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

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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

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

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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

Mathematical modeling of atmospheric fine particle-associated primary organic compound concentrations

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Rogge, Wolfgang F.; Hildemann, Lynn M.; Mazurek, Monica A.; Cass, Glen R.; Simoneit, Bernd R. T.

1996-08-01

An atmospheric transport model has been used to explore the relationship between source emissions and ambient air quality for individual particle phase organic compounds present in primary aerosol source emissions. An inventory of fine particulate organic compound emissions was assembled for the Los Angeles area in the year 1982. Sources characterized included noncatalyst- and catalyst-equipped autos, diesel trucks, paved road dust, tire wear, brake lining dust, meat cooking operations, industrial oil-fired boilers, roofing tar pots, natural gas combustion in residential homes, cigarette smoke, fireplaces burning oak and pine wood, and plant leaf abrasion products. These primary fine particle source emissions were supplied to a computer-based model that simulates atmospheric transport, dispersion, and dry deposition based on the time series of hourly wind observations and mixing depths. Monthly average fine particle organic compound concentrations that would prevail if the primary organic aerosol were transported without chemical reaction were computed for more than 100 organic compounds within an 80 km × 80 km modeling area centered over Los Angeles. The monthly average compound concentrations predicted by the transport model were compared to atmospheric measurements made at monitoring sites within the study area during 1982. The predicted seasonal variation and absolute values of the concentrations of the more stable compounds are found to be in reasonable agreement with the ambient observations. While model predictions for the higher molecular weight polycyclic aromatic hydrocarbons (PAH) are in agreement with ambient observations, lower molecular weight PAH show much higher predicted than measured atmospheric concentrations in the particle phase, indicating atmospheric decay by chemical reactions or evaporation from the particle phase. The atmospheric concentrations of dicarboxylic acids and aromatic polycarboxylic acids greatly exceed the contributions that

MATRIX-VBS Condensing Organic Aerosols in an Aerosol Microphysics Model

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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.

Sources and geographical origins of fine aerosols in Paris (France)

International Nuclear Information System (INIS)

Bressi, M.; Nicolas, J.B.; Sciare, J.; Feron, A.; Nonnaire, N.; Petit, J.E.

2014-01-01

The present study aims at identifying and apportioning fine aerosols to their major sources in Paris (France) - the second most populated - larger urban zone - in Europe - and determining their geographical origins. It is based on the daily chemical composition of PM2.5 examined over 1 year at an urban background site of Paris (Bressi et al., 2013). Positive matrix factorization (EPA PMF3.0) was used to identify and apportion fine aerosols to their sources; bootstrapping was performed to determine the adequate number of PMF factors, and statistics (root mean square error, coefficient of determination, etc.) were examined to better model PM2.5 mass and chemical components. Potential source contribution function (PSCF) and conditional probability function (CPF) allowed the geographical origins of the sources to be assessed; special attention was paid to implement suitable weighting functions. Seven factors, namely ammonium sulfate (A.S.)-rich factor, ammonium nitrate (A.N.)-rich factor, heavy oil combustion, road traffic, biomass burning, marine aerosols and metal industry, were identified; a detailed discussion of their chemical characteristics is reported. They contribute 27, 24, 17, 14, 12, 6 and 1% of PM2.5 mass (14.7 μgm -3 ) respectively on the annual average; their seasonal variability is discussed. The A.S.- and A.N.-rich factors have undergone mid- or long-range transport from continental Europe; heavy oil combustion mainly stems from northern France and the English Channel, whereas road traffic and biomass burning are primarily locally emitted. Therefore, on average more than half of PM2.5 mass measured in the city of Paris is due to mid- or long-range transport of secondary aerosols stemming from continental Europe, whereas local sources only contribute a quarter of the annual averaged mass. These results imply that fine-aerosol abatement policies conducted at the local scale may not be sufficient to notably reduce PM2.5 levels at urban background sites

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

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

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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.

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.

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

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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.

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...

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.

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.

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

Spectroscopic study of the water-soluble organic matter isolated from atmospheric aerosols collected under different atmospheric conditions

International Nuclear Information System (INIS)

Duarte, Regina M.B.O.; Pio, Casimiro A.; Duarte, Armando C.

2005-01-01

The composition of the water-soluble organic matter from fine aerosols collected in a rural location during two different meteorological conditions (summer and autumn) was investigated by UV-vis, synchronous fluorescence (with Δλ = 20 nm), FT-IR and CPMAS- 13 C NMR spectroscopies. A seasonal variation in the concentration of total carbon, organic carbon and water-soluble organic carbon was confirmed, with higher values during the autumn and lower values during the summer season. The chemical characterisation of the water-soluble organic matter showed that both samples are dominated by a high content of aliphatic structures, carboxyl groups and aliphatic carbons single bonded to one oxygen or nitrogen atom. However, the autumn sample exhibits a higher aromatic content than the summer sample, plus signals due to carbons of phenol, ketones and methoxyl groups. These signals were attributed to lignin breakdown products which are likely to be released during wood combustion processes. The obtained results put into evidence the major contribution of biomass burning processes in domestic fireplaces during low temperature conditions into both the concentration and the bulk chemical properties of the WSOC from fine aerosols

Indirect estimation of absorption properties for fine aerosol particles using AATSR observations: a case study of wildfires in Russia in 2010

Science.gov (United States)

Rodriguez, E.; Kolmonen, P.; Virtanen, T. H.; Sogacheva, L.; Sundstrom, A.-M.; de Leeuw, G.

2015-08-01

The Advanced Along-Track Scanning Radiometer (AATSR) on board the ENVISAT satellite is used to study aerosol properties. The retrieval of aerosol properties from satellite data is based on the optimized fit of simulated and measured reflectances at the top of the atmosphere (TOA). The simulations are made using a radiative transfer model with a variety of representative aerosol properties. The retrieval process utilizes a combination of four aerosol components, each of which is defined by their (lognormal) size distribution and a complex refractive index: a weakly and a strongly absorbing fine-mode component, coarse mode sea salt aerosol and coarse mode desert dust aerosol). These components are externally mixed to provide the aerosol model which in turn is used to calculate the aerosol optical depth (AOD). In the AATSR aerosol retrieval algorithm, the mixing of these components is decided by minimizing the error function given by the sum of the differences between measured and calculated path radiances at 3-4 wavelengths, where the path radiances are varied by varying the aerosol component mixing ratios. The continuous variation of the fine-mode components allows for the continuous variation of the fine-mode aerosol absorption. Assuming that the correct aerosol model (i.e. the correct mixing fractions of the four components) is selected during the retrieval process, also other aerosol properties could be computed such as the single scattering albedo (SSA). Implications of this assumption regarding the ratio of the weakly/strongly absorbing fine-mode fraction are investigated in this paper by evaluating the validity of the SSA thus obtained. The SSA is indirectly estimated for aerosol plumes with moderate-to-high AOD resulting from wildfires in Russia in the summer of 2010. Together with the AOD, the SSA provides the aerosol absorbing optical depth (AAOD). The results are compared with AERONET data, i.e. AOD level 2.0 and SSA and AAOD inversion products. The RMSE

Global Estimates of Average Ground-Level Fine Particulate Matter Concentrations from Satellite-Based Aerosol Optical Depth

Science.gov (United States)

Van Donkelaar, A.; Martin, R. V.; Brauer, M.; Kahn, R.; Levy, R.; Verduzco, C.; Villeneuve, P.

2010-01-01

Exposure to airborne particles can cause acute or chronic respiratory disease and can exacerbate heart disease, some cancers, and other conditions in susceptible populations. Ground stations that monitor fine particulate matter in the air (smaller than 2.5 microns, called PM2.5) are positioned primarily to observe severe pollution events in areas of high population density; coverage is very limited, even in developed countries, and is not well designed to capture long-term, lower-level exposure that is increasingly linked to chronic health effects. In many parts of the developing world, air quality observation is absent entirely. Instruments aboard NASA Earth Observing System satellites, such as the MODerate resolution Imaging Spectroradiometer (MODIS) and the Multi-angle Imaging SpectroRadiometer (MISR), monitor aerosols from space, providing once daily and about once-weekly coverage, respectively. However, these data are only rarely used for health applications, in part because the can retrieve the amount of aerosols only summed over the entire atmospheric column, rather than focusing just on the near-surface component, in the airspace humans actually breathe. In addition, air quality monitoring often includes detailed analysis of particle chemical composition, impossible from space. In this paper, near-surface aerosol concentrations are derived globally from the total-column aerosol amounts retrieved by MODIS and MISR. Here a computer aerosol simulation is used to determine how much of the satellite-retrieved total column aerosol amount is near the surface. The five-year average (2001-2006) global near-surface aerosol concentration shows that World Health Organization Air Quality standards are exceeded over parts of central and eastern Asia for nearly half the year.

Functional group analysis by H NMR/chemical derivatization for the characterization of organic aerosol from the SMOCC field campaign

Directory of Open Access Journals (Sweden)

E. Tagliavini

2006-01-01

Full Text Available Water soluble organic compounds (WSOC in aerosol samples collected in the Amazon Basin in a period encompassing the middle/late dry season and the beginning of the wet season, were investigated by H NMR spectroscopy. HiVol filter samples (PM2.5 and PM>2.5 and size-segregated samples from multistage impactor were subjected to H NMR characterization. The H NMR methodology, recently developed for the analysis of organic aerosol samples, has been improved by exploiting chemical methylation of carboxylic groups with diazomethane, which allows the direct determination of the carboxylic acid content of WSOC. The content of carboxylic carbons for the different periods and sizes ranged from 12% to 20% of total measured carbon depending on the season and aerosol size, with higher contents for the fine particles in the transition and wet periods with respect to the dry period. A comprehensive picture is presented of WSOC functional groups in aerosol samples representative of the biomass burning period, as well as of transition and semi-clean atmospheric conditions. A difference in composition between fine (PM2.5 and coarse (PM>2.5 size fractions emerged from the NMR data, the former showing higher alkylic content, the latter being largely dominated by R-O-H (or R-O-R' functional groups. Very small particles (<0.14 μm, however, present higher alkyl-chain content and less oxygenated carbons than larger fine particles (0.42–1.2 μm. More limited variations were found between the average compositions in the different periods of the campaign.

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

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.

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

Intercomparison and closure calculations using measurements of aerosol species and optical properties during the Yosemite Aerosol Characterization Study

Science.gov (United States)

Malm, William C.; Day, Derek E.; Carrico, Christian; Kreidenweis, Sonia M.; Collett, Jeffrey L.; McMeeking, Gavin; Lee, Taehyoung; Carrillo, Jacqueline; Schichtel, Bret

2005-07-01

Physical and optical properties of inorganic aerosols have been extensively studied, but less is known about carbonaceous aerosols, especially as they relate to the non-urban settings such as our nation's national parks and wilderness areas. Therefore an aerosol characterization study was conceived and implemented at one national park that is highly impacted by carbonaceous aerosols, Yosemite. The primary objective of the study was to characterize the physical, chemical, and optical properties of a carbon-dominated aerosol, including the ratio of total organic matter weight to organic carbon, organic mass scattering efficiencies, and the hygroscopic characteristics of a carbon-laden ambient aerosol, while a secondary objective was to evaluate a variety of semi-continuous monitoring systems. Inorganic ions were characterized using 24-hour samples that were collected using the URG and Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring systems, the micro-orifice uniform deposit impactor (MOUDI) cascade impactor, as well as the semi-continuous particle-into-liquid sampler (PILS) technology. Likewise, carbonaceous material was collected over 24-hour periods using IMPROVE technology along with the thermal optical reflectance (TOR) analysis, while semi-continuous total carbon concentrations were measured using the Rupprecht and Patashnick (R&P) instrument. Dry aerosol number size distributions were measured using a differential mobility analyzer (DMA) and optical particle counter, scattering coefficients at near-ambient conditions were measured with nephelometers fitted with PM10 and PM2.5 inlets, and "dry" PM2.5 scattering was measured after passing ambient air through Perma Pure Nafion® dryers. In general, the 24-hour "bulk" measurements of various aerosol species compared more favorably with each other than with the semi-continuous data. Semi-continuous sulfate measurements correlated well with the 24-hour measurements, but were biased low by

Characteristics of fine and coarse particles of natural and urban aerosols of Brazil

International Nuclear Information System (INIS)

Orsini, C.M.Q.; Tabacniks, M.H.; Artaxo Netto, P.E.; Andrade, M.F.; Kerr, A.

1986-02-01

Fine and coarse particles have been sampled from 1982 to 1985 in one natural forest seacoast site (Jureia) and five urban-industrial cities (Vitoria, Salvador, Porto Alegre, Sao Paulo, and Belo Horizonte). The time variations of concentrations in air and the relative elemental compositions of fine and coarse particle fractions, sampled by Nuclepore stacked filter units (SFU), have been determined gravimetrically and by PIXE analysis, respectively. Enrichment factors and correlation coefficients of the trace elements measured lead to unambiguous characterization of soil dust and sea salt, both major aerosol sources that emit coarse particles, and soil dust is also a significant source of fine particles. (Author) [pt

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

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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.

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

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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.

On the dynamics of fine aerosols artificially produced. Application to the atmosphere

International Nuclear Information System (INIS)

Perrin, Marie-Line

1980-01-01

We take advantage of the developments of a new method of measurement, using a diffusion battery, to analyse the evolution of ultra-fine particles generated as a result of gas-phase reactions (radiolysis and photolysis). The evolution of aerosols instantaneously produced by radiolysis of gaseous impurities is studied and a theoretical model from the coagulation equation's resolution is shown to well describe the phenomena. Experiments with aerosols continuously produced by photo-oxidation of SO 2 show the effect of the condensable molecules production rate and the preexisting aerosol, on the subsequent growth of the primary embryos. Different theoretical models are qualitatively and quantitatively verified. Our experiments are then extended to 'in situ' measurements in urban and marine atmospheres, and in every case, we quantitatively determine the importance of each intervening process, namely nucleation, coagulation and condensation. (author) [fr

Sources of carbonaceous aerosol in the Amazon basin

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S. Gilardoni

2011-03-01

Full Text Available The quantification of sources of carbonaceous aerosol is important to understand their atmospheric concentrations and regulating processes and to study possible effects on climate and air quality, in addition to develop mitigation strategies.

In the framework of the European Integrated Project on Aerosol Cloud Climate Interactions (EUCAARI fine (D_p < 2.5 μm and coarse (2.5 μm < D_p <10 μm aerosol particles were sampled from February to June (wet season and from August to September (dry season 2008 in the central Amazon basin. The mass of fine particles averaged 2.4 μg m⁻³ during the wet season and 4.2 μg m⁻³ during the dry season. The average coarse aerosol mass concentration during wet and dry periods was 7.9 and 7.6 μg m⁻³, respectively. The overall chemical composition of fine and coarse mass did not show any seasonality with the largest fraction of fine and coarse aerosol mass explained by organic carbon (OC; the average OC to mass ratio was 0.4 and 0.6 in fine and coarse aerosol modes, respectively. The mass absorbing cross section of soot was determined by comparison of elemental carbon and light absorption coefficient measurements and it was equal to 4.7 m² g⁻¹ at 637 nm. Carbon aerosol sources were identified by Positive Matrix Factorization (PMF analysis of thermograms: 44% of fine total carbon mass was assigned to biomass burning, 43% to secondary organic aerosol (SOA, and 13% to volatile species that are difficult to apportion. In the coarse mode, primary biogenic aerosol particles (PBAP dominated the carbonaceous aerosol mass. The results confirmed the importance of PBAP in forested areas.

The source apportionment results were employed to evaluate the ability of global chemistry transport models to simulate carbonaceous aerosol sources in a regional tropical background site. The comparison showed an overestimation

Origin of the water-soluble organic nitrogen in the maritime aerosol

Science.gov (United States)

Matsumoto, Kiyoshi; Yamamoto, Yuya; Nishizawa, Kotaro; Kaneyasu, Naoki; Irino, Tomohisa; Yoshikawa-Inoue, Hisayuki

2017-10-01

In order to clarify the production process for the particulate WSON in the maritime atmosphere, measurements of the WSON and the associated species in the aerosols were conducted at the coastal site on Rishiri Island near the northern tip of Japan. The mean concentration of the WSON in the aerosols was 0.077 μg m-3, which was within the previous measurements from the remote or rural clean sites. The WSON accounted for about 13% of the WSTN in the aerosols, and about 90% of the WSON was detected in the fine-mode range (d origin. The fine-mode WSON was correlated with nss-SO42- whether nss-SO42- was derived from anthropogenic or marine biogenic sources, suggesting that the WSON in the fine-mode range would be produced by the secondary processes in the acid particulate phase. EC and nss-K+, on the other hand, were not associated with the WSON in the fine-mode range, suggesting that the primary emissions from fossil fuel and/or biomass combustion are not important sources for the WSON. The coarse-mode WSON was not associated with any species. Negligible influence of dust particles and plant debris on coarse particle would cause very low concentrations of the WSON in the coarse-mode range.

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.

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

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.

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.

Analysis of Organic Anionic Surfactants in Fine and Coarse Fractions of Freshly Emitted Sea Spray Aerosol

Energy Technology Data Exchange (ETDEWEB)

Cochran, Richard E.; Laskina, Olga; Jayarathne, Thilina; Laskin, Alexander; Laskin, Julia; Lin, Peng; Sultana, Camile M.; Lee, Christopher; Moore, Kathryn A.; Cappa, Christopher; Bertram, Timothy; Prather, Kimberly; Grassian, Vicki H.; Stone, Elizabeth

2016-02-01

The inclusion of organic compounds in freshly emitted sea spray aerosol (SSA) has been shown to be size-dependent, with an increasing organic fraction in smaller particles. Defining the molecular composition of sea spray aerosol has proven challenging, due to the mix of continental and background particles even in remote marine environments. Here we have used electrospray ionization-high resolution mass spectrometry in negative ion mode to identify organic compounds in nascent sea spray collected throughout a 25-day mesocosm experiment. Over 280 organic compounds from ten major homologous series were identified. These compounds were operationally defined as molecules containing a hydrophobic alkyl chain with a hydrophilic head group making them surface active. The most abundant class of molecules detected were saturated (C8–C24) and unsaturated (C12–C22) fatty acids. Fatty acid derivatives (including saturated oxo-fatty acids (C5–C18) and saturated hydroxy-fatty acids (C5–C18) were also identified. Interestingly, anthropogenic influences on SSA from the seawater were observed in the form of sulfate (C2–C7, C12–C17) and sulfonate (C16–C22) species. During the mesocosm, the distributions of molecules within each homologous series were observed to respond to variations among the levels of phytoplankton and bacteria in the seawater, indicating an important role of biological processes in determining the composition of SSA.

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.

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

Stable carbon and nitrogen isotopic composition of fine mode aerosols (PM2.5 over the Bay of Bengal: impact of continental sources

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Srinivas Bikkina

2016-07-01

Full Text Available This study reports on stable carbon (δ13CTC and nitrogen (δ15NTN isotopic composition of total carbon and nitrogen (TC and TN in the fine mode aerosols (PM2.5; N=31 collected over the Bay of Bengal (BoB. The samples represent two distinct wind regimes during the cruise (27 December 2008–28 January 2009; one from the Indo-Gangetic Plain (referred as IGP-outflow and another from Southeast Asia (SEA-outflow. The PM2.5 samples from the IGP-outflow show higher δ13CTC (−25.0 to −22.8 ‰; −23.8±0.6 ‰ than those from the SEA-outflow (−27.4 to −24.7 ‰; −25.3±0.9 ‰. Similarly, δ15NTN varied from +11.8 to +30.6 ‰ (+20.4±5.4 ‰ and +10.4 to +31.7 ‰ (+19.4±6.1 ‰ for IGP- and SEA-outflows, respectively. Based on the literature data, MODIS-derived fire hotspots and back trajectories, we infer that higher δ13CTC in the IGP-outflow is predominantly associated with fossil fuel and biofuel combustion. In contrast, contribution of primary organic aerosols from the combustion of C3 plants or secondary organic aerosol (SOA formation from biomass/biofuel-burning emissions (BBEs can explain the lower δ13CTC values in the SEA-outflow. This inference is based on the significant linear correlations among δ13CTC, water-soluble organic carbon and non-sea-salt potassium (nss-K+, a proxy for BBEs in the SEA-outflow. A significant linear relationship of δ15N with and equivalent mass ratio of / is evident in both the continental outflows. Since abundance dominates the TN over the BoB (>90 %, atmospheric processes affecting its concentration in fine mode aerosols can explain the observed large variability of δ15NTN.

