Hydroxyl radicals from secondary organic aerosol decomposition in water

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Sources of secondary organic aerosols over North China Plain in winter

NASA Astrophysics Data System (ADS)

Xing, L.; Li, G.; Tie, X.; Junji, C.; Long, X.

2017-12-01

Organic aerosol (OA) concentrations are simulated over the North China Plain (NCP) from 10th to 26th January, 2014 using the Weather Research and Forecasting model coupled to chemistry (WRF-CHEM), with the goal of examining the impact of heterogeneous HONO sources on atmospheric oxidation capacity and consequently on SOA formation and SOA formation from different pathways in winter. Generally, the model well reproduced the spatial and temporal distribution of PM2.5, SO2, NO2, and O3 concentrations. The heterogeneous HONO formation contributed a major part of atmospheric HONO concentrations in Beijing. The heterogeneous HONO sources significantly increased the daily maximum OH concentrations by 260% on average in Beijing, which enhanced the atmospheric oxidation capacity and consequently SOA concentrations by 80% in Beijing on average. Under severe haze pollution on January 16th 2014, the regional average HONO concentration over NCP was 0.86 ppb, which increased SOA concentration by 68% on average. The average mass fractions of ASOA (SOA from oxidation of anthropogenic VOCs), BSOA (SOA from oxidation of biogenic VOCs), PSOA (SOA from oxidation of evaporated POA), and GSOA (SOA from irreversible uptake of glyoxal and methylglyoxal) during the simulation period over NCP were 24%, 5%, 26% and 45%, respectively. GSOA contributed most to the total SOA mass over NCP in winter. The model sensitivity simulation revealed that GSOA in winter was mainly from primary residential sources. The regional average of GSOA from primary residential sources constituted 87% of total GSOA mass.

Is there an aerosol signature of aqueous processing?

NASA Astrophysics Data System (ADS)

Ervens, B.; Sorooshian, A.

2017-12-01

The formation of aerosol mass in cloud water has been recognized as a substantial source of atmospheric aerosol mass. While sulfate formation can be relatively well constrained, the formation of secondary organic aerosol mass in the aqueous phase (aqSOA) is much more complex due to the multitude of precursors and variety in chemical processes. Aqueous phase processing adds aerosol mass to the droplet mode, which is formed due to mass addition to activated particles in clouds. In addition, it has been shown that aqSOA mass has specific characteristics in terms of oxidation state and hygroscopicity that might help to distinguish it from other SOA sources. Many models do not include detailed chemical mechanisms of sulfate and aqSOA formation and also lack details on the mass distribution of newly formed mass. Mass addition inside and outside clouds modifies different parts of an aerosol population and consequently affects predictions of properties and lifetime of particles. Using a combination of field data analysis and model studies for a variety of air masses, we will show which chemical and physical aerosol properties can be used, in order to identify an `aqueous phase signature' in processed aerosol populations. We will discuss differences in this signature in clean (e.g., background), moderately polluted (e.g., urban) and highly polluted (e.g., biomass burning) air masses and suggest air-mass-specific chemical and/or physical properties that will help to quantify the aqueous-phase derived aerosol mass.

Contributions and source identification of biogenic and anthropogenic hydrocarbons to secondary organic aerosols at Mt. Tai in 2014.

PubMed

Zhu, Yanhong; Yang, Lingxiao; Kawamura, Kimitaka; Chen, Jianmin; Ono, Kaori; Wang, Xinfeng; Xue, Likun; Wang, Wenxing

2017-01-01

Ambient fine particulate matter (PM 2.5 ) and volatile organic compounds (VOCs) collected at Mt. Tai in summer 2014 were analysed and the data were used to identify the contribution of biogenic and anthropogenic hydrocarbons to secondary organic aerosols (SOA) and their sources and potential source areas in high mountain regions. Compared with those in 2006, the 2014 anthropogenic SOA tracers in PM 2.5 aerosols and VOC species related to vehicular emissions exhibited higher concentrations, whereas the levels of biogenic SOA tracers were lower, possibly due to decreased biomass burning. Using the SOA tracer and parameterisation method, we estimated the contributions from biogenic and anthropogenic VOCs, respectively. The results showed that the average concentration of biogenic SOA was 1.08 ± 0.51 μg m -3 , among which isoprene SOA tracers were dominant. The anthropogenic VOC-derived SOA were 7.03 ± 1.21 μg m -3 and 1.92 ± 1.34 μg m -3 under low- and high-NO x conditions, respectively, and aromatics made the greatest contribution. However, the sum of biogenic and anthropogenic SOA only contributed 18.1-49.1% of the total SOA. Source apportionment by positive matrix factorisation (PMF) revealed that secondary oxidation and biomass burning were the major sources of biogenic SOA tracers. Anthropogenic aromatics mainly came from solvent use, fuel and plastics combustion and vehicular emissions. However, for > C6 alkanes and cycloalkanes, vehicular emissions and fuel and plastics combustion were the most important contributors. The potential source contribution function (PSCF) identified the Bohai Sea Region (BSR) as the major source area for organic aerosol compounds and VOC species at Mt. Tai. Copyright © 2016 Elsevier Ltd. All rights reserved.

On the Evaporation Kinetics and Phase of Laboratory and Ambient Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Zelenyuk, A.; Vaden, T.; Imre, D. G.; Beránek, J.; Shrivastava, M.

2010-12-01

Field measurements of secondary organic aerosol (SOA) find significantly higher mass loads than predicted by models, sparking intense effort that is focused on finding additional SOA sources, but leaves many of the fundamental assumptions that are used by models unchallenged. Current air-quality models use absorptive partitioning theory assuming SOA particles are liquid droplets that form instantaneous reversible equilibrium with gas phase. Further, they ignore the effects of adsorption of spectator organic species during SOA formation on SOA properties and fate. Using an accurate and highly sensitive experimental approach for studying evaporation kinetics of size-selected single SOA particles, we characterized room-temperature evaporation kinetics of laboratory generated α-pinene SOA and ambient atmospheric SOA. The experimental setup was first tested by measuring the evaporation kinetics of single component organic particles of known vapor pressure. We show that, as expected for liquid droplets, smaller particles evaporate faster, and that these data yield the correct vapor pressure. We then study the evaporation kinetics of α-pinene SOA and find that evaporation proceeds in two stages: a fast stage, during which 50% of the particle volume evaporates in ~100 minutes, followed by a slower stage, when additional 25% evaporate in 1400 minutes, which is in sharp contrast to the ~10 minutes timescale predicted by current kinetic models. α-pinene SOA formed in the presence of “spectator” hydrophobic organic vapors like dioctyl phthalate, dioctyl sebacate, pyrene, or their mixture, were shown to adsorb noticeable amounts of these organics, forming what we term here ‘coated’ SOA particles. We show that these adsorbed coatings reduce evaporation rates of SOA particles. Moreover, aging of coated SOA particles dramatically reduces evaporation rates, and in some cases nearly stops it. For example, aging of SOA with adsorbed pyrene reduces evaporation rate to the point that only ~11% of the particle volume evaporates within 24 hrs. For all cases studied in this work, SOA evaporation behavior is size-independent and does not follow the evaporation kinetics of liquid droplets, which is in sharp contrast with model assumptions. To address the question of how closely the laboratory observations described above reflect reality in the atmosphere we characterized the evaporation kinetics of size-selected atmospheric SOA particles sampled in-situ during the recent Carbonaceous Aerosols and Radiative Effects Study (CARES) field campaign. We find that the evaporation of ambient SOA is very similar to that of coated and aged laboratory-generated α-pinene SOA. Ambient SOA particles in Sacramento, CA lose between 17% and 25% of their volume in 6 hours. Like laboratory SOA, their evaporation is size-independent and does not follow the kinetics of liquid droplets. The findings about SOA phase, evaporation rates, and the importance of spectator gases and aging - all indicate the need to reformulate the way SOA formation and evaporation are treated by models.

Sources, Properties, Aging, and Anthropogenic Influences on OA and SOA over the Southeast US and the Amazon duing SOAS, DC3, SEAC4RS, and GoAmazon

EPA Science Inventory

The SE US and the Amazon have large sources of biogenic VOCs, varying anthropogenic pollution impacts, and often poor organic aerosol (OA) model performance. Recent results on the sources, properties, aging, and impact of anthropogenic pollution on OA and secondary OA (SOA) over ...

Local source impacts on primary and secondary aerosols in the Midwestern United States

NASA Astrophysics Data System (ADS)

Jayarathne, Thilina; Rathnayake, Chathurika M.; Stone, Elizabeth A.

2016-04-01

Atmospheric particulate matter (PM) exhibits heterogeneity in composition across urban areas, leading to poor representation of outdoor air pollutants in human exposure assessments. To examine heterogeneity in PM composition and sources across an urban area, fine particulate matter samples (PM2.5) were chemically profiled in Iowa City, IA from 25 August to 10 November 2011 at two monitoring stations. The urban site is the federal reference monitoring (FRM) station in the city center and the peri-urban site is located 8.0 km to the west on the city edge. Measurements of PM2.5 carbonaceous aerosol, inorganic ions, molecular markers for primary sources, and secondary organic aerosol (SOA) tracers were used to assess statistical differences in composition and sources across the two sites. PM2.5 mass ranged from 3 to 26 μg m-3 during this period, averaging 11.2 ± 4.9 μg m-3 (n = 71). Major components of PM2.5 at the urban site included organic carbon (OC; 22%), ammonium (14%), sulfate (13%), nitrate (7%), calcium (2.9%), and elemental carbon (EC; 2.2%). Periods of elevated PM were driven by increases in ammonium, sulfate, and SOA tracers that coincided with hot and dry conditions and southerly winds. Chemical mass balance (CMB) modeling was used to apportion OC to primary sources; biomass burning, vegetative detritus, diesel engines, and gasoline engines accounted for 28% of OC at the urban site and 24% of OC at the peri-urban site. Secondary organic carbon from isoprene and monoterpene SOA accounted for an additional 13% and 6% of OC at the urban and peri-urban sites, respectively. Differences in biogenic SOA across the two sites were associated with enhanced combustion activities in the urban area and higher aerosol acidity at the urban site. Major PM constituents (e.g., OC, ammonium, sulfate) were generally well-represented by a single monitoring station, indicating a regional source influence. Meanwhile, nitrate, biomass burning, food cooking, suspended dust, and biogenic SOA were not well-represented by a single site and demonstrated local influences. For isoprene SOA, product distributions indicated a larger role for the high-NOx pathway at the urban site. These local sources are largely responsible for differences in population exposures to outdoor PM in the study domain located within the Midwestern US.

Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Kinetics and SOA yields

NASA Astrophysics Data System (ADS)

Richards-Henderson, Nicole K.; Hansel, Amie K.; Valsaraj, Kalliat T.; Anastasio, Cort

2014-10-01

Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) × 109 M-1 s-1 at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol-1 Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 ± 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions.

Modeling Secondary Organic Aerosol Formation From Emissions of Combustion Sources

NASA Astrophysics Data System (ADS)

Jathar, Shantanu Hemant

Atmospheric aerosols exert a large influence on the Earth's climate and cause adverse public health effects, reduced visibility and material degradation. Secondary organic aerosol (SOA), defined as the aerosol mass arising from the oxidation products of gas-phase organic species, accounts for a significant fraction of the submicron atmospheric aerosol mass. Yet, there are large uncertainties surrounding the sources, atmospheric evolution and properties of SOA. This thesis combines laboratory experiments, extensive data analysis and global modeling to investigate the contribution of semi-volatile and intermediate volatility organic compounds (SVOC and IVOC) from combustion sources to SOA formation. The goals are to quantify the contribution of these emissions to ambient PM and to evaluate and improve models to simulate its formation. To create a database for model development and evaluation, a series of smog chamber experiments were conducted on evaporated fuel, which served as surrogates for real-world combustion emissions. Diesel formed the most SOA followed by conventional jet fuel / jet fuel derived from natural gas, gasoline and jet fuel derived from coal. The variability in SOA formation from actual combustion emissions can be partially explained by the composition of the fuel. Several models were developed and tested along with existing models using SOA data from smog chamber experiments conducted using evaporated fuel (this work, gasoline, fischertropschs, jet fuel, diesels) and published data on dilute combustion emissions (aircraft, on- and off-road gasoline, on- and off-road diesel, wood burning, biomass burning). For all of the SOA data, existing models under-predicted SOA formation if SVOC/IVOC were not included. For the evaporated fuel experiments, when SVOC/IVOC were included predictions using the existing SOA model were brought to within a factor of two of measurements with minor adjustments to model parameterizations. Further, a volatility-only model suggested that differences in the volatility of the precursors were able to explain most of the variability observed in the SOA formation. For aircraft exhaust, the previous methods to simulate SOA formation from SVOC and IVOC performed poorly. A more physically-realistic modeling framework was developed, which was then used to show that SOA formation from aircraft exhaust was (a) higher for petroleum-based than synthetically derived jet fuel and (b) higher at lower engine loads and vice versa. All of the SOA data from combustion emissions experiments were used to determine source-specific parameterizations to model SOA formation from SVOC, IVOC and other unspeciated emissions. The new parameterizations were used to investigate their influence on the OA budget in the United States. Combustion sources were estimated to emit about 2.61 Tg yr-1 of SVOC, 1VOC and other unspeciated emissions (sixth of the total anthropogenic organic emissions), which are predicted to double SOA production from combustion sources in the United States. The contribution of SVOC and IVOC emissions to global SOA formation was assessed using a global climate model. Simulations were performed using a modified version of GISS GCM 11'. The modified model predicted that SVOC and IVOC contributed to half of the OA mass in the atmosphere. Their inclusion improved OA model-measurement comparisons for absolute concentrations, POA-SOA split and volatility (gas-particle partitioning) globally suggesting that atmospheric models need to incorporate SOA formation from SVOC and IVOC if they are to reasonably predict the abundance and properties of aerosols. This thesis demonstrates that SVOC/IVOC and possibly other unspeciated organics emitted by combustion sources are very important precursors of SOA and potentially large contributors to the atmospheric aerosol mass. Models used for research and policy applications need to represent them to improve model-predictions of aerosols on climate and health outcomes. The improved modeling frameworks developed in this dissertation are suitable for implementation into chemical transport models.

