-01

    A method is developed following the work of Grieshop et al. (2009) for the determination of the organic aerosol (OA) volatility distribution combining thermodenuder (TD) and isothermal dilution measurements. The approach was tested in experiments that were conducted in a smog chamber using organic aerosol (OA) produced during meat charbroiling. A TD was operated at temperatures ranging from 25 to 250 °C with a 14 s centerline residence time coupled to a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a scanning mobility particle sizer (SMPS). In parallel, a dilution chamber filled with clean air was used to dilute isothermally the aerosol of the larger chamber by approximately a factor of 10. The OA mass fraction remaining was measured as a function of temperature in the TD and as a function of time in the isothermal dilution chamber. These two sets of measurements were used together to estimate the volatility distribution of the OA and its effective vaporization enthalpy and accommodation coefficient. In the isothermal dilution experiments approximately 20 % of the OA evaporated within 15 min. Almost all the OA evaporated in the TD at approximately 200 °C. The resulting volatility distributions suggested that around 60-75 % of the cooking OA (COA) at concentrations around 500 µg m-3 consisted of low-volatility organic compounds (LVOCs), 20-30 % of semivolatile organic compounds (SVOCs), and around 10 % of intermediate-volatility organic compounds (IVOCs). The estimated effective vaporization enthalpy of COA was 100 ± 20 kJ mol-1 and the effective accommodation coefficient was 0.06-0.07. Addition of the dilution measurements to the TD data results in a lower uncertainty of the estimated vaporization enthalpy as well as the SVOC content of the OA.

  14. Atmospheric aerosol compositions and sources at two national background sites in northern and southern China

    Science.gov (United States)

    Zhu, Qiao; He, Ling-Yan; Huang, Xiao-Feng; Cao, Li-Ming; Gong, Zhao-Heng; Wang, Chuan; Zhuang, Xin; Hu, Min

    2016-08-01

    Although China's severe air pollution has become a focus in the field of atmospheric chemistry and the mechanisms of urban air pollution there have been researched extensively, few field sampling campaigns have been conducted at remote background sites in China, where air pollution characteristics on a larger scale are highlighted. In this study, an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), together with an Aethalometer, was deployed at two of China's national background sites in northern (Lake Hongze site; 33.23° N, 118.33° E; altitude 21 m) and southern (Mount Wuzhi site; 18.84° N, 109.49° E; altitude 958 m) China in the spring seasons in 2011 and 2015, respectively, in order to characterize submicron aerosol composition and sources. The campaign-average PM1 concentration was 36.8 ± 19.8 µg m-3 at the northern China background (NCB) site, which was far higher than that at the southern China background (SCB) site (10.9 ± 7.8 µg m-3). Organic aerosol (OA) (27.2 %), nitrate (26.7 %), and sulfate (22.0 %) contributed the most to the PM1 mass at NCB, while OA (43.5 %) and sulfate (30.5 %) were the most abundant components of the PM1 mass at SCB, where nitrate only constituted a small fraction (4.7 %) and might have contained a significant amount of organic nitrates (5-11 %). The aerosol size distributions and organic aerosol elemental compositions all indicated very aged aerosol particles at both sites. The OA at SCB was more oxidized with a higher average oxygen to carbon (O / C) ratio (0.98) than that at NCB (0.67). Positive matrix factorization (PMF) analysis was used to classify OA into three components, including a hydrocarbon-like component (HOA, attributed to fossil fuel combustion) and two oxygenated components (OOA1 and OOA2, attributed to secondary organic aerosols from different source areas) at NCB. PMF analysis at SCB identified a semi-volatile oxygenated component (SV-OOA) and a low-volatility oxygenated

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

    Science.gov (United States)

    McNeill, V Faye

    2015-02-03

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

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

    Science.gov (United States)

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

    2017-12-01

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

  17. Quantitative estimates of the volatility of ambient organic aerosol

    Directory of Open Access Journals (Sweden)

    C. D. Cappa

    2010-06-01

    Full Text Available 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

  18. Method for characterization of low molecular weight organic acids in atmospheric aerosols using ion chromatography mass spectrometry.

    Science.gov (United States)

    Brent, Lacey C; Reiner, Jessica L; Dickerson, Russell R; Sander, Lane C

    2014-08-05

    The structural composition of PM2.5 monitored in the atmosphere is usually divided by the analysis of organic carbon, black (also called elemental) carbon, and inorganic salts. The characterization of the chemical composition of aerosols represents a significant challenge to analysts, and studies are frequently limited to determination of aerosol bulk properties. To better understand the potential health effects and combined interactions of components in aerosols, a variety of measurement techniques for individual analytes in PM2.5 need to be implemented. The method developed here for the measurement of organic acids achieves class separation of aliphatic monoacids, aliphatic diacids, aromatic acids, and polyacids. The selective ion monitoring capability of a triple quadropole mass analyzer was frequently capable of overcoming instances of incomplete separations. Standard Reference Material (SRM) 1649b Urban Dust was characterized; 34 organic acids were qualitatively identified, and 6 organic acids were quantified.

  19. Estimation of atmospheric columnar organic matter (OM) mass concentration from remote sensing measurements of aerosol spectral refractive indices

    Science.gov (United States)

    Zhang, Ying; Li, Zhengqiang; Sun, Yele; Lv, Yang; Xie, Yisong

    2018-04-01

    Aerosols have adverse effects on human health and air quality, changing Earth's energy balance and lead to climate change. The components of aerosol are important because of the different spectral characteristics. Based on the low hygroscopic and high scattering properties of organic matter (OM) in fine modal atmospheric aerosols, we develop an inversion algorithm using remote sensing to obtain aerosol components including black carbon (BC), organic matter (OM), ammonium nitrate-like (AN), dust-like (DU) components and aerosol water content (AW). In the algorithm, the microphysical characteristics (i.e. volume distribution and complex refractive index) of particulates are preliminarily separated to fine and coarse modes, and then aerosol components are retrieved using bimodal parameters. We execute the algorithm using remote sensing measurements of sun-sky radiometer at AERONET site (Beijing RADI) in a period from October of 2014 to January of 2015. The results show a reasonable distribution of aerosol components and a good fit for spectral feature calculations. The mean OM mass concentration in atmospheric column is account for 14.93% of the total and 56.34% of dry and fine-mode aerosol, being a fairly good correlation (R = 0.56) with the in situ observations near the surface layer.

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

    Directory of Open Access Journals (Sweden)

    L. Hildebrandt

    2009-05-01

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

  1. Identification of the sources of primary organic aerosols at urban schools: A molecular marker approach

    International Nuclear Information System (INIS)

    Crilley, Leigh R.; Qadir, Raeed M.; Ayoko, Godwin A.; Schnelle-Kreis, Jürgen; Abbaszade, Gülcin; Orasche, Jürgen; Zimmermann, Ralf; Morawska, Lidia

    2014-01-01

    Children are particularly susceptible to air pollution and schools are examples of urban microenvironments that can account for a large portion of children's exposure to airborne particles. Thus this paper aimed to determine the sources of primary airborne particles that children are exposed to at school by analyzing selected organic molecular markers at 11 urban schools in Brisbane, Australia. Positive matrix factorization analysis identified four sources at the schools: vehicle emissions, biomass burning, meat cooking and plant wax emissions accounting for 45%, 29%, 16% and 7%, of the organic carbon respectively. Biomass burning peaked in winter due to prescribed burning of bushland around Brisbane. Overall, the results indicated that both local (traffic) and regional (biomass burning) sources of primary organic aerosols influence the levels of ambient particles that children are exposed at the schools. These results have implications for potential control strategies for mitigating exposure at schools. - Highlights: • Selected organic molecular markers at 11 urban schools were analyzed. • Four sources of primary organic aerosols were identified by PMF at the schools. • Both local and regional sources were found to influence exposure at the schools. • The results have implications for mitigation of children's exposure at schools. - The identification of the most important sources of primary organic aerosols at urban schools has implications for control strategies for mitigating children's exposure at schools

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-04-11

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

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

    Science.gov (United States)

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

    2014-06-01

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

  4. Coarse mode aerosols in the High Arctic

    Science.gov (United States)

    Baibakov, K.; O'Neill, N. T.; Chaubey, J. P.; Saha, A.; Duck, T. J.; Eloranta, E. W.

    2014-12-01

    Fine mode (submicron) aerosols in the Arctic have received a fair amount of scientific attention in terms of smoke intrusions during the polar summer and Arctic haze pollution during the polar winter. Relatively little is known about coarse mode (supermicron) aerosols, notably dust, volcanic ash and sea salt. Asian dust is a regular springtime event whose optical and radiative forcing effects have been fairly well documented at the lower latitudes over North America but rarely reported for the Arctic. Volcanic ash, whose socio-economic importance has grown dramatically since the fear of its effects on aircraft engines resulted in the virtual shutdown of European civil aviation in the spring of 2010 has rarely been reported in the Arctic in spite of the likely probability that ash from Iceland and the Aleutian Islands makes its way into the Arctic and possibly the high Arctic. Little is known about Arctic sea salt aerosols and we are not aware of any literature on the optical measurement of these aerosols. In this work we present preliminary results of the combined sunphotometry-lidar analysis at two High Arctic stations in North America: PEARL (80°N, 86°W) for 2007-2011 and Barrow (71°N,156°W) for 2011-2014. The multi-years datasets were analyzed to single out potential coarse mode incursions and study their optical characteristics. In particular, CIMEL sunphotometers provided coarse mode optical depths as well as information on particle size and refractive index. Lidar measurements from High Spectral Resolution lidars (AHSRL at PEARL and NSHSRL at Barrow) yielded vertically resolved aerosol profiles and gave an indication of particle shape and size from the depolarization ratio and color ratio profiles. Additionally, we employed supplementary analyses of HYSPLIT backtrajectories, OMI aerosol index, and NAAPS (Navy Aerosol Analysis and Prediction System) outputs to study the spatial context of given events.

  5. Atmospheric residence times of continental aerosols

    International Nuclear Information System (INIS)

    Balkanski, Y.J.