Origins and composition of fine atmospheric carbonaceous aerosol in the Sierra Nevada Mountains, California

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D. R. Worton

2011-10-01

Full Text Available In this paper we report chemically resolved measurements of organic aerosol (OA and related tracers during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX at the Blodgett Forest Research Station, California from 15 August–10 October 2007. OA contributed the majority of the mass to the fine atmospheric particles and was predominately oxygenated (OOA. The highest concentrations of OA were during sporadic wildfire influence when aged plumes were impacting the site. In situ measurements of particle phase molecular markers were dominated by secondary compounds and along with gas phase compounds could be categorized into six factors or sources: (1 aged biomass burning emissions and oxidized urban emissions, (2 oxidized urban emissions (3 oxidation products of monoterpene emissions, (4 monoterpene emissions, (5 anthropogenic emissions and (6 local methyl chavicol emissions and oxidation products. There were multiple biogenic components that contributed to OA at this site whose contributions varied diurnally, seasonally and in response to changing meteorological conditions, e.g. temperature and precipitation events. Concentrations of isoprene oxidation products were larger when temperatures were higher during the first half of the campaign (15 August–12 September due to more substantial emissions of isoprene and enhanced photochemistry. The oxidation of methyl chavicol, an oxygenated terpene emitted by ponderosa pine trees, contributed similarly to OA throughout the campaign. In contrast, the abundances of monoterpene oxidation products in the particle phase were greater during the cooler conditions in the latter half of the campaign (13 September–10 October, even though emissions of the precursors were lower, although the mechanism is not known. OA was correlated with the anthropogenic tracers 2-propyl nitrate and carbon monoxide (CO, consistent with previous observations, while being comprised of mostly non-fossil carbon

Characterization of fine aerosol and its inorganic components at two rural locations in New York State.

Science.gov (United States)

Sunder Raman, Ramya; Hopke, Philip K; Holsen, Thomas M

2008-09-01

Samples of PM(2.5) were collected to measure the concentrations of its chemical constituents at two rural locations, Potsdam and Stockton, NY from November 2002 to August 2005. These samples were collected on multiple filters at both sites, every third day for a 24-h interval with a speciation network sampler. The Teflo filters were analyzed for PM(2.5) mass by gravimetry, and elemental composition by X-ray fluorescence (XRF). Nylasorb filters and Teflo filters were leached with water and analyzed for anions and cations, respectively, by ion chromatography (IC). Fine particulate matter (PM(2.5)) mass and its inorganic component measurements were statistically characterized, and the temporal behavior of these species were assessed. Over the entire study period, PM(2.5) mass concentrations were lower at Potsdam (8.35 microg/m(3)) than at Stockton (10.24 microg/m(3)). At both locations, organic matter (OM) was the highest contributor to mass. Sulfate was the second highest contributor to mass at 27.0% at Potsdam, and 28.7% at Stockton. Nitrate contributions to mass of 8.9 and 9.5% at Potsdam and Stockton, respectively, were the third highest. At both locations, fine PM mass exhibited an annual cycle with a pronounced summer peak and indications of another peak during the winter, consistent with an overall increase in the rate of secondary aerosol formation during the summer, and increased partitioning of ammonium nitrate to the particle phase and condensation of other semi-volatiles during the winter, respectively. An ion-balance analysis indicated that at both locations, during the summers as well as in the winters, the aerosol was acidic. Lognormal frequency distribution fits to the measured mass concentrations on a seasonal basis indicated the overall increase in particle phase secondary aerosol (sulfate and SOA) concentrations during the summers compared to the winters at both locations.

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

OpenAIRE

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

2018-01-01

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

Characterization of fresh and aged organic aerosol emissions from meat charbroiling

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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.

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.

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.

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.

Nicotine, aerosol particles, carbonyls and volatile organic compounds in tobacco- and menthol-flavored e-cigarettes.

Science.gov (United States)

Lee, Mi-Sun; LeBouf, Ryan F; Son, Youn-Suk; Koutrakis, Petros; Christiani, David C

2017-04-27

We aimed to assess the content of electronic cigarette (EC) emissions for five groups of potentially toxic compounds that are known to be present in tobacco smoke: nicotine, particles, carbonyls, volatile organic compounds (VOCs), and trace elements by flavor and puffing time. We used ECs containing a common nicotine strength (1.8%) and the most popular flavors, tobacco and menthol. An automatic multiple smoking machine was used to generate EC aerosols under controlled conditions. Using a dilution chamber, we targeted nicotine concentrations similar to that of exposure in a general indoor environment. The selected toxic compounds were extracted from EC aerosols into a solid or liquid phase and analyzed with chromatographic and spectroscopic methods. We found that EC aerosols contained toxic compounds including nicotine, fine and nanoparticles, carbonyls, and some toxic VOCs such as benzene and toluene. Higher mass and number concentrations of aerosol particles were generated from tobacco-flavored ECs than from menthol-flavored ECs. We found that diluted machine-generated EC aerosols contain some pollutants. These findings are limited by the small number of ECs tested and the conditions of testing. More comprehensive research on EC exposure extending to more brands and flavor compounds is warranted.

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

Source apportionment of airborne particulate matter using organic compounds as tracers

Science.gov (United States)

Schauer, James J.; Rogge, Wolfgang F.; Hildemann, Lynn M.; Mazurek, Monica A.; Cass, Glen R.; Simoneit, Bernd R. T.

A chemical mass balance receptor model based on organic compounds has been developed that relates source contributions to airborne fine particle mass concentrations. Source contributions to the concentrations of specific organic compounds are revealed as well. The model is applied to four air quality monitoring sites in southern California using atmospheric organic compound concentration data and source test data collected specifically for the purpose of testing this model. The contributions of up to nine primary particle source types can be separately identified in ambient samples based on this method, and approximately 85% of the organic fine aerosol is assigned to primary sources on an annual average basis. The model provides information on source contributions to fine mass concentrations, fine organic aerosol concentrations and individual organic compound concentrations. The largest primary source contributors to fine particle mass concentrations in Los Angeles are found to include diesel engine exhaust, paved road dust, gasoline-powered vehicle exhaust, plus emissions from food cooking and wood smoke, with smaller contribution from tire dust, plant fragments, natural gas combustion aerosol, and cigarette smoke. Once these primary aerosol source contributions are added to the secondary sulfates, nitrates and organics present, virtually all of the annual average fine particle mass at Los Angeles area monitoring sites can be assigned to its source.

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.

Determination of permeability of ultra-fine cupric oxide aerosol through military filters and protective filters

Science.gov (United States)

Kellnerová, E.; Večeřa, Z.; Kellner, J.; Zeman, T.; Navrátil, J.

2018-03-01

The paper evaluates the filtration and sorption efficiency of selected types of military combined filters and protective filters. The testing was carried out with the use of ultra-fine aerosol containing cupric oxide nanoparticles ranging in size from 7.6 nm to 299.6 nm. The measurements of nanoparticles were carried out using a scanning mobility particle sizer before and after the passage through the filter and a developed sampling device at the level of particle number concentration approximately 750000 particles·cm-3. The basic parameters of permeability of ultra-fine aerosol passing through the tested material were evaluated, in particular particle size, efficiency of nanoparticle capture by filter, permeability coefficient and overall filtration efficiency. Results indicate that the military filter and particle filters exhibited the highest aerosol permeability especially in the nanoparticle size range between 100–200 nm, while the MOF filters had the highest permeability in the range of 200 to 300 nm. The Filter Nuclear and the Health and Safety filter had 100% nanoparticle capture efficiency and were therefore the most effective. The obtained measurement results have shown that the filtration efficiency over the entire measured range of nanoparticles was sufficient; however, it was different for particular particle sizes.

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.

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.

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

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.

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.

Size Distributions and Formation Pathways of Organic and Inorganic Constituents in Spring Aerosols from Okinawa Island in the Western North Pacific Rim: An Outflow Region of Asian Dusts

Science.gov (United States)

Deshmukh, D. K.; Lazaar, M.; Kawamura, K.; Kunwar, B.; Tachibana, E.; Boreddy, S. K. R.

2015-12-01

Size-segregated aerosols (9-stages) were collected at Okinawa Island in the western North Pacific Rim in spring 2008. The samples were analyzed for diacids (C2-C12), ω-oxoacids (ωC2-ωC9), a-dicarbonyls (C2-C3), organic carbon (OC), water-soluble OC (WSOC) and major ions to understand the sources and atmospheric processes in the outflow region of Asian pollutants. The molecular distribution of diacids showed the predominance of oxalic acid (C2) followed by malonic and succinic acids in all the size-segregated aerosols. ω-Oxoacids showed the predominance of glyoxylic acid (ωC2) whereas glyoxal (Gly) was more abundant than methylglyoxal in all the sizes. The abundant presence of sulfate as well as phthalic and adipic acids in Okinawa aerosols suggested a significant contribution of anthropogenic sources in East Asia via long-range atmospheric transport. Diacids (C2-C5), ωC2 and Gly as well as WSOC and OC peaked at 0.65-1.1 µm in fine mode whereas azelaic (C9) and 9-oxononanoic (ωC9) acids peaked at 3.3-4.7 µm in coarse mode. Sulfate and ammonium are enriched in fine mode whereas sodium and chloride are in coarse mode. An important mechanism for the formation of these organic species in Okinawa aerosols is probably gas phase oxidation of VOCs and subsequent in-cloud processing during long-range transport. Their characteristics size distribution implies that fine particles enriched with these organic and inorganic species could act as CCN to develop the cloud cover over the western North Pacific. The major peak of C9 and ωC9 on coarse mode suggest that they are produced by photooxidation of unsaturated fatty acids mainly derived from phytoplankton via heterogeneous reactions on sea spray particles. This study demonstrates that anthropogenic aerosols emitted from East Asia have significant influence on the compositions of organic and inorganic aerosols in the western North Pacific Rim.

Modelling and numerical simulation of the General Dynamic Equation of aerosols; Modelisation et simulation des aerosols atmospheriques

Energy Technology Data Exchange (ETDEWEB)

Debry, E.

2005-01-15

Chemical-transport models are now able to describe in a realistic way gaseous pollutants behavior in the atmosphere. Nevertheless atmospheric pollution also exists as fine suspended particles, called aerosols, which interact with gaseous phase, solar radiation, and have their own dynamic behavior. The goal of this thesis is the modelling and numerical simulation of the General Dynamic Equation of aerosols (GDE). Part I deals with some theoretical aspects of aerosol modelling. Part II is dedicated to the building of one size resolved aerosol model (SIREAM). In part III we perform the reduction of this model in order to use it in dispersion models as POLAIR3D. Several modelling issues are still opened: organic aerosol matter, externally mixed aerosols, coupling with turbulent mixing, and nano-particles. (author)

Cloud albedo increase from carbonaceous aerosol

Directory of Open Access Journals (Sweden)

W. R. Leaitch

2010-08-01

Full Text Available Airborne measurements from two consecutive days, analysed with the aid of an aerosol-adiabatic cloud parcel model, are used to study the effect of carbonaceous aerosol particles on the reflectivity of sunlight by water clouds. The measurements, including aerosol chemistry, aerosol microphysics, cloud microphysics, cloud gust velocities and cloud light extinction, were made below, in and above stratocumulus over the northwest Atlantic Ocean. On the first day, the history of the below-cloud fine particle aerosol was marine and the fine particle sulphate and organic carbon mass concentrations measured at cloud base were 2.4 μg m⁻³ and 0.9 μg m⁻³ respectively. On the second day, the below-cloud aerosol was continentally influenced and the fine particle sulphate and organic carbon mass concentrations were 2.3 μg m⁻³ and 2.6 μg m⁻³ respectively. Over the range 0.06–0.8 μm diameter, the shapes of the below-cloud size distributions were similar on both days and the number concentrations were approximately a factor of two higher on the second day. The cloud droplet number concentrations (CDNC on the second day were approximately three times higher than the CDNC measured on the first day. Using the parcel model to separate the influence of the differences in gust velocities, we estimate from the vertically integrated cloud light scattering measurements a 6% increase in the cloud albedo principally due to the increase in the carbonaceous components on the second day. Assuming no additional absorption by this aerosol, a 6% albedo increase translates to a local daytime radiative cooling of ∼12 W m⁻². This result provides observational evidence that the role of anthropogenic carbonaceous components in the cloud albedo effect can be much larger than that of anthropogenic sulphate, as some global simulations have indicated.

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

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"...

Religious Burning as a Major Source of Atmospheric Fine Aerosols in Lhasa city in the Tibetan Plateau

Science.gov (United States)

Liu, S.; Cui, Y.; Zhixuan, B.; Bian, J.; McKeen, S. A.; Watts, L. A.; Ciciora, S. J.; Gao, R. S.

2017-12-01

Measurements of aerosols in the Tibetan Plateau are scant due to the high altitude and harsh climate. To bridge this gap, we carried out the first field measurements of aerosol size distributions in Lhasa, a major city in the Tibetan Plateau that has been experiencing fast urbanization and reduced air quality. Aerosol number size distribution was continuously measured using an optical particle size spectrometer near the center of Lhasa city during the Asian summer monsoon season in 2016. The mass concentration of fine particles was modulated by boundary layer dynamics, with an average of 11 µg m-3 and the high values exceeding 50 µg m-3 during religious holidays. Daytime high concentration coincided with the religious burning of biomass and incense in the temples during morning hours, which produced heavy smoke. Factor analysis revealed a factor that is likely induced by religious burning. The factor contributed 34% of the campaign-average fine particle mass and the contribution reached up to 80% during religious holidays. The mass size distribution of aerosols produced from religious burnings peaked at 500 nm, indicating that these particles could efficiently decrease visibility and promote health risk. Because of its significance, our results suggest that more attention should be paid to religious burning, a currently under-studied source, in the Tibetan Plateau and in other regions of the world where religious burnings are frequently practiced.

Aerosol sampler for analysis of fine and ultrafine aerosols

Czech Academy of Sciences Publication Activity Database

Mikuška, Pavel; Čapka, Lukáš; Večeřa, Zbyněk

2018-01-01

Roč. 1020 (2018), s. 123-133 ISSN 0003-2670 R&D Projects: GA ČR(CZ) GA14-25558S Institutional support: RVO:68081715 Keywords : atmospheric aerosols * aerosol collection * chemical composition Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 4.950, year: 2016

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

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

Science.gov (United States)

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

2009-04-15

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

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.

Fine and coarse elemental components in the urban aerosol of Sao Paulo, Brazil

International Nuclear Information System (INIS)

Boueres, L.C.S.; Orsini, C.M.Q.

1981-01-01

Using cascade impactor sampling and PIXE analysis we have measured particle size distributions for approximately 15 elements in the Sao Paulo urban atmosphere. These elements, in our case, may be classified, according to their occurrence in fine or coarse aerosol log-normal modes, into three groups: (a) soil dust reference elements (coarse particle mode): Ti, Si and Ca; (b) anthropogenic fine particle mode: Zn, Br and Pb; and (c) mixed bimodal elements: S, K, V, Cr, Mn, Ni, Cu and Fe. All of the soil dust reference elements show consistently the log-normal parameters MMAD approx. 5.5 μm and sigmasub(g) approx. 3.2 (mass median aerodynamic diameter and geometric standard deviation, respectively). Enrichment factor calculations for Ti, Si, Ca and K in the coarse particle fraction (> 2 μmad), relative to Fe and the standard crustal aerosol values of Lawson and Winchester, show that Ti and Si are mainly soil derived while Ca and K may have significant industrial components in this particle fraction (i.e. coarse mode). The fine mode parameters for the other elements show variations with element suggesting different air pollution sources (such as motor vehicles, resuspended dust, refuse burning, industrial activities, etc.) and/or different chemical pathways, which presumably could be identifiable. For example, the modal parameters for group (b) are: Zn, MMAD = 0.9 μm, sigmasub(g) = 2.2; Br, MMAD = 0.5 μm, sigmasub(g) = 4.0; Pb, MMAD = 0.6 μm, sigmasub(g) = 3.0; thus suggesting a common source (automotive) for Br and Pb, unrelated to the source of Zn (possibly refuse burning). (orig.)

Seasonal variation of water-soluble inorganic species in the coarse and fine atmospheric aerosols at Dar es Salaam, Tanzania

International Nuclear Information System (INIS)

Mkoma, Stelyus L.; Wang Wan; Maenhaut, Willy

2009-01-01

The ionic composition of coarse, fine and total PM10 was investigated in aerosol samples collected from a kerbside in Dar es Salaam during the 2005 dry season and 2006 wet season. A 'Gent' PM10 stacked filter unit sampler with sequential Nuclepore polycarbonate filters, providing coarse (8 μm) and fine (0.4 μm) size fractions, was deployed. The mean concentrations and associated standard deviation of fine, coarse and PM10 were, respectively, 17 ± 4, 52 ± 27, and 69 ± 29 μg/m 3 during the 2005 dry season campaign and 13 ± 5, 34 ± 23 and 47 ± 25 μg/m 3 for the 2006 wet season campaign. The higher PM mass concentrations during the dry season campaign are essentially due to soil dust dispersal, much biomass burning and temperature inversions. Chloride, Na + and Mg 2+ were the dominant ions in coarse fraction, indicating a significant influence of sea-salt aerosols. In the fine fraction, SO 4 2- and NH 4 + and K + were the most important ions. The mean equivalent PM2 NO 3 - concentration in the 2005 dry season campaign was two times higher than in the 2006 wet season campaign, probably due to reaction of NaCl (sea-salt) with HNO 3 as a result of higher levels of NO x during the dry season and/or reduced volatilization of NH 4 NO 3 due to lower temperature in the dry season. The results from our water-soluble ions study strongly suggests that biomass burning and secondary aerosols make a significant contribution to fine particulate mass in Dar es Salaam atmosphere. Thus, burning of waste and biomass are thought to be the major causes for the atmospheric particulate pollution in Dar es Salaam during the dry season.

Seasonal variation of water-soluble inorganic species in the coarse and fine atmospheric aerosols at Dar es Salaam, Tanzania

Science.gov (United States)

Mkoma, Stelyus L.; Wang, Wan; Maenhaut, Willy

2009-09-01

The ionic composition of coarse, fine and total PM10 was investigated in aerosol samples collected from a kerbside in Dar es Salaam during the 2005 dry season and 2006 wet season. A "Gent" PM10 stacked filter unit sampler with sequential Nuclepore polycarbonate filters, providing coarse (8 μm) and fine (0.4 μm) size fractions, was deployed. The mean concentrations and associated standard deviation of fine, coarse and PM10 were, respectively, 17 ± 4, 52 ± 27, and 69 ± 29 μg/m 3 during the 2005 dry season campaign and 13 ± 5, 34 ± 23 and 47 ± 25 μg/m 3 for the 2006 wet season campaign. The higher PM mass concentrations during the dry season campaign are essentially due to soil dust dispersal, much biomass burning and temperature inversions. Chloride, Na + and Mg 2+ were the dominant ions in coarse fraction, indicating a significant influence of sea-salt aerosols. In the fine fraction, SO42- and NH4+ and K + were the most important ions. The mean equivalent PM2 NO3- concentration in the 2005 dry season campaign was two times higher than in the 2006 wet season campaign, probably due to reaction of NaCl (sea-salt) with HNO 3 as a result of higher levels of NO x during the dry season and/or reduced volatilization of NH 4NO 3 due to lower temperature in the dry season. The results from our water-soluble ions study strongly suggests that biomass burning and secondary aerosols make a significant contribution to fine particulate mass in Dar es Salaam atmosphere. Thus, burning of waste and biomass are thought to be the major causes for the atmospheric particulate pollution in Dar es Salaam during the dry season.

Water content of aged aerosol

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G. J. Engelhart

2011-02-01

Full Text Available The composition and physical properties of aged atmospheric aerosol were characterized at a remote sampling site on the northern coast of Crete, Greece during the Finokalia Aerosol Measurement Experiment in May 2008 (FAME-2008. A reduced Dry-Ambient Aerosol Size Spectrometer (DAASS was deployed to measure the aerosol water content and volumetric growth factor of fine particulate matter. The particles remained wet even at relative humidity (RH as low as 20%. The aerosol was acidic during most of the measurement campaign, which likely contributed to the water uptake at low RH. The water content observations were compared to the thermodynamic model E-AIM, neglecting any contribution of the organics to aerosol water content. There was good agreement between the water measurements and the model predictions. Adding the small amount of water associated with the organic aerosol based on monoterpene water absorption did not change the quality of the agreement. These results strongly suggest that the water uptake by aged organic aerosol is relatively small (a few percent of the total water for the conditions during FAME-08 and generally consistent with what has been observed in laboratory experiments. The water concentration measured by a Q-AMS was well correlated with the DAASS measurements and in good agreement with the predicted values for the RH of the Q-AMS inlet. This suggests that, at least for the conditions of the study, the Q-AMS can provide valuable information about the aerosol water concentrations if the sample is not dried.

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

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

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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, NO_x and NO_y 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.

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

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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.