Modeling the formation and aging of secondary organic aerosols in the Los Angeles metropolitan region during the CalNex 2010 field campaign

NASA Astrophysics Data System (ADS)

Hayes, P. L.; Ma, P. K.; Jimenez, J. L.; Zhao, Y.; Robinson, A. L.; Carlton, A. M. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S. L.; Rappenglück, B.; Gilman, J.; Kuster, W.; De Gouw, J. A.; Prevot, A. S.; Zotter, P.; Szidat, S.; Kleindienst, T. E.; Offenberg, J. H.

2015-12-01

Several different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) are evaluated using a box model representing the Los Angeles Region during CalNex. The model SOA formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. Including SOA from primary semi-volatile and intermediate volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model/measurement agreement for mass concentration at shorter photochemical ages (0.5 days). Our results strongly suggest that other precursors besides VOCs are needed to explain the observed SOA concentrations. In contrast, all of the literature P-S/IVOC parameterizations over-predict urban SOA formation at long photochemical ages (3 days) compared to observations from multiple sites, which can lead to problems in regional and global modeling. Sensitivity studies that reduce the IVOC emissions by one-half in the model improve SOA predictions at these long ages. In addition, when IVOC emissions in the Robinson et al. parameterization are constrained using recently reported measurements of these species model/measurement agreement is achieved. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16 - 27%, 35 - 61%, and 19 - 35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(±3)%. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in SOA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in urban SOA, possibly cooking emissions, that was not accounted for in those previous studies, and which is higher on weekends.

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Modeling the Current and Future Roles of Particulate Organic Nitrates in the Southeastern United States.

PubMed

Pye, Havala O T; Luecken, Deborah J; Xu, Lu; Boyd, Christopher M; Ng, Nga L; Baker, Kirk R; Ayres, Benjamin R; Bash, Jesse O; Baumann, Karsten; Carter, William P L; Edgerton, Eric; Fry, Juliane L; Hutzell, William T; Schwede, Donna B; Shepson, Paul B

2015-12-15

Organic nitrates are an important aerosol constituent in locations where biogenic hydrocarbon emissions mix with anthropogenic NOx sources. While regional and global chemical transport models may include a representation of organic aerosol from monoterpene reactions with nitrate radicals (the primary source of particle-phase organic nitrates in the Southeast United States), secondary organic aerosol (SOA) models can underestimate yields. Furthermore, SOA parametrizations do not explicitly take into account organic nitrate compounds produced in the gas phase. In this work, we developed a coupled gas and aerosol system to describe the formation and subsequent aerosol-phase partitioning of organic nitrates from isoprene and monoterpenes with a focus on the Southeast United States. The concentrations of organic aerosol and gas-phase organic nitrates were improved when particulate organic nitrates were assumed to undergo rapid (τ = 3 h) pseudohydrolysis resulting in nitric acid and nonvolatile secondary organic aerosol. In addition, up to 60% of less oxidized-oxygenated organic aerosol (LO-OOA) could be accounted for via organic nitrate mediated chemistry during the Southern Oxidants and Aerosol Study (SOAS). A 25% reduction in nitrogen oxide (NO + NO2) emissions was predicted to cause a 9% reduction in organic aerosol for June 2013 SOAS conditions at Centreville, Alabama.

Formation and evolution of molecular products in α-pinene secondary organic aerosol.

PubMed

Zhang, Xuan; McVay, Renee C; Huang, Dan D; Dalleska, Nathan F; Aumont, Bernard; Flagan, Richard C; Seinfeld, John H

2015-11-17

Much of our understanding of atmospheric secondary organic aerosol (SOA) formation from volatile organic compounds derives from laboratory chamber measurements, including mass yield and elemental composition. These measurements alone are insufficient to identify the chemical mechanisms of SOA production. We present here a comprehensive dataset on the molecular identity, abundance, and kinetics of α-pinene SOA, a canonical system that has received much attention owing to its importance as an organic aerosol source in the pristine atmosphere. Identified organic species account for ∼58-72% of the α-pinene SOA mass, and are characterized as semivolatile/low-volatility monomers and extremely low volatility dimers, which exhibit comparable oxidation states yet different functionalities. Features of the α-pinene SOA formation process are revealed for the first time, to our knowledge, from the dynamics of individual particle-phase components. Although monomeric products dominate the overall aerosol mass, rapid production of dimers plays a key role in initiating particle growth. Continuous production of monomers is observed after the parent α-pinene is consumed, which cannot be explained solely by gas-phase photochemical production. Additionally, distinct responses of monomers and dimers to α-pinene oxidation by ozone vs. hydroxyl radicals, temperature, and relative humidity are observed. Gas-phase radical combination reactions together with condensed phase rearrangement of labile molecules potentially explain the newly characterized SOA features, thereby opening up further avenues for understanding formation and evolution mechanisms of α-pinene SOA.

[Three types of self-esteem: its characteristic differences of contingency and contentment of sources of self-esteem].

PubMed

Ito, Masaya; Kawasaki, Naoki; Kodama, Masahiro

2011-02-01

Previous research and theory (Crocker & Wolfe, 2001; Kernis, 2003) suggests that adaptive self-esteem stems from just being oneself, and is characterized by a sense of authenticity (SOA). Maladaptive self-esteem is derived from meeting external standards and social comparisons, and is characterized by a sense of superiority (SOS). Thus, the qualitative difference between SOA and SOS depends on the sources of self-esteem. We hypothesized that SOA is related to internal sources of self-esteem, while SOS is related to external sources. In order to control for covariance, global self-esteem was also examined in a questionnaire survey of self-esteem that was administered to 273 university students. The results of a partial correlation analysis showed that SOA was positively correlated with internal sources of self-esteem such as committed activities and efforts for self-development. In contrast, SOS was positively correlated with external sources of self-esteem such as approval from others and appearance. These results mainly support our hypotheses.

Sources of primary and secondary organic aerosols in Chinese versus European Cities during winter time

NASA Astrophysics Data System (ADS)

Prevot, A. S.; Slowik, J.; El-Haddad, I.; Pieber, S. M.; Yuan, B.; Stefenelli, G.; Pospisilova, V.; Lopez-Hilfiker, F.; Qi, L.; Tong, Y.; Wang, L.; Daellenbach, K.; Klein, F.; Elser, M.; Junji, C.; Huang, R. J. J.; Baltensperger, U.

2017-12-01

In the recent years, aerosol mass spectrometric (AMS) measurements were performed in Beijing (China), Zurich (Switzerland) and other Chinese and European cities indicating the importance of not only primary sources but also secondary organic aerosol (SOA) sources despite low radiation levels for photooxidation. Among the primary sources, residential burning is especially important in winter including wood and coal burning. Also for secondary organic aerosols, VOC emissions of residential burning are likely an important source in winter. An interesting question is whether daytime photooxidation and/or night-time NO3 radical chemistry are important pathways for the SOA formation. Recently we developed a new measurement technique based on exctractive electrospray ionization (EESI) that allow for the study of the organic molecules in the particulate phase without fragmentation. Combined measurements with AMS and EESI will be discussed for smogchamber experiments (simulating both nighttime and daytime chemistry) SOA formation potential, the link between VOCs and SOA and the SOA composition. In-situ and off-line measurements in Europe and China are analyzed in the light of those experiments with a focus on the importance of residential burning to both primary and secondary organic aerosols in cities during winter.

Development and Application of an Oxidation Flow Reactor to Study Secondary Organic Aerosol Formation from Ambient Air

NASA Astrophysics Data System (ADS)

Palm, Brett Brian

Secondary organic aerosols (SOA) in the atmosphere play an important role in air quality, human health, and climate. However, the sources, formation pathways, and fate of SOA are poorly constrained. In this dissertation, I present development and application of the oxidation flow reactor (OFR) technique for studying SOA formation from OH, O3, and NO3 oxidation of ambient air. With a several-minute residence time and a portable design with no inlet, OFRs are particularly well-suited for this purpose. I first introduce the OFR concept, and discuss several advances I have made in performing and interpreting OFR experiments. This includes estimating oxidant exposures, modeling the fate of low-volatility gases in the OFR (wall loss, condensation, and oxidation), and comparing SOA yields of single precursors in the OFR with yields measured in environmental chambers. When these experimental details are carefully considered, SOA formation in an OFR can be more reliably compared with ambient SOA formation processes. I then present an overview of what OFR measurements have taught us about SOA formation in the atmosphere. I provide a comparison of SOA formation from OH, O3, and NO3 oxidation of ambient air in a wide variety of environments, from rural forests to urban air. In a rural forest, the SOA formation correlated with biogenic precursors (e.g., monoterpenes). In urban air, it correlated instead with reactive anthropogenic tracers (e.g., trimethylbenzene). In mixed-source regions, the SOA formation did not correlate well with any single precursor, but could be predicted by multilinear regression from several precursors. Despite these correlations, the concentrations of speciated ambient VOCs could only explain approximately 10-50% of the total SOA formed from OH oxidation. In contrast, ambient VOCs could explain all of the SOA formation observed from O3 and NO3 oxidation. Evidence suggests that lower-volatility gases (semivolatile and intermediate-volatility organic compounds; S/IVOCs) were present in ambient air and were the likely source of SOA formation that could not be explained by VOCs. These measurements show that S/IVOCs likely play an important intermediary role in ambient SOA formation in all of the sampled locations, from rural forests to urban air.

Source apportionment of submicron organic aerosol at an urban background and a road site in Barcelona (Spain) during SAPUSS

NASA Astrophysics Data System (ADS)

Alier, M.; van Drooge, B. L.; Dall'Osto, M.; Querol, X.; Grimalt, J. O.; Tauler, R.

2013-10-01

This study investigates the contribution of potential sources to the submicron (PM1) organic aerosol (OA) simultaneously detected at an urban background (UB) and a road site (RS) in Barcelona during the 30 days of the intensive field campaign of SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies, September-October 2010). A total of 103 filters at 12 h sampling time resolution were collected at both sites. Thirty-six neutral and polar organic compounds of known emission sources and photo-chemical transformation processes were analyzed by gas chromatography-mass spectrometry (GC-MS). The concentrations of the trace chemical compounds analyzed are herein presented and discussed. Additionally, OA source apportionment was performed by multivariate curve resolution-alternating least squares (MCR-ALS) and six OA components were identified at both sites: two were of primary anthropogenic OA origin and three of secondary OA origin, while a sixth one was not clearly defined. Primary organics from emissions of local anthropogenic activities (urban primary organic aerosol, or POA Urban), mainly traffic emissions but also cigarette smoke, contributed 43% (1.5 μg OC m-3) and 18% (0.4 μg OC m-3) to OA at RS and UB, respectively. A secondary primary source - biomass burning (BBOA) - was found in all the samples (average values 7% RS; 12% UB; 0.3 μg OC m-3), but this component was substantially contributing to OA only when the sampling sites were under influence of regional air mass circulation (REG.). Three secondary organic aerosol (SOA) components (describing overall 60% of the variance) were observed in the urban ambient PM1. Products of isoprene oxidation (SOA ISO) - i.e. 2-methylglyceric acid, C5 alkene triols and 2-methyltetrols - showed the highest abundance at both sites when the city was under influence of inland air masses. The overall concentrations of SOA ISO were similar at both sites (0.4 and 0.3 μg m-3, or 16% and 7%, at UB and RS, respectively). By contrast, a SOA biogenic component attributed to α-pinene oxidation (SOA BIO PIN) presented average concentrations of 0.5 μg m-3 at UB (24% of OA) and 0.2 μg m-3 at RS (7%), respectively, suggesting that this SOA component did not impact the two monitoring sites at the same level. A clear anti-correlation was observed between SOA ISO and SOA PIN during nucleation days, surprisingly suggesting that some of the growth of urban freshly nucleating particles may be driven by biogenic α-pinene oxidation products but inhibited by isoprene organic compounds. A third SOA component was formed by a mixture of aged anthropogenic and biogenic secondary organic compounds (SOA Aged) that accumulated under stagnant atmospheric conditions, contributing for 12% to OA at RS (0.4 μg OC m-3) and for 18% at UB (0.4 μg OC m-3). A sixth component, formed by C7-C9 dicarboxylic acids and detected especially during daytime, was called "urban oxygenated organic aerosol" (OOA Urban) due to its high abundance at urban RS (23%; 0.8 μg OCm-3) vs. UB (10%; 0.2 μg OCm-3), with a well-defined daytime maximum. This temporal trend and geographical differentiation suggests that local anthropogenic sources were determining this component. However, the changes of these organic molecules were also influenced by the air mass trajectories, indicating that atmospheric conditions have an influence on this component, although the specific origin on this component remains unclear. It points to a secondary organic component driven by primary urban sources including cooking and traffic (mainly gasoline) activities.

Source apportionment of submicron organic aerosol at an urban background and a road site in Barcelona, Spain

NASA Astrophysics Data System (ADS)

Alier, M.; van Drooge, B. L.; Dall'Osto, M.; Querol, X.; Grimalt, J. O.; Tauler, R.

2013-04-01

This study investigates the contribution of potential sources to the sub-micron (PM1) organic aerosol (OA) simultaneously detected at an urban background (UB) and a road site (RS) in Barcelona during the 30 days of the intensive field campaign of SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies, September-October 2010). 103 filters at 12 h sampling time resolution were collected at both sites. Thirty-six neutral and polar organic compounds of known emission sources and photo-chemical transformation processes were analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). The concentrations of the trace chemical compounds analyzed are herein presented and discussed. Additionally, OA source apportionment was performed by Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) and six OA components were identified at both sites: two were of primary anthropogenic OA origin, three of secondary OA origin while a sixth one was not clearly defined. Primary organics from emissions of local anthropogenic activities (Urban primary organic aerosol, Urban POA) contributed for 43% (1.5 μg OC m-3) and 18% (0.4 μg OC m-3) to OA in RS and UB, respectively. A secondary primary source - biomass burning (BBOA) - was found in all the samples (average values 7% RS; 12% UB; 0.3 μg OC m-3), but this component was substantially contributing to OA only when the sampling sites were under influence of regional air mass circulation. Three Secondary Organic Aerosol (SOA) components (describing overall 60% of the variance) were observed in the urban ambient PM1. Products of isoprene oxidation (SOA ISO), i.e. 2-methylglyceric acid, C5 alkene triols and 2-methyltetrols, showed the highest abundance at both sites when the city was under influence of inland air masses. The overall concentrations of SOA ISO were similar at both sites (0.4 and 0.3 μg m-3, 16% and 7%, at UB and RS, respectively). By contrast, a SOA biogenic component attributed to α-pinene oxidation (SOA BIO PIN) presented average concentrations of 0.5 μg m-3 at UB (24% of OA) and 0.2 μg m-3 at RS (7%), respectively, suggesting that this SOA component did not impact the two monitoring site at the same level. A clear anti correlation was observed between SOA ISO and SOA PIN during nucleation days, surprisingly suggesting that some of the growth of urban freshly nucleating particles may be driven by biogenic α-pinene oxidation products but inhibited by isoprene organic compounds. A third SOA component was formed by a mixture of aged anthropogenic and biogenic secondary organic compounds (Aged SOA) that accumulated under stagnant atmospheric conditions, contributing for 12% to OA at RS (0.4 μg OC m-3) and for 18% at UB (0.4 μg OC m-3). A sixth component, formed by C7-C9 dicarboxylic acids and detected especially during daytime, was called "urban oxygenated organic aerosol" (Urban OOA) due to its high abundance in urban RS (23%; 0.8 μg OC m-3) vs. UB (10%; 0.2 μg OC m-3), with a well-defined daytime maximum. This temporal trend and geographical differentiation suggests that local anthropogenic sources were determining this component. However, the changes of these organic molecules were also influenced by the air mass trajectories, indicating that atmospheric conditions had an influence on this component although the specific origin on this component remains unclear. It points to a secondary organic component driven by primary urban sources including cooking and traffic (mainly gasoline) activities.