    1991-01-01

    The global atmospheric distributions of Rn-222 are simulated with a three-dimensional model of atmospheric transport based on the meteorology of the NASA Goddard Institute for Space Studies (GISS) general circulation model. The short-lived radioactive gas Rn-222 (half-life = 3.8d) is emitted almost exclusively from land, at a relatively uniform rate; hence it is an excellent tracer of continental influences. Lead-210 is produced by decay of Rn-222 and immediately condenses to preexisting aerosol surfaces. It provides an excellent measure of aerosol residence times in the atmosphere because its source is accurately defined by the Rn-222 distribution. Results from the three-dimensional model are compared to measurements of Rn-222 and Pb-210 atmospheric concentrations to evaluate model's long-range transport over oceanic regions and to study the deposition mechanisms of atmospheric aerosols. Model results for Rn-222 are used to examine the long-range transport of continental air over two selected oceanic regions, the subantarctic Indian Ocean and the North Pacific. It is shown that the fast transport of air from southern Africa causes substantial continental pollution at southern mid-latitudes, a region usually regarded as pristine. Air over the North Pacific is heavily impacted by continental influences year round, but the altitude at which the transport occurs varies seasonally. Observations of aerosols at island sites, which are commonly used as diagnostics of continental influences, may be misleading because they do not account for influences at high altitude and because aerosols are efficiently scavenged by deposition during transport. The study of Pb-210 focuses on defining the residence times of submicron aerosols in the troposphere. Scavenging in wet convective updrafts is found to provide the dominant sink on a global scale

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

    Science.gov (United States)

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

    2009-04-01

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

  7. Chemical and physical characteristics of aerosol particles at a remote coastal location, Mace Head, Ireland, during NAMBLEX

    Directory of Open Access Journals (Sweden)

    H. Coe

    2006-01-01

    characteristics to western Europe. During NAMBLEX the submicron aerosol was predominately acidified sulphate and organic material, which was most likely internally mixed. The remaining accumulation mode aerosol was sea salt. The organic and sulphate fractions were approximately equally important, though the mass ratio varies considerably between air masses. Mass spectral fingerprints of the organic fraction in polluted conditions are similar to those observed at other locations that are characterised by aged continental aerosol. In marine conditions, the background input of both sulphate and organic aerosol into Europe was observed to be between 0.5 and 1 µg m−3. Key differences in the mass spectra were observed during the few clean periods but were insufficient to ascertain whether these changes reflect differences in the source fingerprint of the organic aerosol. The coarse mode was composed of sea salt and showed significant displacement of chloride by nitrate and to a lesser extent sulphate in polluted conditions.

  8. Evidence for the role of organics in aerosol particle formation under atmospheric conditions

    International Nuclear Information System (INIS)

    Metzger, A.; Dommen, J.; Duplissy, J.; Prevot, A.S.H.; Weingartner, E.; Baltensperger, U.; Verheggen, B.; Riipinen, I.; Kulmala, M.; Spracklen, D.V.; Carslaw, K.S.

    2010-01-01

    New particle formation in the atmosphere is an important parameter in governing the radiative forcing of atmospheric aerosols. However, detailed nucleation mechanisms remain ambiguous, as laboratory data have so far not been successful in explaining atmospheric nucleation. We investigated the formation of new particles in a smog chamber simulating the photochemical formation of H2SO4 and organic condensable species. Nucleation occurs at H2SO4 concentrations similar to those found in the ambient atmosphere during nucleation events. The measured particle formation rates are proportional to the product of the concentrations of H2SO4 and an organic molecule. This suggests that only one H2SO4 molecule and one organic molecule are involved in the rate-limiting step of the observed nucleation process. Parameterizing this process in a global aerosol model results in substantially better agreement with ambient observations compared to control runs.

  9. Research of the arid aerosol carrying out with a help of a set of sodars

    International Nuclear Information System (INIS)

    Valery, K; Igor, G

    2008-01-01

    Study of spatial and vertical distribution of vertical wind velocity was carried out in the 'Har-Gzyr 2007' field program in the 'Black Sands' region, Russia, with the help of four sodars. Continuous (about half an hour) and stable anabatic motions of the air were revealed for altitudes 10m to 800m over the area of some square kilometres. The measured vertical speed reached 2m/s. Permanent and quick transfer of sub-micron aerosol particles from the surface layer to the troposphere can be explained by this phenomenon. The scheme is proposed to design a mass balance equation to calculate aerosol concentration in the upper layers of the ABL

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

    Directory of Open Access Journals (Sweden)

    J. F. Hamilton

    2009-06-01

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

  11. Chemical composition of aerosol particles and light extinction apportionment before and during the heating season in Beijing, China

    Science.gov (United States)

    Wang, Qingqing; Sun, Yele; Jiang, Qi; Du, Wei; Sun, Chengzhu; Fu, Pingqing; Wang, Zifa

    2015-12-01

    Despite extensive efforts into characterization of the sources and formation mechanisms of severe haze pollution in the megacity of Beijing, the response of aerosol composition and optical properties to coal combustion emissions in the heating season remain poorly understood. Here we conducted a 3 month real-time measurement of submicron aerosol (PM1) composition by an Aerosol Chemical Speciation Monitor and particle light extinction by a Cavity Attenuated Phase Shift extinction monitor in Beijing, China, from 1 October to 31 December 2012. The average (±σ) PM1 concentration was 82.4 (±73.1) µg/m3 during the heating period (HP, 15 November to 31 December), which was nearly 50% higher than that before HP (1 October to 14 November). While nitrate and secondary organic aerosol (SOA) showed relatively small changes, organics, sulfate, and chloride were observed to have significant increases during HP, indicating the dominant impacts of coal combustion sources on these three species. The relative humidity-dependent composition further illustrated an important role of aqueous-phase processing for the sulfate enhancement during HP. We also observed great increases of hydrocarbon-like OA (HOA) and coal combustion OA (CCOA) during HP, which was attributed to higher emissions at lower temperatures and coal combustion emissions, respectively. The relationship between light extinction and chemical composition was investigated using a multiple linear regression model. Our results showed that the largest contributors to particle extinction were ammonium nitrate (32%) and ammonium sulfate (28%) before and during HP, respectively. In addition, the contributions of SOA and primary OA to particle light extinction were quantified. The results showed that the OA extinction was mainly caused by SOA before HP and by SOA and CCOA during HP, yet with small contributions from HOA and cooking aerosol for the entire study period. Our results elucidate substantial changes of aerosol

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

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

    Science.gov (United States)

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

    2011-03-01

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

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

    Science.gov (United States)

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

    2018-05-01

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

  15. Effects of Ocean Ecosystem on Marine Aerosol-Cloud Interaction

    Directory of Open Access Journals (Sweden)

    Nicholas Meskhidze

    2010-01-01

    Full Text Available Using satellite data for the surface ocean, aerosol optical depth (AOD, and cloud microphysical parameters, we show that statistically significant positive correlations exist between ocean ecosystem productivity, the abundance of submicron aerosols, and cloud microphysical properties over different parts of the remote oceans. The correlation coefficient for remotely sensed surface chlorophyll a concentration ([Chl-a] and liquid cloud effective radii over productive areas of the oceans varies between −0.2 and −0.6. Special attention is given to identifying (and addressing problems from correlation analysis used in the previous studies that can lead to erroneous conclusions. A new approach (using the difference between retrieved AOD and predicted sea salt aerosol optical depth, AODdiff is developed to explore causal links between ocean physical and biological systems and the abundance of cloud condensation nuclei (CCN in the remote marine atmosphere. We have found that over multiple time periods, 550 nm AODdiff (sensitive to accumulation mode aerosol, which is the prime contributor to CCN correlates well with [Chl-a] over the productive waters of the Southern Ocean. Since [Chl-a] can be used as a proxy of ocean biological productivity, our analysis demonstrates the role of ocean ecology in contributing CCN, thus shaping the microphysical properties of low-level marine clouds.

  16. Development of Methodologies from Determination of Organic Components from Atmospheric Aerosol

    International Nuclear Information System (INIS)

    Pindado, O.; Perez, R.; Garcia, R.; Barrado, A. I.; Sevillano, M. L.; Gonzalez, D.

    2006-01-01

    It is presented method for the organic compound determination, such as n-alkanes, PAH's, alcohols and fatty acids that are comprised the particulate matter of aerosol. The procedure is based on sampling the particulate matter over quartz fibre filters that will be extracted by means of the Soxhiet technique, and later they will be divided by means of silicagel column. PAH's is analyzed by means of HPLCm whereas the rest is analyzed by GC-MS and for it, acids and alcohol must be previously derivatized with BSTFA.12 samples took shelter of fractions PMIO and PM2.5 of the aerosol of country side like application of the method. (Author) 60 refs

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

    Directory of Open Access Journals (Sweden)

    V. Varutbangkul

    2006-01-01

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

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

    Science.gov (United States)

    Bastelberger, Sandra; Krieger, Ulrich K.; Luo, Beiping; Peter, Thomas

    2017-07-01

    Field measurements indicating that atmospheric secondary organic aerosol (SOA) particles can be present in a highly viscous, glassy state have spurred numerous studies addressing low diffusivities of water in glassy aerosols. The focus of these studies is on kinetic limitations of hygroscopic growth and the plasticizing effect of water. In contrast, much less is known about diffusion limitations of organic molecules and oxidants in viscous matrices. These may affect atmospheric chemistry and gas-particle partitioning of complex mixtures with constituents of different volatility. In this study, we quantify the diffusivity of a volatile organic in a viscous matrix. Evaporation of single particles generated from an aqueous solution of sucrose and small amounts of volatile tetraethylene glycol (PEG-4) is investigated in an electrodynamic balance at controlled relative humidity (RH) and temperature. The evaporative loss of PEG-4 as determined by Mie resonance spectroscopy is used in conjunction with a radially resolved diffusion model to retrieve translational diffusion coefficients of PEG-4. Comparison of the experimentally derived diffusivities with viscosity estimates for the ternary system reveals a breakdown of the Stokes-Einstein relationship, which has often been invoked to infer diffusivity from viscosity. The evaporation of PEG-4 shows pronounced RH and temperature dependencies and is severely depressed for RH ≲ 30 %, corresponding to diffusivities pollutant molecules such as polycyclic aromatic hydrocarbons (PAHs).

  19. Experimental determination of submicron aerosol dry deposition velocity onto rural canopies: influence of aerosol size, of micro meteorological parameters and of the substrate

    International Nuclear Information System (INIS)

    Damay, P.