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

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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 NO_x 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.

Chemical characteristics of size-resolved atmospheric aerosols in Iasi, north-eastern Romania: nitrogen-containing inorganic compounds control aerosol chemistry in the area

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Giorgiana Galon-Negru, Alina; Iulian Olariu, Romeo; Arsene, Cecilia

2018-04-01

This study assesses the effects of particle size and season on the content of the major inorganic and organic aerosol ionic components in the Iasi urban area, north-eastern Romania. Continuous measurements were carried out over 2016 using a cascade Dekati low-pressure impactor (DLPI) performing aerosol size classification in 13 specific fractions over the 0.0276-9.94 µm size range. Fine-particulate Cl-, NO3-, NH4+, and K+ exhibited clear minima during the warm season and clear maxima over the cold season, mainly due to trends in emission sources, changes in the mixing layer depth and specific meteorological conditions. Fine-particulate SO42- did not show much variation with respect to seasons. Particulate NH4+ and NO3- ions were identified as critical parameters controlling aerosol chemistry in the area, and their measured concentrations in fine-mode (PM2.5) aerosols were found to be in reasonable good agreement with modelled values for winter but not for summer. The likely reason is that NH4NO3 aerosols are lost due to volatility over the warm season. We found that NH4+ in PM2.5 is primarily associated with SO42- and NO3- but not with Cl-. Actually, indirect ISORROPIA-II estimations showed that the atmosphere in the Iasi area might be ammonia rich during both the cold and warm seasons, enabling enough NH3 to be present to neutralize H2SO4, HNO3, and HCl acidic components and to generate fine-particulate ammonium salts, in the form of (NH4)2SO4, NH4NO3, and NH4Cl. ISORROPIA-II runs allowed us to estimate that over the warm season ˜ 35 % of the total analysed samples had very strongly acidic pH (0-3), a fraction that rose to ˜ 43 % over the cold season. Moreover, while in the cold season the acidity is mainly accounted for by inorganic acids, in the warm ones there is an important contribution by other compounds, possibly organic. Indeed, changes in aerosol acidity would most likely impact the gas-particle partitioning of semi-volatile organic acids. Overall, we

An analysis of high fine aerosol loading episodes in north-central Spain in the summer 2013 - Impact of Canadian biomass burning episode and local emissions

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Burgos, M. A.; Mateos, D.; Cachorro, V. E.; Toledano, C.; de Frutos, A. M.; Calle, A.; Herguedas, A.; Marcos, J. L.

2018-07-01

This work presents an evaluation of a surprising and unusual high turbidity summer period in 2013 recorded in the north-central Iberian Peninsula (IP). The study is made up of three main pollution episodes characterized by very high aerosol optical depth (AOD) values with the presence of fine aerosol particles: the strongest long-range transport Canadian Biomass Burning (BB) event recorded, one of the longest-lasting European Anthropogenic (A) episodes and an extremely strong regional BB. The Canadian BB episode was unusually strong with maximum values of AOD(440 nm) ∼ 0.8, giving rise to the highest value recorded by photometer data in the IP with a clearly established Canadian origin. The anthropogenic pollution episode originated in Europe is mainly a consequence of the strong impact of Canadian BB events over north-central Europe. As regards the local episode, a forest fire in the nature reserve near the Duero River (north-central IP) impacted on the population over 200 km away from its source. These three episodes exhibited fingerprints in different aerosol columnar properties retrieved by sun-photometers of the AErosol RObotic NETwork (AERONET) as well as in particle mass surface concentrations, PMx, measured by the European Monitoring and Evaluation Programme (EMEP). Main statistics, time series and scatterplots relate aerosol loads (aerosol optical depth, AOD and particulate matter, PM) with aerosol size quantities (Ångström Exponent and PM ratio). More detailed microphysical/optical properties retrieved by AERONET inversion products are analysed in depth to describe these events: contribution of fine and coarse particles to AOD and its ratio (the fine mode fraction), volume particle size distribution, fine volume fraction, effective radius, sphericity fraction, single scattering albedo and absorption optical depth. Due to its relevance in climate studies, the aerosol radiative effect has been quantified for the top and bottom of the atmosphere

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.

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.

Vertical profiles of fine and coarse aerosol particles over Cyprus: Comparison between in-situ drone measurements and remote sensing observations

Science.gov (United States)

Mamali, Dimitra; Marinou, Eleni; Pikridas, Michael; Kottas, Michael; Binietoglou, Ioannis; Kokkalis, Panagiotis; Tsekeri, Aleksandra; Amiridis, Vasilis; Sciare, Jean; Keleshis, Christos; Engelmann, Ronny; Ansmann, Albert; Russchenberg, Herman W. J.; Biskos, George

2017-04-01

Vertical profiles of the aerosol mass concentration derived from light detection and ranging (lidar) measurements were compared to airborne dried optical particle counter (OPC MetOne; Model 212) measurements during the INUIT-BACCHUS-ACTRIS campaign. The campaign took place in April 2016 and its main focus was the study of aerosol dust particles. During the campaign the NOA Polly-XT Raman lidar located at Nicosia (35.08° N, 33.22° E) was providing round-the-clock vertical profiles of aerosol optical properties. In addition, an unmanned aerial vehicle (UAV) carrying an OPC flew on 7 days during the first morning hours. The flights were performed at Orounda (35.1018° N, 33.0944° E) reaching altitudes of 2.5 km a.s.l, which allows comparison with a good fraction of the recorded lidar data. The polarization lidar photometer networking method (POLIPHON) was used for the estimation of the fine (non-dust) and coarse (dust) mode aerosol mass concentration profiles. This method uses as input the particle backscatter coefficient and the particle depolarization profiles of the lidar at 532 nm wavelength and derives the aerosol mass concentration. The first step in this approach makes use of the lidar observations to separate the backscatter and extinction contributions of the weakly depolarizing non-dust aerosol components from the contributions of the strongly depolarizing dust particles, under the assumption of an externally mixed two-component aerosol. In the second step, sun photometer retrievals of the fine and the coarse modes aerosol optical thickness (AOT) and volume concentration are used to calculate the associated concentrations from the extinction coefficients retrieved from the lidar. The estimated aerosol volume concentrations were converted into mass concentration with an assumption for the bulk aerosol density, and compared with the OPC measurements. The first results show agreement within the experimental uncertainty. This project received funding from the

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

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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.

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

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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.

Spectral Discrimination of Fine and Coarse Mode Aerosol Optical Depth from AERONET Direct Sun Data of Singapore and South-East Asia

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Salinas Cortijo, S.; Chew, B.; Liew, S.

2009-12-01

Aerosol optical depth combined with the Angstrom exponent and its derivative, are often used as a qualitative indicator of aerosol particle size, with Angstrom exp. values greater than 2 indicating small (fine mode) particles associated with urban pollution and bio-mass burning. Around this region, forest fires are a regular occurrence during the dry season, specially near the large land masses of Sumatra and Borneo. The practice of clearing land by burning the primary and sometimes secondary forest, results in a smog-like haze covering large areas of regional cities such as cities Singapore, Kuala Lumpur and sometimes the south of Thailand, often reducing visibility and increasing health problems for the local population. In Singapore, the sources of aerosols are mostly from fossil fuel burning (energy stations, incinerators, urban transport etc.) and from the industrial and urban areas. The proximity to the sea adds a possible oceanic source. However, as stated above and depending on the time of the year, there can be a strong bio-mass component coming from forest fires from various regions of the neighboring countries. Bio-mass related aerosol particles are typically characterized by showing a large optical depth and small, sub-micron particle size distributions. In this work, we analyze three years of direct Sun measurements performed with a multi-channel Cimel Sun-Photometer (part of the AERONET network) located at our site. In order to identify bio-mass burning events in this region, we perform a spectral discrimination between coarse and fine mode optical depth; subsequently, the fine mode parameters such as optical depth, optical ratio and fine mode Angstrom exponents (and its derivative) are used to identify possible bio-mass related events within the data set.

Characteristics, sources and evolution of fine aerosol (PM1) at urban, coastal and forest background sites in Lithuania

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Masalaite, A.; Holzinger, R.; Remeikis, V.; Röckmann, T.; Dusek, U.

2017-01-01

The chemical and isotopic composition of organic aerosol (OA) samples collected on PM1 filters was determined as a function of desorption temperature to investigate the main sources of organic carbon and the effects of photochemical processing on atmospheric aerosol. The filter samples were collected at an urban (54°38‧ N, 25°18‧ E), coastal (55°55‧ N, 21°00‧ E) and forest (55°27‧ N, 26°00' E) site in Lithuania in March 2013. They can be interpreted as winter-time samples because the monthly averaged temperature was -4 °C. The detailed chemical composition of organic compounds was analysed with a thermal desorption PTR-MS. The mass concentration of organic aerosol at the forest site was roughly by a factor of 30 lower than at the urban and coastal site. This fact could be an indication that in this cold month the biogenic secondary organic aerosol (SOA) formation was very low. Moreover, the organic aerosol collected at the forest site was more refractory and contained a larger fraction of heavy molecules with m/z > 200. The isotopic composition of the aerosol was used to differentiate the two main sources of organic aerosol in winter, i.e. biomass burning (BB) and fossil fuel (FF) combustion. Organic aerosol from biomass burning is enriched in 13C compared to OA from fossil fuel emissions. δ13COC values of the OA samples showed a positive correlation with the mass fraction of several individual organic compounds. Most of these organic compounds contained nitrogen indicating that organic nitrogen compounds formed during the combustion of biomass may be indicative of BB. Other compounds that showed negative correlations with δ13COC were possibly indicative of FF. These compounds included heavy hydrocarbons and were on the average less oxidized than the bulk organic carbon. The correlation of δ13COC and the O/C ratio was positive at low but negative at high desorption temperatures at the forest site. We propose that this might be due to

Quantitative LC–MS for water-soluble heterocyclic amines in fine aerosols (PM2.5) at Duke Forest, USA

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In this study, a quantitative liquid chromatography-mass spectrometry (LC-MS) technique capable of measuring the concentrations of heterocyclic nitrogen compounds in ambient fine aerosols (PM2.5) has been developed. Quadrupole time-of-flight (Q-TOF) MS technology is used to provi...

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.

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.

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

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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.

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

Carbonaceous aerosol particles from common vegetation in the Grand Canyon

International Nuclear Information System (INIS)

Hallock, K.A.; Mazurek, M.A.; Cass, G.R.

1992-05-01

The problem of visibility reduction in the Grand Canyon due to fine organic aerosol particles in the atmosphere has become an area of increased environmental concern. Aerosol particles can be derived from many emission sources. In this report, we focus on identifying organic aerosols derived from common vegetation in the Grand Canyon. These aerosols are expected to be significant contributors to the total atmospheric organic aerosol content. Aerosol samples from living vegetation were collected by resuspension of surface wax and resin components liberated from the leaves of vegetation common to areas of the Grand Canyon. The samples were analyzed using high-resolution gas chromatography/mass spectrometry (GC/MS). Probable identification of compounds was made by comparison of sample spectra with National Institute of Standards and Technology (NIST) mass spectral references and positive identification of compounds was made when possible by comparison with authentic standards as well as NIST references. Using these references, we have been able to positively identify the presence of n-alkane and n-alkanoic acid homolog series in the surface waxes of the vegetation sampled. Several monoterpenes, sesquiterpenes, and diterpenes were identified also as possible biogenic aerosols which may contribute to the total organic aerosol abundance leading to visibility reduction in the Grand Canyon

Modelization and numerical simulation of atmospheric aerosols dynamics

International Nuclear Information System (INIS)

Debry, Edouard

2004-01-01

Chemical-transport models are now able to describe in a realistic way gaseous pollutants behavior in the atmosphere. Nevertheless atmospheric pollution also exists as a fine suspended particles, called aerosols which interact with gaseous phase, solar radiation, and have their own dynamic behavior. The goal of this thesis is the modelization and numerical simulation of the General Dynamic Equation of aerosols (GDE). Part I deals with some theoretical aspects of aerosol modelization. Part II is dedicated to the building of one size resolved aerosol model (SIREAM). In part III we perform the reduction of this model in order to use it in dispersion models as POLAIR3D. Several modelization issues are still opened: organic aerosol matter, externally mixed aerosols, coupling with turbulent mixing, and nano-particles. (author) [fr

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

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.

Impacts of springtime biomass burning in the northern Southeast Asia on marine organic aerosols over the Gulf of Tonkin, China.

Science.gov (United States)

Zheng, Lishan; Yang, Xiaoyang; Lai, Senchao; Ren, Hong; Yue, Siyao; Zhang, Yingyi; Huang, Xin; Gao, Yuanguan; Sun, Yele; Wang, Zifa; Fu, Pingqing

2018-06-01

Fine particles (PM 2.5 ) samples, collected at Weizhou Island over the Gulf of Tonkin on a daytime and nighttime basis in the spring of 2015, were analyzed for primary and secondary organic tracers, together with organic carbon (OC), elemental carbon (EC), and stable carbon isotopic composition (δ 13 C) of total carbon (TC). Five organic compound classes, including saccharides, lignin/resin products, fatty acids, biogenic SOA tracers and phthalic acids, were quantified by gas chromatography/mass spectrometry (GC/MS). Levoglucosan was the most abundant organic species, indicating that the sampling site was under strong influence of biomass burning. Based on the tracer-based methods, the biomass-burning-derived fraction was estimated to be the dominant contributor to aerosol OC, accounting for 15.7% ± 11.1% and 22.2% ± 17.4% of OC in daytime and nighttime samples, respectively. In two episodes E1 and E2, organic aerosols characterized by elevated concentrations of levoglucosan as well as its isomers, sugar compounds, lignin products, high molecular weight (HMW) fatty acids and β-caryophyllinic acid, were attributed to the influence of intensive biomass burning in the northern Southeast Asia (SEA). However, the discrepancies in the ratios of levoglucosan to mannosan (L/M) and OC (L/OC) as well as the δ 13 C values suggest the type of biomass burning and the sources of organic aerosols in E1 and E2 were different. Hardwood and/or C 4 plants were the major burning materials in E1, while burning of softwood and/or C 3 plants played important role in E2. Furthermore, more complex sources and enhanced secondary contribution were found to play a part in organic aerosols in E2. This study highlights the significant influence of springtime biomass burning in the northern SEA to the organic molecular compositions of marine aerosols over the Gulf of Tonkin. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

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

Religious burning as a potential major source of atmospheric fine aerosols in summertime Lhasa on the Tibetan Plateau

Science.gov (United States)

Cui, Yu Yan; Liu, Shang; Bai, Zhixuan; Bian, Jianchun; Li, Dan; Fan, Kaiyu; McKeen, Stuart A.; Watts, Laurel A.; Ciciora, Steven J.; Gao, Ru-Shan

2018-05-01

We carried out field measurements of aerosols in Lhasa, a major city in the Tibetan Plateau that has been experiencing fast urbanization and industrialization. Aerosol number size distribution was continuously measured using an optical particle size spectrometer near the center of Lhasa city during the Asian summer monsoon season in 2016. The mass concentration of fine particles was modulated by boundary layer dynamics, with an average of 11 μg m-3 and the high values exceeding 50 μg m-3 during religious holidays. Daytime high concentration coincided with the religious burning of biomass and incense in the temples during morning hours, which produced heavy smoke. Factor analysis revealed a factor that likely represented religious burning. The factor contributed 34% of the campaign-average fine particle mass and the contribution reached up to 80% during religious holidays. The mass size distribution of aerosols produced from religious burnings peaked at ∼500 nm, indicating that these particles could efficiently decrease visibility and promote health risk. Because of its significance, our results suggest that further studies of religious burning, a currently under-studied source, are needed in the Tibetan Plateau and in other regions of the world where religious burnings are frequently practiced.

Enhanced UV Absorption in Carbonaceous Aerosols during MILAGRO and Identification of Potential Organic Contributors.

Science.gov (United States)

Mangu, A.; Kelley, K. L.; Marchany-Rivera, A.; Kilaparty, S.; Gunawan, G.; Gaffney, J. S.; Marley, N. A.

2007-12-01

Measurements of aerosol absorption were obtained as part of the MAX-Mex component of the MILAGRO field campaign at site T0 (Instituto Mexicano de Petroleo in Mexico City) during the month of March, 2006 by using a 7- channel aethalometer (Thermo-Anderson). These measurements, obtained at 370, 470, 520, 590, 660, 880, and 950 nm at a 5 minute time resolution, showed an enhanced absorption in the UV over that expected from carbon soot alone. Samples of fine atmospheric aerosols (less than 0.1micron) were also collected at site T0 and T1 (Universidad Technologica de Tecamac, State of Mexico) from 5 am to 5 pm (day) and from 5 pm to 5 am (night) during the month of March 2006. The samples were collected on quartz fiber filters with high volume impactor samplers. The samples have been characterized for total carbon content (stable isotope ratio mass spectroscopy) and natural radionuclide tracers (210Pb, 210Po, 210Bi, 7Be, 13C, 14C, 40K, 15N). Continuous absorption spectra of these aerosol samples have been obtained in the laboratory from 280 to 900nm with the use of an integrating sphere coupled to a UV-visible spectrometer (Beckman DU with a Labsphere accessory). The integrating sphere allows the detector to collect and spatially integrate the total radiant flux reflected from the sample and therefore allows for the measurement of absorption on highly reflective or diffusely scattering samples (1). The continuous spectra also show an enhanced UV absorption over that expected from carbon soot and the general profiles are quite similar to those observed for humic and fulvic acids found as colloidal materials in surface and groundwaters (2), indicating the presence of humic-like substances (HULIS) in the fine aerosols. The spectra also show evidence of narrow band absorbers below 400 nm typical of polycyclic aromatics (PAH) and nitrated aromatic compounds. Spectra were also obtained on NIST standard diesel soot (SRM 2975), NIST standard air particulate matter (SRM 8785

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-NO_x and low-NO_x 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.

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

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...

Secondary organic material formed by methylglyoxal in aqueous aerosol mimics

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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 k_NH4+^II=5×10⁻⁶ M⁻¹ min⁻¹ and k_H3O+^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.

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...

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

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.

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

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.

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

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

Atmospheric particulate matter (PM), especially fine particles (particles with aerodynamic diameter less than 1 m, PM1), has been found to play an important role in global climate change, air quality, and human health. The continuous study of aerosol parameters is therefore imperative for better understanding the environmental effects of the atmospheric particles, as well as their sources, formation and transformation processes. The particle size distribution is particularly important, since this physical parameter determines the mass and number density, lifetime and atmospheric transport, or optical scattering behavior of the particles in the atmosphere (Jaenicke, 1998). Over the years several efforts have been made to improve the knowledge about the chemical composition of atmospheric particles as a function of size (Samara and Voutsa, 2005) and to characterize the relative contribution of different components to the fine particulate matter. It is well established that organic materials constitute a highly variable fraction of the atmospheric aerosol. This fraction is predominantly found in the fine size mode in concentrations ranging from 10 to 70% of the total dry fine particle mass (Middlebrook et al., 1998). Although organic compounds are major components of the fine particles, the composition, formation mechanism of organic aerosols are not well understood. This is because particulate organic matter is part of a complex atmospheric system with hundreds of different compounds, both natural and anthropogenic, covering a wide range of chemical properties. The aim of this study was to characterize the forest PM1, and investigate effects of air mass transport on the aerosol size distribution and chemical composition, estimate and provide insights into the sources and characteristics of carbonaceous aerosols through analysis ^13C/12C isotopic ratio as a function of the aerosol particles size. The measurements were performed at the Rugšteliškis integrated

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

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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.

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.

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

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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.

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)

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

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 (NO_x 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 NO_x 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

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

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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 O_x(= 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

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...

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)

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.

Spatiotemporal variability and contribution of different aerosol types to the aerosol optical depth over the Eastern Mediterranean

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A. K. Georgoulias

2016-11-01

Full Text Available This study characterizes the spatiotemporal variability and relative contribution of different types of aerosols to the aerosol optical depth (AOD over the Eastern Mediterranean as derived from MODIS (Moderate Resolution Imaging Spectroradiometer Terra (March 2000–December 2012 and Aqua (July 2002–December 2012 satellite instruments. For this purpose, a 0.1° × 0.1° gridded MODIS dataset was compiled and validated against sun photometric observations from the AErosol RObotic NETwork (AERONET. The high spatial resolution and long temporal coverage of the dataset allows for the determination of local hot spots like megacities, medium-sized cities, industrial zones and power plant complexes, seasonal variabilities and decadal averages. The average AOD at 550 nm (AOD550 for the entire region is ∼ 0.22 ± 0.19, with maximum values in summer and seasonal variabilities that can be attributed to precipitation, photochemical production of secondary organic aerosols, transport of pollution and smoke from biomass burning in central and eastern Europe and transport of dust from the Sahara and the Middle East. The MODIS data were analyzed together with data from other satellite sensors, reanalysis projects and a chemistry–aerosol-transport model using an optimized algorithm tailored for the region and capable of estimating the contribution of different aerosol types to the total AOD550. The spatial and temporal variability of anthropogenic, dust and fine-mode natural aerosols over land and anthropogenic, dust and marine aerosols over the sea is examined. The relative contribution of the different aerosol types to the total AOD550 exhibits a low/high seasonal variability over land/sea areas, respectively. Overall, anthropogenic aerosols, dust and fine-mode natural aerosols account for ∼ 51, ∼ 34 and ∼ 15 % of the total AOD550 over land, while, anthropogenic aerosols, dust and marine aerosols account ∼ 40, ∼ 34

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...