SOA Measurements vs. Models: a Status Report

NASA Astrophysics Data System (ADS)

Jimenez, J. L.; de Gouw, J. A.

2009-12-01

The advent of fast and more detailed organic aerosol (OA) and VOC measurements in the last decade has allowed clearer model-measurement comparisons for OA and secondary OA (SOA). Here we summarize the patterns emerging from studies to date.

Source apportionment of secondary organic aerosol in China using a regional source-oriented chemical transport model and two emission inventories.

PubMed

Wang, Peng; Ying, Qi; Zhang, Hongliang; Hu, Jianlin; Lin, Yingchao; Mao, Hongjun

2018-06-01

A Community Multiscale Air Quality (CMAQ) model with source-oriented lumped SAPRC-11 (S11L) photochemical mechanism and secondary organic aerosol (SOA) module was applied to determine the contributions of anthropogenic and biogenic sources to SOA concentrations in China. A one-year simulation of 2013 using the Multi-resolution Emission Inventory for China (MEIC) shows that summer SOA are generally higher (10-15 μg m -3 ) due to large contributions of biogenic (country average 60%) and industrial sources (17%). In winter, SOA formation was mostly due to anthropogenic emissions from industries (40%) and residential sources (38%). Emissions from other countries in southeast China account for approximately 14% of the SOA in both summer and winter, and 46% in spring due to elevated open biomass burning in southeast Asia. The Regional Emission inventory in ASia v2.1 (REAS2) was applied in this study for January and August 2013. Two sets of simulations with the REAS2 inventory were conducted using two different methods to speciate total non-methane carbon into model species. One approach uses total non-methane hydrocarbon (NMHC) emissions and representative speciation profiles from the SPECIATE database. The other approach retains the REAS2 speciated species that can be directly mapped to S11L model species and uses source specific splitting factors to map other REAS2 lumped NMHC species. Biogenic emissions are still the most significant contributor in summer based on these two sets of simulations. However, contributions from the transportation sector to SOA in January are predicted to be much more important based on the two REAS2 emission inventories (∼30-40% vs. ∼5% by MEIC), and contributions from residential sources according to REAS2 was much lower (∼21-24% vs. ∼42%). These discrepancies in source contributions to SOA need to be further investigated as the country seeks for optimal emission control strategies to fight severe air pollution. Copyright © 2017 Elsevier Ltd. All rights reserved.

A critical role for autoxidation in the alpha-pinene + OH aerosol system

EPA Science Inventory

Oxidation of monoterpenes results in efficient formation of secondary organic aerosol (SOA) and is included as an SOA source in most chemical transport models. However, current model parameterizations lack a mechanistic dependence of monoterpene SOA on NOx and oxidant identity (e...

SOA derived from isoprene epoxydiols: Insights into formation, aging and distribution over the continental US from the DC3 and SEAC4RS campaigns

NASA Astrophysics Data System (ADS)

Campuzano Jost, P.; Hu, W.; Palm, B. B.; Day, D. A.; Jimenez, J. L.; Rivera, J. C.; Keutsch, F. N.; Zhao, R.; Lee, A.; Abbatt, J.; Marais, E. A.; Liao, J.; Froyd, K. D.; Pollack, I. B.; Peischl, J.; Ryerson, T. B.; St Clair, J. M.; Crounse, J. D.; Wennberg, P. O.; Mikoviny, T.; Armin, W.; Scarino, A. J.; Hair, J. W.; Ferrare, R. A.

2017-12-01

Secondary Organic Aerosol (SOA) formed by uptake of isoprene epoxide (IEPOX), a key isoprene oxidation product under low-NO conditions (<100 pptv), has been recently shown to be a major contributor to the total aerosol burden in many regions of the world with high isoprene emissions, such as the SE US or Amazonia. In the present study, we have used Positive Matrix Factorization (PMF) to extract and identify IEPOX-SOA factors from data recorded by the CU High-Resolution Aerosol Mass Spectrometer (AMS) during the DC3 and SEAC4RS aircraft missions on the NASA DC-8. These campaigns sampled the continental US over the Spring of 2012 and the Summer of 2013, respectively. The contribution of IEPOX-SOA to total OA mass in the SE US was substantial for both DC3 (28% on average) and SEAC4RS flights (26%). IEPOX-SOA was observed in isoprene-rich areas in the W US, albeit with smaller contributions (up to 10% of OA). Highest concentrations of IEPOX-SOA were mostly found downwind and/or aloft of source regions, where IEPOX was already depleted but both inorganic sulfate and particle water/relative humidity were higher. IEPOX sulfate, a specific product of IEPOX uptake, correlates reasonably well with total IEPOX-SOA close to sources at low RH, with an observed contribution between 1-10% to total IEPOX-SOA in the SEUS. While the IEPOX-SOA mass spectrum near the ground was very similar to other ground studies in the SEUS, at higher altitudes differences were observed, likely reflecting aging chemistry aloft. In particular we identify, near the top of the boundary layer/cloud deck, a new OA factor likely resulting from aqueous oxidation of IEPOX-SOA. This factor closely matches the spectrum obtained in recent laboratory experiments simulating aqueous IEPOX-SOA aging, and contributed about 25% to total IEPOX-SOA during SEAC4RS; modeling of this new factor in GEOS-Chem will be presented. Measured IEPOX-SOA concentrations and their overall contribution to the total OA burden were substantially higher for SEAC4RS than those measured at the SOAS ground site the same summer (both total and site overflights). Average daily ground temperatures were substantially higher during the SEAC4RS period, with the overall dependence of concentrations of IEPOX-SOA closely following the isoprene source temperature dependence used in the MEGAN inventory.

Spatial and temporal variation of sources contributing to quasi-ultrafine particulate matter PM0.36 in Augsburg, Germany.

PubMed

Li, Fengxia; Schnelle-Kreis, Jürgen; Cyrys, Josef; Wolf, Kathrin; Karg, Erwin; Gu, Jianwei; Orasche, Jürgen; Abbaszade, Gülcin; Peters, Annette; Zimmermann, Ralf

2018-08-01

to study the sources contributing to quasi-ultrafine particle (UFP) organic carbon and the spatial temporal variability of the sources. 24h quasi-UFP (particulate matter <0.36μm in this study) was sampled at a reference site continuously and at one of 5 other sites (T1, T2, T3, T4 and B1) in parallel in Augsburg, Germany from April 11th, 2014 to February 22nd, 2015, attempting to conduct 2-week campaigns at each site in 3 different seasons. Positive matrix factorization (PMF) was applied to measured organic tracers for source apportionment analyses. Pearson correlation coefficient r and coefficient of divergence (COD) were calculated to investigate spatial temporal variation of source contributions. 5 sources were identified comprising biomass burning (BB), traffic emissions (Traffic), biogenic secondary organic aerosol (bioSOA), isoprene originated secondary organic aerosol (isoSOA) and biomass burning related secondary organic aerosol (bbSOA). In general, good temporal correlation and uniform distribution within the study area are found for bioSOA and bbSOA, probably resulting from regional formation/transport. Lower temporal correlation and spatial heterogeneity of isoSOA were found at the city background site with local influence from green space and less traffic impact. BB demonstrated very good temporal correlation, but higher contributions at sites influenced by local residential heating emissions were observed. Traffic showed the least seasonality and lower correlation over time among the sources. However, it demonstrated low spatial heterogeneity of absolute contribution, and only a few days of elevated contribution was found at T3 when wind came directly from the street nearby. temporal correlation and spatial variability of sources contributing to the organic fraction of quasi-UFP vary among sites and source types and show source-specific characteristics. Therefore, caution should be taken when using one monitor site measurement to assess human exposure in health effect studies of quasi-UFP. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed

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

2014-10-21

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

SOA VOLATILITY EVOLUTION: FORMATION AND OXIDATION OVER THE LIFECYCLE OF PM2.5

EPA Science Inventory

Secondary Organic Aerosols are a major, possibly dominant, source of organic PM_2.5 that remain enigmatic. Enormous progress has been made in the past 15 years regarding SOA formation, starting with recognition that most SOA products are semivolatile, continuing to a...

Global transformation and fate of SOA: Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrivastava, ManishKumar B.; Easter, Richard C.; Liu, Xiaohong

2015-05-16

Secondary organic aerosols (SOA) are large contributors to fine particle loadings and radiative forcing, but are often represented crudely in global models. We have implemented three new detailed SOA treatments within the Community Atmosphere Model version 5 (CAM5) that allow us to compare the semi-volatile versus non-volatile SOA treatments (based on some of the latest experimental findings) and also investigate the effects of gas-phase fragmentation reactions. For semi-volatile SOA treatments, fragmentation reactions decrease simulated SOA burden from 7.5 Tg to 1.8 Tg. For the non-volatile SOA treatment with fragmentation, the burden is 3.1 Tg. Larger differences between non-volatile and semi-volatilemore » SOA (upto a factor of 5) correspond to continental outflow over the oceans. Compared to a global dataset of surface Aerosol Mass Spectrometer measurements and the US IMPROVE network measurements, the non-volatile SOA with fragmentation treatment (FragNVSOA) agrees best at rural locations. Urban SOA is under-predicted but this may be due to the coarse model resolution. All our three revised treatments show much better agreement with aircraft measurements of organic aerosols (OA) over the N. American Arctic and sub-Arctic in spring and summer, compared to the standard CAM5 formulation. This is due to treating SOA precursor gases from biomass burning, and long-range transport of biomass burning OA at elevated levels. The revised model configuration that include fragmentation (both semi-volatile and non-volatile SOA) show much better agreement with MODIS AOD data over regions dominated by biomass burning during the summer, and predict biomass burning as the largest global source of OA followed by biogenic and anthropogenic sources. The non-volatile and semi-volatile configuration predict the direct radiative forcing of SOA as -0.5 W m-2 and -0.26 W m-2 respectively, at top of the atmosphere, which are higher than previously estimated by most models, but in reasonable agreement with a recent constrained modeling study. This study highlights the importance of improving process-level representation of SOA in global models.« less

Word Effects in Dual-Task Studies Using Lexical Decision and Naming as Task 2

NASA Technical Reports Server (NTRS)

Remington, Roger; McCann, Robert S.; VanSelst, Mark; Shafto, Michael (Technical Monitor)

1997-01-01

Word frequency effects in dual-task, lexical decision are variously reported to be additive or under-additive across SOA. We replicate and extend earlier lexical decision studies and find word frequency to be additive across SOA. To more directly capture lexical processing, we examine dual-task naming. Once again we find word frequency to be additive across SOA. Lexical processing appears to be constrained by central processing limitations.

Ice core records of monoterpene- and isoprene-SOA tracers from Aurora Peak in Alaska since 1660s: Implication for climate change variability in the North Pacific Rim

NASA Astrophysics Data System (ADS)

Pokhrel, Ambarish; Kawamura, Kimitaka; Ono, Kaori; Seki, Osamu; Fu, Pingqing; Matoba, Sumio; Shiraiwa, Takayuki

2016-04-01

Monoterpene and isoprene secondary organic aerosol (SOA) tracers are reported for the first time in an Alaskan ice core to better understand the biological source strength before and after the industrial revolution in the Northern Hemisphere. We found significantly high concentrations of monoterpene- and isoprene-SOA tracers (e.g., pinic, pinonic, and 2-methylglyceric acids, 2-methylthreitol and 2-methylerythritol) in the ice core, which show historical trends with good correlation to each other since 1660s. They show positive correlations with sugar compounds (e.g., mannitol, fructose, glucose, inositol and sucrose), and anti-correlations with α-dicarbonyls (glyoxal and methylglyoxal) and fatty acids (e.g., C18:1) in the same ice core. These results suggest similar sources and transport pathways for monoterpene- and isoprene-SOA tracers. In addition, we found that concentrations of C5-alkene triols (e.g., 3-methyl-2,3,4-trihydroxy-1-butene, cis-2-methyl 1,3,4-trihydroxy-1-butene and trans-2-methyl-1,3,4-trihydroxy-1-butene) in the ice core have increased after the Great Pacific Climate Shift (late 1970s). They show positive correlations with α-dicarbonyls and fatty acids (e.g., C18:1) in the ice core, suggesting that enhanced oceanic emissions of biogenic organic compounds through the marine boundary layer are recorded in the ice core from Alaska. Photochemical oxidation process for these monoterpene- and isoprene-/sesquiterpene-SOA tracers are suggested to be linked with the periodicity of multi-decadal climate oscillations and retreat of sea ice in the Northern Hemisphere.

Wide tuning range wavelength-swept laser with a single SOA at 1020 nm for ultrahigh resolution Fourier-domain optical coherence tomography.