    2010-04-01

    To evaluate the impact of accidental or chronic pollutant releases on ecosystems, we must study the dry deposition of aerosols in rural areas. The lack of experimental data on the dry deposition velocity of particle sizes below 1 μm over rural environments leads to uncertainties regarding models and differences between them, which exceed one order of magnitude. The aim of this study is to develop a method, especially using an Electrical Low Pressure Impactor (Outdoor ELPIDEKATI) to determine aerosol dry deposition velocities (Vd) over rural areas through experimental measurements. This method is based on eddy covariance flux calculation and spectral analysis correction. Dry deposition velocities were obtained for atmospheric aerosols sizing from 7 nm to 2 μm, in the South-West of France on a flat terrain under varied meteorological conditions and varied substrates (maize, grass and earth). Vd was analysed as a function of the particle diameters, and the impact of micro meteorological parameters was studied. (author)

  20. An in situ cell to study phase transitions in individual aerosol particles on a substrate using scanning transmission x-ray microspectroscopy

    International Nuclear Information System (INIS)

    Huthwelker, T.; Zelenay, V.; Birrer, M.; Krepelova, A.; Raabe, J.; Ammann, M.; Tzvetkov, G.; Vernooij, M. G. C.

    2010-01-01

    A new in situ cell to study phase transitions and chemical processes on individual aerosol particles in the x-ray transmission microscope at the PolLux beamline of the Swiss light source has been built. The cell is machined from stainless steel and aluminum components and is designed to be used in the standard mount of the microscope without need of complicated rearrangements of the microscope. The cell consists of two parts, a back part which contains connections for the gas supply, heating, cooling devices, and temperature measurement. The second part is a removable clip, which hosts the sample. This clip can be easily exchanged and brought into a sampling unit for aerosol particles. Currently, the cell can be operated at temperatures ranging from -40 to +50 deg. C. The function of the cell is demonstrated using two systems of submicron size: inorganic sodium bromide aerosols and soot originating from a diesel passenger car. For the sodium bromide we demonstrate how phase transitions can be studied in these systems and that O1s spectra from aqueous sodium bromide solution can be taken from submicron sized particles. For the case of soot, we demonstrate that the uptake of water onto individual soot particles can be studied.

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

    Directory of Open Access Journals (Sweden)

    R. Bröske

    2003-01-01

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

  2. Light absorbing organic aerosols (brown carbon) over the tropical Indian Ocean: impact of biomass burning emissions

    International Nuclear Information System (INIS)

    Srinivas, Bikkina; Sarin, M M

    2013-01-01

    The first field measurements of light absorbing water-soluble organic carbon (WSOC), referred as brown carbon (BrC), have been made in the marine atmospheric boundary layer (MABL) during the continental outflow to the Bay of Bengal (BoB) and the Arabian Sea (ARS). The absorption signal measured at 365 nm in aqueous extracts of aerosols shows a systematic linear increase with WSOC concentration, suggesting a significant contribution from BrC to the absorption properties of organic aerosols. The mass absorption coefficient (b abs ) of BrC shows an inverse hyperbolic relation with wavelength (from ∼300 to 700 nm), providing an estimate of the Angstrom exponent (α P , range: 3–19; Av: 9 ± 3). The mass absorption efficiency of brown carbon (σ abs−BrC ) in the MABL varies from 0.17 to 0.72 m 2  g −1 (Av: 0.45 ± 0.14 m 2  g −1 ). The α P and σ abs−BrC over the BoB are quite similar to that studied from a sampling site in the Indo-Gangetic Plain (IGP), suggesting the dominant impact of organic aerosols associated with the continental outflow. A comparison of the mass absorption efficiency of BrC and elemental carbon (EC) brings to focus the significant role of light absorbing organic aerosols (from biomass burning emissions) in atmospheric radiative forcing over oceanic regions located downwind of the pollution sources. (letter)

  3. Unexpectedly high ultrafine aerosol concentrations above East Antarctic sea ice

    Directory of Open Access Journals (Sweden)

    R. S. Humphries

    2016-02-01

    Full Text Available Better characterisation of aerosol processes in pristine, natural environments, such as Antarctica, have recently been shown to lead to the largest reduction in uncertainties in our understanding of radiative forcing. Our understanding of aerosols in the Antarctic region is currently based on measurements that are often limited to boundary layer air masses at spatially sparse coastal and continental research stations, with only a handful of studies in the vast sea-ice region. In this paper, the first observational study of sub-micron aerosols in the East Antarctic sea ice region is presented. Measurements were conducted aboard the icebreaker Aurora Australis in spring 2012 and found that boundary layer condensation nuclei (CN3 concentrations exhibited a five-fold increase moving across the polar front, with mean polar cell concentrations of 1130 cm−3 – higher than any observed elsewhere in the Antarctic and Southern Ocean region. The absence of evidence for aerosol growth suggested that nucleation was unlikely to be local. Air parcel trajectories indicated significant influence from the free troposphere above the Antarctic continent, implicating this as the likely nucleation region for surface aerosol, a similar conclusion to previous Antarctic aerosol studies. The highest aerosol concentrations were found to correlate with low-pressure systems, suggesting that the passage of cyclones provided an accelerated pathway, delivering air masses quickly from the free troposphere to the surface. After descent from the Antarctic free troposphere, trajectories suggest that sea-ice boundary layer air masses travelled equatorward into the low-albedo Southern Ocean region, transporting with them emissions and these aerosol nuclei which, after growth, may potentially impact on the region's radiative balance. The high aerosol concentrations and their transport pathways described here, could help reduce the discrepancy currently present between

  4. Unexpectedly high ultrafine aerosol concentrations above East Antarctic sea ice

    Science.gov (United States)

    Humphries, R. S.; Klekociuk, A. R.; Schofield, R.; Keywood, M.; Ward, J.; Wilson, S. R.

    2016-02-01

    Better characterisation of aerosol processes in pristine, natural environments, such as Antarctica, have recently been shown to lead to the largest reduction in uncertainties in our understanding of radiative forcing. Our understanding of aerosols in the Antarctic region is currently based on measurements that are often limited to boundary layer air masses at spatially sparse coastal and continental research stations, with only a handful of studies in the vast sea-ice region. In this paper, the first observational study of sub-micron aerosols in the East Antarctic sea ice region is presented. Measurements were conducted aboard the icebreaker Aurora Australis in spring 2012 and found that boundary layer condensation nuclei (CN3) concentrations exhibited a five-fold increase moving across the polar front, with mean polar cell concentrations of 1130 cm-3 - higher than any observed elsewhere in the Antarctic and Southern Ocean region. The absence of evidence for aerosol growth suggested that nucleation was unlikely to be local. Air parcel trajectories indicated significant influence from the free troposphere above the Antarctic continent, implicating this as the likely nucleation region for surface aerosol, a similar conclusion to previous Antarctic aerosol studies. The highest aerosol concentrations were found to correlate with low-pressure systems, suggesting that the passage of cyclones provided an accelerated pathway, delivering air masses quickly from the free troposphere to the surface. After descent from the Antarctic free troposphere, trajectories suggest that sea-ice boundary layer air masses travelled equatorward into the low-albedo Southern Ocean region, transporting with them emissions and these aerosol nuclei which, after growth, may potentially impact on the region's radiative balance. The high aerosol concentrations and their transport pathways described here, could help reduce the discrepancy currently present between simulations and observations of

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

    Science.gov (United States)

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

    2017-08-01

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

  6. Characterization of primary organic aerosol emissions from meat cooking, trash burning, and motor vehicles with high-resolution aerosol mass spectrometry and comparison with ambient and chamber observations.

    Science.gov (United States)

    Mohr, Claudia; Huffman, Alex; Cubison, Michael J; Aiken, Allison C; Docherty, Kenneth S; Kimmel, Joel R; Ulbrich, Ingrid M; Hannigan, Michael; Jimenez, Jose L

    2009-04-01

    Organic aerosol (OA) emissions from motor vehicles, meat-cooking and trash burning are analyzed here using a high-resolution aerosol mass spectrometer (AMS). High resolution data show that aerosols emitted by combustion engines and plastic burning are dominated by hydrocarbon-like organic compounds. Meat cooking and especially paper burning emissions contain significant fractions of oxygenated organic compounds; however, their unit-resolution mass spectral signatures are very similar to those from ambient hydrocarbon-like OA, and very different from the mass spectra of ambient secondary or oxygenated OA (OOA). Thus, primary OA from these sources is unlikelyto be a significant direct source of ambient OOA. There are significant differences in high-resolution tracer m/zs that may be useful for differentiating some of these sources. Unlike in most ambient spectra, all of these sources have low total m/z 44 and this signal is not dominated by the CO2+ ion. All sources have high m/z 57, which is low during high OOA ambient periods. Spectra from paper burning are similar to some types of biomass burning OA, with elevated m/z 60. Meat cooking aerosols also have slightly elevated m/z 60, whereas motor vehicle emissions have very low signal at this m/z.

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

    Directory of Open Access Journals (Sweden)

    R. K. Pathak

    2007-07-01

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

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

    Directory of Open Access Journals (Sweden)

    A. Zuend

    2012-05-01

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

  9. Effects of continental anthropogenic sources on organic aerosols in the coastal atmosphere of East China.

    Science.gov (United States)

    Shang, Dongjie; Hu, Min; Guo, Qingfeng; Zou, Qi; Zheng, Jing; Guo, Song

    2017-10-01

    Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM 2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM 2.5 samples from the marine and Changdao Island atmospheres were 5.5 ± 3.1 μgC/m 3 and 6.9 ± 2.4 μgC/m 3 , respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM 2.5 samples was 17.0 ± 20.2 ng/m 3 , indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the "North China" marine atmospheric samples. The "Northeast China" marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM 2.5 without considering high spatial resolution source

  10. Experimental study of heterogeneous organic chemistry induced by far ultraviolet light: Implications for growth of organic aerosols by CH3 addition in the atmospheres of Titan and early Earth

    Science.gov (United States)

    Hong, Peng; Sekine, Yasuhito; Sasamori, Tsutoni; Sugita, Seiji

    2018-06-01

    Formation of organic aerosols driven by photochemical reactions has been observed and suggested in CH4-containing atmospheres, including Titan and early Earth. However, the detailed production and growth mechanisms of organic aerosols driven by solar far ultraviolet (FUV) light remain poorly constrained. We conducted laboratory experiments simulating photochemical reactions in a CH4sbnd CO2 atmosphere driven by the FUV radiations dominated by the Lyman-α line. In the experiments, we analyzed time variations in thickness and infrared spectra of solid organic film formed on an optical window in a reaction cell. Gas species formed by FUV irradiation were also analyzed and compared with photochemical model calculations. Our experimental results show that the growth rate of the organic film decreases as the CH4/CO2 ratio of reactant gas mixture decreases, and that the decrease becomes very steep for CH4/CO2 organic film but that the addition reaction of CH3 radicals onto the organic film with the reaction probability around 10-2 can explain the growth rate. At CH4/CO2 organic film. Our results suggest that organic aerosols would grow through CH3 addition onto the surface during the precipitation of aerosol particles in the middle atmosphere of Titan and early Earth. On Titan, effective CH3 addition would reduce C2H6 production in the atmosphere. On early Earth, growth of aerosol particles would be less efficient than those on Titan, possibly resulting in small-sized monomers and influencing UV shielding.