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

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 ...

Biogenic, anthropogenic and sea salt sulfate size-segregated aerosols in the Arctic summer

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R. Ghahremaninezhad

2016-04-01

Full Text Available Size-segregated aerosol sulfate concentrations were measured on board the Canadian Coast Guard Ship (CCGS Amundsen in the Arctic during July 2014. The objective of this study was to utilize the isotopic composition of sulfate to address the contribution of anthropogenic and biogenic sources of aerosols to the growth of the different aerosol size fractions in the Arctic atmosphere. Non-sea-salt sulfate is divided into biogenic and anthropogenic sulfate using stable isotope apportionment techniques. A considerable amount of the average sulfate concentration in the fine aerosols with a diameter  <  0.49 µm was from biogenic sources (>  63 %, which is higher than in previous Arctic studies measuring above the ocean during fall (<  15 % (Rempillo et al., 2011 and total aerosol sulfate at higher latitudes at Alert in summer (>  30 % (Norman et al., 1999. The anthropogenic sulfate concentration was less than that of biogenic sulfate, with potential sources being long-range transport and, more locally, the Amundsen's emissions. Despite attempts to minimize the influence of ship stack emissions, evidence from larger-sized particles demonstrates a contribution from local pollution. A comparison of δ34S values for SO2 and fine aerosols was used to show that gas-to-particle conversion likely occurred during most sampling periods. δ34S values for SO2 and fine aerosols were similar, suggesting the same source for SO2 and aerosol sulfate, except for two samples with a relatively high anthropogenic fraction in particles  <  0.49 µm in diameter (15–17 and 17–19 July. The high biogenic fraction of sulfate fine aerosol and similar isotope ratio values of these particles and SO2 emphasize the role of marine organisms (e.g., phytoplankton, algae, bacteria in the formation of fine particles above the Arctic Ocean during the productive summer months.

Classification of aerosol properties derived from AERONET direct sun data

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G. P. Gobbi

2007-01-01

Full Text Available Aerosol spectral measurements by sunphotometers can be characterized by three independent pieces of information: 1 the optical thickness (AOT, a measure of the column aerosol concentration, 2 the optical thickness average spectral dependence, given by the Angstrom exponent (α, and 3 the spectral curvature of α (δα. We propose a simple graphical method to visually convert (α, δα to the contribution of fine aerosol to the AOT and the size of the fine aerosols. This information can be used to track mixtures of pollution aerosol with dust, to distinguish aerosol growth from cloud contamination and to observe aerosol humidification. The graphical method is applied to the analysis of yearly records at 8 sites in 3 continents, characterized by different levels of pollution, biomass burning and mineral dust concentrations. Results depict the dominance of fine mode aerosols in driving the AOT at polluted sites. In stable meteorological conditions, we see an increase in the size of the fine aerosol as the pollution stagnates and increases in optical thickness. Coexistence of coarse and fine particles is evidenced at the polluted sites downwind of arid regions.

Improved source apportionment of organic aerosols in complex urban air pollution using the multilinear engine (ME-2)

Science.gov (United States)

Zhu, Qiao; Huang, Xiao-Feng; Cao, Li-Ming; Wei, Lin-Tong; Zhang, Bin; He, Ling-Yan; Elser, Miriam; Canonaco, Francesco; Slowik, Jay G.; Bozzetti, Carlo; El-Haddad, Imad; Prévôt, André S. H.

2018-02-01

Organic aerosols (OAs), which consist of thousands of complex compounds emitted from various sources, constitute one of the major components of fine particulate matter. The traditional positive matrix factorization (PMF) method often apportions aerosol mass spectrometer (AMS) organic datasets into less meaningful or mixed factors, especially in complex urban cases. In this study, an improved source apportionment method using a bilinear model of the multilinear engine (ME-2) was applied to OAs collected during the heavily polluted season from two Chinese megacities located in the north and south with an Aerodyne high-resolution aerosol mass spectrometer (HR-ToF-AMS). We applied a rather novel procedure for utilization of prior information and selecting optimal solutions, which does not necessarily depend on other studies. Ultimately, six reasonable factors were clearly resolved and quantified for both sites by constraining one or more factors: hydrocarbon-like OA (HOA), cooking-related OA (COA), biomass burning OA (BBOA), coal combustion (CCOA), less-oxidized oxygenated OA (LO-OOA) and more-oxidized oxygenated OA (MO-OOA). In comparison, the traditional PMF method could not effectively resolve the appropriate factors, e.g., BBOA and CCOA, in the solutions. Moreover, coal combustion and traffic emissions were determined to be primarily responsible for the concentrations of PAHs and BC, respectively, through the regression analyses of the ME-2 results.

Aerosol concentrations and composition in the North Pacific marine boundary layer

Science.gov (United States)

Choi, Yongjoo; Rhee, Tae Siek; Collett, Jeffrey L.; Park, Taehyun; Park, Seung-Myung; Seo, Beom-Keun; Park, Gyutae; Park, Keyhong; Lee, Taehyoung

2017-12-01

Ship-borne measurements of inorganic and organic aerosols, including methanesulfonic acid (MSA), were conducted over the Northern Pacific using a High Resolution Time of Flight Aerosol Mass Spectrometer (AMS). This study, conducted aboard the Korean ice breaker R/V Araon, was part of the SHIP-borne Pole-to-Pole Observations (SHIPPO) project. Based on air mass source region, the cruise track could be divided into five sections. Overall, the South Asia and Northern Japan ship transects showed higher aerosol concentrations due to continental pollution and biomass burning sources, respectively. In all five regions, the average mass concentrations of sulfate and organic aerosols (OA) were much higher than concentrations of nitrate and ammonium. Positive matrix factorization (PMF) analysis distinguished two organic aerosol factors as hydrocarbon-like and oxidized OA (HOA and OOA). HOA peaked in South Asia under the influence of anthropogenic pollution source areas, such as China and Korea, and generally decreased with increasing latitude across the full study region. OOA concentrations peaked in Northern Japan near the Tsugaru Strait and appear to reflect fine particle contributions from biomass burning. The mean HOA concentration in the clean marine area (Aleutian Island to Siberia) was 0.06 μg/m3 and comprised approximately 8% of the OA mass fraction. The highest MSA concentrations peaked in the Aleutian Islands at nearly 15 μg/m3, suggesting influence from higher dimethyl sulfide (DMS) emissions resulting from biological nutrient uptake during summer. The MSA/sulfate ratio, an indicator of the relative fine particle contributions of DMS and anthropogenic sources, revealed a sharp gradient as the ship approached the clean marine areas where the dominance of DMS increased. The patterns in OOA, HOA, and MSA concentrations found in this study provide a better understanding of the characteristics of inorganic and organic aerosols in the Northern Pacific Ocean.

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...

Sources of atmospheric aerosol from long-term measurements (5 years) of chemical composition in Athens, Greece.

Science.gov (United States)

Paraskevopoulou, D; Liakakou, E; Gerasopoulos, E; Mihalopoulos, N

2015-09-15

To identify the sources of aerosols in Greater Athens Area (GAA), a total of 1510 daily samples of fine (PM 2.5) and coarse (PM 10-2,5) aerosols were collected at a suburban site (Penteli), during a five year period (May 2008-April 2013) corresponding to the period before and during the financial crisis. In addition, aerosol sampling was also conducted in parallel at an urban site (Thissio), during specific, short-term campaigns during all seasons. In all these samples mass and chemical composition measurements were performed, the latest only at the fine fraction. Particulate organic matter (POM) and ionic masses (IM) are the main contributors of aerosol mass, equally contributing by accounting for about 24% of the fine aerosol mass. In the IM, nss-SO4(-2) is the prevailing specie followed by NO3(-) and NH4(+) and shows a decreasing trend during the 2008-2013 period similar to that observed for PM masses. The contribution of water in fine aerosol is equally significant (21 ± 2%), while during dust transport, the contribution of dust increases from 7 ± 2% to 31 ± 9%. Source apportionment (PCA and PMF) and mass closure exercises identified the presence of six sources of fine aerosols: secondary photochemistry, primary combustion, soil, biomass burning, sea salt and traffic. Finally, from winter 2012 to winter 2013 the contribution of POM to the urban aerosol mass is increased by almost 30%, reflecting the impact of wood combustion (dominant fuel for domestic heating) to air quality in Athens, which massively started in winter 2013. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

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

2015-12-01

Secondary organic aerosol (SOA) accounts for 20-70% of atmospheric fine aerosol. NOx plays crucial roles in SOA formation and consequently affects the composition and yield of SOA. SOA component speciation is incomplete due to its complex composition of polar oxygenated and multifunctional species. In this study, ultrahigh resolution mass spectrometry (UHR MS) was applied to improve the understanding of NOx effects on biogenic SOA formation by identifying the elemental composition of SOA. Additional research aim was to investigate oligomer components that are considered as a driving force for SOA formation and growth. In this study α-pinene SOA from photochemical reaction was examined. SOA formation was performed in the absence and presence of NOx at dry condition (grant funded by the Korea government (MEST) (No. 2011-01350000).

Characteristics, sources and evolution of fine aerosol (PM1) at urban, coastal and forest background sites in Lithuania

NARCIS (Netherlands)

Masalaite, A.; Holzinger, R.; Remeikis, V.; Roeckmann, Thomas; Dusek, U.

The chemical and isotopic composition of organic aerosol (OA) samples collected on PM1 filters was determined as a function of desorption temperature to investigate the main sources of organic carbon and the effects of photochemical processing on atmospheric aerosol. The filter samples were

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

Science.gov (United States)

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

2017-12-01

Organic Aerosols (OAs) are typically defined as highly complex matrices whose composition changes in time and space. Focusing on time vector, this work uses two-dimensional nuclear magnetic resonance (2D NMR) techniques to examine the structural features of water-soluble (WSOM) and alkaline-soluble organic matter (ASOM) sequentially extracted from fine atmospheric aerosols collected in an urban setting during cold and warm seasons. This study reveals molecular signatures not previously decoded in NMR-related studies of OAs as meaningful source markers. Although the ASOM is less hydrophilic and structurally diverse than its WSOM counterpart, both fractions feature a core with heteroatom-rich branched aliphatics from both primary (natural and anthropogenic) and secondary origin, aromatic secondary organics originated from anthropogenic aromatic precursors, as well as primary saccharides and amino sugar derivatives from biogenic emissions. These common structures represent those 2D NMR spectral signatures that are present in both seasons and can thus be seen as an "annual background" profile of the structural composition of OAs at the urban location. Lignin-derived structures, nitroaromatics, disaccharides, and anhydrosaccharides signatures were also identified in the WSOM samples only from periods identified as smoke impacted, which reflects the influence of biomass-burning sources. The NMR dataset on the H-C molecules backbone was also used to propose a semi-quantitative structural model of urban WSOM, which will aid efforts for more realistic studies relating the chemical properties of OAs with their atmospheric behavior. Copyright © 2017 Elsevier Ltd. All rights reserved.

Long term fine aerosol analysis by XRF and PIXE techniques in the city of Rijeka, Croatia

International Nuclear Information System (INIS)

Ivošević, Tatjana; Orlić, Ivica; Radović, Iva Bogdanović

2015-01-01

Highlights: • For the first time in Croatia, long term of fine aerosol pollution is reported. - Abstract: The results of a long term, multi elemental XRF and PIXE analysis of fine aerosol pollution in the city of Rijeka, Croatia, are reported for the first time. The samples were collected during a seven months period (6th Aug 2013–28th Feb 2014) on thin stretched Teflon filters and analyzed by energy dispersive X-ray fluorescence (EDXRF) at the Laboratory for Elemental Micro-Analysis (LEMA), University of Rijeka and by Particle Induced X-ray Emission (PIXE) using 1.6 MeV protons at the Laboratory for Ion Beam Interactions (LIBI), Ruđer Bošković Institute, Zagreb. The newly developed micro-XRF system at LEMA provided results for 19 elements in the range from Si to Pb. The PIXE at the LIBI provided information for the same elements as well for the light elements such as Na, Mg and Al. Black carbon was determined with the Laser Integrated Plate Method (LIPM). The results were statistically evaluated by means of the positive matrix factorization (PMF). The seven major pollution sources were identified together with their relative contributions, these are: secondary sulfates, road traffic, smoke, road dust, sea spray, ship emissions and soil dust.

Long term fine aerosol analysis by XRF and PIXE techniques in the city of Rijeka, Croatia

Energy Technology Data Exchange (ETDEWEB)

Ivošević, Tatjana [Faculty of Engineering, University of Rijeka, Vukovarska 58, HR-51000 Rijeka (Croatia); Orlić, Ivica [Department of Physics, University of Rijeka, Radmile Matejčić 2, HR-51000 Rijeka (Croatia); Radović, Iva Bogdanović [Laboratory for Ion Beam Interaction, Ruđer Bošković Institute, Bijenička 54, HR-10000 Zagreb (Croatia)

2015-11-15

Highlights: • For the first time in Croatia, long term of fine aerosol pollution is reported. - Abstract: The results of a long term, multi elemental XRF and PIXE analysis of fine aerosol pollution in the city of Rijeka, Croatia, are reported for the first time. The samples were collected during a seven months period (6th Aug 2013–28th Feb 2014) on thin stretched Teflon filters and analyzed by energy dispersive X-ray fluorescence (EDXRF) at the Laboratory for Elemental Micro-Analysis (LEMA), University of Rijeka and by Particle Induced X-ray Emission (PIXE) using 1.6 MeV protons at the Laboratory for Ion Beam Interactions (LIBI), Ruđer Bošković Institute, Zagreb. The newly developed micro-XRF system at LEMA provided results for 19 elements in the range from Si to Pb. The PIXE at the LIBI provided information for the same elements as well for the light elements such as Na, Mg and Al. Black carbon was determined with the Laser Integrated Plate Method (LIPM). The results were statistically evaluated by means of the positive matrix factorization (PMF). The seven major pollution sources were identified together with their relative contributions, these are: secondary sulfates, road traffic, smoke, road dust, sea spray, ship emissions and soil dust.

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

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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.

Classifying Aerosols Based on Fuzzy Clustering and Their Optical and Microphysical Properties Study in Beijing, China

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Wenhao Zhang

2017-01-01

Full Text Available Classification of Beijing aerosol is carried out based on clustering optical properties obtained from three Aerosol Robotic Network (AERONET sites. The fuzzy c-mean (FCM clustering algorithm is used to classify fourteen-year (2001–2014 observations, totally of 6,732 records, into six aerosol types. They are identified as fine particle nonabsorbing, two kinds of fine particle moderately absorbing (fine-MA1 and fine-MA2, fine particle highly absorbing, polluted dust, and desert dust aerosol. These aerosol types exhibit obvious optical characteristics difference. While five of them show similarities with aerosol types identified elsewhere, the polluted dust aerosol has no comparable prototype. Then the membership degree, a significant parameter provided by fuzzy clustering, is used to analyze internal variation of optical properties of each aerosol type. Finally, temporal variations of aerosol types are investigated. The dominant aerosol types are polluted dust and desert dust in spring, fine particle nonabsorbing aerosol in summer, and fine particle highly absorbing aerosol in winter. The fine particle moderately absorbing aerosol occurs during the whole year. Optical properties of the six types can also be used for radiative forcing estimation and satellite aerosol retrieval. Additionally, methodology of this study can be applied to identify aerosol types on a global scale.

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

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.

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.

Present role of PIXE in atmospheric aerosol research

Energy Technology Data Exchange (ETDEWEB)

Maenhaut, Willy, E-mail: Willy.Maenhaut@UGent.be

2015-11-15

In the 1980s and 1990s nearly half of the elemental analyses of atmospheric aerosol samples were performed by PIXE. Since then, other techniques for elemental analysis became available and there has been a steady increase in studies on organic aerosol constituents and other aspects of aerosols, especially in the areas of nucleation (new particle formation), optical properties, and the role of aerosol particles in cloud formation and properties. First, a brief overview and discussion is given of the developments and trends in atmospheric aerosol analysis and research of the past three decades. Subsequently, it is indicated that there is still invaluable work to be done by PIXE in atmospheric aerosol research, especially if one teams up with other aerosol researchers and performs complementary measurements, e.g., on small aerosol samples that are taken with high-time resolution. Fine examples of such research are the work done by the Lund group in the CARIBIC aircraft studies and the analysis of circular streaker samples by the Florence PIXE group. These and other examples are presented and other possibilities of PIXE are indicated.

Composition analyses of size-resolved aerosol samples taken from aircraft downwind of Kuwait, Spring 1991

Energy Technology Data Exchange (ETDEWEB)

Cahill, T.A.; Wilkinson, K. [Univ. of California, Davis, CA (United States); Schnell, R. [National Center for Atmospheric Research, Boulder, CO (United States)

1992-09-20

Analyses are reported for eight aerosol samples taken from the National Center for Atmospheric Research Electra typically 200 to 250 km downwind of Kuwait between May 19 and June 1, 1991. Aerosols were separated into fine (D{sub p} < 2.5 {mu}m) and coarse (2.5 < D{sub p} 10 {mu}m) particles for optical, gravimetric, X ray and nuclear analyses, yielding information on the morphology, mass, and composition of aerosols downwind of Kuwait. The mass of coarse aerosols ranged between 60 and 1971 {mu}g/m{sup 3} and, while dominated by soil derived aerosols, contained considerable content of sulfates and salt (NaCl) and soot in the form of fluffy agglomerates. The mass of fine aerosols varied between 70 and 785 {mu}g/m{sup 3}, of which about 70% was accounted for via compositional analyses performed in vacuum. While most components varied greatly from flight to flight, organic matter and fine soils each accounted for about 1/4 of the fine mass, while salt and sulfates contributed about 10% and 7%, respectively. The Cl/S ratios were remarkably constant, 2.4 {+-} 1.2 for coarse particles and 2.0 {+-} 0.2 for fine particles, with one flight deleted in each case. Vanadium, when observed, ranged from 9 to 27 ng/m{sup 3}, while nickel ranged from 5 to 25 ng/m{sup 3}. In fact, fine sulfates, vanadium, and nickel occurred in levels typical of Los Angeles, California, during summer 1986. The V/Ni ratio, 1.7 {+-} 0.4, was very similar to the ratios measured in fine particles from combusted Kuwaiti oil, 1.4 {+-} 0.9. Bromine, copper, zinc, and arsenic/lead were also observed at levels between 2 and 190 ng/m{sup 3}. The presence of massive amounts of fine, typically alkaline soils in the Kuwaiti smoke plumes significantly modified their behavior and probably mitigated their impacts, locally and globally. 16 refs., 1 fig., 3 tabs.

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.

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

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...

Evidence for Asian dust effects from aerosol plume measurements during INTEX-B 2006 near Whistler, BC

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W. R. Leaitch

2009-06-01

Full Text Available Several cases of aerosol plumes resulting from trans-Pacific transport were observed between 2 km and 5.3 km at Whistler, BC from 22 April 2006 to 15 May 2006. The fine particle (<1 μm chemical composition of most of the plumes was dominated by sulphate that ranged from 1–5 μg m⁻³ as measured with a Quadrapole Aerosol Mass Spectrometer (Q-AMS. Coarse particles (>1 μm were enhanced in all sulphate plumes. Fine particle organic mass concentrations were relatively low in most plumes and were nominally anti-correlated with the increases in the number concentrations of coarse particles. The ion chemistry of coarse particles sampled at Whistler Peak was dominated by calcium, sodium, nitrate, sulphate and formate. Scanning transmission X-ray microscopy of coarse particles sampled from the NCAR C-130 aircraft relatively close to Whistler indicated carbonate, potassium and organic functional groups, in particular the carboxyl group. Asian plumes reaching Whistler, BC during the INTEX-B study were not only significantly reduced of fine particle organic material, but organic compounds were attached to coarse particles in significant quantities. Suspension of dust with deposited organic material and scavenging of organic materials by dust near anthropogenic sources are suggested, and if any secondary organic aerosol (SOA was formed during transport from Asian source regions across the Pacific it was principally associated with the coarse particles. An average of profiles indicates that trans-Pacific transport between 2 and 5 km during this period increased ozone by about 10 ppbv and fine particle sulphate by 0.2–0.5 μg m⁻³. The mean sizes of the fine particles in the sulphate plumes were larger when dust particles were present and smaller when the fine particle organic mass concentration was larger and dust was absent. The coarse particles of dust act to accumulate sulphate, nitrate and organic material in larger particles

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

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

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.