PubMed

Lee, Sang-Won; Song, Hyun-Woo; Jung, Moon-Youn; Kim, Seung-Hwan

2011-10-24

In this study, we demonstrated a wide tuning range wavelength-swept laser with a single semiconductor optical amplifier (SOA) at 1020 nm for ultrahigh resolution, Fourier-domain optical coherence tomography (UHR, FD-OCT). The wavelength-swept laser was constructed with an external line-cavity based on a Littman configuration. An optical wavelength selection filter consisted of a grating, a telescope, and a polygon scanner. Before constructing the optical wavelength selection filter, we observed that the optical power, the spectrum bandwidth, and the center wavelength of the SOA were affected by the temperature of the thermoelectric (TE) cooler in the SOA mount as well as the applied current. Therefore, to obtain a wide wavelength tuning range, we adjusted the temperature of the TE cooler in the SOA mount. When the temperature in the TE cooler was 9 °C, our swept source had a tuning range of 142 nm and a full-width at half-maximum (FWHM) of 121.5 nm at 18 kHz. The measured instantaneous spectral bandwidth (δλ) is 0.085 nm, which was measured by an optical spectrum analyzer with a resolution bandwidth of 0.06 nm. This value corresponds to an imaging depth of 3.1 mm in air. Additionally, the averaged optical power of our swept source was 8.2 mW. In UHR, FD/SS-OCT using our swept laser, the measured axial resolution was 4.0 μm in air corresponding to 2.9 μm in tissue (n = 1.35). The sensitivity was measured to be 93.1 dB at a depth of 100 μm. Finally, we obtained retinal images (macular and optic disk) and a corneal image. © 2011 Optical Society of America

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

PubMed

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

2016-03-10

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

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plumes of megacities can affect regional air quality. In the framework of the FP7/EU MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) project, an intensive campaign was launched in the greater Paris region in July 2009. The major objective was to quantify different sources of organic aerosol (OA) within a megacity and in its plume. In this study, we use airborne measurements aboard the French ATR-42 aircraft to evaluate the regional chemistry-transport model CHIMERE within and downwind of the Paris region. Two mechanisms of secondary OA (SOA) formation are used, both including SOA formation from oxidation and chemical aging of primary semivolatile and intermediate volatility organic compounds (SI-SOA) in the volatility basis set (VBS) framework. As for SOA formed from traditional VOC (volatile organic compound) precursors (traditional SOA), one applies chemical aging in the VBS framework adopting different SOA yields for high- and low-NOx environments, while another applies a single-step oxidation scheme without chemical aging. Two emission inventories are used for discussion of emission uncertainties. The slopes of the airborne OA levels versus Ox (i.e., O3 + NO2) show SOA formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. The simulated slopes were overestimated slightly by factors of 1.1, 1.7 and 1.3 with respect to those observed for the three airborne measurements, when the most realistic "high-NOx" yields for traditional SOA formation in the VBS scheme are used in the model. In addition, these slopes are relatively stable from one day to another, which suggests that they are characteristic for the given megacity plume environment. The configuration with increased primary organic aerosol (POA) emissions and with a single-step oxidation scheme of traditional SOA also agrees with the OA / Ox slopes (about ± 50 % with respect to the observed ones); however, it underestimates the background. Both configurations are coherent with observed OA plume buildup, but they show very different SI-SOA and traditional anthropogenic SOA (ASOA) contributions. It is hence concluded that available theoretical knowledge and available data in this study are not sufficient to discern the relative contributions of different types of anthropogenic SOA in the Paris pollution plume, while its sum is correctly simulated. Based on these simulations, for specific plumes, the anthropogenic OA buildup can reach between 8 and 10μg m-3. For the average of the month of July 2009, maximum OA increases due to emissions from the Paris agglomeration are noticed close to the agglomeration at various length scales: several tens (for primary OA) to hundreds (for SI-SOA and ASOA) of kilometers from the Paris agglomeration. In addition, BSOA (SOA formed from biogenic VOC precursors) is an important contributor to regional OA levels (inside and outside the Paris plume).

Primary sources and secondary formation of organic aerosols in Beijing, China.

PubMed

Guo, Song; Hu, Min; Guo, Qingfeng; Zhang, Xin; Zheng, Mei; Zheng, Jun; Chang, Chih Chung; Schauer, James J; Zhang, Renyi

2012-09-18

Ambient aerosol samples were collected at an urban site and an upwind rural site of Beijing during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region) summer field campaign. Contributions of primary particles and secondary organic aerosols (SOA) were estimated by chemical mass balance (CMB) modeling and tracer-yield method. The apportioned primary and secondary sources explain 73.8% ± 9.7% and 79.6% ± 10.1% of the measured OC at the urban and rural sites, respectively. Secondary organic carbon (SOC) contributes to 32.5 ± 15.9% of the organic carbon (OC) at the urban site, with 17.4 ± 7.6% from toluene, 9.7 ± 5.4% from isoprene, 5.1 ± 2.0% from α-pinene, and 2.3 ± 1.7% from β-caryophyllene. At the rural site, the secondary sources are responsible for 38.4 ± 14.4% of the OC, with the contributions of 17.3 ± 6.9%, 13.9 ± 9.1%, 5.6 ± 1.9%, and 1.7 ± 1.0% from toluene, isoprene, α-pinene, and β-caryophyllene, respectively. Compared with other regions in the world, SOA in Beijing is less aged, but the concentrations are much higher; between the sites, SOA is more aged and affected by regional transport at the urban site. The high SOA loading in Beijing is probably attributed to the high regional SOC background (~2 μg m(-3)). The toluene SOC concentration is high and comparable at the two sites, implying that some anthropogenic components, at least toluene SOA, are widespread in Beijing and represents a major factor in affecting the regional air quality. The aerosol gaseous precursor concentrations and temperature correlate well with SOA, both affecting SOA formation. The significant SOA enhancement with increasing water uptake and acidification indicates that the aqueous-phase reactions are largely responsible SOA formation in Beijing.

SOA governance in healthcare organisations.

PubMed

Koumaditis, Konstantinos; Themistocleous, Marinos; Vassilakopoulos, Georgios

2013-01-01

Service Oriented Architecture (SOA) is increasingly adopted by many sectors, including healthcare. Due to the nature of healthcare systems there is a need to increase SOA adoption success rates as the non integrated nature of healthcare systems is responsible for medical errors that cause the loss of tens of thousands patients per year. Following our previous research [1] we propose that SOA governance is a critical success factor for SOA success in healthcare. Literature reports multiple SOA governance models that have limitations and they are confusing. In addition to this, there is a lack of healthcare specific SOA governance models. This highlights a literature void and thus the purpose of this paper is to proposed a healthcare specific SOA governance framework.

Improving the Performance of an Auditory Brain-Computer Interface Using Virtual Sound Sources by Shortening Stimulus Onset Asynchrony

PubMed Central

Sugi, Miho; Hagimoto, Yutaka; Nambu, Isao; Gonzalez, Alejandro; Takei, Yoshinori; Yano, Shohei; Hokari, Haruhide; Wada, Yasuhiro

2018-01-01

Recently, a brain-computer interface (BCI) using virtual sound sources has been proposed for estimating user intention via electroencephalogram (EEG) in an oddball task. However, its performance is still insufficient for practical use. In this study, we examine the impact that shortening the stimulus onset asynchrony (SOA) has on this auditory BCI. While very short SOA might improve its performance, sound perception and task performance become difficult, and event-related potentials (ERPs) may not be induced if the SOA is too short. Therefore, we carried out behavioral and EEG experiments to determine the optimal SOA. In the experiments, participants were instructed to direct attention to one of six virtual sounds (target direction). We used eight different SOA conditions: 200, 300, 400, 500, 600, 700, 800, and 1,100 ms. In the behavioral experiment, we recorded participant behavioral responses to target direction and evaluated recognition performance of the stimuli. In all SOA conditions, recognition accuracy was over 85%, indicating that participants could recognize the target stimuli correctly. Next, using a silent counting task in the EEG experiment, we found significant differences between target and non-target sound directions in all but the 200-ms SOA condition. When we calculated an identification accuracy using Fisher discriminant analysis (FDA), the SOA could be shortened by 400 ms without decreasing the identification accuracies. Thus, improvements in performance (evaluated by BCI utility) could be achieved. On average, higher BCI utilities were obtained in the 400 and 500-ms SOA conditions. Thus, auditory BCI performance can be optimized for both behavioral and neurophysiological responses by shortening the SOA. PMID:29535602

Speciation of organic fractions does matter for aerosol source apportionment. Part 2: Intensive short-term campaign in the Paris area (France).

PubMed

Srivastava, D; Favez, O; Bonnaire, N; Lucarelli, F; Haeffelin, M; Perraudin, E; Gros, V; Villenave, E; Albinet, A

2018-09-01

The present study aimed at performing PM 10 source apportionment, using positive matrix factorization (PMF), based on filter samples collected every 4h at a sub-urban station in the Paris region (France) during a PM pollution event in March 2015 (PM 10 >50μgm -3 for several consecutive days). The PMF model allowed to deconvolve 11 source factors. The use of specific primary and secondary organic molecular markers favoured the determination of common sources such as biomass burning and primary traffic emissions, as well as 2 specific biogenic SOA (marine+isoprene) and 3 anthropogenic SOA (nitro-PAHs+oxy-PAHs+phenolic compounds oxidation) factors. This study is probably the first one to report the use of methylnitrocatechol isomers as well as 1-nitropyrene to apportion secondary OA linked to biomass burning emissions and primary traffic emissions, respectively. Secondary organic carbon (SOC) fractions were found to account for 47% of the total OC. The use of organic molecular markers allowed the identification of 41% of the total SOC composed of anthropogenic SOA (namely, oxy-PAHs, nitro-PAHs and phenolic compounds oxidation, representing 15%, 9%, 11% of the total OC, respectively) and biogenic SOA (marine+isoprene) (6% in total). Results obtained also showed that 35% of the total SOC originated from anthropogenic sources and especially PAH SOA (oxy-PAHs+nitro-PAHs), accounting for 24% of the total SOC, highlighting its significant contribution in urban influenced environments. Anthropogenic SOA related to nitro-PAHs and phenolic compounds exhibited a clear diurnal pattern with high concentrations during the night indicating the prominent role of night-time chemistry but with different chemical processes involved. Copyright © 2018 Elsevier B.V. All rights reserved.

Word Frequency Effects in Dual-Task Studies Using Lexical Decision and Naming as Task 2

NASA Technical Reports Server (NTRS)

Remington, Roger W.; McCann, Robert S.; VanSelst, Mark; Shafto, Michael G. (Technical Monitor)

1997-01-01

Word frequency effects in dual-task lexical decision are variously reported to be additive or underadditive across SOA. We replicate and extend earlier lexical decision studies and find word frequency to be additive across SOA. To more directly capture lexical processing, we examine dual-task naming. Once again, we find word frequency to be additive across SOA. Lexical processing appears to be constrained by central processing limitations.

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

DOE PAGES

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

2015-05-26

Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidationmore » of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model–measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model–measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the recent parameterizations overpredict urban SOA formation at long photochemical ages (≈ 3 days) compared to observations from multiple sites, which can lead to problems in regional and especially global modeling. However, reducing IVOC emissions by one-half in the model to better match recent IVOC measurements improves SOA predictions at these long photochemical ages. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Measured polycyclic aromatic hydrocarbons (naphthalenes) contribute 0.7% of the modeled SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16–27, 35–61, and 19–35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(±3) %. The relative contribution of each source is uncertain by almost a factor of 2 depending on the parameterization used. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μg m −3 is also present due to the long-distance transport of highly aged OA, likely with a substantial contribution from regional biogenic SOA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies and which is higher on weekends. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr −1 of SOA globally, or 17% of global SOA, one-third of which is likely to be non-fossil.« less

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

NASA Astrophysics Data System (ADS)

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

2015-05-01

Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model-measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model-measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the recent parameterizations overpredict urban SOA formation at long photochemical ages (~ 3 days) compared to observations from multiple sites, which can lead to problems in regional and especially global modeling. However, reducing IVOC emissions by one-half in the model to better match recent IVOC measurements improves SOA predictions at these long photochemical ages. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Measured polycyclic aromatic hydrocarbons (naphthalenes) contribute 0.7% of the modeled SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16-27, 35-61, and 19-35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(±3) %. The relative contribution of each source is uncertain by almost a factor of 2 depending on the parameterization used. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μg m-3 is also present due to the long-distance transport of highly aged OA, likely with a substantial contribution from regional biogenic SOA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies and which is higher on weekends. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr-1 of SOA globally, or 17% of global SOA, one-third of which is likely to be non-fossil.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidationmore » of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model–measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model–measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the recent parameterizations overpredict urban SOA formation at long photochemical ages (≈ 3 days) compared to observations from multiple sites, which can lead to problems in regional and especially global modeling. However, reducing IVOC emissions by one-half in the model to better match recent IVOC measurements improves SOA predictions at these long photochemical ages. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Measured polycyclic aromatic hydrocarbons (naphthalenes) contribute 0.7% of the modeled SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16–27, 35–61, and 19–35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(±3) %. The relative contribution of each source is uncertain by almost a factor of 2 depending on the parameterization used. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μg m −3 is also present due to the long-distance transport of highly aged OA, likely with a substantial contribution from regional biogenic SOA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies and which is higher on weekends. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr −1 of SOA globally, or 17% of global SOA, one-third of which is likely to be non-fossil.« less

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

PubMed Central

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

2012-01-01

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

Photosensitized Formation of Secondary Organic Aerosols above the Air/Water Interface

PubMed Central

2016-01-01

In this study, we evaluated photosensitized chemistry at the air–sea interface as a source of secondary organic aerosols (SOA). Our results show that, in addition to biogenic emissions, abiotic processes could also be important in the marine boundary layer. Photosensitized production of marine secondary organic aerosol was studied in a custom-built multiphase atmospheric simulation chamber. The experimental chamber contained water, humic acid (1–10 mg L–1) as a proxy for dissolved organic matter, and nonanoic acid (0.1–10 mM), a fatty acid proxy which formed an organic film at the air–water interface. Dark secondary reaction with ozone after illumination resulted in SOA particle concentrations in excess of 1000 cm–3, illustrating the production of unsaturated compounds by chemical reactions at the air–water interface. SOA numbers via photosensitization alone and in the absence of ozone did not exceed background levels. From these results, we derived a dependence of SOA numbers on nonanoic acid surface coverage and dissolved organic matter concentration. We present a discussion on the potential role of the air–sea interface in the production of atmospheric organic aerosol from photosensitized origins. PMID:27434860

SOA formation from gasoline vehicles: from the tailpipe to the atmosphere

NASA Astrophysics Data System (ADS)

Robinson, A. L.; Zhao, Y.; Lambe, A. T.; Saleh, R.; Saliba, G.; Tkacik, D. S.