  11. Measurements of organic gases during aerosol formation events in the boreal forest atmosphere during QUEST

    Directory of Open Access Journals (Sweden)

    K. Sellegri

    2005-01-01

    Full Text Available Biogenic VOCs are important in the growth and possibly also in the early stages of formation of atmospheric aerosol particles. In this work, we present 10 min-time resolution measurements of organic trace gases at Hyytiälä, Finland during March 2002. The measurements were part of the project QUEST (Quantification of Aerosol Nucleation in the European Boundary Layer and took place during a two-week period when nucleation events occurred with various intensities nearly every day. Using a ground-based Chemical Ionization Mass Spectrometer (CIMS instrument, the following trace gases were detected: acetone, TMA, DMA, mass 68amu (candidate=isoprene, monoterpenes, methyl vinyl ketone (MVK and methacrolein (MaCR and monoterpene oxidation products (MTOP. For all of them except for the amines, we present daily variations during different classes of nucleation events, and non-event days. BVOC oxidation products (MVK, MaCR and MTOP show a higher ratio to the CS on event days compared to non-event days, indicating that their abundance relative to the surface of aerosol available is higher on nucleation days. Moreover, BVOC oxidation products are found to show significant correlations with the condensational sink (CS on nucleation event days, which indicates that they are representative of less volatile organic compounds that contribute to the growth of the nucleated particles and generally secondary organic aerosol formation. Behaviors of BVOC on event and non event days are compared to the behavior of CO.

  12. Investigation of the atmospheric behavior of dicarboxylic acids and other polar organic aerosol constituents

    International Nuclear Information System (INIS)

    Limbeck, A.

    2001-05-01

    The objective of the present work was to improve the present knowledge about the atmospheric behavior of polar organic aerosol constituents with special respect to dicarboxylic acids. To enable the simultaneous determination of polar organic compounds in atmospheric samples like aerosol or precipitation samples (atmospheric hydrometeors) a new GCMS method was developed. Almost all classes of oxygenated organic compounds like mono- and dicarboxylic acids, aldehydes, alcohols or polar aromatic compounds like phthalates could be determined with only one sample preparation scheme. The separation into two classes of organic compounds with different polarity was performed using solid phase extraction. After a sample pre-treatment of the derived fractions, including esterification of the acids and extraction with cyclohexane, the samples were analyzed with a GCMS system. The new method was applied for the analysis of simultaneously collected interstitial aerosol and cloud water samples from a continental background site in Central Europe (Sonnblick Observatory, located at 3106-m elevation in the Austrian Alps). In all samples a large variety of mono- and dicarboxylic acids were identified and quantified, together with some aldehydes, alcohols and aromatic compounds. Using the obtained data set, for the first time in-cloud scavenging efficiencies for dicarboxylic acids, monocarboxylic acids, and other polar organic compounds were calculated. The results were compared to sulfate, which exhibited an average scavenging efficiency of 0.94. In the last part of the present work the results from laboratory and field investigations conducted with the intention to yield an improved sampling technique for the correction of the positive sampling artifact (adsorption of gas phase organics onto the filter substrate) were presented. (author)

  13. Creation of device for monitoring of inhalation exposure doses in 'Ukryttia' object conditions considering submicron aerosols

    International Nuclear Information System (INIS)

    Melenevskij, A.Eh.; Kravchuk, T.A.; Ushakov, I.A.

    2003-01-01

    In the conditions of air enriched with Short-Lived Aerosols (SLA), the examinations of created device ASMA sampler were conducted in order to define its ability of educing rougher fractions from aspirated aerosol compositions. It is shown that in airflow velocity intervals from 100 to 140 m/s aerodynamic diameter of an effluent fraction varies from 0.9 to 0.7 microns. The algorithm of measurement result processing of aspirated filter strata activity is described.Using the numerical modeling, the efficiency of offered procedure of relative measurements is demonstrated

  14. Micromagnetic simulations of submicron cobalt dots

    International Nuclear Information System (INIS)

    Parker, G. J.; Cerjan, C.

    2000-01-01

    Numerical simulations of submicron Co extruded elliptical dots were performed to illustrate the relative importance of different physical parameters on the switching behavior in the easy direction. Shape, size, magnetic moment magnitude, and the magnitude and distribution of the crystalline anisotropicity were varied. The simulation represents magnetostatic, exchange, and crystalline anisotropicity fields on a structured mesh using finite difference techniques. The smooth boundary of the dots is accurately represented by use of the embedded curve boundary method. Agreement with experimental hysteresis measurements of submicron dot arrays is obtained when an appropriate angular distribution of the grain anisotropicity axes is invoked. (c) 2000 American Institute of Physics

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Science.gov (United States)

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

    2011-06-01

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

  17. Modelling iodide – iodate speciation in atmospheric aerosol: Contributions of inorganic and organic iodine chemistry

    Directory of Open Access Journals (Sweden)

    S. Pechtl

    2007-01-01

    Full Text Available The speciation of iodine in atmospheric aerosol is currently poorly understood. Models predict negligible iodide concentrations but accumulation of iodate in aerosol, both of which is not confirmed by recent measurements. We present an updated aqueous phase iodine chemistry scheme for use in atmospheric chemistry models and discuss sensitivity studies with the marine boundary layer model MISTRA. These studies show that iodate can be reduced in acidic aerosol by inorganic reactions, i.e., iodate does not necessarily accumulate in particles. Furthermore, the transformation of particulate iodide to volatile iodine species likely has been overestimated in previous model studies due to negligence of collision-induced upper limits for the reaction rates. However, inorganic reaction cycles still do not seem to be sufficient to reproduce the observed range of iodide – iodate speciation in atmospheric aerosol. Therefore, we also investigate the effects of the recently suggested reaction of HOI with dissolved organic matter to produce iodide. If this reaction is fast enough to compete with the inorganic mechanism, it would not only directly lead to enhanced iodide concentrations but, indirectly via speed-up of the inorganic iodate reduction cycles, also to a decrease in iodate concentrations. Hence, according to our model studies, organic iodine chemistry, combined with inorganic reaction cycles, is able to reproduce observations. The presented chemistry cycles are highly dependent on pH and thus offer an explanation for the large observed variability of the iodide – iodate speciation in atmospheric aerosol.

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

    Directory of Open Access Journals (Sweden)

    A. K. Y. Lee

    2016-06-01

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

  19. Atmospheric aerosol compositions and sources at two national background sites in northern and southern China

    Directory of Open Access Journals (Sweden)

    Q. Zhu

    2016-08-01

    Full Text Available Although China's severe air pollution has become a focus in the field of atmospheric chemistry and the mechanisms of urban air pollution there have been researched extensively, few field sampling campaigns have been conducted at remote background sites in China, where air pollution characteristics on a larger scale are highlighted. In this study, an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS, together with an Aethalometer, was deployed at two of China's national background sites in northern (Lake Hongze site; 33.23° N, 118.33° E; altitude 21 m and southern (Mount Wuzhi site; 18.84° N, 109.49° E; altitude 958 m China in the spring seasons in 2011 and 2015, respectively, in order to characterize submicron aerosol composition and sources. The campaign-average PM1 concentration was 36.8 ± 19.8 µg m−3 at the northern China background (NCB site, which was far higher than that at the southern China background (SCB site (10.9 ± 7.8 µg m−3. Organic aerosol (OA (27.2 %, nitrate (26.7 %, and sulfate (22.0 % contributed the most to the PM1 mass at NCB, while OA (43.5 % and sulfate (30.5 % were the most abundant components of the PM1 mass at SCB, where nitrate only constituted a small fraction (4.7 % and might have contained a significant amount of organic nitrates (5–11 %. The aerosol size distributions and organic aerosol elemental compositions all indicated very aged aerosol particles at both sites. The OA at SCB was more oxidized with a higher average oxygen to carbon (O ∕ C ratio (0.98 than that at NCB (0.67. Positive matrix factorization (PMF analysis was used to classify OA into three components, including a hydrocarbon-like component (HOA, attributed to fossil fuel combustion and two oxygenated components (OOA1 and OOA2, attributed to secondary organic aerosols from different source areas at NCB. PMF analysis at SCB identified a semi-volatile oxygenated

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

    Directory of Open Access Journals (Sweden)

    A. T. Lambe

    2011-03-01

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

  1. Proceedings of submicron multiphase materials

    International Nuclear Information System (INIS)

    Baney, R.; Gilliom, L.; Hirano, S.I.; Schmidt, H.