Aerosol composition and source apportionment in Santiago de Chile

Science.gov (United States)

Artaxo, Paulo; Oyola, Pedro; Martinez, Roberto

1999-04-01

Santiago de Chile, São Paulo and Mexico City are Latin American urban areas that suffer from heavy air pollution. In order to study air pollution in Santiago area, an aerosol source apportionment study was designed to measure ambient aerosol composition and size distribution for two downtown sampling sites in Santiago. The aerosol monitoring stations were operated in Gotuzo and Las Condes during July and August 1996. The study employed stacked filter units (SFU) for aerosol sampling, collecting fine mode aerosol (dpsource apportionment was performed using Absolute Principal Factor Analysis (APFA). Very high aerosol concentrations were observed (up to 400 μg/m 3 PM 10). The main aerosol particle sources in Santiago are resuspended soil dust and traffic emissions. Coarse particles account for 63% of PM 10 aerosol in Gotuzo and 53% in Las Condes. A major part of this component is resuspended soil dust. In the fine fraction, resuspended soil dust accounts for 15% of fine mass, and the aerosols associated with transportation activities account for a high 64% of the fine particle mass. Sulfate particle is an important component of the aerosol in Santiago, mainly originating from gas-to-particle conversion from SO 2. In the Gotuzo site, sulfates are the highest aerosol component, accounting for 64.5% of fine mass. Direct traffic emissions are generally mixed with resuspended soil dust. It is difficult to separate the two components, because the soil dust in downtown Santiago is contaminated with Pb, Br, Cl, and other heavy metals that are also tracers for traffic emissions. Residual oil combustion is observed, with the presence of V, S and Ni. An aerosol components from industrial emissions is also present, with the presence of several heavy metals such as Zn, Cu and others. A factor with molybdenum, arsenic, copper and sulfur was observed frequently, and it results from emissions of copper smelters.

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.

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,...

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.

Geochemical perspectives from a new aerosol chemical mass closure

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B. Guinot

2007-01-01

Full Text Available The aerosol chemical mass closure is revisited and a simple and inexpensive methodology is proposed. This methodology relies on data obtained for aerosol mass, and concentration of the major ions and the two main carbon components, the organic carbon (OC and the black carbon (BC. Atmospheric particles are separated into coarse (AD>2 μm and fine (AD<2 μm fractions and are treated separately. For the coarse fraction the carbonaceous component is minor and assumption is made for the conversion factor k of OC-to-POM (Particulate Organic Matter which is fixed to the value of 1.8 accounting for secondary species. The coarse soluble calcium is shown to display a correlation (regression coefficient f, y axis intercept b with the missing mass. Conversely, the fine fraction is dominated by organic species and assumption is made for dust which is assumed to have the same f factor as the coarse mode dust. The fine mode mass obtained from chemical analyses is then adjusted to the actual weighed mass by tuning the k conversion factor. The k coefficient is kept different in the two modes due to the expected different origins of the organic particles. Using the f and k coefficient obtained from the data set, the mass closure is reached for each individual sample with an undetermined fraction less than 10%. The procedure has been applied to different urban and peri-urban environments in Europe and in Beijing and its efficiency and uncertainties on f and k values are discussed. The f and k coefficients are shown to offer consistent geochemical indications on aerosol origin and transformations. f allows to retrieve dust mass and its value accounting for Ca abundance in dust at the site of investigation may serve as an indicator of dust origin and aerosol interactions with anthropogenic acids. f values were found to vary in the 0.08–0.12 range in European urban areas, and a broader range in Beijing (0.01–0.16. As expected, k appears to be a relevant proxy for

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.

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

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S. P. Hersey

2011-08-01

in accumulation mode aerosol, while afternoon SOA production coincides with the appearance of a distinct fine mode dominated by organics. Particulate NH₄NO₃ and (NH₄₂SO₄ appear to be NH₃-limited in regimes I and II, but a significant excess of particulate NH₄⁺ in the hot, dry regime III suggests less SO₄²⁻ and the presence of either organic amines or NH₄⁺-associated organic acids. C-ToF-AMS data were analyzed by Positive Matrix Factorization (PMF, which resolved three factors, corresponding to a hydrocarbon-like OA (HOA, semivolatile OOA (SV-OOA, and low-volatility OOA (LV-OOA. HOA appears to be a periodic plume source, while SV-OOA exhibits a strong diurnal pattern correlating with ozone. Peaks in SV-OOA concentration correspond to peaks in DMA number concentration and the appearance of a fine organic mode. LV-OOA appears to be an aged accumulation mode constituent that may be associated with aqueous-phase processing, correlating strongly with sulfate and representing the dominant background organic component. Periods characterized by high SV-OOA and LV-OOA were analyzed by filter analysis, revealing a complex mixture of species during periods dominated by SV-OOA and LV-OOA, with LV-OOA periods characterized by shorter-chain dicarboxylic acids (higher O:C ratio, as well as appreciable amounts of nitrate- and sulfate-substituted organics. Phthalic acid was ubiquitous in filter samples, suggesting that PAH photochemistry may be an important SOA pathway in Los Angeles. Aerosol composition was related to water uptake characteristics, and it is concluded that hygroscopicity is largely controlled by organic mass fraction (OMF. The hygroscopicity parameter κ averaged 0.31 ± 0.08, approaching 0.5 at low OMF and 0.1 at high OMF, with increasing OMF suppressing hygroscopic growth and increasing critical dry diameter for CCN activation

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

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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.

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.

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

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

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.

Stable generator of polydisperse aerosol

Czech Academy of Sciences Publication Activity Database

Mikuška, Pavel

2001-01-01

Roč. 32, Suppl. 1 (2001), s. S823-S824 ISSN 0021-8502. [European Aerosol Conference 2001. Leipzig, 03.09.2001-07.09.2001] R&D Projects: GA AV ČR IAA4031105 Institutional research plan: CEZ:AV0Z4031919 Keywords : aerosol generator * fine aerosol * polydisperse aerosol Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.605, year: 2001

Lab-scale development of a high temperature aerosol particle sampling probe system for field measurements in thermochemical conversion of biomass

Energy Technology Data Exchange (ETDEWEB)

Lindskog, M.; Malik, A.; Pagels, J.; Sanati, M. [Lund Univ., Lund (Sweden). Div. of Ergonomics and Aerosol Technology

2010-07-01

Thermochemical conversion of biomass requires both combustion in an oxygen rich environment and gasification in an oxygen deficient environment. Therefore, the mass concentration of fly ash from combustion processes is dominated by inorganic compounds, and the particulate matter obtained from gasification is dominated by carbonaceous compounds. The fine fly ash particles can initiate corrosion and fouling and also increases emissions of fine particulates to the atmosphere. This study involved the design of a laboratory scale setup consisting of a high temperature sampling probe and an aerosol generation system to study the formation of fine particle from biomass gasification processes. An aerosol model system using potassium chloride (KCl) as the ash compound and Di Octyl Sebacate oil (DOS) as the volatile organic part was used to test the high temperature sampling probe. Tests conducted at 200 degrees C showed good reproducibility of the aerosol generator. The tests also demonstrated suitable dilution ratios which enabled the denuder to absorb all of the gaseous organic compounds in the set up, thus enabling measurement of only the particle phase. Condensable organic concentrations of 1-68 mg/m{sup 3} were easily handled by the high temperature sampling probe system, indicating that the denuder worked well. Additional tests will be performed using an Aerosol Mass Spectrometer (AMST) to verify that the denuder can capture all of the gaseous organic compounds also when condensed onto agglomerated soot particles. 6 refs., 1 tab., 9 figs.

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

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.

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.

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

Elemental composition and oxidation of chamber organic aerosol

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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-NO_x 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

Background aerosol over the Himalayas and Tibetan Plateau: observed characteristics of aerosol mass loading

Science.gov (United States)

Liu, Bin; Cong, Zhiyuan; Wang, Yuesi; Xin, Jinyuan; Wan, Xin; Pan, Yuepeng; Liu, Zirui; Wang, Yonghong; Zhang, Guoshuai; Wang, Zhongyan; Wang, Yongjie; Kang, Shichang

2017-01-01

To investigate the atmospheric aerosols of the Himalayas and Tibetan Plateau (HTP), an observation network was established within the region's various ecosystems, including at the Ngari, Qomolangma (QOMS), Nam Co, and Southeastern Tibetan (SET) stations. In this paper we illustrate aerosol mass loadings by integrating in situ measurements with satellite and ground-based remote sensing datasets for the 2011-2013 period, on both local and large scales. Mass concentrations of these surface atmospheric aerosols were relatively low and varied with land cover, showing a general tendency of Ngari and QOMS (barren sites) > Nam Co (grassland site) > SET (forest site). Daily averages of online PM2.5 (particulates with aerodynamic diameters below 2.5 µm) at these sites were sequentially 18.2 ± 8.9, 14.5 ± 7.4, 11.9 ± 4.9 and 11.7 ± 4.7 µg m-3. Correspondingly, the ratios of PM2.5 to total suspended particles (TSP) were 27.4 ± 6.65, 22.3 ± 10.9, 37.3 ± 11.1 and 54.4 ± 6.72 %. Bimodal mass distributions of size-segregated particles were found at all sites, with a relatively small peak in accumulation mode and a more notable peak in coarse mode. Diurnal variations in fine-aerosol masses generally displayed a bi-peak pattern at the QOMS, Nam Co and SET stations and a single-peak pattern at the Ngari station, controlled by the effects of local geomorphology, mountain-valley breeze circulation and aerosol emissions. Dust aerosol content in PM2.1 samples gave fractions of 26 % at the Ngari station and 29 % at the QOMS station, or ˜ 2-3 times that of reported results at human-influenced sites. Furthermore, observed evidence confirmed the existence of the aerodynamic conditions necessary for the uplift of fine particles from a barren land surface. Combining surface aerosol data and atmospheric-column aerosol optical properties, the TSP mass and aerosol optical depth (AOD) of the Multi-angle Imaging Spectroradiometer (MISR) generally decreased as land cover changed from

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

The penetration of aerosols through fine capillaries

International Nuclear Information System (INIS)

Mitchell, J.P.; Edwards, R.T.; Ball, M.H.E.

1989-10-01

A novel experimental technique has been developed to study the penetration of aerosol particles ranging from about 1 to 15 μm aerodynamic diameter through capillaries varying from 20 to 80 μm bore and from 10 to 50 mm in length. When the driving pressure was 100 kPa, the penetration of the airborne particles was considerably smaller than expected from a simple comparison of particle diameter with the bore of the capillary. Particle size distributions determined after penetration through the capillaries were in almost all cases similar to the particle size distribution of the aerosol at the capillary entrance. This lack of size-selectivity can be explained in terms of the capillary behaving as a conventional suction-based sampler from a near still (calm) air environment. The resulting particle penetration data are important in assessing the potential for the leakage of aerosols through seals in containers used to transport radioactive materials. (author)

Physicochemical properties of fine aerosols at Plan d'Aups during ESCOMPTE

Science.gov (United States)

Marinoni, Angela; Laj, Paolo; Deveau, Pierre Alexandre; Marino, Federica; Ghermandi, Grazia; Aulagnier, Fabien; Cachier, Hélène

2005-03-01

The physical and chemical properties of aerosol particles were investigated at Plan d'Aups, one of the ESCOMPTE sites located in the St. Baume mountain area (700 m a.s.l.), 50 km east of Marseilles (France). The site is ideally located for assessing the vertical and horizontal extent of the pollution plume from the Marseilles-Berre area. Our study showed that polluted air masses from the Marseilles-Berre area are advected to Plan d'Aups in the early afternoon. Average daily concentration of particles reaches up to 40 μg m -3 while 1-h average particle number concentration is greater than 30,000 cm -3. Most of the particle mass is composed of SO 42- and organic carbon (OC). The chemical properties of the particles revealed that an additional source, possibly from the industrial area of Gardanne, contributes to the aerosol mass. This last source is characterised by significant emissions of elements, such as Zn, V, Al and Si. In addition to transport, we found that gas-to-particle conversion takes place at the interface between the free troposphere and the boundary layer. We estimated that on average, 30% of the particle number is accounted for by direct nucleation. This is potentially a major aerosol source to the free troposphere.

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-05-14

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

Water content of aged aerosol

OpenAIRE

G. J. Engelhart; L. Hildebrandt; E. Kostenidou; N. Mihalopoulos; N. M. Donahue; S. N. Pandis

2010-01-01

The composition and physical properties of aged atmospheric aerosol were characterized at a remote sampling site on the northern coast of Crete, Greece during the Finokalia Aerosol Measurement Experiment in May 2008 (FAME-2008). A reduced Dry-Ambient Aerosol Size Spectrometer (DAASS) was deployed to measure the aerosol water content and volumetric growth factor of fine particulate matter. The particles remained wet even at relative humidity (RH) as low as 20%. The aerosol was acidic during mo...

Scanning Transmission X-ray Microscopy: Applications in Atmospheric Aerosol Research

Energy Technology Data Exchange (ETDEWEB)

Moffet, Ryan C.; Tivanski, Alexei V.; Gilles, Mary K.

2011-01-20

Scanning transmission x-ray microscopy (STXM) combines x-ray microscopy and near edge x-ray absorption fine structure spectroscopy (NEXAFS). This combination provides spatially resolved bonding and oxidation state information. While there are reviews relevant to STXM/NEXAFS applications in other environmental fields (and magnetic materials) this chapter focuses on atmospheric aerosols. It provides an introduction to this technique in a manner approachable to non-experts. It begins with relevant background information on synchrotron radiation sources and a description of NEXAFS spectroscopy. The bulk of the chapter provides a survey of STXM/NEXAFS aerosol studies and is organized according to the type of aerosol investigated. The purpose is to illustrate the current range and recent growth of scientific investigations employing STXM-NEXAFS to probe atmospheric aerosol morphology, surface coatings, mixing states, and atmospheric processing.

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.

Preparation of an ultra-fine, slightly dispersed silver iodide aerosol

International Nuclear Information System (INIS)

Poc, Marie-Martine

1973-01-01

A silver iodide aerosol was prepared under clean conditions. The method was to react iodine vapor with a silver aerosol in an inert dry atmosphere and in darkness. Great care was taken to avoid contamination from atmosphere air. The ice nucleating properties of the ultrafine AgI aerosol obtained were studied in a cloud mixing chamber: the aerosol was found to be strangely inactive. (author) [fr

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.

Aerosol Indirect effect on Stratocumulus Organization

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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.

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

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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.

THE EFFECTS OF FINE LACTOSE AS A THIRD COMPONENT ON AEROSOLIZATION OF CEFOTAXIME SODIUM FROM DRY POWDER FORMULATIONS

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ABDOLHOSEIN ROUHOLAMINI NAJAFABADI

2006-06-01

Full Text Available Dry powder inhaler (DPI formulations usually contain micronized drug particles and lactose as a carrier. Fine lactose could be used as a ternary component to improve drug delivery from DPIs. The aim of this study was to investigate the deposition profile of a model drug, cefotaxime sodium (CS, using coarse and fine carriers after aerosolization at 60 l/min via a spinhaler® into a twin stage liquid impinger (TSI. Two micronization methods. jet milling and spray drying were used to micronize the active drug and carrier. The particle size of CS and lactose were characterized by laser diffraction, and the morphology of formulations was examined by scanning electron microscopy. X-ray diffraction of jet milled lactose showed crystalline nature, but spray dried lactose exhibited an amorphous state. The results showed the existence of fine lactose in formulations significantly (p0.05 difference was observed between the effect of jet milled and spray dried lactose. On the other hand selection of micronization technique to reduce particle size of CS, was very effective on deposition profile. The highest influence of fine lactose was obtained by formulation containing jet milled CS in ratio of drug/carrier 1/1 and 10% of fine lactose as third component.

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

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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

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

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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 f₄₄–f₄₃ 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 κ_org, ranged from 8.4×10⁻⁴ to 0.28 over measured O/C ratios ranging from 0.05 to 1.42. This range of κ_org and O/C ratio is significantly wider than has been previously obtained. To first order, the κ_org-to-O/C relationship is well represented by a linear function of the form κ_org = (0.18±0.04 ×O/C + 0.03, suggesting that a simple, semi-empirical parameterization of OOA hygroscopicity and

Smoke aerosol chemistry and aging of Siberian biomass burning emissions in a large aerosol chamber

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Kalogridis, A.-C.; Popovicheva, O. B.; Engling, G.; Diapouli, E.; Kawamura, K.; Tachibana, E.; Ono, K.; Kozlov, V. S.; Eleftheriadis, K.

2018-07-01

Vegetation open fires constitute a significant source of particulate pollutants on a global scale and play an important role in both atmospheric chemistry and climate change. To better understand the emission and aging characteristics of smoke aerosols, we performed small-scale fire experiments using the Large Aerosol Chamber (LAC, 1800 m3) with a focus on biomass burning from Siberian boreal coniferous forests. A series of burn experiments were conducted with typical Siberian biomass (pine and debris), simulating separately different combustion conditions, namely, flaming, smoldering and mixed phase. Following smoke emission and dispersion in the combustion chamber, we investigated aging of aerosols under dark conditions. Here, we present experimental data on emission factors of total, elemental and organic carbon, as well as individual organic compounds, such as anhydrosugars, phenolic and dicarboxylic acids. We found that total carbon accounts for up to 80% of the fine mode (PM2.5) smoke aerosol. Higher PM2.5 emission factors were observed in the smoldering compared to flaming phase and in pine compared to debris smoldering phase. For low-temperature combustion, organic carbon (OC) contributed to more than 90% of total carbon, whereas elemental carbon (EC) dominated the aerosol composition in flaming burns with a 60-70% contribution to the total carbon mass. For all smoldering burns, levoglucosan (LG), a cellulose decomposition product, was the most abundant organic species (average LG/OC = 0.26 for pine smoldering), followed by its isomer mannosan or dehydroabietic acid (DA), an important constituent of conifer resin (DA/OC = 0.033). A levoglucosan-to-mannosan ratio of about 3 was observed, which is consistent with ratios reported for coniferous biomass and more generally softwood. The rates of aerosol removal for OC and individual organic compounds were investigated during aging in the chamber in terms of mass concentration loss rates over time under dark

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

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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.

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

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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.

Aerosol composition and source apportionment in Santiago de Chile

International Nuclear Information System (INIS)

Artaxo, Paulo; Oyola, Pedro; Martinez, Roberto

1999-01-01

Santiago de Chile, Sao Paulo and Mexico City are Latin American urban areas that suffer from heavy air pollution. In order to study air pollution in Santiago area, an aerosol source apportionment study was designed to measure ambient aerosol composition and size distribution for two downtown sampling sites in Santiago. The aerosol monitoring stations were operated in Gotuzo and Las Condes during July and August 1996. The study employed stacked filter units (SFU) for aerosol sampling, collecting fine mode aerosol (dp 10 mass of particles smaller than 10 μm) and black carbon concentration were also measured. Particle-Induced X-ray Emission (PIXE) was used to measure the concentration of 22 trace elements at levels below 0.5 ng m -3 . Quantitative aerosol source apportionment was performed using Absolute Principal Factor Analysis (APFA). Very high aerosol concentrations were observed (up to 400 μg/m 3 PM 10 ). The main aerosol particle sources in Santiago are resuspended soil dust and traffic emissions. Coarse particles account for 63% of PM 10 aerosol in Gotuzo and 53% in Las Condes. A major part of this component is resuspended soil dust. In the fine fraction, resuspended soil dust accounts for 15% of fine mass, and the aerosols associated with transportation activities account for a high 64% of the fine particle mass. Sulfate particle is an important component of the aerosol in Santiago, mainly originating from gas-to-particle conversion from SO 2 . In the Gotuzo site, sulfates are the highest aerosol component, accounting for 64.5% of fine mass. Direct traffic emissions are generally mixed with resuspended soil dust. It is difficult to separate the two components, because the soil dust in downtown Santiago is contaminated with Pb, Br, Cl, and other heavy metals that are also tracers for traffic emissions. Residual oil combustion is observed, with the presence of V, S and Ni. An aerosol components from industrial emissions is also present, with the presence of

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.

Physico-Chemical Evolution of Organic Aerosol from Wildfire Emissions

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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

Characterization of Fine Particulate Matter (PM) and Secondary PM Precursor Gases in the Mexico City Metropolitan Area

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Molina, Luisa T.; Volkamer, Rainer; de Foy, Benjamin; Lei, Wenfang; Zavala, Miguel; Velasco, Erik; Molina; Mario J.