2017-12-01

Secondary organic aerosol (SOA) formation from gasoline vehicles has been indicated as an important source of atmospheric SOA, but its contribution to atmospheric SOA is loosely constrained due to the lack of measurements to link SOA formation from the tailpipe to atmospheric SOA. In this study, we determine the contribution of SOA formation based on measurements made with a Potential Aerosol Mass (PAM) oxidation flow reactor by oxidizing vehicular exhaust and ambient air. We first investigate SOA formation from dilute gasoline-vehicle exhaust during chassis dynamometer testing. The test fleet consists of both vehicles equipped with gasoline direct injection engines (GDI vehicles) and those equipped with port fuel injection engines (PFI vehicles). These vehicles span a wide range of emissions standards from Tier0 to Super Ultra-Low Emission Vehicles (SULEV). Then, we combine our measurements of SOA formation from gasoline vehicles during dynamometer testing with measurements of SOA formation using a PAM reactor conducted in a highway tunnel and in the unban atmosphere. Comparisons of SOA formation between these datasets enable us to quantitatively connect SOA formation from individual vehicles, to a large on-road fleet, and to the atmosphere. To facilitate the comparisons, we account for the effects of both the photochemical age and dilution on SOA formation. Our results show that SOA formation from gasoline vehicles can contribute over 50% of fossil fuel-related atmospheric SOA in the Los Angeles area. Furthermore, our results demonstrate that the tightening of emissions standards effectively reduces SOA formation from gasoline vehicles, including both PFI and GDI vehicles, if the atmospheric chemistry regime remains the same.

Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions on SOA Loadings and their Spatial and Temporal Evolution in the Atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrivastava, ManishKumar B.; Zelenyuk, Alla; Imre, Dan

2013-04-27

Recent laboratory and field measurements by a number of groups show that secondary organic aerosol (SOA) evaporates orders of magnitude slower than traditional models assume. In addition, chemical transport models using volatility basis set (VBS) SOA schemes neglect gas-phase fragmentation reactions, which are known to be extremely important. In this work, we present modeling studies to investigate the implications of non-evaporating SOA and gas-phase fragmentation reactions. Using the 3-D chemical transport model, WRF-Chem, we show that previous parameterizations, which neglect fragmentation during multi-generational gas-phase chemistry of semi-volatile/inter-mediate volatility organics ("aging SIVOC"), significantly over-predict SOA as compared to aircraft measurements downwindmore » of Mexico City. In sharp contrast, the revised models, which include gas-phase fragmentation, show much better agreement with measurements downwind of Mexico City. We also demonstrate complex differences in spatial SOA distributions when we transform SOA to non-volatile secondary organic aerosol (NVSOA) to account for experimental observations. Using a simple box model, we show that for same amount of SOA precursors, earlier models that do not employ multi-generation gas-phase chemistry of precursors ("non-aging SIVOC"), produce orders of magnitude lower SOA than "aging SIVOC" parameterizations both with and without fragmentation. In addition, traditional absorptive partitioning models predict almost complete SOA evaporation at farther downwind locations for both "non-aging SIVOC" and "aging SIVOC" with fragmentation. In contrast, in our revised approach, SOA transformed to NVSOA implies significantly higher background concentrations as it remains in particle phase even under highly dilute conditions. This work has significant implications on understanding the role of multi-generational chemistry and NVSOA formation on SOA evolution in the atmosphere.« less

Chemical transport model simulations of organic aerosol in southern California: model evaluation and gasoline and diesel source contributions

NASA Astrophysics Data System (ADS)

Jathar, Shantanu H.; Woody, Matthew; Pye, Havala O. T.; Baker, Kirk R.; Robinson, Allen L.

2017-03-01

Gasoline- and diesel-fueled engines are ubiquitous sources of air pollution in urban environments. They emit both primary particulate matter and precursor gases that react to form secondary particulate matter in the atmosphere. In this work, we updated the organic aerosol module and organic emissions inventory of a three-dimensional chemical transport model, the Community Multiscale Air Quality Model (CMAQ), using recent, experimentally derived inputs and parameterizations for mobile sources. The updated model included a revised volatile organic compound (VOC) speciation for mobile sources and secondary organic aerosol (SOA) formation from unspeciated intermediate volatility organic compounds (IVOCs). The updated model was used to simulate air quality in southern California during May and June 2010, when the California Research at the Nexus of Air Quality and Climate Change (CalNex) study was conducted. Compared to the Traditional version of CMAQ, which is commonly used for regulatory applications, the updated model did not significantly alter the predicted organic aerosol (OA) mass concentrations but did substantially improve predictions of OA sources and composition (e.g., POA-SOA split), as well as ambient IVOC concentrations. The updated model, despite substantial differences in emissions and chemistry, performed similar to a recently released research version of CMAQ (Woody et al., 2016) that did not include the updated VOC and IVOC emissions and SOA data. Mobile sources were predicted to contribute 30-40 % of the OA in southern California (half of which was SOA), making mobile sources the single largest source contributor to OA in southern California. The remainder of the OA was attributed to non-mobile anthropogenic sources (e.g., cooking, biomass burning) with biogenic sources contributing to less than 5 % to the total OA. Gasoline sources were predicted to contribute about 13 times more OA than diesel sources; this difference was driven by differences in SOA production. Model predictions highlighted the need to better constrain multi-generational oxidation reactions in chemical transport models.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

Secondary organic aerosol (SOA) accounts for 20-70% of atmospheric fine aerosol. NOx plays crucial roles in SOA formation and consequently affects the composition and yield of SOA. SOA component speciation is incomplete due to its complex composition of polar oxygenated and multifunctional species. In this study, ultrahigh resolution mass spectrometry (UHR MS) was applied to improve the understanding of NOx effects on biogenic SOA formation by identifying the elemental composition of SOA. Additional research aim was to investigate oligomer components that are considered as a driving force for SOA formation and growth. In this study α-pinene SOA from photochemical reaction was examined. SOA formation was performed in the absence and presence of NOx at dry condition (<5% RH) of room temperature (~25oC) in ~8 m3 KNU smog chamber. SOA was collected on Teflon-coated glass fiber filter, which was extracted using acetonitrile and analyzed by ultrahigh resolution 15T FT-ICR MS. UHR MS data were interpreted in various ways including molecular formula, Kendrick diagram, van Krevelen diagram, and double bond equivalent values. Substantially large fractions of them are nitrogen containing species. Thousands of individual species of SOA were identified. For SOA in the absence of NOx. intensity normalized mean O/C, H/C, N/C, OM/OC ratios were 0.43, 1.52, 0.02, and 1.68, respectively. For SOA in the presence of NOx, those ratios were 0.52, 0.95, 0.08, and 1.48, respectively. 4 different oligomer formation mechanisms (addition, H abstraction, hydrolysis and de-hydrolysis reaction) were examined on the basis of SOA compositions. Detailed discussion will be presented on the molecular structure and building block of oligomers in SOA as well as the evolution of individual elemental composition by multi-generation reactions. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2011-01350000).

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

Four different parameterizations for the formation and evolution of secondary organic aerosol (SOA) are evaluated using a 0-D box model representing the Los Angeles Metropolitan Region during the CalNex 2010 field campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model-measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model/measurement agreement for mass concentration. When comparing the three parameterizations, the Grieshop et al. (2009) parameterization more accurately reproduces both the SOA mass concentration and oxygen-to-carbon ratio inside the urban area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the parameterizations over-predict urban SOA formation at long photochemical ages (≈ 3 days) compared to observations from multiple sites, which can lead to problems in regional and global modeling. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Polycyclic aromatic hydrocarbons (PAHs) are less important precursors and contribute less than 4% of the SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16-27, 35-61, and 19-35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71 (±3) %. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μg m-3 is also present due to the long distance transport of highly aged OA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr-1 of SOA globally, or 17% of global SOA, 1/3 of which is likely to be non-fossil.

SOA Measurements vs. Models: A Status Report

NASA Astrophysics Data System (ADS)

Jimenez, Jose-Luis; de Gouw, Joost; Hodzic, Alma

2010-05-01

The advent of fast and chemically-resolved organic aerosol (OA) and VOC measurements in the last decade has allowed more detailed model-measurement comparisons for OA and secondary OA (SOA). Large model underpredictions have been reported for SOA at many locations, but this is not always the case. Here we summarize the patterns emerging from studies to date, focusing on studies that use highly time and/or chemically resolved OA measurements. The model-measurement comparisons exhibit clear patterns depending on the region of the atmosphere. • At least 8 studies have reported a large (x5-10) underestimation of SOA for polluted regions when using traditional models (those developed until ~2006) (Heald GRL05, Volkamer GRL06, Johnson ACP06, Kleinman ACP08, Matsui JGR09, Dzepina ACP09, Hodzic ACP09, Tsimpidi ACP09). This is especially obvious when models are evaluated with the ΔOA/ΔCO ratio. • Close to pollution sources, discrepancies of an order-of-magnitude in SOA lead to smaller discrepancies (often x2-3) for total OA due to the presence of primary OA (de Gouw EST09). Such OA discrepancies have been repeatedly observed (e.g. Vutukuru JGR06, McKeen JGR07&09, Heald JGR07, Fast ACP09, Hodzic ACP09). • The discrepancy is reduced when recently-updated yields for aromatics (Ng ACP07) and SOA from glyoxal (Volkamer GRL07) are used, and is eliminated when using SOA formation from S/IVOC (Robinson Sci07) although with an overprediction of SOA at long aging times (Dzepina ACP09; Hodzic ACP10), especially with the Grieshop (ACP09) update of the Robison mechanism (Hodzic10). It is not clear whether the urban discrepancy is removed for the right reasons. • 4 evaluations of biogenic SOA formed in unpolluted regions find reasonable agreement between SOA from traditional models and field measurements (Tunved Sci06; Hodzic ACP09; Chen GRL09; Slowik ACPD09). One evaluation reports a significant underprediction (Capes ACP09), although the amount of precursor reacted was difficult to ascertain for that case. The difference with the systematic underprediction observed for anthropogenic SOA may be due to the lack of primary S/IVOC in biogenic emissions, or to other reasons (NOx, SO2, POA, etc.). • Comparisons for biogenic SOA formed in polluted regions are more complex. Several studies have reported a lack of clear influence of biogenic VOCs in SOA formation in polluted regions (de Gouw JGR05, GRL09; Weber JGR07; Bahreini JGR09), but 14C studies suggest a large fraction of modern C (Weber JGR07). Synergistic effects of pollution and BVOCs appear likely (e.g. de Gouw JGR05; Weber JGR07; Goldstein PNAS09). • Net SOA formation (above the POA mass emission) from biomass burning appears very variable in the field (Capes JGR09; Yokelson ACP09; DeCarlo ACPD10) as well as in the laboratory (Ortega AGU09; Prevot AGU09; Hennigan in prep.), likely due flaming vs. smoldering fraction and biomass identity, and perhaps also to prompt SOA formation triggered by HONO photolysis. Several studies report significant SOA formation, given enough photochemical processing. Models based on traditional precursors appear to underpredict SOA from BB sources (Grieshop ACP09; Hodzic ACP09). • The very large SOA source in the free troposphere postulated by Heald (GRL05) has not been confirmed nor disproved by later studies. Dunlea (ACP09) did not find evidence of this source across the Pacific near North America, though precipitation removal precludes any strong conclusions. However Carlton (EST09) reported better comparisons after implementing in-cloud SOA formation. • Evaluation of models against measured total OA or OC or SOA levels is thoroughly unsufficient to model verification. OA measurements can be matched through a large number of mechanism permutations, but investigators need to push further to determine whether the agreement is for the right reasons. Future model evaluations should compare POA, SOA precursors, OVOCs, oxidants, and boundary conditions. Multiple OA measurements (WSOC, OC, AMS, molecular tracers, 14C, etc.) are necessary to overcome the limitations of any one method. Measurements of semivolatile species are critically needed to constrain models. These advanced diagnostics are needed in order to build confidence on SOA models, which is needed to predict the changes in SOA concentrations in response to precursor and climate changes.

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

NASA Astrophysics Data System (ADS)

Smith, J.; Anastasio, C.

2014-12-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hodzic, Alma; Jimenez, Jose L.

2015-04-09

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

Supercritical Fluid Extraction of Biogenic SOA in Northern Michigan

NASA Astrophysics Data System (ADS)

Flores, R. M.; Doskey, P. V.; Perlinger, J. A.

2010-12-01

Secondary organic aerosols (SOA) are formed by photooxidation of volatile organic compounds (VOCs) and nucleation and condensation of the oxygenated products. On a global scale, monoaromatic hydrocarbons of anthropogenic origin are estimated to be the source of 12% of the SOA while biogenic emissions of isoprene (C5H8), monoterpenes (C10H16), and sesquiterpenes (C15H24) are estimated to be the source of 46, 29 and 7% of SOA, respectively. The functional groups of organic substances comprising SOA (i.e., hydroxyl, carbonyl, carboxylic acid, sulfate, and nitrate) complicate sample processing, analysis, and identification of the characteristic aerosol products of VOC oxidation pathways. Only a very small fraction of the organic molecular species in SOA have been identified due to the complexity of precursor oxidation reactions and the need for (1) methodologies that are less labor intensive and suitable for thermally labile compounds and (2) analytic instrumentation that provides more complete resolution of complex mixtures for sensitive detection of molecular species. Extraction techniques commonly used include solvent extraction, which requires large amounts of solvent and is labor intensive and thermal desorption, which evolves organic substances from aerosol at temperatures not suitable for thermally labile compounds. A promising technique that does not involve sample processing with solvents or high temperatures is supercritical fluid extraction (SFE). In this work, the composition of biogenic SOA was studied in Northern Michigan. Aerosol samples were collected on quartz fiber filters with a high-volume air sampler and extracted with supercritical CO2. Carboxylic and hydroxyl compounds were derivatized during static extraction conditions and identified by comprehensive two dimensional gas chromatography with time-of-flight mass spectrometric detection (GC×GC-TOFMS). The overall goal of the research is to couple the post-collection analytic scheme developed here with a rapid sampling technique to evaluate SOA produced from a variety of biogenic and anthropogenic sources of precursors in the Midwestern United States.