    1992-01-01

    This book contains the papers presented at Symposium R of the spring 1992 Materials Research Society meeting held in San Francisco, California. The title of the symposium, Submicron Multiphase Materials, was selected by the organizers to encompass the realm of composite materials from those smaller than conventional fiber matrix composites to those with phase separation dimensions approaching molecular dimensions. The development of composite materials is as old as the development of materials. Humans quickly learned that, by combining materials, the best properties of each can be realized and that, in fact, synergistic effects often arise. For example, chopped straw was used by the Israelites to limit cracking in bricks. The famed Japanese samurai swords were multilayers of hard oxide and tough ductile materials. One also finds in nature examples of composite materials. These range form bone to wood, consisting of a hard phase which provides strength and stiffness and a softer phase for toughness. Advanced composites are generally thought of as those which are based on a high modulus, discontinuous, chopped or woven fiber phase and a continuous polymer phase. In multiphase composites, dimensions can range from meters in materials such as steel rod-reinforced concrete structures to angstroms. In macrophase separated composite materials, properties frequently follow the rule of mixtures with the properties approximating the arithmetic mean of the properties of each individual phase, if there is good coupling between the phases. As the phases become smaller, the surface to volume ratio grows in importance with respect to properties. Interfacial and interphase phenomena being to dominate. Surface free energies play an ever increasing role in controlling properties. In recent years, much research in materials science has been directed at multiphase systems where phase separations are submicron in at least some dimension

  2. Unexpectedly high ultrafine aerosol concentrations above East Antarctic sea-ice

    Science.gov (United States)

    Humphries, R. S.; Klekociuk, A. R.; Schofield, R.; Keywood, M.; Ward, J.; Wilson, S. R.

    2015-10-01

    The effect of aerosols on clouds and their radiative properties is one of the largest uncertainties in our understanding of radiative forcing. A recent study has concluded that better characterisation of pristine, natural aerosol processes leads to the largest reduction in these uncertainties. Antarctica, being far from anthropogenic activities, is an ideal location for the study of natural aerosol processes. Aerosol measurements in Antarctica are often limited to boundary layer air-masses at spatially sparse coastal and continental research stations, with only a handful of studies in the sea ice region. In this paper, the first observational study of sub-micron aerosols in the East Antarctic sea ice region is presented. Measurements were conducted aboard the ice-breaker Aurora Australis in spring 2012 and found that boundary layer condensation nuclei (CN3) concentrations exhibited a five-fold increase moving across the Polar Front, with mean Polar Cell concentrations of 1130 cm-3 - higher than any observed elsewhere in the Antarctic and Southern Ocean region. The absence of evidence for aerosol growth suggested that nucleation was unlikely to be local. Air parcel trajectories indicated significant influence from the free troposphere above the Antarctic continent, implicating this as the likely nucleation region for surface aerosol, a similar conclusion to previous Antarctic aerosol studies. The highest aerosol concentrations were found to correlate with low pressure systems, suggesting that the passage of cyclones provided an accelerated pathway, delivering air-masses quickly from the free-troposphere to the surface. After descent from the Antarctic free troposphere, trajectories suggest that sea ice boundary layer air-masses travelled equator-ward into the low albedo Southern Ocean region, transporting with them emissions and these aerosol nuclei where, after growth, may potentially impact on the region's radiative balance. The high aerosol concentrations and

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

    Directory of Open Access Journals (Sweden)

    B. Ervens

    2010-09-01

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

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

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

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

    Directory of Open Access Journals (Sweden)

    A. Richard

    2011-09-01

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

  5. Cavity cooling of an optically levitated submicron particle

    Science.gov (United States)

    Kiesel, Nikolai; Blaser, Florian; Delić, Uroš; Grass, David; Kaltenbaek, Rainer; Aspelmeyer, Markus

    2013-01-01

    The coupling of a levitated submicron particle and an optical cavity field promises access to a unique parameter regime both for macroscopic quantum experiments and for high-precision force sensing. We report a demonstration of such controlled interactions by cavity cooling the center-of-mass motion of an optically trapped submicron particle. This paves the way for a light–matter interface that can enable room-temperature quantum experiments with mesoscopic mechanical systems. PMID:23940352

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

    Directory of Open Access Journals (Sweden)

    T. B. Nguyen

    2011-07-01

    Full Text Available The effect of relative humidity (RH on the composition and concentrations of gas-phase products and secondary organic aerosol (SOA generated from the photooxidation of isoprene under high-NOx conditions was investigated. Experiments were performed with hydrogen peroxide as the OH precursor and in the absence of seed aerosol. The relative yields of most gas-phase products were the same regardless of initial water vapor concentration with exception of hydroxyacetone and glycolaldehyde, which were considerably affected by RH. A significant change was observed in the SOA composition, with many unique condensed-phase products formed under humid (90 % RH vs. dry (<2 % RH conditions, without any detectable effect on the rate and extent of the SOA mass growth. There is a 40 % reduction in the number and relative abundance of distinct particle-phase nitrogen-containing organic compounds (NOC detected by high resolution mass spectrometry. The suppression of condensation reactions, which produce water as a product, is the most important chemical effect of the increased RH. For example, the total signal from oligomeric esters of 2-methylglyceric acid was reduced by about 60 % under humid conditions and the maximum oligomer chain lengths were reduced by 7–11 carbons. Oligomers formed by addition mechanisms, without direct involvement of water, also decreased at elevated RH but to a much smaller extent. The observed reduction in the extent of condensation-type oligomerization at high RH may have substantial impact on the phase characteristics and hygroscopicity of the isoprene aerosol. The reduction in the amount of organic nitrates in the particle phase has implications for understanding the budget of NOC compounds.

  7. A technique for rapid source apportionment applied to ambient organic aerosol measurements from a thermal desorption aerosol gas chromatograph (TAG

    Directory of Open Access Journals (Sweden)

    Y. Zhang

    2016-11-01

    Full Text Available We present a rapid method for apportioning the sources of atmospheric organic aerosol composition measured by gas chromatography–mass spectrometry methods. Here, we specifically apply this new analysis method to data acquired on a thermal desorption aerosol gas chromatograph (TAG system. Gas chromatograms are divided by retention time into evenly spaced bins, within which the mass spectra are summed. A previous chromatogram binning method was introduced for the purpose of chromatogram structure deconvolution (e.g., major compound classes (Zhang et al., 2014. Here we extend the method development for the specific purpose of determining aerosol samples' sources. Chromatogram bins are arranged into an input data matrix for positive matrix factorization (PMF, where the sample number is the row dimension and the mass-spectra-resolved eluting time intervals (bins are the column dimension. Then two-dimensional PMF can effectively do three-dimensional factorization on the three-dimensional TAG mass spectra data. The retention time shift of the chromatogram is corrected by applying the median values of the different peaks' shifts. Bin width affects chemical resolution but does not affect PMF retrieval of the sources' time variations for low-factor solutions. A bin width smaller than the maximum retention shift among all samples requires retention time shift correction. A six-factor PMF comparison among aerosol mass spectrometry (AMS, TAG binning, and conventional TAG compound integration methods shows that the TAG binning method performs similarly to the integration method. However, the new binning method incorporates the entirety of the data set and requires significantly less pre-processing of the data than conventional single compound identification and integration. In addition, while a fraction of the most oxygenated aerosol does not elute through an underivatized TAG analysis, the TAG binning method does have the ability to achieve molecular level

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

    Science.gov (United States)

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

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

    Directory of Open Access Journals (Sweden)

    M. N. Chan

    2009-08-01

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

  10. Primary sources of PM2.5 organic aerosol in an industrial Mediterranean city, Marseille

    Science.gov (United States)

    El Haddad, I.; Marchand, N.; Wortham, H.; Piot, C.; Besombes, J.-L.; Cozic, J.; Chauvel, C.; Armengaud, A.; Robin, D.; Jaffrezo, J.-L.

    2011-03-01

    Marseille, the most important port of the Mediterranean Sea, represents a challenging case study for source apportionment exercises, combining an active photochemistry and multiple emission sources, including fugitive emissions from industrial sources and shipping. This paper presents a Chemical Mass Balance (CMB) approach based on organic markers and metals to apportion the primary sources of organic aerosol in Marseille, with a special focus on industrial emissions. Overall, the CMB model accounts for the major primary anthropogenic sources including motor vehicles, biomass burning and the aggregate emissions from three industrial processes (heavy fuel oil combustion/shipping, coke production and steel manufacturing) as well as some primary biogenic emissions. This source apportionment exercise is well corroborated by 14C measurements. Primary OC estimated by the CMB accounts on average for 22% of total OC and is dominated by the vehicular emissions that contribute on average for 17% of OC mass concentration (vehicular PM contributes for 17% of PM2.5). Even though industrial emissions contribute only 2.3% of the total OC (7% of PM2.5), they are associated with ultrafine particles (Dpheavy metals such as Pb, Ni and V. On one hand, given that industrial emissions governed key primary markers, their omission would lead to substantial uncertainties in the CMB analysis performed in areas heavily impacted by such sources, hindering accurate estimation of non-industrial primary sources and secondary sources. On the other hand, being associated with bursts of submicron particles and carcinogenic and mutagenic components such as PAH, these emissions are most likely related with acute ill-health outcomes and should be regulated despite their small contributions to OC. Another important result is the fact that 78% of OC mass cannot be attributed to the major primary sources and, thus, remains un-apportioned. We have consequently critically investigated the uncertainties

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

    Science.gov (United States)

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

    2007-12-01

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

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

    Directory of Open Access Journals (Sweden)

    J. Liu

    2016-10-01

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

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

    Directory of Open Access Journals (Sweden)

    P. Q. Fu

    2010-03-01

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

  14. Characterization of water-soluble organic aerosol in coastal New England: Implications of variations in size distribution

    Science.gov (United States)

    Ziemba, L. D.; Griffin, R. J.; Whitlow, S.; Talbot, R. W.

    2011-12-01

    Size distributions up to 10-micron aerosol diameter ( DP) of organic carbon (OC) and water-soluble organic carbon (WSOC) were measured at two sites in coastal New England, slightly inland at Thompson Farm (TF) and offshore at Isles of Shoals (IOS). Significant OC concentrations were measured across the full size distribution at TF and IOS, respectively. The WSOC fraction (WSOC/OC) was largest in the accumulation mode with values of 0.86 and 0.93 and smallest in the coarse mode with values of 0.61 and 0.79 at TF and IOS, respectively. Dicarboxylic acids containing up to five carbon atoms (C 5) were concentrated in droplet and accumulation mode aerosol with only minor contributions in the coarse mode. C 1-C 3 monocarboxylic acids were generally near or below detection limits. Results from proton nuclear magnetic resonance (H +-NMR) spectroscopy analyses showed that the organic functional group characterized by protons in the alpha position to an unsaturated carbon atoms ([H-C-C dbnd ]) was the dominant WSOC functionality at both TF and IOS, constituting 34 and 43% of carbon-weighted H +-NMR signal, respectively. Size distributions of each H +-NMR-resolved organic functionality are presented. Source apportionment using H +-NMR fingerprints is also presented, and results indicate that nearly all of the WSOC at TF and IOS spectroscopically resembled secondary organic aerosol, regardless of DP.