2008-10-31

This project was one of three collaborating grants funded by DOE/ASP to characterize the fine particulate matter (PM) and secondary PM precursors in the Mexico City Metropolitan Area (MCMA) during the MILAGRO Campaign. The overall effort of MCMA-2006, one of the four components, focused on i) examination of the primary emissions of fine particles and precursor gases leading to photochemical production of atmospheric oxidants and secondary aerosol particles; ii) measurement and analysis of secondary oxidants and secondary fine PM production, with particular emphasis on secondary organic aerosol (SOA), and iii) evaluation of the photochemical and meteorological processes characteristic of the Mexico City Basin. The collaborative teams pursued the goals through three main tasks: i) analyses of fine PM and secondary PM precursor gaseous species data taken during the MCMA-2002/2003 campaigns and preparation of publications; ii) planning of the MILAGRO Campaign and deployment of the instrument around the MCMA; and iii) analysis of MCMA-2006 data and publication preparation.

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

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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.

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

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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.

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

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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

Carbonaceous material in fine particulate matter (PM10) of urban areas

International Nuclear Information System (INIS)

Brocco, Domenico; Leonardi, Vittorio; Maso; Marco; Prignani, Patrizia

2006-01-01

Total carbon (TC), elemental carbon (EC) and organic carbon (OC) in the fine particulate matter (PM10) were measured in the urban areas of Rome and Marino (Castelli Romani) by means a thermal method with a non-dispersive infrared detector (NDIR). The results showed that carbonaceous material constitutes 30-40% of the total aerosols in Rome and about 20% in Marino [it

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

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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.

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

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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

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

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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

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

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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

Retrieving global aerosol sources from satellites using inverse modeling

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O. Dubovik

2008-01-01

Full Text Available Understanding aerosol effects on global climate requires knowing the global distribution of tropospheric aerosols. By accounting for aerosol sources, transports, and removal processes, chemical transport models simulate the global aerosol distribution using archived meteorological fields. We develop an algorithm for retrieving global aerosol sources from satellite observations of aerosol distribution by inverting the GOCART aerosol transport model.

The inversion is based on a generalized, multi-term least-squares-type fitting, allowing flexible selection and refinement of a priori algorithm constraints. For example, limitations can be placed on retrieved quantity partial derivatives, to constrain global aerosol emission space and time variability in the results. Similarities and differences between commonly used inverse modeling and remote sensing techniques are analyzed. To retain the high space and time resolution of long-period, global observational records, the algorithm is expressed using adjoint operators.

Successful global aerosol emission retrievals at 2°×2.5 resolution were obtained by inverting GOCART aerosol transport model output, assuming constant emissions over the diurnal cycle, and neglecting aerosol compositional differences. In addition, fine and coarse mode aerosol emission sources were inverted separately from MODIS fine and coarse mode aerosol optical thickness data, respectively. These assumptions are justified, based on observational coverage and accuracy limitations, producing valuable aerosol source locations and emission strengths. From two weeks of daily MODIS observations during August 2000, the global placement of fine mode aerosol sources agreed with available independent knowledge, even though the inverse method did not use any a priori information about aerosol sources, and was initialized with a "zero aerosol emission" assumption. Retrieving coarse mode aerosol emissions was less successful

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

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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.

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

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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.

Aerosol physical and optical properties in the Eastern Mediterranean Basin, Crete, from Aerosol Robotic Network data

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A. Fotiadi

2006-01-01

Full Text Available In this study, we investigate the aerosol optical properties, namely aerosol extinction optical thickness (AOT, Angström parameter and size distribution over the Eastern Mediterranean Basin, using spectral measurements from the recently established FORTH (Foundation for Research and Technology-Hellas AERONET station in Crete, for the two-year period 2003–2004. The location of the FORTH-AERONET station offers a unique opportunity to monitor aerosols from different sources. Maximum values of AOT are found primarily in spring, which together with small values of the Angström parameter indicate dust transported from African deserts, whereas the minimum values of AOT occur in winter. In autumn, large AOT values observed at near-infrared wavelengths arise also from dust transport. In summer, large AOT values at ultraviolet (340 nm and visible wavelengths (500 nm, together with large values of the Angström parameter, are associated with transport of fine aerosols of urban/industrial and biomass burning origin. The Angström parameter values vary on a daily basis within the range 0.05–2.20, and on a monthly basis within the range 0.68–1.9. This behaviour, together with broad frequency distributions and back-trajectory analyses, indicates a great variety of aerosol types over the study region including dust, urban-industrial and biomass-burning pollution, and maritime, as well as mixed aerosol types. Large temporal variability is observed in AOT, Angström parameter, aerosol content and size. The fine and coarse aerosol modes persist throughout the year, with the coarse mode dominant except in summer. The highest values of AOT are related primarily to southeasterly winds, associated with coarse aerosols, and to a less extent to northwesterly winds associated with fine aerosols. The results of this study show that the FORTH AERONET station in Crete is well suited for studying the transport and mixing of different types of aerosols from a variety

Inverse Relationship of Marine Aerosol and Dust in Antarctic Ice with Fine-Grained Sediment in the South Atlantic Ocean: Implications for Sea-Ice Coverage and Wind Strength

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Sharon L. Kanfoush

2012-03-01

Full Text Available This research seeks to test the hypothesis that natural gamma radiation (NGR from Ocean Drilling Program Site 1094, which displays variability over the last glacial-interglacial cycle similar to dust in the Vostok ice core, reflects fine-grained terrigenous sediment delivered by eolian processes. Grain size was measured on 400 samples spanning 0–20 m in a composite core. Accumulation of the <63μ size fraction at Site 1094 and dust in Vostok exhibit a negative correlation, suggesting the fine sediments are not dominantly eolian. However the technique used for grain size measurements cannot distinguish between terrigenous and biogenous materials; therefore it is possible much fine-grained material is diatoms. An inverse correlation between fine sediments and NGR supports this interpretation, and implies terrigenous materials were at times diluted by microfossils from high biological productivity. Fine marine sediments correlate positively with temperature and negatively with marine aerosol Na+ in Vostok. One plausible explanation is extensive sea-ice of cold intervals steepened ocean-continent temperature gradients, intensified winds, and led to increased transport of dust and marine aerosol to Antarctica yet also reduced biological productivity at Site 1094. Such a reduction despite increases in NGR, potentially representing Fe-rich dust influx, would require light limitation or stratification associated with sea-ice.

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.

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).

Aerosol counterflow two-jets unit for continuous measurement of the soluble fraction of atmospheric aerosols.

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Mikuska, Pavel; Vecera, Zbynek

2005-09-01

A new type of aerosol collector employing a liquid at laboratory temperature for continuous sampling of atmospheric particles is described. The collector operates on the principle of a Venturi scrubber. Sampled air flows at high linear velocity through two Venturi nozzles "atomizing" the liquid to form two jets of a polydisperse aerosol of fine droplets situated against each other. Counterflow jets of droplets collide, and within this process, the aerosol particles are captured into dispersed liquid. Under optimum conditions (air flow rate of 5 L/min and water flow rate of 2 mL/min), aerosol particles down to 0.3 microm in diameter are quantitatively collected in the collector into deionized water while the collection efficiency of smaller particles decreases. There is very little loss of fine aerosol within the aerosol counterflow two-jets unit (ACTJU). Coupling of the aerosol collector with an annular diffusion denuder located upstream of the collector ensures an artifact-free sampling of atmospheric aerosols. Operation of the ACTJU in combination with on-line detection devices allows in situ automated analysis of water-soluble aerosol species (e.g., NO2-, NO3-)with high time resolution (as high as 1 s). Under the optimum conditions, the limit of detection for particulate nitrite and nitrate is 28 and 77 ng/m(3), respectively. The instrument is sufficiently rugged for its application at routine monitoring of aerosol composition in the real time.

Aerosol chemistry over a high altitude station at northeastern Himalayas, India.

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Abhijit Chatterjee

Full Text Available BACKGROUND: There is an urgent need for an improved understanding of the sources, distributions and properties of atmospheric aerosol in order to control the atmospheric pollution over northeastern Himalayas where rising anthropogenic interferences from rapid urbanization and development is becoming an increasing concern. METHODOLOGY/PRINCIPAL FINDINGS: An extensive aerosol sampling program was conducted in Darjeeling (altitude approximately 2200 meter above sea level (masl, latitude 27 degrees 01'N and longitude 88 degrees 15'E, a high altitude station in northeastern Himalayas, during January-December 2005. Samples were collected using a respirable dust sampler and a fine dust sampler simultaneously. Ion chromatograph was used to analyze the water soluble ionic species of aerosol. The average concentrations of fine and coarse mode aerosol were found to be 29.5+/-20.8 microg m(-3 and 19.6+/-11.1 microg m(-3 respectively. Fine mode aerosol dominated during dry seasons and coarse mode aerosol dominated during monsoon. Nitrate existed as NH(4NO(3 in fine mode aerosol during winter and as NaNO(3 in coarse mode aerosol during monsoon. Gas phase photochemical oxidation of SO(2 during premonsoon and aqueous phase oxidation during winter and postmonsoon were the major pathways for the formation of SO(4(2- in the atmosphere. Long range transport of dust aerosol from arid regions of western India was observed during premonsoon. The acidity of fine mode aerosol was higher in dry seasons compared to monsoon whereas the coarse mode acidity was higher in monsoon compared to dry seasons. Biomass burning, vehicular emissions and dust particles were the major types of aerosol from local and continental regions whereas sea salt particles were the major types of aerosol from marine source regions. CONCLUSIONS/SIGNIFICANCE: The year-long data presented in this paper provide substantial improvements to the heretofore poor knowledge regarding aerosol chemistry over

Aerosol chemistry over a high altitude station at northeastern Himalayas, India.

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Chatterjee, Abhijit; Adak, Anandamay; Singh, Ajay K; Srivastava, Manoj K; Ghosh, Sanjay K; Tiwari, Suresh; Devara, Panuganti C S; Raha, Sibaji

2010-06-16

There is an urgent need for an improved understanding of the sources, distributions and properties of atmospheric aerosol in order to control the atmospheric pollution over northeastern Himalayas where rising anthropogenic interferences from rapid urbanization and development is becoming an increasing concern. An extensive aerosol sampling program was conducted in Darjeeling (altitude approximately 2200 meter above sea level (masl), latitude 27 degrees 01'N and longitude 88 degrees 15'E), a high altitude station in northeastern Himalayas, during January-December 2005. Samples were collected using a respirable dust sampler and a fine dust sampler simultaneously. Ion chromatograph was used to analyze the water soluble ionic species of aerosol. The average concentrations of fine and coarse mode aerosol were found to be 29.5+/-20.8 microg m(-3) and 19.6+/-11.1 microg m(-3) respectively. Fine mode aerosol dominated during dry seasons and coarse mode aerosol dominated during monsoon. Nitrate existed as NH(4)NO(3) in fine mode aerosol during winter and as NaNO(3) in coarse mode aerosol during monsoon. Gas phase photochemical oxidation of SO(2) during premonsoon and aqueous phase oxidation during winter and postmonsoon were the major pathways for the formation of SO(4)(2-) in the atmosphere. Long range transport of dust aerosol from arid regions of western India was observed during premonsoon. The acidity of fine mode aerosol was higher in dry seasons compared to monsoon whereas the coarse mode acidity was higher in monsoon compared to dry seasons. Biomass burning, vehicular emissions and dust particles were the major types of aerosol from local and continental regions whereas sea salt particles were the major types of aerosol from marine source regions. The year-long data presented in this paper provide substantial improvements to the heretofore poor knowledge regarding aerosol chemistry over northeastern Himalayas, and should be useful to policy makers in making control

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

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

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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.

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

Aerosol modelling and validation during ESCOMPTE 2001

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Cousin, F.; Liousse, C.; Cachier, H.; Bessagnet, B.; Guillaume, B.; Rosset, R.

The ESCOMPTE 2001 programme (Atmospheric Research. 69(3-4) (2004) 241) has resulted in an exhaustive set of dynamical, radiative, gas and aerosol observations (surface and aircraft measurements). A previous paper (Atmospheric Research. (2004) in press) has dealt with dynamics and gas-phase chemistry. The present paper is an extension to aerosol formation, transport and evolution. To account for important loadings of primary and secondary aerosols and their transformation processes in the ESCOMPTE domain, the ORISAM aerosol module (Atmospheric Environment. 35 (2001) 4751) was implemented on-line in the air-quality Meso-NH-C model. Additional developments have been introduced in ORganic and Inorganic Spectral Aerosol Module (ORISAM) to improve the comparison between simulations and experimental surface and aircraft field data. This paper discusses this comparison for a simulation performed during one selected day, 24 June 2001, during the Intensive Observation Period IOP2b. Our work relies on BC and OCp emission inventories specifically developed for ESCOMPTE. This study confirms the need for a fine resolution aerosol inventory with spectral chemical speciation. BC levels are satisfactorily reproduced, thus validating our emission inventory and its processing through Meso-NH-C. However, comparisons for reactive species generally denote an underestimation of concentrations. Organic aerosol levels are rather well simulated though with a trend to underestimation in the afternoon. Inorganic aerosol species are underestimated for several reasons, some of them have been identified. For sulphates, primary emissions were introduced. Improvement was obtained too for modelled nitrate and ammonium levels after introducing heterogeneous chemistry. However, no modelling of terrigeneous particles is probably a major cause for nitrates and ammonium underestimations. Particle numbers and size distributions are well reproduced, but only in the submicrometer range. Our work points out

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

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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.

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

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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.

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

Aerosol comparisons between sunphotometry / sky radiometry and the GEOS-Chem model

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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.

Interannual variation in the fine-mode MODIS aerosol optical depth and its relationship to the changes in sulfur dioxide emissions in China between 2000 and 2010

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S. Itahashi

2012-03-01

Full Text Available Anthropogenic SO₂ emissions increased alongside economic development in China at a rate of 12.7% yr⁻¹ from 2000 to 2005. However, under new Chinese government policy, SO₂ emissions declined by 3.9% yr⁻¹ between 2005 and 2009. Between 2000 and 2010, we found that the variability in the fine-mode (submicron aerosol optical depth (AOD over the oceans adjacent to East Asia increased by 3–8% yr⁻¹ to a peak around 2005–2006 and subsequently decreased by 2–7% yr⁻¹, based on observations by the Moderate Resolution Imaging Spectroradiometer (MODIS on board NASA's Terra satellite and simulations by a chemical transport model. This trend is consistent with ground-based observations of aerosol particles at a mountainous background observation site in central Japan. These fluctuations in SO₂ emission intensity and fine-mode AOD are thought to reflect the widespread installation of fuel-gas desulfurization (FGD devices in power plants in China, because aerosol sulfate is a major determinant of the fine-mode AOD in East Asia. Using a chemical transport model, we confirmed that the contribution of particulate sulfate to the fine-mode AOD is more than 70% of the annual mean and that the abovementioned fluctuation in fine-mode AOD is caused mainly by changes in SO₂ emission rather than by other factors such as varying meteorological conditions in East Asia. A strong correlation was also found between satellite-retrieved SO₂ vertical column density and bottom-up SO₂ emissions, both of which were also consistent with observed fine-mode AOD trends. We propose a simplified approach for evaluating changes in SO₂ emissions in China, combining the use of modeled sensitivity coefficients that describe the variation of fine-mode AOD with changes in SO₂ emissions and satellite retrieval. Satellite measurements of fine-mode AOD

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.

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).

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

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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.

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.

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

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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.

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

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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.

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

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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...

Natural Radionuclides and Isotopic Signatures for Determining Carbonaceous Aerosol Sources, Aerosol Lifetimes, and Washout Processes

International Nuclear Information System (INIS)

Gaffney, Jeffrey

2012-01-01

This is the final technical report. The project description is as follows: to determine the role of aerosol radiative forcing on climate, the processes that control their atmospheric concentrations must be understood, and aerosol sources need to be determined for mitigation. Measurements of naturally occurring radionuclides and stable isotopic signatures allow the sources, removal and transport processes, as well as atmospheric lifetimes of fine carbonaceous aerosols, to be evaluated.

Natural Radionuclides and Isotopic Signatures for Determining Carbonaceous Aerosol Sources, Aerosol Lifetimes, and Washout Processes

Energy Technology Data Exchange (ETDEWEB)

Gaffney, Jeffrey [Univ. of Arkansas, Little Rock, AR (United States)

2012-12-12

This is the final technical report. The project description is as follows: to determine the role of aerosol radiative forcing on climate, the processes that control their atmospheric concentrations must be understood, and aerosol sources need to be determined for mitigation. Measurements of naturally occurring radionuclides and stable isotopic signatures allow the sources, removal and transport processes, as well as atmospheric lifetimes of fine carbonaceous aerosols, to be evaluated.

Investigating organic aerosol loading in the remote marine environment

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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.

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

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

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.

Aerosol Optical Depth Over India

Science.gov (United States)

David, Liji Mary; Ravishankara, A. R.; Kodros, John K.; Venkataraman, Chandra; Sadavarte, Pankaj; Pierce, Jeffrey R.; Chaliyakunnel, Sreelekha; Millet, Dylan B.

2018-04-01

Tropospheric aerosol optical depth (AOD) over India was simulated by Goddard Earth Observing System (GEOS)-Chem, a global 3-D chemical-transport model, using SMOG (Speciated Multi-pOllutant Generator from Indian Institute of Technology Bombay) and GEOS-Chem (GC) (current inventories used in the GEOS-Chem model) inventories for 2012. The simulated AODs were 80% (SMOG) and 60% (GC) of those measured by the satellites (Moderate Resolution Imaging Spectroradiometer and Multi-angle Imaging SpectroRadiometer). There is no strong seasonal variation in AOD over India. The peak AOD values are observed/simulated during summer. The simulated AOD using SMOG inventory has particulate black and organic carbon AOD higher by a factor 5 and 3, respectively, compared to GC inventory. The model underpredicted coarse-mode AOD but agreed for fine-mode AOD with Aerosol Robotic Network data. It captured dust only over Western India, which is a desert, and not elsewhere, probably due to inaccurate dust transport and/or noninclusion of other dust sources. The calculated AOD, after dust correction, showed the general features in its observed spatial variation. Highest AOD values were observed over the Indo-Gangetic Plain followed by Central and Southern India with lowest values in Northern India. Transport of aerosols from Indo-Gangetic Plain and Central India into Eastern India, where emissions are low, is significant. The major contributors to total AOD over India are inorganic aerosol (41-64%), organic carbon (14-26%), and dust (7-32%). AOD over most regions of India is a factor of 5 or higher than over the United States.

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

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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

Nonurban aerosol composition near Beijing, China

International Nuclear Information System (INIS)

Winchester, J.W.; Darzi, M.; Leslie, A.C.D.; Wang, M.; Ren, L.; Lue, W.; Hansson, H.C.; Lannefors, H.

1981-01-01

The urban aerosol plume of Beijing has been sampled as a function of particle size and time at a site 110 km NE of the city, 9-16 March 1980, during the season for space heating by coal combustion. A fine particle mode, contained mostly in the 0.5-2 μm aerodynamic diameter range, could be distinguished from a coarse mode of dust having terrestrial composition by reference to the size distribution of Ca. Elemental composition determined by PIXE analysis for 17 elements, including S and heavy metals, indicates fine mode concentrations higher than background aerosol but with a similarity to cleaner air with respect to both relative elemental abundances and elemental particle size distributions. The results indicate that elements contained in aged coal combustion aerosol occur mainly in 0.5-2 μMAD particles, not smaller, and the aerosol is not substantially different from background aerosol except in overall concentrations. This result may simplify the prediction of the impact of coal combustion on air quality. The results also hint that the background aerosol in more remote continental areas may also be combustion derived. (orig.)

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

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

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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

Diffusivity measurements of volatile organics in levitated viscous aerosol particles

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S. Bastelberger

2017-07-01

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

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.

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

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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

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

Inorganic markers, carbonaceous components and stable carbon isotope from biomass burning aerosols in northeast China

Science.gov (United States)

Cao, F.; Zhang, Y.; Kawamura, K.

2015-12-01

To better characterize the sources of fine particulate matter (i.e. PM2.5) in Sanjiang Plain, Northeast China, aerosol chemical composition such total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions were studied as well as stable carbon isotopic composition (δ13C) of TC. Intensively open biomass burning episodes were identified from late September to early October by satellite fire and aerosol optical depth maps. During the biomass burning episodes, concentrations of PM2.5, OC, EC, and WSOC increased by a factor of 4-12 compared to non-biomass-burning periods. Non-sea-salt potassium is strongly correlated with PM2.5, OC, EC and WSOC, suggesting an important contribution of biomass burning emission. The enrichment in both the non-sea-salt potassium and chlorine is significantly larger than other inorganic species, indicating that biomass burning aerosols in Sanjiang Plain is mostly fresh and less aged. In addition, WSOC to OC ratio is relatively lower compared to that reported in biomass burning aerosols in tropical regions, supporting that biomass burning aerosols in Sanjiang Plain is mostly primary and secondary organic aerosols is not significant. A lower average δ13C value (-26.2‰) is found for the biomass-burning aerosols, suggesting a dominant contribution from combustion of C3 plants in the studied region.