Characterizing Oxidized North American Fire Emissions and Their Aqueous/Multiphase Atmospheric Transformations Through the FIREX Campaign

NASA Astrophysics Data System (ADS)

Tomaz, S.; Cui, T.; Chen, Y.; Sexton, K.; Surratt, J. D.; Turpin, B. J.

2017-12-01

Aqueous multiphase chemistry of water-soluble organic gases (WSOGs) is now recognized to be a potential and significant source of atmospheric secondary organic aerosol (SOA). SOA formation through aqueous-phase chemistry of WSOGs, known to be present in wildfire emissions, such as glycolaldehyde or phenols, remains unclear. Furthermore, most oxidized organic constituents of biomass burning (BB) emissions still remain unidentified and may represent a major source of atmospheric aqueous SOA (aqSOA). In the present work, we investigated the chemical composition of gas-phase emissions from the combustion of several western U.S. fuels at the Fire Science Laboratory as part of FIREX, using a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) equipped with iodide reagent ion chemistry. By using the HR-ToF-CIMS, more than 50 oxygen (O)-containing and 15 nitrogen (N)-containing organic compounds were identified in the gas-phase emissions from BB of the western U.S. fuel types. Amongst these compounds, potential precursors of aqSOA were selected based on their atomic O/C ratio, water solubility, abundance and potential reactivity toward hydroxyl (OH) radical using literature data. These results indicated the high potency of BB as a source of aqSOA. We compared these results with water samples collected during the FIREX experiments, by scrubbing gaseous emissions into water using mist chamber samplers. We investigated the composition of these samples using both ion chromatography (IC) and high-resolution quadrupole time-of-flight mass spectrometry equipped with electrospray ionization (ESI-HR-QTOFMS). The presence of potential reactive compounds was evaluated by oxidizing these samples with OH radical (H2O2/UV). Known precursors of aqSOA, such as acetic and glycolic acids, were identified in those samples. The formation of low-volatility organics, such as oxalic and pyruvic acids, through OH oxidation also indicates the potential formation of aqSOA from BB emissions during wildfires.

Linking Load, Fuel, and Emission Controls to Photochemical Production of Secondary Organic Aerosol from a Diesel Engine.

PubMed

Jathar, Shantanu H; Friedman, Beth; Galang, Abril A; Link, Michael F; Brophy, Patrick; Volckens, John; Eluri, Sailaja; Farmer, Delphine K

2017-02-07

Diesel engines are important sources of fine particle pollution in urban environments, but their contribution to the atmospheric formation of secondary organic aerosol (SOA) is not well constrained. We investigated direct emissions of primary organic aerosol (POA) and photochemical production of SOA from a diesel engine using an oxidation flow reactor (OFR). In less than a day of simulated atmospheric aging, SOA production exceeded POA emissions by an order of magnitude or more. Efficient combustion at higher engine loads coupled to the removal of SOA precursors and particle emissions by aftertreatment systems reduced POA emission factors by an order of magnitude and SOA production factors by factors of 2-10. The only exception was that the retrofitted aftertreatment did not reduce SOA production at idle loads where exhaust temperatures were low enough to limit removal of SOA precursors in the oxidation catalyst. Use of biodiesel resulted in nearly identical POA and SOA compared to diesel. The effective SOA yield of diesel exhaust was similar to that of unburned diesel fuel. While OFRs can help study the multiday evolution, at low particle concentrations OFRs may not allow for complete gas/particle partitioning and bias the potential of precursors to form SOA.

Reducing secondary organic aerosol formation from gasoline vehicle exhaust

PubMed Central

Zhao, Yunliang; Saleh, Rawad; Presto, Albert A.; Gordon, Timothy D.; Drozd, Greg T.; Goldstein, Allen H.; Robinson, Allen L.

2017-01-01

On-road gasoline vehicles are a major source of secondary organic aerosol (SOA) in urban areas. We investigated SOA formation by oxidizing dilute, ambient-level exhaust concentrations from a fleet of on-road gasoline vehicles in a smog chamber. We measured less SOA formation from newer vehicles meeting more stringent emissions standards. This suggests that the natural replacement of older vehicles with newer ones that meet more stringent emissions standards should reduce SOA levels in urban environments. However, SOA production depends on both precursor concentrations (emissions) and atmospheric chemistry (SOA yields). We found a strongly nonlinear relationship between SOA formation and the ratio of nonmethane organic gas to oxides of nitrogen (NOx) (NMOG:NOx), which affects the fate of peroxy radicals. For example, changing the NMOG:NOx from 4 to 10 ppbC/ppbNOx increased the SOA yield from dilute gasoline vehicle exhaust by a factor of 8. We investigated the implications of this relationship for the Los Angeles area. Although organic gas emissions from gasoline vehicles in Los Angeles are expected to fall by almost 80% over the next two decades, we predict no reduction in SOA production from these emissions due to the effects of rising NMOG:NOx on SOA yields. This highlights the importance of integrated emission control policies for NOx and organic gases. PMID:28630318

Global distribution of particle phase state in atmospheric secondary organic aerosols

NASA Astrophysics Data System (ADS)

Shiraiwa, Manabu; Li, Ying; Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Berkemeier, Thomas; Pandis, Spyros N.; Lelieveld, Jos; Koop, Thomas; Pöschl, Ulrich

2017-04-01

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA.

Global distribution of particle phase state in atmospheric secondary organic aerosols.

PubMed

Shiraiwa, Manabu; Li, Ying; Tsimpidi, Alexandra P; Karydis, Vlassis A; Berkemeier, Thomas; Pandis, Spyros N; Lelieveld, Jos; Koop, Thomas; Pöschl, Ulrich

2017-04-21

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA.

Direct observation of aqueous secondary organic aerosol from biomass-burning emissions

PubMed Central

Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Pietrogrande, Maria Chiara; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

2016-01-01

The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the “brown” carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1–0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4–20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate. PMID:27551086

Global distribution of particle phase state in atmospheric secondary organic aerosols

PubMed Central

Shiraiwa, Manabu; Li, Ying; Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Berkemeier, Thomas; Pandis, Spyros N.; Lelieveld, Jos; Koop, Thomas; Pöschl, Ulrich

2017-01-01

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas–particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA. PMID:28429776

Secondary organic aerosol formation from isoprene photooxidation

NASA Astrophysics Data System (ADS)

Kroll, J. H.; Ng, N. L.; Murphy, S. M.; Flagan, R. C.; Seinfeld, J. H.

2005-12-01

We report chamber studies of the formation of secondary organic aerosol (SOA) from the oxidation of isoprene (2-methyl-1,3-butadiene). Isoprene is the most abundant non-methane hydrocarbon emitted into the troposphere (source strength of ~500 Tg/year), so even small SOA yields may have a large impact on global SOA production. Reactions are carried out in Caltech's dual 28 m3 Teflon chambers, and aerosol growth is monitored by a differential mobility analyzer (DMA) and an Aerodyne time-of-flight aerosol mass spectrometer (AMS). Isoprene oxidation is initiated by the UV irradiation of isoprene in the presence of hydrogen peroxide, with NO added for high-NOx experiments. These conditions ensure that isoprene oxidation is initiated by reaction with the OH radical, with negligible interference from other oxidants (ozone, nitrate radicals, and O atoms). Aerosol growth is observed under both high-NOx and low-NOx conditions, at isoprene concentrations lower than measured in previous studies (down to 8 ppb). SOA yields are found to be in the range of 1-2%. Yields exhibit a complex dependence on NOx concentration, likely a result of changes in the chemistry of organic peroxy radicals. It is shown that condensable compounds are formed from further reactions of first-generation isoprene oxidation products; the rates and products of such gas-phase reactions are at present poorly understood. Additionally, measurements of SOA composition indicate that these products undergo reactions in the aerosol phase, leading to the formation of low-volatility oligomeric products.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

SOA formation potential of emissions from soil and leaf litter.

PubMed

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

2014-01-21

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

Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

DOE PAGES

Yu, L.; Smith, J.; Laskin, A.; ...

2014-08-19

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl ( 3C*) and hydroxyl radical (·OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules aremore » identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than ·OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

Symmetric 40-Gb/s TWDM-PON with 51-dB loss budget by using a single SOA as preamplifier, booster and format converter in ONU.

PubMed

Li, Zhengxuan; Yi, Lilin; Hu, Weisheng

2014-10-06

In this paper, we propose to use a semiconductor optical amplifier (SOA) in the optical network unit (ONU) to improve the loss budget in time and wavelength division multiplexed-passive optical network (TWDM-PON) systems. The SOA boosts the upstream signal to increase the output power of the electro-absorption modulated laser (EML) and simultaneously pre-amplifies the downstream signal for sensitivity improvement. The penalty caused by cross gain modulation (XGM) effect is negligible due to the low extinction ratio (ER) of upstream signal and the large wavelength difference between upstream and downstream links. In order to achieve a higher output power, the SOA is driven into its saturation region, where the self-phase modulation (SPM) effect converts the intensity into phase information and realizes on-off-keying (OOK) to phase-shifted-keying (PSK) format conversion. In this way, the pattern effect is eliminated, which releases the requirement of gain-clamping on SOA. To further improve the loss budget of upstream link, an Erbium doped fiber amplifier (EDFA) is used in the optical line terminal (OLT) to pre-amplify the received signal. For the downstream direction, directly modulated laser (DML) is used as the laser source. Taking advantage of its carrier-less characteristic, directly modulated signal shows high tolerance to fiber nonlinearity, which could support a downstream launch power as high as + 16 dBm per channel. In addition, the signal is pre-amplified by the SOA in ONU before being detected, so the sensitivity limitation for downstream link is also removed. As a result, a truly passive symmetric 40-Gb/s TWDM-PON was demonstrated, achieving a link loss budget of 51 dB.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seinfeld, John H.

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 laboratorymore » chambers are understated or that all major organic precursors have not been identified. In this research program we are systematically exploring these possibilities.« less

Thermal decomposition in thermal desorption instruments: importance of thermogram measurements for analysis of secondary organic aerosol

NASA Astrophysics Data System (ADS)

Stark, H.; Yatavelli, R. L. N.; Thompson, S.; Kang, H.; Krechmer, J. E.; Kimmel, J.; Palm, B. B.; Hu, W.; Hayes, P.; Day, D. A.; Campuzano Jost, P.; Ye, P.; Canagaratna, M. R.; Jayne, J. T.; Worsnop, D. R.; Jimenez, J. L.

2017-12-01

Understanding the chemical composition of secondary organic aerosol (SOA) is crucial for explaining sources and fate of this important aerosol class in tropospheric chemistry. Further, determining SOA volatility is key in predicting its atmospheric lifetime and fate, due to partitioning from and to the gas phase. We present three analysis approaches to determine SOA volatility distributions from two field campaigns in areas with strong biogenic emissions, a Ponderosa pine forest in Colorado, USA, from the BEACHON-RoMBAS campaign, and a mixed forest in Alabama, USA, from the SOAS campaign. We used a high-resolution-time-of-flight chemical ionization mass spectrometer (CIMS) for both campaigns, equipped with a micro-orifice volatilization impactor (MOVI) inlet for BEACHON and a filter inlet for gases and aerosols (FIGAERO) for SOAS. These inlets allow near simultaneous analysis of particle and gas-phase species by the CIMS. While gas-phase species are directly measured without heating, particles undergo thermal desorption prior to analysis. Volatility distributions can be estimated in three ways: (1) analysis of the thermograms (signal vs. temperature); (2) via partitioning theory using the gas- and particle-phase measurements; (3) from measured chemical formulas via a group contribution model. Comparison of the SOA volatility distributions from the three methods shows large discrepancies for both campaigns. Results from the thermogram method are the most consistent of the methods when compared with independent AMS-thermal denuder measurements. The volatility distributions estimated from partitioning measurements are very narrow, likely due to signal-to-noise limits in the measurements. The discrepancy between the formula and the thermogram methods indicates large-scale thermal decomposition of the SOA species. We will also show results of citric acid thermal decomposition, where, in addition to the mass spectra, measurements of CO, CO2 and H2O were made, showing thermal decomposition of up to 65% of the citric acid molecules.

A synthesis theory for self-oscillating adaptive systems /SOAS/

NASA Technical Reports Server (NTRS)

Horowitz, I.; Smay, J.; Shapiro, A.

1974-01-01

A quantitative synthesis theory is presented for the Self-Oscillating Adaptive System (SOAS), whose nonlinear element has a static, odd character with hard saturation. The synthesis theory is based upon the quasilinear properties of the SOAS to forced inputs, which permits the extension of quantitative linear feedback theory to the SOAS. A reasonable definition of optimum design is shown to be the minimization of the limit cycle frequency. The great advantages of the SOAS is its zero sensitivity to pure gain changes. However, quasilinearity and control of the limit cycle amplitude at the system output, impose additional constraints which partially or completely cancel this advantage, depending on the numerical values of the design parameters. By means of narrow-band filtering, an additional factor is introduced which permits trade-off between filter complexity and limit cycle frequency minimization.