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

    Directory of Open Access Journals (Sweden)

    J. G. Slowik

    2011-03-01

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

  16. Development and first application of an Aerosol Collection Module (ACM) for quasi online compound specific aerosol measurements

    Science.gov (United States)

    Hohaus, Thorsten; Kiendler-Scharr, Astrid; Trimborn, Dagmar; Jayne, John; Wahner, Andreas; Worsnop, Doug

    2010-05-01

    Atmospheric aerosols influence climate and human health on regional and global scales (IPCC, 2007). In many environments organics are a major fraction of the aerosol influencing its properties. Due to the huge variety of organic compounds present in atmospheric aerosol current measurement techniques are far from providing a full speciation of organic aerosol (Hallquist et al., 2009). The development of new techniques for compound specific measurements with high time resolution is a timely issue in organic aerosol research. Here we present first laboratory characterisations of an aerosol collection module (ACM) which was developed to allow for the sampling and transfer of atmospheric PM1 aerosol. The system consists of an aerodynamic lens system focussing particles on a beam. This beam is directed to a 3.4 mm in diameter surface which is cooled to -30 °C with liquid nitrogen. After collection the aerosol sample can be evaporated from the surface by heating it to up to 270 °C. The sample is transferred through a 60cm long line with a carrier gas. In order to test the ACM for linearity and sensitivity we combined it with a GC-MS system. The tests were performed with octadecane aerosol. The octadecane mass as measured with the ACM-GC-MS was compared versus the mass as calculated from SMPS derived total volume. The data correlate well (R2 0.99, slope of linear fit 1.1) indicating 100 % collection efficiency. From 150 °C to 270 °C no effect of desorption temperature on transfer efficiency could be observed. The ACM-GC-MS system was proven to be linear over the mass range 2-100 ng and has a detection limit of ~ 2 ng. First experiments applying the ACM-GC-MS system were conducted at the Jülich Aerosol Chamber. Secondary organic aerosol (SOA) was formed from ozonolysis of 600 ppbv of b-pinene. The major oxidation product nopinone was detected in the aerosol and could be shown to decrease from 2 % of the total aerosol to 0.5 % of the aerosol over the 48 hours of

  17. Particle water and pH in the Eastern Mediterranean: sources variability and implications for nutrients availability

    Science.gov (United States)

    Nikolaou, P.; Bougiatioti, A.; Stavroulas, I.; Kouvarakis, G.; Nenes, A.; Weber, R.; Kanakidou, M.; Mihalopoulos, N.

    2015-10-01

    Particle water (LWC) and aerosol pH drive the aerosol phase, heterogeneous chemistry and bioavailability of nutrients that profoundly impact cloud formation, atmospheric composition and atmospheric fluxes of nutrients to ecosystems. Few measurements of in-situ LWC and pH however exist in the published literature. Using concurrent measurements of aerosol chemical composition, cloud condensation nuclei activity and tandem light scattering coefficients, the particle water mass concentrations associated with the aerosol inorganic (Winorg) and organic (Worg) components are determined for measurements conducted at the Finokalia atmospheric observation station in the eastern Mediterranean between August and November 2012. These data are interpreted using the ISORROPIA-II thermodynamic model to predict pH of aerosols originating from the various sources that influence air quality in the region. On average, closure between predicted aerosol water and that determined by comparison of ambient with dry light scattering coefficients was achieved to within 8 % (slope = 0.92, R2 = 0.8, n = 5201 points). Based on the scattering measurements a parameterization is also derived, capable of reproducing the hygroscopic growth factor (f(RH)) within 15 % of the measured values. The highest aerosol water concentrations are observed during nighttime, when relative humidity is highest and the collapse of the boundary layer increases the aerosol concentration. A significant diurnal variability is found for Worg with morning and afternoon average mass concentrations being 10-15 times lower than nighttime concentrations, thus rendering Winorg the main form of particle water during daytime. The average value of total aerosol water was 2.19 ± 1.75 μg m-3, contributing on average up to 33 % of the total submicron mass concentration. Average aerosol water associated with organics, Worg, was equal to 0.56 ± 0.37 μg m-3, thus organics contributed about 27.5 % to the total aerosol water, mostly

  18. Particle water and pH in the eastern Mediterranean: source variability and implications for nutrient availability

    Science.gov (United States)

    Bougiatioti, Aikaterini; Nikolaou, Panayiota; Stavroulas, Iasonas; Kouvarakis, Giorgos; Weber, Rodney; Nenes, Athanasios; Kanakidou, Maria; Mihalopoulos, Nikolaos

    2016-04-01

    Particle water (liquid water content, LWC) and aerosol pH are important parameters of the aerosol phase, affecting heterogeneous chemistry and bioavailability of nutrients that profoundly impact cloud formation, atmospheric composition, and atmospheric fluxes of nutrients to ecosystems. Few measurements of in situ LWC and pH, however, exist in the published literature. Using concurrent measurements of aerosol chemical composition, cloud condensation nuclei activity, and tandem light scattering coefficients, the particle water mass concentrations associated with the aerosol inorganic (Winorg) and organic (Worg) components are determined for measurements conducted at the Finokalia atmospheric observation station in the eastern Mediterranean between June and November 2012. These data are interpreted using the ISORROPIA-II thermodynamic model to predict the pH of aerosols originating from the various sources that influence air quality in the region. On average, closure between predicted aerosol water and that determined by comparison of ambient with dry light scattering coefficients was achieved to within 8 % (slope = 0.92, R2 = 0.8, n = 5201 points). Based on the scattering measurements, a parameterization is also derived, capable of reproducing the hygroscopic growth factor (f(RH)) within 15 % of the measured values. The highest aerosol water concentrations are observed during nighttime, when relative humidity is highest and the collapse of the boundary layer increases the aerosol concentration. A significant diurnal variability is found for Worg with morning and afternoon average mass concentrations being 10-15 times lower than nighttime concentrations, thus rendering Winorg the main form of particle water during daytime. The average value of total aerosol water was 2.19 ± 1.75 µg m-3, contributing on average up to 33 % of the total submicron mass concentration. Average aerosol water associated with organics, Worg, was equal to 0.56 ± 0.37 µg m-3; thus, organics

  19. Chemical characterization of long-range transport biomass burning emissions to the Himalayas: insights from high-resolution aerosol mass spectrometry

    Science.gov (United States)

    Zhang, Xinghua; Xu, Jianzhong; Kang, Shichang; Liu, Yanmei; Zhang, Qi

    2018-04-01

    An intensive field measurement was conducted at a remote, background, high-altitude site (Qomolangma Station, QOMS, 4276 m a.s.l.) in the northern Himalayas, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) along with other collocated instruments. The field measurement was performed from 12 April to 12 May 2016 to chemically characterize the high time-resolved submicron particulate matter (PM1) and obtain the dynamic processes (emissions, transport, and chemical evolution) of biomass burning (BB), frequently transported from South Asia to the Himalayas during pre-monsoon season. Overall, the average (±1σ) PM1 mass concentration was 4.44 (±4.54) µg m-3 for the entire study, which is comparable with those observed at other remote sites worldwide. Organic aerosol (OA) was the dominant PM1 species (accounting for 54.3 % of total PM1 on average) followed by black carbon (BC) (25.0 %), sulfate (9.3 %), ammonium (5.8 %), nitrate (5.1 %), and chloride (0.4 %). The average size distributions of PM1 species all peaked at an overlapping accumulation mode (˜ 500 nm), suggesting that aerosol particles were internally well-mixed and aged during long-range transport. Positive matrix factorization (PMF) analysis on the high-resolution organic mass spectra identified three distinct OA factors, including a BB-related OA (BBOA, 43.7 %), a nitrogen-containing OA (NOA, 13.9 %) and a more-oxidized oxygenated OA (MO-OOA, 42.4 %). Two polluted episodes with enhanced PM1 mass loadings and elevated BBOA contributions from the west and southwest of QOMS during the study were observed. A typical BB plume was investigated in detail to illustrate the chemical evolution of aerosol characteristics under distinct air mass origins, meteorological conditions, and atmospheric oxidation processes.

  20. Influence of biomass burning on mixing state of sub-micron aerosol particles in the North China Plain

    Science.gov (United States)

    Kecorius, Simonas; Ma, Nan; Teich, Monique; van Pinxteren, Dominik; Zhang, Shenglan; Gröβ, Johannes; Spindler, Gerald; Müller, Konrad; Iinuma, Yoshiteru; Hu, Min; Herrmann, Hartmut; Wiedensohler, Alfred

    2017-09-01

    Particulate emissions from crop residue burning decrease the air quality as well as influence aerosol radiative properties on a regional scale. The North China Plain (NCP) is known for the large scale biomass burning (BB) of field residues, which often results in heavy haze pollution episodes across the region. We have been able to capture a unique BB episode during the international CAREBeijing-NCP intensive field campaign in Wangdu in the NCP (38.6°N, 115.2°E) from June to July 2014. It was found that aerosol particles originating from this BB event showed a significantly different mixing state compared with clean and non-BB pollution episodes. BB originated particles showed a narrower probability density function (PDF) of shrink factor (SF). And the maximum was found at shrink factor of 0.6, which is higher than in other episodes. The non-volatile particle number fraction during the BB episode decreased to 3% and was the lowest measured value compared to all other predefined episodes. To evaluate the influence of particle mixing state on aerosol single scattering albedo (SSA), SSA at different RHs was simulated using the measured aerosol physical-chemical properties. The differences between the calculated SSA for biomass burning, clean and pollution episodes are significant, meaning that the variation of SSA in different pollution conditions needs to be considered in the evaluation of aerosol direct radiative effects in the NCP. And the calculated SSA was found to be quite sensitive on the mixing state of BC, especially at low-RH condition. The simulated SSA was also compared with the measured values. For all the three predefined episodes, the measured SSA are very close to the calculated ones with assumed mixing states of homogeneously internal and core-shell internal mixing, indicating that both of the conception models are appropriate for the calculation of ambient SSA in the NCP.