OH-initiated Aging of Biomass Burning Aerosol during FIREX

Science.gov (United States)

Lim, C. Y.; Hagan, D. H.; Cappa, C. D.; Kroll, J. H.; Coggon, M.; Koss, A.; Sekimoto, K.; De Gouw, J. A.; Warneke, C.

2017-12-01

Biomass burning emissions represent a major source of fine particulate matter to the atmosphere, and this source will likely become increasingly important in the future due to changes in the Earth's climate. Understanding the effects that increased fire emissions have on both air quality and climate requires understanding the composition of the particles emitted, since chemical and physical composition directly impact important particle properties such as absorptivity, toxicity, and cloud condensation nuclei activity. However, the composition of biomass burning particles in the atmosphere is dynamic, as the particles are subject to the condensation of low-volatility vapors and reaction with oxidants such as the hydroxyl radical (OH) during transport. Here we present a series of laboratory chamber experiments on the OH-initiated aging of biomass burning aerosol performed at the Fire Sciences Laboratory in Missoula, MT as part of the Fire Influences on Regional and Global Environments Experiment (FIREX) campaign. We describe the evolution of biomass burning aerosol produced from a variety of fuels operating the chamber in both particle-only and gas + particle mode, focusing on changes to the organic composition. In particle-only mode, gas-phase biomass burning emissions are removed before oxidation to focus on heterogeneous oxidation, while gas + particle mode includes both heterogeneous oxidation and condensation of oxidized volatile organic compounds onto the particles (secondary organic aerosol formation). Variability in fuels and burning conditions lead to differences in aerosol loading and secondary aerosol production, but in all cases aging results in a significant and rapid increases in the carbon oxidation state of the particles.

Chemical characteristics and source apportionment of fine particulate organic carbon in Hong Kong during high particulate matter episodes in winter 2003

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Li, Yun-Chun; Yu, Jian Zhen; Ho, Steven Sai Hang; Schauer, James J.; Yuan, Zibing; Lau, Alexis K. H.; Louie, Peter K. K.

2013-02-01

PM2.5 samples were collected at six general stations and one roadside station in Hong Kong in two periods of high particulate matter (PM) in 2003 (27 October-4 November and 30 November-13 December). The highest PM2.5 reached 216 μg m- 3 during the first high PM period and 113 μg m- 3 during the second high PM period. Analysis of synoptic weather conditions identified individual sampling days under dominant influence of one of three types of air masses, that is, local, regional and long-range transported (LRT) air masses. Roadside samples were discussed separately due to heavy influences from vehicular emissions. This research examines source apportionment of fine organic carbon (OC) and contribution of secondary organic aerosol on high PM days under different synoptic conditions. Six primary OC (POC) sources (vehicle exhaust, biomass burning, cooking, cigarette smoke, vegetative detritus, and coal combustion) were identified on the basis of characteristic organic tracers. Individual POC source contributions were estimated using chemical mass balance model. In the roadside and the local samples, OC was dominated by the primary sources, accounting for more than 74% of OC. In the samples influenced by regional and LRT air masses, secondary OC (SOC), which was approximated to be the difference between the total measured OC and the apportioned POC, contributed more than 54% of fine OC. SOC was highly correlated with water-soluble organic carbon and sulfate, consistent with its secondary nature.

Tracing of aerosol sources in an urban environment using chemical, Sr isotope, and mineralogical characterization.

Science.gov (United States)

Duarte, Regina M B O; Matos, João T V; Paula, Andreia S; Lopes, Sónia P; Ribeiro, Sara; Santos, José Francisco; Patinha, Carla; da Silva, Eduardo Ferreira; Soares, Rosário; Duarte, Armando C

2017-04-01

In the framework of two national research projects (ORGANOSOL and CN-linkAIR), fine particulate matter (PM 2.5 ) was sampled for 17 months at an urban location in the Western European Coast. The PM 2.5 samples were analyzed for organic carbon (OC), water-soluble organic carbon (WSOC), elemental carbon (EC), major water-soluble inorganic ions, mineralogical, and for the first time in this region, strontium isotope ( 87 Sr/ 86 Sr) composition. Organic matter dominates the identifiable urban PM 2.5 mass, followed by secondary inorganic aerosols. The acquired data resulted also in a seasonal overview of the carbonaceous and inorganic aerosol composition, with an important contribution from primary biomass burning and secondary formation processes in colder and warmer periods, respectively. The fossil-related primary EC seems to be continually present throughout the sampling period. The 87 Sr/ 86 Sr ratios were measured on both the labile and residual PM 2.5 fractions as well as on the bulk PM 2.5 samples. Regardless of the air mass origin, the residual fractions are more radiogenic (representative of a natural crustal dust source) than the labile fractions, whose 87 Sr/ 86 Sr ratios are comparable to that of seawater. The 87 Sr/ 86 Sr ratios and the mineralogical composition data further suggest that sea salt and mineral dust are important primary natural sources of fine aerosols throughout the sampling period.

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.

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

The aerosol optical properties and PM2.5 components over the world's largest industrial zone in Tangshan, North China

Science.gov (United States)

Zhang, Kequan; Ma, Yongjing; Xin, Jinyuan; Liu, Zirui; Ma, Yining; Gao, Dongdong; Wu, Junsong; Zhang, Wenyu; Wang, Yuesi; Shen, Pengke

2018-03-01

To achieve an in-depth understanding of the aerosol optical properties in the highly-industrial region of Tangshan, we provided systematic aerosol optical properties analysis in this largest industrial zone for the first time. The aerosol optical datasets (2013.05-2015.04) and chemical component data of PM2.5 (2014-2015) obtained from the Tangshan site of the campaign on atmospheric aerosol research (CARE-China) network were analyzed. The results showed that the Tangshan region was seriously affected by fine-mode industrial aerosols all year, which would promote the accumulation of pollutants and influence the atmospheric circulation through changing the vertical temperature gradient. The annual average aerosol optical depth (AOD) and Ångstrӧm exponent (α) were 0.80 ± 0.26 and 1.05 ± 0.10, respectively. The aerosol optical properties revealed significant seasonal characteristics. The maximum seasonal average AOD (1.03 ± 0.62) and α (1.12 ± 0.19) accompanied the highest seasonal secondary inorganic aerosol concentrations (SIA: SO42 -, NO3-, NH4+), 53.33 μg/m3, occurred in summer, and this phenomenon was attributed to the photochemical reactions favored by the high temperature and humidity. During the spring, frequent dust events led to the maximum Ca2 + concentration of 6.57 μg/m3 and the lowest seasonal α of 0.98 ± 0.31. Coal was used for generating heat in winter, resulting in the highest levels of pollutant emissions (Cl-, Elemental carbon (EC) and organic carbon (OC)). The aerosol type classifications showed that the industrial aerosols were the main controls in the summer and fall, representing 56%-58% of the total aerosols. While for spring and winter, mixed aerosols represented 53%-54% of the total aerosols. Hygroscopic growth effect of aerosols existed all year, which could enhance the negative radiative forcing and eventually cool the earth-atmosphere system. The classification Wing for Tangshan data showed high AOD values (> 0.70) were mainly

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-NO_x, 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-NO_x SOA resemble that of OOA, but the spectrum of glyoxal uptake does not resemble that of any ambient organic aerosol PMF component.

Seasonal variation of fine- and coarse-mode nitrates and related aerosols over East Asia: synergetic observations and chemical transport model analysis

Science.gov (United States)

Uno, Itsushi; Osada, Kazuo; Yumimoto, Keiya; Wang, Zhe; Itahashi, Syuichi; Pan, Xiaole; Hara, Yukari; Kanaya, Yugo; Yamamoto, Shigekazu; Fairlie, Thomas Duncan

2017-11-01

We analyzed long-term fine- and coarse-mode synergetic observations of nitrate and related aerosols (SO42-, NO3-, NH4+, Na+, Ca2+) at Fukuoka (33.52° N, 130.47° E) from August 2014 to October 2015. A Goddard Earth Observing System chemical transport model (GEOS-Chem) including dust and sea salt acid uptake processes was used to assess the observed seasonal variation and the impact of long-range transport (LRT) from the Asian continent. For fine aerosols (fSO42-, fNO3-, and fNH4+), numerical results explained the seasonal changes, and a sensitivity analysis excluding Japanese domestic emissions clarified the LRT fraction at Fukuoka (85 % for fSO42-, 47 % for fNO3-, 73 % for fNH4+). Observational data confirmed that coarse NO3- (cNO3-) made up the largest proportion (i.e., 40-55 %) of the total nitrate (defined as the sum of fNO3-, cNO3-, and HNO3) during the winter, while HNO3 gas constituted approximately 40 % of the total nitrate in summer and fNO3- peaked during the winter. Large-scale dust-nitrate (mainly cNO3-) outflow from China to Fukuoka was confirmed during all dust events that occurred between January and June. The modeled cNO3- was in good agreement with observations between July and November (mainly coming from sea salt NO3-). During the winter, however, the model underestimated cNO3- levels compared to the observed levels. The reason for this underestimation was examined statistically using multiple regression analysis (MRA). We used cNa+, nss-cCa2+, and cNH4+ as independent variables to describe the observed cNO3- levels; these variables were considered representative of sea salt cNO3-, dust cNO3-, and cNO3- accompanied by cNH4+), respectively. The MRA results explained the observed seasonal changes in dust cNO3- and indicated that the dust-acid uptake scheme reproduced the observed dust-nitrate levels even in winter. The annual average contributions of each component were 43 % (sea salt cNO3-), 19 % (dust cNO3-), and 38 % (cNH4+ term). The MRA dust

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%.

Modeling of meteorology, chemistry and aerosol for the 2017 Utah Winter Fine Particle Study

Science.gov (United States)

McKeen, S. A.; Angevine, W. M.; McDonald, B.; Ahmadov, R.; Franchin, A.; Middlebrook, A. M.; Fibiger, D. L.; McDuffie, E. E.; Womack, C.; Brown, S. S.; Moravek, A.; Murphy, J. G.; Trainer, M.

2017-12-01

The Utah Winter Fine Particle Study (UWFPS-17) field project took place during January and February of 2017 within the populated region of the Great Salt Lake, Utah. The study focused on understanding the meteorology and chemistry associated with high particulate matter (PM) levels often observed near Salt Lake City during stable wintertime conditions. Detailed composition and meteorological observations were taken from the NOAA Twin-Otter aircraft and several surface sites during the study period, and extremely high aerosol conditions were encountered for two cold-pool episodes occurring in the last 2 weeks of January. A clear understanding of the photochemical and aerosol processes leading to these high PM events is still lacking. Here we present high spatiotemporal resolution simulations of meteorology, PM and chemistry over Utah from January 13 to February 1, 2017 using the WRF/Chem photochemical model. Correctly characterizing the meteorology is difficult due to the complex terrain and shallow inversion layers. We discuss the approach and limitations of the simulated meteorology, and evaluate low-level pollutant mixing using vertical profiles from missed airport approaches by the NOAA Twin-Otter performed routinely during each flight. Full photochemical simulations are calculated using NOx, ammonia and VOC emissions from the U.S. EPA NEI-2011 emissions inventory. Comparisons of the observed vertical column amounts of NOx, ammonia, aerosol nitrate and ammonium with model results shows the inventory estimates for ammonia emissions are low by a factor of four and NOx emissions are low by nearly a factor of two. The partitioning of both nitrate and NH3 between gas and particle phase depends strongly on the NH3 and NOx emissions to the model and calculated NOx to nitrate conversion rates. These rates are underestimated by gas-phase chemistry alone, even though surface snow albedo increases photolysis rates by nearly a factor of two. Several additional conversion

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.

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).

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...

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.

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.

Carbonaceous Aerosol Characterization during 2016 KOR-US 2016

Science.gov (United States)

Rodriguez, B.; Santos, G. M.; Sanchez, D.; Jeong, D.; Czimczik, C. I.; Kim, S.

2017-12-01

Atmospheric carbonaceous aerosols are a major component of fine particulate matter and assume important roles in Earth's climate and human health. Because atmospheric carbonaceous aerosols exist as a continuum ranging from small, light-scattering organic carbon (OC), to highly-condensed, light-absorbing elemental carbon (EC) they have contrasting effects on interaction with incoming and outgoing radiation, cloud formation, and snow/ice albedo. By strengthening our understanding of the relative contribution and sources of OC and EC we will be able to further describe aerosol formation and mixing at the regional level. To understand the relative anthropogenic and biogenic contributions to carbonaceous aerosol, 12 PM10 aerosols samples were collected on quartz fiber filters at the Mt. Taewha Research Forest in South Korea during the KORUS-AQ 2016 campaign over periods of 24-48 hours with a high-volume air sampler. Analysis of bulk C and N concentrations and absorption properties of filter extracts interspersed with HYSPLIT model results indicated that continental outflow across the Yellow Sea in enriched in bulk nitrogen loading and enhanced bulk absorptive properties of the aerosols. Bulk radiocarbon analysis also indicated enriched values in all samples indicating contamination from a nuclear power plant or the combustion of biomedical waste nearby. Here, we aim to investigate further the chemical characterization of VOCs adsorbed unto the aerosol through TD-GC-TOFMS. With this dataset we aim to determine the relative contribution of anthropogenic and biogenic aerosols by utilizing specific chemical tracers for source apportionment.

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.

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

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.

Aerosols and Climate

Indian Academy of Sciences (India)

aerosols, clouds, radiation and climate. ... the solar radiation to pass through but absorb most of infrared radiation emitted .... Fine soil and sand particles become airborne due to wind. Over ..... its sampling is difficult compared to other species.

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

Aerosols from biomass combustion

Energy Technology Data Exchange (ETDEWEB)

Nussbaumer, T

2001-07-01

This report is the proceedings of a seminar on biomass combustion and aerosol production organised jointly by the International Energy Agency's (IEA) Task 32 on bio energy and the Swiss Federal Office of Energy (SFOE). This collection of 16 papers discusses the production of aerosols and fine particles by the burning of biomass and their effects. Expert knowledge on the environmental impact of aerosols, formation mechanisms, measurement technologies, methods of analysis and measures to be taken to reduce such emissions is presented. The seminar, visited by 50 participants from 11 countries, shows, according to the authors, that the reduction of aerosol emissions resulting from biomass combustion will remain a challenge for the future.

Aerosols from biomass combustion

Energy Technology Data Exchange (ETDEWEB)

Nussbaumer, T.

2001-07-01

This report is the proceedings of a seminar on biomass combustion and aerosol production organised jointly by the International Energy Agency's (IEA) Task 32 on bio energy and the Swiss Federal Office of Energy (SFOE). This collection of 16 papers discusses the production of aerosols and fine particles by the burning of biomass and their effects. Expert knowledge on the environmental impact of aerosols, formation mechanisms, measurement technologies, methods of analysis and measures to be taken to reduce such emissions is presented. The seminar, visited by 50 participants from 11 countries, shows, according to the authors, that the reduction of aerosol emissions resulting from biomass combustion will remain a challenge for the future.

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.

Occurrence of organic pollutants in recovered soil fines from construction and demolition waste.

Science.gov (United States)

Jang, Y C; Townsend, T G

2001-01-01

The objective of this study was to characterize recovered soil fines from construction and demolition (C&D) waste recycling facilities for trace organic pollutants. Over a period of 18 months, five sampling trips were made to 14 C&D waste recycling facilities in Florida. Screened soil fines were collected from older stockpiles and newly generated piles at the sites. The samples were analyzed for the total concentration (mg/kg) of a series of volatile organic compound (VOCs) and semi-volatile organic compounds (semi-VOCs). The synthetic precipitation leaching procedure (SPLP) test was also performed to evaluate the leachability of the trace organic chemicals. During the total analysis only a few volatile organic compounds were commonly found in the samples (trichlorofluoromethane, toluene, 4-isopropyltoluene, trimethylbenzene, xylenes, and methylene chloride). A total of nine VOCs were detected in the leaching test. Toluene showed the highest leachability among the compounds (61.3-92.0%), while trichlorofluoromethane, the most commonly detected compound from both the total and leaching tests, resulted in the lowest leachability (1.4-39.9%). For the semi-VOC analysis, three base-neutral semi-VOC compounds (bis(2-ethylhexyl)phthalate, butyl benzyl phthalate, and di-n-butyl phthalate) and several PAHs (acenaphthene, pyrene, fluoranthene, and phenanthrene) were commonly detected in C&D fines samples. These compounds also leached during the SPLP leaching test (0.1-25%). No acid extractable compounds, pesticides, or PCBs were detected. The results of this study were further investigated to assess risk from land applied recovered soil fines by comparing total and leaching concentrations of recovered soil fines samples to risk-based standards. The results of this indicate that the organic chemicals in recovered soil fines from C&D debris recycling facilities were not of a major concern in terms of human risk and leaching risk to groundwater under reuse and contact scenarios.

Primary and secondary organic aerosols in summer 2016 in Beijing

Science.gov (United States)

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

2018-03-01

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

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

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E. A. Marais

2016-02-01

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

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

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.

TEM investigations of microstructures of combustion aerosols

International Nuclear Information System (INIS)

Marquardt, A.; Hackfort, H.; Borchardt, J.; Schober, T.; Friedrich, J.

1992-12-01

In the incineration of organic material, apart from a series of gaseous pollutants, particulate pollutants or combustion aerosols also arise. The latter frequently consist of particles with a solid core of carbon to which a large number of inorganic and organic compounds are attached. These primarily include the polycyclic aromatic hydrocarbons (PAH) and their nitro-derivatives (NPAH), whose mutagenic or carcinogenic effect is known. The invisible particle sizes in the nanometer range, whose retention in the incineration off-gas is not state of the art, are of increasing significance for man and environment. On the one hand, they are deposited almost completely in the human lung. On the other hand, due to their fine dispersity they have along residence time in the atmosphere where they participate in chemical reactions and climatically significant processes. Important insights about the formation process of combustion aerosols are to be expected from the imaging of their microstructures in the transmission electron microscope (TEM). The present contribution describes the development and application of a representative sampling procedure for aerosols from a partial flow of flue gas from a fluidized-bed furnace. The method developed consists of electrically charging aerosol particles in situ and subsequently selectively precipitating them onto a microscope slide in an electric field. TEM studies of aerosol microstructures on the microscope slides revealed that in the combustion of petrol and heating oil under different combustion conditions in principle the same particle structures result, whereas in the incineration of used lubricating oil quite different particle structures were found. Results from the literature on aerosol microstructures in exhaust gases from petrol and diesel engines demonstrate agreement with the results of this study in the basic structure of the particles. (orig.) [de

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.

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.

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.

Aerosol optical properties and direct radiative forcing based on measurements from the China Aerosol Remote Sensing Network (CARSNET) in eastern China

Science.gov (United States)

Che, Huizheng; Qi, Bing; Zhao, Hujia; Xia, Xiangao; Eck, Thomas F.; Goloub, Philippe; Dubovik, Oleg; Estelles, Victor; Cuevas-Agulló, Emilio; Blarel, Luc; Wu, Yunfei; Zhu, Jun; Du, Rongguang; Wang, Yaqiang; Wang, Hong; Gui, Ke; Yu, Jie; Zheng, Yu; Sun, Tianze; Chen, Quanliang; Shi, Guangyu; Zhang, Xiaoye

2018-01-01

Aerosol pollution in eastern China is an unfortunate consequence of the region's rapid economic and industrial growth. Here, sun photometer measurements from seven sites in the Yangtze River Delta (YRD) from 2011 to 2015 were used to characterize the climatology of aerosol microphysical and optical properties, calculate direct aerosol radiative forcing (DARF) and classify the aerosols based on size and absorption. Bimodal size distributions were found throughout the year, but larger volumes and effective radii of fine-mode particles occurred in June and September due to hygroscopic growth and/or cloud processing. Increases in the fine-mode particles in June and September caused AOD440 nm > 1.00 at most sites, and annual mean AOD440 nm values of 0.71-0.76 were found at the urban sites and 0.68 at the rural site. Unlike northern China, the AOD440 nm was lower in July and August (˜ 0.40-0.60) than in January and February (0.71-0.89) due to particle dispersion associated with subtropical anticyclones in summer. Low volumes and large bandwidths of both fine-mode and coarse-mode aerosol size distributions occurred in July and August because of biomass burning. Single-scattering albedos at 440 nm (SSA440 nm) from 0.91 to 0.94 indicated particles with relatively strong to moderate absorption. Strongly absorbing particles from biomass burning with a significant SSA wavelength dependence were found in July and August at most sites, while coarse particles in March to May were mineral dust. Absorbing aerosols were distributed more or less homogeneously throughout the region with absorption aerosol optical depths at 440 nm ˜ 0.04-0.06, but inter-site differences in the absorption Angström exponent indicate a degree of spatial heterogeneity in particle composition. The annual mean DARF was -93 ± 44 to -79 ± 39 W m-2 at the Earth's surface and ˜ -40 W m-2 at the top of the atmosphere (for the solar zenith angle range of 50 to 80°) under cloud-free conditions. The fine mode

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...