Composition and formation of organic aerosol particles in the Amazon

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

Transformation of logwood combustion emissions in a smog chamber: formation of secondary organic aerosol and changes in the primary organic aerosol upon daytime and nighttime aging

NASA Astrophysics Data System (ADS)

Tiitta, Petri; Leskinen, Ari; Hao, Liqing; Yli-Pirilä, Pasi; Kortelainen, Miika; Grigonyte, Julija; Tissari, Jarkko; Lamberg, Heikki; Hartikainen, Anni; Kuuspalo, Kari; Kortelainen, Aki-Matti; Virtanen, Annele; Lehtinen, Kari E. J.; Komppula, Mika; Pieber, Simone; Prévôt, André S. H.; Onasch, Timothy B.; Worsnop, Douglas R.; Czech, Hendryk; Zimmermann, Ralf; Jokiniemi, Jorma; Sippula, Olli

2016-10-01

Organic aerosols (OA) derived from small-scale wood combustion emissions are not well represented by current emissions inventories and models, although they contribute substantially to the atmospheric particulate matter (PM) levels. In this work, a 29 m3 smog chamber in the ILMARI facility of the University of Eastern Finland was utilized to investigate the formation of secondary organic aerosol (SOA) from a small-scale modern masonry heater commonly used in northern Europe. Emissions were oxidatively aged in the smog chamber for a variety of dark (i.e., O3 and NO3) and UV (i.e., OH) conditions, with OH concentration levels of (0.5-5) × 106 molecules cm-3, achieving equivalent atmospheric aging of up to 18 h. An aerosol mass spectrometer characterized the direct OA emissions and the SOA formed from the combustion of three wood species (birch, beech and spruce) using two ignition processes (fast ignition with a VOC-to-NOx ratio of 3 and slow ignition with a ratio of 5).Dark and UV aging increased the SOA mass fraction with average SOA productions 2.0 times the initial OA mass loadings. SOA enhancement was found to be higher for the slow ignition compared with fast ignition conditions. Positive matrix factorization (PMF) was used to separate SOA, primary organic aerosol (POA) and their subgroups from the total OA mass spectra. PMF analysis identified two POA and three SOA factors that correlated with the three major oxidizers: ozone, the nitrate radical and the OH radical. Organonitrates (ONs) were observed to be emitted directly from the wood combustion and additionally formed during oxidation via NO3 radicals (dark aging), suggesting small-scale wood combustion may be a significant ON source. POA was oxidized after the ozone addition, forming aged POA, and after 7 h of aging more than 75 % of the original POA was transformed. This process may involve evaporation and homogeneous gas-phase oxidation as well as heterogeneous oxidation of particulate organic matter. The results generally prove that logwood burning emissions are the subject of intensive chemical processing in the atmosphere, and the timescale for these transformations is relatively short, i.e., hours.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Diagnostic Air Quality Model Evaluation of Source-Specific ...

EPA Pesticide Factsheets

Ambient measurements of 78 source-specific tracers of primary and secondary carbonaceous fine particulate matter collected at four midwestern United States locations over a full year (March 2004–February 2005) provided an unprecedented opportunity to diagnostically evaluate the results of a numerical air quality model. Previous analyses of these measurements demonstrated excellent mass closure for the variety of contributing sources. In this study, a carbon-apportionment version of the Community Multiscale Air Quality (CMAQ) model was used to track primary organic and elemental carbon emissions from 15 independent sources such as mobile sources and biomass burning in addition to four precursor-specific classes of secondary organic aerosol (SOA) originating from isoprene, terpenes, aromatics, and sesquiterpenes. Conversion of the source-resolved model output into organic tracer concentrations yielded a total of 2416 data pairs for comparison with observations. While emission source contributions to the total model bias varied by season and measurement location, the largest absolute bias of −0.55 μgC/m3 was attributed to insufficient isoprene SOA in the summertime CMAQ simulation. Biomass combustion was responsible for the second largest summertime model bias (−0.46 μgC/m3 on average). Several instances of compensating errors were also evident; model underpredictions in some sectors were masked by overpredictions in others. The National Exposure Research L

Diagnostic air quality model evaluation of source-specific primary and secondary fine particulate carbon.

PubMed

Napelenok, Sergey L; Simon, Heather; Bhave, Prakash V; Pye, Havala O T; Pouliot, George A; Sheesley, Rebecca J; Schauer, James J

2014-01-01

Ambient measurements of 78 source-specific tracers of primary and secondary carbonaceous fine particulate matter collected at four midwestern United States locations over a full year (March 2004-February 2005) provided an unprecedented opportunity to diagnostically evaluate the results of a numerical air quality model. Previous analyses of these measurements demonstrated excellent mass closure for the variety of contributing sources. In this study, a carbon-apportionment version of the Community Multiscale Air Quality (CMAQ) model was used to track primary organic and elemental carbon emissions from 15 independent sources such as mobile sources and biomass burning in addition to four precursor-specific classes of secondary organic aerosol (SOA) originating from isoprene, terpenes, aromatics, and sesquiterpenes. Conversion of the source-resolved model output into organic tracer concentrations yielded a total of 2416 data pairs for comparison with observations. While emission source contributions to the total model bias varied by season and measurement location, the largest absolute bias of -0.55 μgC/m(3) was attributed to insufficient isoprene SOA in the summertime CMAQ simulation. Biomass combustion was responsible for the second largest summertime model bias (-0.46 μgC/m(3) on average). Several instances of compensating errors were also evident; model underpredictions in some sectors were masked by overpredictions in others.

SNR of swept SLEDs and swept lasers for OCT (Conference Presentation)

NASA Astrophysics Data System (ADS)

Johnson, Bart C.; Atia, Walid; Flanders, Dale; Kuznetsov, Mark; Goldberg, Brian; Kemp, Nate; Whitney, Peter

2016-03-01

A back-to-back comparison of a tunable narrow-band SLED (TSLED) and a swept laser are made for OCT applications. Both are 1310 nm sources sweeping at 50 kHz over a 100 nm tuning range and have similar coherence lengths. The TSLED consists of a seed SOA and two amplification SOAs. The ASE is filtered twice by a tunable MEMS Fabry Perot in a polarization multiplexed double-pass arrangement on either side of the middle SOA. This allows very long coherence lengths to be achieved. A fundamental issue with a SLED is that the RIN is proportional to 1/Linewidth, meaning that the longer the coherence length, the higher the RIN. High RIN also leads to increased clock jitter. Most swept source SNR calculations assume that the noise is independent of the amplitude of the signal light: The higher the signal, the higher the SNR. We show that in the case of the TSLED, that the high signal RIN and clock jitter give rise to additional noises that scale with signal power. This leads to an SNR limit in the case of the TSLED: The higher the signal, the higher the noise, so the SNR reaches a limit. While the TSLED has respectable sensitivity, the SNR limit causes noise streaks in an image where the A-line has a high reflectivity point. The laser, which is shot noise limited, does not exhibit this effect. This is illustrated with SNR data and side-by-side images taken with the two sources.

Molecular composition of organic aerosol over an agricultural site in North China Plain: Contribution of biogenic sources to PM2.5

NASA Astrophysics Data System (ADS)

Li, Xingru; Liu, Yusi; Li, Dong; Wang, Guoan; Bai, Yu; Diao, Heling; Shen, Rongrong; Hu, Bo; Xin, Jinyuan; Liu, Zirui; Wang, Yuesi; Guo, Xueqing; Wang, Lili

2017-09-01

Sugars and biogenic secondary organic aerosols (BSOAs) are substantial components of particulate organic matter, which affects regional and global air quality and climate. Fine particulate matter (PM2.5) samples were collected from 20 June to 30 July 2015 on a diurnal/nocturnal cycle in Yucheng, China in the North China Plain. The PM2.5 samples were analyzed for sugars and SOA tracers derived from biogenic volatile organic compounds (BVOCs) and other compounds, such as water soluble ions, element carbon (EC), organic carbon (OC) and water soluble organic carbon (WSOC). The quantified organic components accounted for 4.7% and 0.4% of the OC and PM2.5, respectively. SOA tracer concentrations were weakly higher during the day (101.6 ± 61.7 ng m-3) than at night (90.2 ± 41.5 ng m-3)(t = 0.610, P > 0.05), whereas sugar showed higher concentrations at night (227.0 ± 196.9 ng m-3) than during the day (177.9 ± 145.4 ng m-3)(t = -1.329, P > 0.05). Anhydro sugar (mannosan, galactosan, and levoglucosan) were the main components of the measured sugars and accounted for 58.5% and 75.6% of the daytime and nighttime measurements. The levoglucosan/mannosan ratios were 20.2 ± 12.9 and 17.6 ± 9.1 for the daytime and nighttime samples, respectively, indicating that crop residues, herbaceous plants and hardwood were the dominant types of biomass burned in the Yucheng region. Isoprene SOA tracers exhibited the highest levels among the measured SOA tracers, followed by α-pinene SOA tracers. The concentration of BSOC estimated using the tracer method was 3.9-1817.5 ng C m-3 and accounted for 0.1-26.0% of the OC. A clear negative correlation (r = 0.53) between isoprene-derived SOA and in-situ pH demonstrated that acid-catalyzed heterogeneous reactions can significantly enhance SOA mass. In addition, isoprene-derived SOA increased with the relative humidity (RH) when the RH was lower than 50%, whereas it decreased when the RH was higher than 50%.

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

NASA Astrophysics Data System (ADS)

Flores, Rosa M.; Doskey, Paul V.

2016-04-01

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

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

NASA Astrophysics Data System (ADS)

Pan, Xiang

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

Mapping gas-phase organic reactivity and concomitant secondary organic aerosol formation: chemometric dimension reduction techniques for the deconvolution of complex atmospheric data sets

NASA Astrophysics Data System (ADS)

Wyche, K. P.; Monks, P. S.; Smallbone, K. L.; Hamilton, J. F.; Alfarra, M. R.; Rickard, A. R.; McFiggans, G. B.; Jenkin, M. E.; Bloss, W. J.; Ryan, A. C.; Hewitt, C. N.; MacKenzie, A. R.

2015-07-01

Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modelling in order to ultimately identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least-squares discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Results show that "model" biogenic oxidative systems can be successfully separated and classified according to their oxidation products. Furthermore, a holistic view of results obtained across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidised gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i.e. toluene) oxidation and "more realistic" plant mesocosm systems, demonstrates that such an ensemble of chemometric mapping has the potential to be used for the classification of more complex spectra of unknown origin. More specifically, the addition of mesocosm data from fig and birch tree experiments shows that isoprene and monoterpene emitting sources, respectively, can be mapped onto the statistical model structure and their positional vectors can provide insight into their biological sources and controlling oxidative chemistry. The potential to extend the methodology to the analysis of ambient air is discussed using results obtained from a zero-dimensional box model incorporating mechanistic data obtained from the Master Chemical Mechanism (MCMv3.2). Such an extension to analysing ambient air would prove a powerful asset in assisting with the identification of SOA sources and the elucidation of the underlying chemical mechanisms involved.

Contrasting Secondary Organic Aerosol Formation in Aerosol Liquid Water During Summer and Winter

NASA Astrophysics Data System (ADS)

El-Sayed, M.; Hennigan, C. J.

2017-12-01

In this study, we characterize the formation of aqueous secondary organic aerosols (aqSOA) in the eastern United States during summer and winter. The aim was to identify the main factors affecting the reversible and irreversible uptake of water-soluble organic gases to aerosol liquid water under variable influence from biogenic and anthropogenic sources. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was measured in Baltimore, MD using a recently developed on-line method. The formation of aqSOA was observed during the summer and the winter; however, the amount of aqSOA varied significantly between the two seasons, as did the reversible and irreversible nature of the uptake. While the availability of aerosol liquid water (ALW) predominantly controlled aqSOA formation in the summer, wintertime aqSOA formation was limited by precursor VOCs as well. During the summer, aqSOA formation was tightly linked with isoprene oxidation, while the aqSOA formed in the winter was associated with biomass burning. Irreversible aqSOA was formed in both seasons; however, reversible aqSOA was only observed in the summer. Overall, these results demonstrate the importance of multi-phase chemistry in aerosol formation and underscore the significance of soluble organic gases partitioning to aerosol water both reversibly and irreversibly.

Constraining the Volatility Distributions and Possible Diffusion Limitations of Secondary Organic Aerosols Using Laboratory Dilution Experiments

NASA Astrophysics Data System (ADS)

Ye, Q.; Robinson, E. S.; Mahfouz, N.; Sullivan, R. C.; Donahue, N. M.

2016-12-01

Secondary organic aerosols (SOA) dominate the mass of fine particles in the atmosphere. Their formation involves both oxidation of volatile organics from various sources that produce products with uncertain volatilities, and diffusion of these products into the condensed phase. Therefore, constraining volatility distribution and diffusion timescales of the constituents in SOA are important in predicting size, concentration and composition of SOA, as well as how these properties of SOA evolve in the atmosphere. In this work, we demonstrate how carefully designed laboratory isothermal dilution experiments in smog chambers can shed light into the volatility distribution and any diffusion barriers of common types of SOA over time scales relevant to atmospheric transport and diurnal cycling. We choose SOA made from mono-terpenes (alpha-pinene and limonene) and toluene to represent biogenic and anthropogenic SOA. We look into how moisture content can alter any evaporation behaviors of SOA by varying relative humidity during SOA generation and during dilution process. This provides insight into whether diffusion in the condensed phase is rate limiting in reaching gas/particle equilibrium of semi-volatile organic compounds. Our preliminary results show that SOA from alpha-pinene evaporates continuously over several hours of experiments, and there is no substantial discernible differences over wide ranges of the chamber humidity. SOA from toluene oxidation shows slower evaporation. We fit these experimental data using absorptive partitioning theory and a particle dynamic model to obtain volatility distributions and to predict particle size evolution. This in the end will help us to improve representation of SOA in large scale chemical transport models.

OH radical-initiated oxidation of (E)- and (Z)-β-ocimene in the presence of NOx: the role of light-dependent monoterpenes in organic nitrate and secondary organic aerosol formation in the above-canopy forest environment

NASA Astrophysics Data System (ADS)

Slade, J. H., Jr.; Jayarathne, T.; Morales, A. C.; Shepson, P. B.

2017-12-01

Biogenic volatile organic compound (BVOC) oxidation represents a significant pathway in the production of secondary organic aerosol (SOA). BVOC oxidation products, including organic nitrates (ON), impact both the SOA burden and the oxidative capacity of the atmosphere by sequestering NOx. A recent field study in the mixed deciduous/coniferous forest of northern Michigan showed that concentrations of multifunctional monoterpene-derived hydroxy nitrates (MTN) and SOA can be greater in the above-canopy environment during daytime, but the source of MTN is unclear as model simulations cannot replicate the higher concentrations above canopy. Light-dependent monoterpenes, including the polyolefinic species, trans-ocimene, may be one such contributor to the higher measured ON and SOA above canopy as this compound has been predicted to be an important source of monoterpene-derived ON during daytime in this environment. However, there are currently no measurements of the ON (and SOA yields) from trans-ocimene oxidation by OH in the presence of NOx, the dominant pathway for daytime ON production. Here we conduct photochemical reaction chamber studies of the OH radical-initiated oxidation of authentic (E)- and (Z)-β-ocimene isomers in the presence of NOx to examine the total (gas and particle) ON, hydroxy nitrate, and SOA yields. The effects of variable chamber relative humidity and seed particle acidity on the ON and SOA yields are examined to better understand the role of hydrolysis on SOA formation and the lifetime of ocimene-derived ON in the particles. This work underscores the importance of light-dependent monoterpenes on mediating the oxidative capacity of the near canopy forest environment and has important implications for understanding NOx cycling and the formation of SOA in forests, which are not currently included in atmospheric models.