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

    Science.gov (United States)

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

    2014-06-01

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

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

    Science.gov (United States)

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

    2014-02-01

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

  3. Isolating and identifying atmospheric ice-nucleating aerosols: a new technique

    Science.gov (United States)

    Kreidenweis, S. M.; Chen, Y.; Rogers, D. C.; DeMott, P. J.

    Laboratory studies examined two key aspects of the performance of a continuous-flow diffusion chamber (CFD) instrument that detects ice nuclei (IN) concentrations in air samples: separating IN from non-IN, and collecting IN aerosols to determine chemical composition. In the first study, submicron AgI IN particles were mixed in a sample stream with submicron non-IN salt particles, and the sample stream was processed in the CFD at -19°C and 23% supersaturation with respect to ice. Examination of the residual particles from crystals nucleated in the CFD confirmed that only AgI particles served as IN in the mixed stream. The second study applied this technique to separate and analyze IN and non-IN particles in a natural air sample. Energy-dispersive X-ray analyses (EDS) of the elemental composition of selected particles from the IN and non-IN fractions in ambient air showed chemical differences: Si and Ca were present in both, but S, Fe and K were also detected in the non-IN fraction.

  4. Stable Carbon Fractionation In Size Segregated Aerosol Particles Produced By Controlled Biomass Burning

    Science.gov (United States)

    Masalaite, Agne; Garbaras, Andrius; Garbariene, Inga; Ceburnis, Darius; Martuzevicius, Dainius; Puida, Egidijus; Kvietkus, Kestutis; Remeikis, Vidmantas

    2014-05-01

    Biomass burning is the largest source of primary fine fraction carbonaceous particles and the second largest source of trace gases in the global atmosphere with a strong effect not only on the regional scale but also in areas distant from the source . Many studies have often assumed no significant carbon isotope fractionation occurring between black carbon and the original vegetation during combustion. However, other studies suggested that stable carbon isotope ratios of char or BC may not reliably reflect carbon isotopic signatures of the source vegetation. Overall, the apparently conflicting results throughout the literature regarding the observed fractionation suggest that combustion conditions may be responsible for the observed effects. The purpose of the present study was to gather more quantitative information on carbonaceous aerosols produced in controlled biomass burning, thereby having a potential impact on interpreting ambient atmospheric observations. Seven different biomass fuel types were burned under controlled conditions to determine the effect of the biomass type on the emitted particulate matter mass and stable carbon isotope composition of bulk and size segregated particles. Size segregated aerosol particles were collected using the total suspended particle (TSP) sampler and a micro-orifice uniform deposit impactor (MOUDI). The results demonstrated that particle emissions were dominated by the submicron particles in all biomass types. However, significant differences in emissions of submicron particles and their dominant sizes were found between different biomass fuels. The largest negative fractionation was obtained for the wood pellet fuel type while the largest positive isotopic fractionation was observed during the buckwheat shells combustion. The carbon isotope composition of MOUDI samples compared very well with isotope composition of TSP samples indicating consistency of the results. The measurements of the stable carbon isotope ratio in

  5. A program to operate the TSI electrical aerosol analyser using an IBM-PC microcomputer - technical background

    International Nuclear Information System (INIS)

    Horton, K.D.; Mitchell, J.P.; Snelling, K.W.

    1988-02-01

    A program has been written to enable the TSI Electrical Aerosol Analyser (EAA model 3030) to be operated using an IBM-PC microcomputer. Although much of the program is based on the software supplied by TSI Inc to collect and process data from the EAA, it incorporates numerous improvements including the option to operate the EAA automatically via a TSI Differential Mobility Particle Sizer interface. When compiled, the program enables the data reduction which takes into account the significant cross-channel sensitivity of the EAA, to be performed in about 30 seconds making it possible to use the EAA to monitor rapid changes in the behaviour of sub-micron aerosol particles. (author)

  6. Influence of continental organic aerosols to the marine atmosphere over the East China Sea: Insights from lipids, PAHs and phthalates.

    Science.gov (United States)

    Kang, Mingjie; Yang, Fan; Ren, Hong; Zhao, Wanyu; Zhao, Ye; Li, Linjie; Yan, Yu; Zhang, Yingjie; Lai, Senchao; Zhang, Yingyi; Yang, Yang; Wang, Zifa; Sun, Yele; Fu, Pingqing

    2017-12-31

    Total suspended particle (TSP) samples were collected during a marine cruise in the East China Sea from May 18 to June 12, 2014. They were analyzed for solvent extractable organic compounds (lipid compounds, PAHs and phthalates) using gas chromatography/mass spectrometry (GC/MS) to better understand the sources and source apportionment of aerosol pollution in the western North Pacific. Higher concentrations were observed in the terrestrially influenced aerosol samples on the basis of five-day backward air mass trajectories, especially for aerosols collected near coastal areas. Phthalates were found to be the dominant species among these measured compound classes (707±401ngm -3 for daytime and 313±155ngm -3 for nighttime), followed by fatty acids, fatty alcohols, n-alkanes and PAHs. In general, the daytime abundances for these compounds are higher than nighttime, possibly attributable to more intensive anthropogenic activities during the daytime. The factor analysis indicates that biomass burning, fungal activities and fossil fuel combustion maybe the main emission sources for organic aerosols over the East China Sea. This study demonstrates that the East Asian continent can be a natural emitter of biogenic and anthropogenic organics to the marine atmosphere through long-range transport, which controls the chemical composition and concentration of organic aerosols over the East China Sea. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. The critical assessment of vapour pressure estimation methods for use in modelling the formation of atmospheric organic aerosol

    Directory of Open Access Journals (Sweden)

    M. H. Barley

    2010-01-01

    Full Text Available A selection of models for estimating vapour pressures have been tested against experimental data for a set of compounds selected for their particular relevance to the formation of atmospheric aerosol by gas-liquid partitioning. The experimental vapour pressure data (all <100 Pa of 45 multifunctional compounds provide a stringent test of the estimation techniques, with a recent complex group contribution method providing the best overall results. The effect of errors in vapour pressures upon the formation of organic aerosol by gas-liquid partitioning in an atmospherically relevant example is also investigated. The mass of organic aerosol formed under typical atmospheric conditions was found to be very sensitive to the variation in vapour pressure values typically present when comparing estimation methods.

  8. Measurement and analysis of the concentration and size distribution of aerosols in a copper mine

    International Nuclear Information System (INIS)

    Li Dehong; Zhuo Weihai; Huang Gang; Su Xu; Sun Quanfu

    2008-01-01

    Objective: To explore the general characteristics of the concentration and size distribution of aerosols in a mine. Methods: In different areas of a non-uranium mine, the particle number and mass concentration of aerosols were surveyed with a condensation particle counter and a personal aerosol monitor, respectively, and the size distribution of aerosols larger than 1 μm in size was estimated according to the size- selective measurements of mass concentrations. The size distribution of submicron aerosols was evaluated based on the method of screen diffusion battery (SOB), and the measurements were performed in both inside and outside of a control room. Results: The mass concentration of inhaled particles (PM10) was averaged to be 0.42 mg/m 3 in the whole mine, and it varied with different working areas and significantly affected with human activities. In the mine, particles lager than 1 μm in size widely distributed, while the particles less than 5 nm in size were seldom observed. Conclusions: The characteristics of aerosol significantly change with different working areas, human activities and Antilation condition in mine. The dose contribution from inhaled radioactive particles larger than 1 μm in size should be considered in mine. (authors)

  9. Source identification and airborne chemical characterisation of aerosol pollution from long-range transport over Greenland during POLARCAT summer campaign 2008

    Science.gov (United States)

    Schmale, J.; Schneider, J.; Ancellet, G.; Quennehen, B.; Stohl, A.; Sodemann, H.; Burkhart, J. F.; Hamburger, T.; Arnold, S. R.; Schwarzenboeck, A.; Borrmann, S.; Law, K. S.

    2011-10-01

    We deployed an aerosol mass spectrometer during the POLARCAT (Polar Study using Aircraft, Remote Sensing, Surface Measurements and Models, of Climate, Chemistry, Aerosols, and Transport) summer campaign in Greenland in June/July 2008 on the research aircraft ATR-42. Online size resolved chemical composition data of submicron aerosol were collected up to 7.6 km altitude in the region 60 to 71° N and 40 to 60° W. Biomass burning (BB) and fossil fuel combustion (FF) plumes originating from North America, Asia, Siberia and Europe were sampled. Transport pathways of detected plumes included advection below 700 hPa, air mass uplifting in warm conveyor belts, and high altitude transport in the upper troposphere. By means of the Lagrangian particle dispersion model FLEXPART, trace gas analysis of O3 and CO, particle size distributions and aerosol chemical composition 48 pollution events were identified and classified into five chemically distinct categories. Aerosol from North American BB consisted of 22% particulate sulphate, while with increasing anthropogenic and Asian influence aerosol in Asian FF dominated plumes was composed of up to 37% sulphate category mean value. Overall, it was found that the organic matter fraction was larger (85%) in pollution plumes than for background conditions (71%). Despite different source regions and emission types the particle oxygen to carbon ratio of all plume classes was around 1 indicating low-volatility highly oxygenated aerosol. The volume size distribution of out-of-plume aerosol showed markedly smaller modes than all other distributions with two Aitken mode diameters of 24 and 43 nm and a geometric standard deviation σg of 1.12 and 1.22, respectively, while another very broad mode was found at 490 nm (σg = 2.35). Nearly pure BB particles from North America exhibited an Aitken mode at 66 nm (σg = 1.46) and an accumulation mode diameter of 392 nm (σg = 1.76). An aerosol lifetime, including all processes from emission to

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

    Directory of Open Access Journals (Sweden)

    Y. Li

    2016-03-01

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

  11. Characterization of organic nitrogen in aerosols at a forest site in the southern Appalachian Mountains

    Science.gov (United States)

    Chen, Xi; Xie, Mingjie; Hays, Michael D.; Edgerton, Eric; Schwede, Donna; Walker, John T.