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

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

Science.gov (United States)

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

2008-12-01

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

Optical, microphysical and radiative properties of aerosols over a tropical rural site in Kenya, East Africa: Source identification, modification and aerosol type discrimination

Science.gov (United States)

Boiyo, Richard; Kumar, K. Raghavendra; Zhao, Tianliang

2018-03-01

A better understanding of aerosol optical, microphysical and radiative properties is a crucial challenge for climate change studies. In the present study, column-integrated aerosol optical and radiative properties observed at a rural site, Mbita (0.42°S, 34.20 °E, and 1125 m above sea level) located in Kenya, East Africa (EA) are investigated using ground-based Aerosol Robotic Network (AERONET) data retrieved during January, 2007 to December, 2015. The annual mean aerosol optical depth (AOD500 nm), Ångström exponent (AE440-870 nm), fine mode fraction of AOD500 nm (FMF500 nm), and columnar water vapor (CWV, cm) were found to be 0.23 ± 0.08, 1.01 ± 0.16, 0.60 ± 0.07, and 2.72 ± 0.20, respectively. The aerosol optical properties exhibited a unimodal distribution with substantial seasonal heterogeneity in their peak values being low (high) during the local wet (dry) seasons. The observed data showed that Mbita and its environs are significantly influenced by various types of aerosols, with biomass burning and/or urban-industrial (BUI), mixed (MXD), and desert dust (DDT) aerosol types contributing to 37.72%, 32.81%, and 1.40%, respectively during the local dry season (JJA). The aerosol volume size distribution (VSD) exhibited bimodal lognormal structure with a geometric mean radius of 0.15 μm and 3.86-5.06 μm for fine- and coarse-mode aerosols, respectively. Further, analysis of single scattering albedo (SSA), asymmetry parameter (ASY) and refractive index (RI) revealed dominance of fine-mode absorbing aerosols during JJA. The averaged aerosol direct radiative forcing (ARF) retrieved from the AERONET showed a strong cooling effect at the bottom of the atmosphere (BOA) and significant warming within the atmosphere (ATM), representing the important role of aerosols played in this rural site of Kenya. Finally, the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model revealed that aerosols from distinct sources resulted in enhanced loading

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/NO_x ratio on SOA formation was explored, as was the effect of acid seeding. It was found that low NO_x 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.

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.

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

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.

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.

Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondônia, Brazil: sources and source processes, time series, diel variations and size distributions

Directory of Open Access Journals (Sweden)

M. Claeys

2010-10-01

Full Text Available Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondônia, Brazil using a high-volume dichotomous sampler (HVDS and a Micro-Orifice Uniform Deposit Impactor (MOUDI within the framework of the 2002 LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazônia – Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate campaign. The campaign spanned the late dry season (biomass burning, a transition period, and the onset of the wet season (clean conditions. In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including levoglucosan, malic acid, isoprene secondary organic aerosol (SOA tracers and tracers for fungal spores. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM_2.5 size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 μg m⁻³ and exhibited diel variations with a nighttime prevalence. It was closely associated with the PM mass in the size-segregated samples and was mainly present in the fine mode, except during the wet period where it peaked in the coarse mode. Isoprene SOA tracers showed an average concentration of 250 ng m⁻³ during the dry period versus 157 ng m⁻³ during the transition period and 52 ng m⁻³ during the wet period. Malic acid and the 2-methyltetrols exhibited a different size distribution pattern, which is consistent with different aerosol formation processes (i.e., gas-to-particle partitioning in the case of malic acid and heterogeneous formation from gas-phase precursors in the case of

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

The effects of aerosols on climate

International Nuclear Information System (INIS)

Boucher, O.

1997-01-01

Atmospheric aerosols (fine particles suspended in the atmosphere) can play two roles in the Earth’s radiation budget. In cloud-free air, aerosols scatter sunlight, some of which is reflected back to space (direct effect). Aerosols also determine the microphysical and optical properties of clouds (indirect effect). Whereas changes in natural aerosols are probably small during the last 100 years, there has been a large increase in the concentration of anthropogenic aerosols. The magnitude of their radiative effects is still very uncertain but seems to be sufficient to mask part of the global warming expected to stem from anthropogenic greenhouse gases. This paper presents the physical mechanisms of aerosol influence on climate. We then estimate the anthropogenic aerosol radiative effects and assess the climate response to these perturbations. (author) [fr

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.

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.

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.

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

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

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.

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...

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

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)

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

In situ, satellite measurement and model evidence on the dominant regional contribution to fine particulate matter levels in the Paris megacity

Science.gov (United States)

Beekmann, M.; Prévôt, A. S. H.; Drewnick, F.; Sciare, J.; Pandis, S. N.; Denier van der Gon, H. A. C.; Crippa, M.; Freutel, F.; Poulain, L.; Ghersi, V.; Rodriguez, E.; Beirle, S.; Zotter, P.; von der Weiden-Reinmüller, S.-L.; Bressi, M.; Fountoukis, C.; Petetin, H.; Szidat, S.; Schneider, J.; Rosso, A.; El Haddad, I.; Megaritis, A.; Zhang, Q. J.; Michoud, V.; Slowik, J. G.; Moukhtar, S.; Kolmonen, P.; Stohl, A.; Eckhardt, S.; Borbon, A.; Gros, V.; Marchand, N.; Jaffrezo, J. L.; Schwarzenboeck, A.; Colomb, A.; Wiedensohler, A.; Borrmann, S.; Lawrence, M.; Baklanov, A.; Baltensperger, U.

2015-08-01

A detailed characterization of air quality in the megacity of Paris (France) during two 1-month intensive campaigns and from additional 1-year observations revealed that about 70 % of the urban background fine particulate matter (PM) is transported on average into the megacity from upwind regions. This dominant influence of regional sources was confirmed by in situ measurements during short intensive and longer-term campaigns, aerosol optical depth (AOD) measurements from ENVISAT, and modeling results from PMCAMx and CHIMERE chemistry transport models. While advection of sulfate is well documented for other megacities, there was surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The origin of organic PM was investigated by comprehensive analysis of aerosol mass spectrometer (AMS), radiocarbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions constituted less than 20 % in winter and 40 % in summer of carbonaceous fine PM, unexpectedly small for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin, i.e., from biogenic precursors and from wood burning. Black carbon concentrations are on the lower end of values encountered in megacities worldwide, but still represent an issue for air quality. These comparatively low air pollution levels are due to a combination of low emissions per inhabitant, flat terrain, and a meteorology that is in general not conducive to local pollution build-up. This revised picture of a megacity only being partially responsible for its own average and peak PM levels has important implications for air pollution regulation policies.

In-situ, satellite measurement and model evidence for a~dominant regional contribution to fine particulate matter levels in the Paris Megacity

Science.gov (United States)

Beekmann, M.; Prévôt, A. S. H.; Drewnick, F.; Sciare, J.; Pandis, S. N.; Denier van der Gon, H. A. C.; Crippa, M.; Freutel, F.; Poulain, L.; Ghersi, V.; Rodriguez, E.; Beirle, S.; Zotter, P.; von der Weiden-Reinmüller, S.-L.; Bressi, M.; Fountoukis, C.; Petetin, H.; Szidat, S.; Schneider, J.; Rosso, A.; El Haddad, I.; Megaritis, A.; Zhang, Q. J.; Michoud, V.; Slowik, J. G.; Moukhtar, S.; Kolmonen, P.; Stohl, A.; Eckhardt, S.; Borbon, A.; Gros, V.; Marchand, N.; Jaffrezo, J. L.; Schwarzenboeck, A.; Colomb, A.; Wiedensohler, A.; Borrmann, S.; Lawrence, M.; Baklanov, A.; Baltensperger, U.

2015-03-01

A detailed characterization of air quality in Paris (France), a megacity of more than 10 million inhabitants, during two one month intensive campaigns and from additional one year observations, revealed that about 70% of the fine particulate matter (PM) at urban background is transported on average into the megacity from upwind regions. This dominant influence of regional sources was confirmed by in-situ measurements during short intensive and longer term campaigns, aerosol optical depth (AOD) measurements from ENVISAT, and modeling results from PMCAMx and CHIMERE. While advection of sulfate is well documented for other megacities, there was surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The origin of organic PM was investigated by a comprehensive analysis of aerosol mass spectrometer (AMS), radiocarbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions contributed less than 20% in winter and 40% in summer to carbonaceous fine PM, unexpectedly little for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin, i.e. from biogenic precursors and from wood burning. Black carbon concentrations are on the lower end of values encountered in megacities worldwide, but still represent an issue for air quality. These comparatively low air pollution levels are due to a combination of low emissions per inhabitant, flat terrain, and a meteorology that is in general not conducive to local pollution build-up. This revised picture of a megacity only controlling part of its own average and peak PM levels has important implications for air pollution regulation policies.

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.

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)

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

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.

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

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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

Secondary organic aerosol from VOC mixtures in an oxidation flow reactor

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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.

Aerosol optical properties and direct radiative forcing based on measurements from the China Aerosol Remote Sensing Network (CARSNET in eastern China

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H. Che

2018-01-01

Full Text Available Aerosol pollution in eastern China is an unfortunate consequence of the region's rapid economic and industrial growth. Here, sun photometer measurements from seven sites in the Yangtze River Delta (YRD from 2011 to 2015 were used to characterize the climatology of aerosol microphysical and optical properties, calculate direct aerosol radiative forcing (DARF and classify the aerosols based on size and absorption. Bimodal size distributions were found throughout the year, but larger volumes and effective radii of fine-mode particles occurred in June and September due to hygroscopic growth and/or cloud processing. Increases in the fine-mode particles in June and September caused AOD440 nm  >  1.00 at most sites, and annual mean AOD440 nm values of 0.71–0.76 were found at the urban sites and 0.68 at the rural site. Unlike northern China, the AOD440 nm was lower in July and August (∼ 0.40–0.60 than in January and February (0.71–0.89 due to particle dispersion associated with subtropical anticyclones in summer. Low volumes and large bandwidths of both fine-mode and coarse-mode aerosol size distributions occurred in July and August because of biomass burning. Single-scattering albedos at 440 nm (SSA440 nm from 0.91 to 0.94 indicated particles with relatively strong to moderate absorption. Strongly absorbing particles from biomass burning with a significant SSA wavelength dependence were found in July and August at most sites, while coarse particles in March to May were mineral dust. Absorbing aerosols were distributed more or less homogeneously throughout the region with absorption aerosol optical depths at 440 nm  ∼  0.04–0.06, but inter-site differences in the absorption Angström exponent indicate a degree of spatial heterogeneity in particle composition. The annual mean DARF was −93 ± 44 to −79 ± 39 W m−2 at the Earth's surface and ∼ −40 W m−2 at the top of the atmosphere (for

Climatology of Aerosol Optical Properties in Southern Africa

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Queface, Antonio J.; Piketh, Stuart J.; Eck, Thomas F.; Tsay, Si-Chee

2011-01-01

A thorough regionally dependent understanding of optical properties of aerosols and their spatial and temporal distribution is required before we can accurately evaluate aerosol effects in the climate system. Long term measurements of aerosol optical depth, Angstrom exponent and retrieved single scattering albedo and size distribution, were analyzed and compiled into an aerosol optical properties climatology for southern Africa. Monitoring of aerosol parameters have been made by the AERONET program since the middle of the last decade in southern Africa. This valuable information provided an opportunity for understanding how aerosols of different types influence the regional radiation budget. Two long term sites, Mongu in Zambia and Skukuza in South Africa formed the core sources of data in this study. Results show that seasonal variation of aerosol optical thicknesses at 500 nm in southern Africa are characterized by low seasonal multi-month mean values (0.11 to 0.17) from December to May, medium values (0.20 to 0.27) between June and August, and high to very high values (0.30 to 0.46) during September to November. The spatial distribution of aerosol loadings shows that the north has high magnitudes than the south in the biomass burning season and the opposite in none biomass burning season. From the present aerosol data, no long term discernable trends are observable in aerosol concentrations in this region. This study also reveals that biomass burning aerosols contribute the bulk of the aerosol loading in August-October. Therefore if biomass burning could be controlled, southern Africa will experience a significant reduction in total atmospheric aerosol loading. In addition to that, aerosol volume size distribution is characterized by low concentrations in the non biomass burning period and well balanced particle size contributions of both coarse and fine modes. In contrast high concentrations are characteristic of biomass burning period, combined with

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

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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

Modeling organic aerosol from the oxidation of α-pinene in a Potential Aerosol Mass (PAM chamber

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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.

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.

Modelling organic aerosol concentrations and properties during ChArMEx summer campaigns of 2012 and 2013 in the western Mediterranean region

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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.

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.

An algorithm for hyperspectral remote sensing of aerosols: 2. Information content analysis for aerosol parameters and principal components of surface spectra

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Hou, Weizhen; Wang, Jun; Xu, Xiaoguang; Reid, Jeffrey S.

2017-05-01

This paper describes the second part of a series of investigation to develop algorithms for simultaneous retrieval of aerosol parameters and surface reflectance from the future hyperspectral and geostationary satellite sensors such as Tropospheric Emissions: Monitoring of POllution (TEMPO). The information content in these hyperspectral measurements is analyzed for 6 principal components (PCs) of surface spectra and a total of 14 aerosol parameters that describe the columnar aerosol volume Vtotal, fine-mode aerosol volume fraction, and the size distribution and wavelength-dependent index of refraction in both coarse and fine mode aerosols. Forward simulations of atmospheric radiative transfer are conducted for 5 surface types (green vegetation, bare soil, rangeland, concrete and mixed surface case) and a wide range of aerosol mixtures. It is shown that the PCs of surface spectra in the atmospheric window channel could be derived from the top-of-the-atmosphere reflectance in the conditions of low aerosol optical depth (AOD ≤ 0.2 at 550 nm), with a relative error of 1%. With degree freedom for signal analysis and the sequential forward selection method, the common bands for different aerosol mixture types and surface types can be selected for aerosol retrieval. The first 20% of our selected bands accounts for more than 90% of information content for aerosols, and only 4 PCs are needed to reconstruct surface reflectance. However, the information content in these common bands from each TEMPO individual observation is insufficient for the simultaneous retrieval of surface's PC weight coefficients and multiple aerosol parameters (other than Vtotal). In contrast, with multiple observations for the same location from TEMPO in multiple consecutive days, 1-3 additional aerosol parameters could be retrieved. Consequently, a self-adjustable aerosol retrieval algorithm to account for surface types, AOD conditions, and multiple-consecutive observations is recommended to derive

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.

Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

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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.

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

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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.

Long-term measurements of aerosol optical parameters in Athens, Greece

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Paraskevopoulou, Despoina; Liakakou, Eleni; Gerasopoulos, Evangelos; Mihalopoulos, Nikolaos

2015-04-01

Aerosol chemical composition was studied in conjunction with its optical properties in the area of Athens Greece. For this purpose, sampling of fine aerosol fraction (PM2,5) took place on a daily basis from August 2010 to April 2013 at an urban background location. The samples are subsequently analyzed for their content in organic (OC) and elemental carbon (EC), major ions and trace metals, resulting in the exercise of chemical mass closure. In parallel, the optical properties of aerosols are recorded using a nephelometer and a particle soot absorption photometer (PSAP), leading to the calculation of scattering (σscat) and absorption (σabs) coefficients, respectively; while single scattering albedo (SSA) and mass scattering and absorption efficiencies are thereinafter calculated. Daily σscat values provide an average of 30.1±3.9 Μm-1 while, the average of σabs is 5.2±1.4 Μm-1. The seasonal cycle of σscat presents maximum during summer and in November, due to long-range transport of aerosol from continental Europe and dust transfer from Africa, respectively. The estimated mass absorption efficiency of EC is estimated to be 8.3±0.2 m2 g-1 for the whole studied period, while the corresponding estimated mass scattering efficiency of PM2.5 is 1.7±0.1 m2 g-1 and does not affected by the presence of dust. The average SSA equals to 0.87±0.11 for the three-year period. On a seasonal basis, SSA presents maximum values during summer that is consistent with the reduction of EC - the main absorbing specie. Finally, the reconstruction of scattering coefficients was performed taking into consideration the measured chemistry of fine aerosol.

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

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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.

Modeling regional air quality and climate: improving organic aerosol and aerosol activation processes in WRF/Chem version 3.7.1

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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

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

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Y. Gómez-González

2012-01-01

Full Text Available Measurements of organic marker compounds and inorganic species were performed on PM_2.5 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.

Fine-particle sodium tracer for long-range transport of the Kuwaiti oil-fire smoke

Energy Technology Data Exchange (ETDEWEB)

Lowenthal, D.H.; Borys, R.D.; Rogers, C.F.; Chow, J.C.; Stevens, R.K.

1993-04-23

Evidence for long-range transport of the Kuwaiti oil-fire smoke during the months following the Persian Gulf War has been more or less indirect. However, more-recent data on the aerosol chemistry of Kuwaiti oil-fire plumes provides a direct link between those fires and aerosols collected at the Mauna Loa Observatory (MLO) during the late spring and summer of 1991. By itself, temporal covariation of fine-particle concentrations of elemental carbon, sulfur, and the noncrustal V/Zn ratio in MLO aerosols suggested a link to large-scale oil-combustion sources, but not necessarily to Kuwait. However, high concentrations of fine-particle (0.1-1.0 microm diameter) NaCl were observed in the 'white' oil-fire plumes over Kuwait during the summer of 1991. In the absence of other demonstratable sources of fine-particle Na, these relationships provide a direct link between the Kuwaiti oil-fires and aerosol composition observed at MLO. (Copyright (c) 1993 American Geophysical Union.)

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.

Experimental study of radioactive aerosols in the vicinity of the Chernobyl Nuclear Power Plant

International Nuclear Information System (INIS)

Boulyga, S.F.; Lomonosova, E.M.; Zhuk, I.V.; Yaroshevich, O.I.; Kudrjashov, V.P.; Mironov, V.P.

1999-01-01

Study of radioactive aerosols in the relocation zone and in the populated areas have been carried out for a number of years. The experiments on modelling resuspension were performed while conducting agricultural work. Nuclear track radiography and alpha spectrometry with radiochemical extraction of plutonium were used as analytical methods for the determination of the transuranium elements contents. The distributions of radioactive particles were obtained as to activity and sizes. Specific activity of 'hot particles' increases with decreasing diameter. In aerosols selected at a distance of more than 10 km from the Chernobyl NPP pure fuel particles with sizes of more than 5 μm were not found. The activity of the finely dispersed fraction of aerosols, which is more dangerous when inhaled by the organism, is comparable with a total activity of large particles

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.

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

African aerosol and large-scale precipitation variability over West Africa

International Nuclear Information System (INIS)

Huang Jingfeng; Zhang Chidong; Prospero, Joseph M

2009-01-01

We investigated the large-scale connection between African aerosol and precipitation in the West African Monsoon (WAM) region using 8-year (2000-2007) monthly and daily Moderate Resolution Imaging Spectroradiometer (MODIS) aerosol products (aerosol optical depth, fine mode fraction) and Tropical Rainfall Measuring Mission (TRMM) precipitation and rain type. These high-quality data further confirmed our previous results that the large-scale link between aerosol and precipitation in this region undergoes distinct seasonal and spatial variability. Previously detected suppression of precipitation during months of high aerosol concentration occurs in both convective and stratiform rain, but not systematically in shallow rain. This suggests the suppression of deep convection due to the aerosol. Based on the seasonal cycle of dust and smoke and their geographical distribution, our data suggest that both dust (coarse mode aerosol) and smoke (fine mode aerosol) contribute to the precipitation suppression. However, the dust effect is evident over the Gulf of Guinea while the smoke effect is evident over both land and ocean. A back trajectory analysis further demonstrates that the precipitation reduction is statistically linked to the upwind aerosol concentration. This study suggests that African aerosol outbreaks in the WAM region can influence precipitation in the local monsoon system which has direct societal impact on the local community. It calls for more systematic investigations to determine the modulating mechanisms using both observational and modeling approaches.

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)