    2018-05-01

    This study investigates the composition of organic particulate matter in PM2.5 in a remote montane forest in the southeastern US, focusing on the role of organic nitrogen (N) in sulfur-containing secondary organic aerosol (nitrooxy-organosulfates) and aerosols associated with biomass burning (nitro-aromatics). Bulk water-soluble organic N (WSON) represented ˜ 14 % w/w of water-soluble total N (WSTN) in PM2.5 on average across seasonal measurement campaigns conducted in the spring, summer, and fall of 2015. The largest contributions of WSON to WSTN were observed in spring ( ˜ 18 % w/w) and the lowest in the fall ( ˜ 10 % w/w). On average, identified nitro-aromatic and nitrooxy-organosulfate compounds accounted for a small fraction of WSON, ranging from ˜ 1 % in spring to ˜ 4 % in fall, though were observed to contribute as much as 28 % w/w of WSON in individual samples that were impacted by local biomass burning. The highest concentrations of oxidized organic N species occurred during summer (average of 0.65 ng N m-3) along with a greater relative abundance of higher-generation oxygenated terpenoic acids, indicating an association with more aged aerosol. The highest concentrations of nitro-aromatics (e.g., nitrocatechol and methyl-nitrocatechol), levoglucosan, and aged SOA tracers were observed during fall, associated with aged biomass burning plumes. Nighttime nitrate radical chemistry is the most likely formation pathway for nitrooxy-organosulfates observed at this low NOx site (generally chemistry and deposition of reactive N.

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

    Directory of Open Access Journals (Sweden)

    B. Yan

    2008-11-01

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

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

    Science.gov (United States)

    Kalberer, Markus; Sax, Mirjam; Samburova, Vera

    2006-10-01

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

  14. On the sub-micron aerosol size distribution in a coastal-rural site at El Arenosillo Station (SW – Spain

    Directory of Open Access Journals (Sweden)

    M. Sorribas

    2011-11-01

    Full Text Available This study focuses on the analysis of the sub-micron aerosol characteristics at El Arenosillo Station, a rural and coastal environment in South-western Spain between 1 August 2004 and 31 July 2006 (594 days. The mean total concentration (NT was 8660 cm−3 and the mean concentrations in the nucleation (NNUC, Aitken (NAIT and accumulation (NACC particle size ranges were 2830 cm−3, 4110 cm−3 and 1720 cm−3, respectively. Median size distribution was characterised by a single-modal fit, with a geometric diameter, median number concentration and geometric standard deviation of 60 nm, 5390 cm−3 and 2.31, respectively. Characterisation of primary emissions, secondary particle formation, changes to meteorology and long-term transport has been necessary to understand the seasonal and annual variability of the total and modal particle concentration. Number concentrations exhibited a diurnal pattern with maximum concentrations around noon. This was governed by the concentrations of the nucleation and Aitken modes during the warm seasons and only by the nucleation mode during the cold seasons. Similar monthly mean total concentrations were observed throughout the year due to a clear inverse variation between the monthly mean NNUC and NACC. It was related to the impact of desert dust and continental air masses on the monthly mean particle levels. These air masses were associated with high values of NACC which suppressed the new particle formation (decreasing NNUC. Each day was classified according to a land breeze flow or a synoptic pattern influence. The median size distribution for desert dust and continental aerosol was dominated by the Aitken and accumulation modes, and marine air masses were dominated by the nucleation and Aitken modes. Particles

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

    Directory of Open Access Journals (Sweden)

    M. Karl

    2009-09-01

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

  16. Investigations into the penetration and pressure drop of HEPA filter media during loading with submicron particle aerosols at high concentrations

    International Nuclear Information System (INIS)

    Leibold, H; Wilhelm, J.G.

    1991-01-01

    High Efficiency Particulate Air (HEPA) filters are typically employed in particle removal and retention within the air cleaning systems of clean rooms in the pharmaceutical, nuclear and semiconductor industries for dust concentrations of some μg/m 3 . Their extremely high removal efficiencies for submicron particles make them attractive candidates in complying with increasingly lower emission limits for industrial processes that involve dust concentrations of up to several g/m 3 . Cost-effective operation under such conditions requires the filter units to be recleanable. The recleanability of HEPA filter media depends not only on the operating conditions during the cleaning process but also on the filtration conditions during particle loading. The structure and location of the particles captured by the glass fiber matrix greatly affect the degree to which they can be subsequently dislodged and removed from the filter medium. Changes in filtration efficiency with service time for various particle diameters in the critical submicron size range, as well as the effects of filtration velocity on the increase in pressure drop, are important criteria with regard to recleaning HEPA filter units. Of special significance for the recleanability of HEPA filter media is knowledge of how operating conditions affect dust cake formation. (author)

  17. Volatility of organic aerosol and its components in the Megacity of Paris

    Science.gov (United States)

    Paciga, A.; Karnezi, E.; Kostenidou, E.; Hildebrandt, L.; Psichoudaki, M.; Engelhart, G. J.; Lee, B.-H.; Crippa, M.; Prévôt, A. S. H.; Baltensperger, U.; Pandis, S. N.

    2015-08-01

    Using a mass transfer model and the volatility basis set, we estimate the volatility distribution for the organic aerosol (OA) components during summer and winter in Paris, France as part of the collaborative project MEGAPOLI. The concentrations of the OA components as a function of temperature were measured combining data from a thermodenuder and an aerosol mass spectrometer (AMS) with Positive Matrix Factorization (PMF) analysis. The hydrocarbon-like organic aerosol (HOA) had similar volatility distributions for the summer and winter campaigns with half of the material in the saturation concentration bin of 10 μg m-3 and another 35-40 % consisting of low and extremely low volatility organic compounds (LVOCs and ELVOCs, respectively). The winter cooking OA (COA) was more than an order of magnitude less volatile than the summer COA. The low volatility oxygenated OA (LV-OOA) factor detected in the summer had the lowest volatility of all the derived factors and consisted almost exclusively of ELVOCs. The volatility for the semi-volatile oxygenated OA (SV-OOA) was significantly higher than that of the LV-OOA, containing both semi-volatile organic components (SVOCs) and LVOCs. The oxygenated OA (OOA) factor in winter consisted of SVOCs (45 %), LVOCs (25 %) and ELVOCs (30 %). The volatility of marine OA (MOA) was higher than that of the other factors containing around 60 % SVOCs. The biomass burning OA (BBOA) factor contained components with a wide range of volatilities with significant contributions from both SVOCs (50 %) and LVOCs (30 %). Finally, combining the O : C ratio and volatility distributions of the various factors, we incorporated our results into the two-dimensional volatility basis set (2D-VBS). Our results show that the factors cover a broad spectrum of volatilities with no direct link between the average volatility and average O : C of the OA components. Agreement between our findings and previous publications is encouraging for our understanding of the

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

    Directory of Open Access Journals (Sweden)

    S. Guo

    2013-08-01

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

  19. Atmospheric Residence Times of Continental Aerosols.

    Science.gov (United States)

    Balkanski, Yves Jacques

    The global atmospheric distributions of ^{222}Rn and ^{210 }Pb are simulated with a three-dimensional model of atmospheric transport based on the meteorology of the NASA GISS^1>=neral circulation model. The short-lived radioactive gas ^ {222}Rn (half-life = 3.8d) is emitted almost exclusively from land, at a relatively uniform rate; hence it is an excellent tracer of continental influences. Lead -210 is produced by decay of ^{222} Rn and immediately condenses to preexisting aerosol surfaces. It provides an excellent measure of aerosol residence times in the atmosphere because its source is accurately defined by the ^{222} Rn distribution. Results from the three-dimensional model are compared to measurements of ^ {222}Rn and ^{210 }Pb atmospheric concentrations to evaluate model's long-range transport over oceanic regions and to study the deposition mechanisms of atmospheric aerosols. Model results for ^{222} Rn are used to examine the long-range transport of continental air over two selected oceanic regions, the subantartic Indian Ocean and the North Pacific. It is shown that fast transport of air from southern Africa causes substantial continental pollution at southern mid-latitudes, a region usually regarded as pristine. Air over the North Pacific is heavily impacted by continental influences year round, but the altitude at which the transport occurs varies seasonally. Observations of aerosols at island sites, which are commonly used as diagnostics of continental influences, may be misleading because they do not account for influences at high altitude and because aerosols are efficiently scavenged by deposition during transport. The study of ^{210}Pb focuses on defining the residence times of submicron aerosols in the troposphere. Scavenging in wet convective updrafts is found to provide the dominant sink on a global scale. The globally averaged residence time for ^{210 }Pb-containing aerosols in the troposphere is 7 days. The average increase in residence time

  20. Hygroscopicity of organic surrogate compounds from biomass burning and their effect on the efflorescence of ammonium sulfate in mixed aerosol particles

    Science.gov (United States)

    Lei, Ting; Zuend, Andreas; Cheng, Yafang; Su, Hang; Wang, Weigang; Ge, Maofa

    2018-01-01

    Hygroscopic growth factors of organic surrogate compounds representing biomass burning and mixed organic-inorganic aerosol particles exhibit variability during dehydration experiments depending on their chemical composition, which we observed using a hygroscopicity tandem differential mobility analyzer (HTDMA). We observed that levoglucosan and humic acid aerosol particles release water upon dehumidification in the range from 90 to 5 % relative humidity (RH). However, 4-Hydroxybenzoic acid aerosol particles remain in the solid state upon dehumidification and exhibit a small shrinking in size at higher RH compared to the dry size. For example, the measured growth factor of 4-hyroxybenzoic acid aerosol particles is ˜ 0.96 at 90 % RH. The measurements were accompanied by RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model and Extended Aerosol Inorganics Model (E-AIM), the Zdanovskii-Stokes-Robinson (ZSR) relation, and a fitted hygroscopicity expression. We observed several effects of organic components on the hygroscopicity behavior of mixtures containing ammonium sulfate (AS) in relation to the different mass fractions of organic compounds: (1) a shift of efflorescence relative humidity (ERH) of ammonium sulfate to higher RH due to the presence of 25 wt % levoglucosan in the mixture. (2) There is a distinct efflorescence transition at 25 % RH for mixtures consisting of 25 wt % of 4-hydroxybenzoic acid compared to the ERH at 35 % for organic-free AS particles. (3) There is indication for a liquid-to-solid phase transition of 4-hydroxybenzoic acid in the mixed particles during dehydration. (4) A humic acid component shows no significant effect on the efflorescence of AS in mixed aerosol particles. In addition, consideration of a composition-dependent degree of dissolution of crystallization AS (solid-liquid equilibrium) in the AIOMFAC and E-AIM models leads to a