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

NASA Astrophysics Data System (ADS)

Li, Lijie; Cocker, David R.

2018-05-01

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

SOA formation from photooxidation of naphthalene and methylnaphthalenes with m-xylene and surrogate mixtures

NASA Astrophysics Data System (ADS)

Chen, Chia-Li; Li, Lijie; Tang, Ping; Cocker, David R.

2018-05-01

SOA formation is not well predicted in current models in urban area. The interaction among multiple anthropogenic volatile organic compounds is essential for the SOA formation in the complex urban atmosphere. Secondary organic aerosol (SOA) from the photooxidation of naphthalene, 1-methylnaphthalene, and 2-methylnaphthalene as well as individual polycyclic aromatic hydrocarbons (PAHs) mixed with m-xylene or an atmospheric surrogate mixture was explored in the UCR CE-CERT environmental chamber under urban relevant low NOx and extremely low NOx (H2O2) conditions. Addition of m-xylene suppressed SOA formation from the individual PAH precursor. A similar suppression effect on SOA formation was observed during the surrogate mixture photooxidation suggesting the importance of gas-phase chemical reactivity to SOA formation. The SOA growth rate for different PAH-m-xylene mixtures was strongly correlated with initial [HO2]/[RO2] ratio but negatively correlated with initial m-xylene/NO ratio. Decreasing SOA formation was observed for increasing m-xylene/PAHs ratios and increasing initial m-xylene/NO ratio. The SOA chemical composition characteristics such as f44 versus f43, H/C ratio, O/C ratio, and the oxidation state of the carbon OSbarc were consistent with a continuously aging with the SOA exhibiting characteristics of both individual precursors. SOA formation from PAHs was also suppressed within an atmospheric surrogate mixture compared to the SOA formed from individual PAHs, indicating that atmospheric reactivity directly influences SOA formation from PAHs.

Primary gas- and particle-phase emissions and secondary organic aerosol production from gasoline and diesel off-road engines.

PubMed

Gordon, Timothy D; Tkacik, Daniel S; Presto, Albert A; Zhang, Mang; Jathar, Shantanu H; Nguyen, Ngoc T; Massetti, John; Truong, Tin; Cicero-Fernandez, Pablo; Maddox, Christine; Rieger, Paul; Chattopadhyay, Sulekha; Maldonado, Hector; Maricq, M Matti; Robinson, Allen L

2013-12-17

Dilution and smog chamber experiments were performed to characterize the primary emissions and secondary organic aerosol (SOA) formation from gasoline and diesel small off-road engines (SOREs). These engines are high emitters of primary gas- and particle-phase pollutants relative to their fuel consumption. Two- and 4-stroke gasoline SOREs emit much more (up to 3 orders of magnitude more) nonmethane organic gases (NMOGs), primary PM and organic carbon than newer on-road gasoline vehicles (per kg of fuel burned). The primary emissions from a diesel transportation refrigeration unit were similar to those of older, uncontrolled diesel engines used in on-road vehicles (e.g., premodel year 2007 heavy-duty diesel trucks). Two-strokes emitted the largest fractional (and absolute) amount of SOA precursors compared to diesel and 4-stroke gasoline SOREs; however, 35-80% of the NMOG emissions from the engines could not be speciated using traditional gas chromatography or high-performance liquid chromatography. After 3 h of photo-oxidation in a smog chamber, dilute emissions from both 2- and 4-stroke gasoline SOREs produced large amounts of semivolatile SOA. The effective SOA yield (defined as the ratio of SOA mass to estimated mass of reacted precursors) was 2-4% for 2- and 4-stroke SOREs, which is comparable to yields from dilute exhaust from older passenger cars and unburned gasoline. This suggests that much of the SOA production was due to unburned fuel and/or lubrication oil. The total PM contribution of different mobile source categories to the ambient PM burden was calculated by combining primary emission, SOA production and fuel consumption data. Relative to their fuel consumption, SOREs are disproportionately high total PM sources; however, the vastly greater fuel consumption of on-road vehicles renders them (on-road vehicles) the dominant mobile source of ambient PM in the Los Angeles area.

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

NASA Astrophysics Data System (ADS)

Mahmud, A.; Barsanti, K.

2013-07-01

The secondary organic aerosol (SOA) module in the Model for Ozone and Related Chemical Tracers, version 4 (MOZART-4) was updated by replacing existing two-product (2p) parameters with those obtained from two-product volatility basis set (2p-VBS) fits (MZ4-C1), and by treating SOA formation from the following additional volatile organic compounds (VOCs): isoprene, propene and lumped alkenes (MZ4-C2). Strong seasonal and spatial variations in global SOA distributions were demonstrated, with significant differences in the predicted concentrations between the base case and updated model simulations. Updates to the model resulted in significant increases in annual average SOA mass concentrations, particularly for the MZ4-C2 simulation in which the additional SOA precursor VOCs were treated. Annual average SOA concentrations predicted by the MZ4-C2 simulation were 1.00 ± 1.04 μg m-3 in South America, 1.57 ± 1.88 μg m-3 in Indonesia, 0.37 ± 0.27 μg m-3 in the USA, and 0.47 ± 0.29 μg m-3 in Europe with corresponding increases of 178, 406, 311 and 292% over the base-case simulation, respectively, primarily due to inclusion of isoprene. The increases in predicted SOA mass concentrations resulted in corresponding increases in SOA contributions to annual average total aerosol optical depth (AOD) by ~ 1-6%. Estimated global SOA production was 5.8, 6.6 and 19.1 Tg yr-1 with corresponding burdens of 0.22, 0.24 and 0.59 Tg for the base-case, MZ4-C1 and MZ4-C2 simulations, respectively. The predicted SOA budgets fell well within reported ranges for comparable modeling studies, 6.7 to 96 Tg yr-1, but were lower than recently reported observationally constrained values, 50 to 380 Tg yr-1. For MZ4-C2, simulated SOA concentrations at the surface also were in reasonable agreement with comparable modeling studies and observations. Total organic aerosol (OA) mass concentrations at the surface, however, were slightly over-predicted in Europe, Amazonian regions and Malaysian Borneo (Southeast Asia) during certain months of the year, and under-predicted in most sites in Asia; relative to those regions, the model performed better for sites in North America. Overall, with the inclusion of additional SOA precursors (MZ4-C2), namely isoprene, MOZART-4 showed consistently better skill (NMB (normalized mean bias) of -11 vs. -26%) in predicting total OA levels and spatial distributions of SOA as compared with unmodified MOZART-4. Treatment of SOA formation by these known precursors (isoprene, propene and lumped alkenes) may be particularly important when MOZART-4 output is used to generate boundary conditions for regional air quality simulations that require more accurate representation of SOA concentrations and distributions.

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

NASA Astrophysics Data System (ADS)

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

2013-03-01

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

Reactive intermediates revealed in secondary organic aerosol formation from isoprene

PubMed Central

Surratt, Jason D.; Chan, Arthur W. H.; Eddingsaas, Nathan C.; Chan, ManNin; Loza, Christine L.; Kwan, Alan J.; Hersey, Scott P.; Flagan, Richard C.; Wennberg, Paul O.; Seinfeld, John H.

2010-01-01

Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = β-IEPOX + δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NOx conditions, respectively. Isoprene low-NOx SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NOx conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NOx SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO2 and NO2, respectively) could be a substantial source of “missing urban SOA” not included in current atmospheric models. PMID:20080572

SOA formation potential of emissions from soil and leaf litter

DOE PAGES

Faiola, Celia L.; VanderSchelden, Graham S.; Wen, Miao; ...

2013-12-13

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

3rd hand smoking; heterogeneous oxidation of nicotine and secondary aerosol formation in the indoor environment

NASA Astrophysics Data System (ADS)

Petrick, Lauren; Dubowski, Yael

2010-05-01

Tobacco smoking is well known as a significant source of primary indoor air pollutants. However, only recently has it been recognized that the impact of Tobacco smoking may continue even after the cigarette has been extinguished (i.e., third hand smoke) due to the effect of indoor surfaces. These surfaces may affect the fate of tobacco smoke in the form of secondary reactions and pollutants, including secondary organic aerosol (SOA) formation. Fourier Transform Infrared spectrometry with Attenuated Total Reflection (FTIR-ATR) in tandem with a Scanning Mobility Particle Sizing (SMPS) system was used to monitor the ozonation of cellulose sorbed nicotine and resulting SOA formation. SOA formation began at onset of ozone introduction ([O3] = 60 ± 5 ppb) with a size distribution of dp ≤ 25 nm, and was determined to be a result of heterogeneous reaction (opposed to homogeneous). SOA yield from reacted surface nicotine was on the order of 10 %. Simultaneous to SOA monitoring, FTIR-ATR spectra showed surface changes in the nicotine film as the reaction progressed, revealing a pseudo first-order surface reaction rate of 0.0026 ± 0.0008 min-1. Identified surface oxidation products included: cotinine, myosmine, methylnicotinamide and nicotyrine. Surface reaction rate was found to be partially inhibited at high relative humidity. Given the toxicity of some of the identified products (e.g., cotinine has shown potential mutagenicity and teratogenicity) and that small particles may contribute to adverse health effects, the present study indicates that exposure to 3rd hand smoke ozonation products may pose additional health risks.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

PubMed

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

2012-05-15

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

SOURCES AND RADIATIVE PROPERTIES OF ORGANOSULFATES IN THE ATMOSPHERE

EPA Science Inventory

It is expected that these studies will provide mechanistic insight to how SOA forms under acidic conditions and how it impacts direct and indirect radiative forcing. Understanding the chemical and physical properties of SOA will lead to future advancements in the predictive...

Secondary organic aerosol formation from in situ OH, O3, and NO3 oxidation of ambient forest air in an oxidation flow reactor

NASA Astrophysics Data System (ADS)

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.; Ortega, Amber M.; Fry, Juliane L.; Brown, Steven S.; Zarzana, Kyle J.; Dube, William; Wagner, Nicholas L.; Draper, Danielle C.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Gutiérrez-Montes, Cándido; Jimenez, Jose L.

2017-04-01

Ambient pine forest air was oxidized by OH, O3, or NO3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O3 and NO3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20-30 min, in order to determine how the availability of SOA precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O3 or NO3 oxidation. This is likely because O3 and NO3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O3 and NO3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O3 and NO3 oxidation produced SOA with elemental O : C and H : C similar to the least-oxidized OA observed in local ambient air, and neither oxidant led to net mass loss at the highest exposures, in contrast to OH oxidation. An OH exposure in the OFR equivalent to several hours of atmospheric aging also produced SOA with O : C and H : C values similar to ambient OA, while higher aging (days-weeks) led to formation of SOA with progressively higher O : C and lower H : C (and net mass loss at the highest exposures). NO3 oxidation led to the production of particulate organic nitrates (pRONO2), while OH and O3 oxidation (under low NO) did not, as expected. These measurements of SOA formation provide the first direct comparison of SOA formation potential and chemical evolution from OH, O3, and NO3 oxidation in the real atmosphere and help to clarify the oxidation processes that lead to SOA formation from biogenic hydrocarbons.

Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site

NASA Astrophysics Data System (ADS)

Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

2015-08-01

A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 > 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black carbon (BC ~ 0.2 μg m-3). Particle-phase sulfate is fairly correlated (r2 ~ 0.3) with both methacrylic acid epoxide (MAE)/hydroxymethyl-methyl-α-lactone (HMML)- (henceforth called methacrolein (MACR)-derived SOA tracers) and IEPOX-derived SOA tracers, and more strongly correlated (r2 ~ 0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the MACR-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2 = 0.38) and nitrate (r2 = 0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2 ~ 0.5 and ~ 0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC as well as aerosol viscosity and morphology becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions

PubMed Central

Gentner, Drew R.; Isaacman, Gabriel; Worton, David R.; Chan, Arthur W. H.; Dallmann, Timothy R.; Davis, Laura; Liu, Shang; Day, Douglas A.; Russell, Lynn M.; Wilson, Kevin R.; Weber, Robin; Guha, Abhinav; Harley, Robert A.; Goldstein, Allen H.

2012-01-01

Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region’s fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies. PMID:23091031

Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions.

PubMed

Gentner, Drew R; Isaacman, Gabriel; Worton, David R; Chan, Arthur W H; Dallmann, Timothy R; Davis, Laura; Liu, Shang; Day, Douglas A; Russell, Lynn M; Wilson, Kevin R; Weber, Robin; Guha, Abhinav; Harley, Robert A; Goldstein, Allen H

2012-11-06

Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region's fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.

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

PubMed

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

2009-11-01

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

Review of Urban Secondary Organic Aerosol Formation from Gasoline and Diesel Motor Vehicle Emissions.

PubMed

Gentner, Drew R; Jathar, Shantanu H; Gordon, Timothy D; Bahreini, Roya; Day, Douglas A; El Haddad, Imad; Hayes, Patrick L; Pieber, Simone M; Platt, Stephen M; de Gouw, Joost; Goldstein, Allen H; Harley, Robert A; Jimenez, Jose L; Prévôt, André S H; Robinson, Allen L

2017-02-07

Secondary organic aerosol (SOA) is formed from the atmospheric oxidation of gas-phase organic compounds leading to the formation of particle mass. Gasoline- and diesel-powered motor vehicles, both on/off-road, are important sources of SOA precursors. They emit complex mixtures of gas-phase organic compounds that vary in volatility and molecular structure-factors that influence their contributions to urban SOA. However, the relative importance of each vehicle type with respect to SOA formation remains unclear due to conflicting evidence from recent laboratory, field, and modeling studies. Both are likely important, with evolving contributions that vary with location and over short time scales. This review summarizes evidence, research needs, and discrepancies between top-down and bottom-up approaches used to estimate SOA from motor vehicles, focusing on inconsistencies between molecular-level understanding and regional observations. The effect of emission controls (e.g., exhaust aftertreatment technologies, fuel formulation) on SOA precursor emissions needs comprehensive evaluation, especially with international perspective given heterogeneity in regulations and technology penetration. Novel studies are needed to identify and quantify "missing" emissions that appear to contribute substantially to SOA production, especially in gasoline vehicles with the most advanced aftertreatment. Initial evidence suggests catalyzed diesel particulate filters greatly reduce emissions of SOA precursors along with primary aerosol.

The influences of ammonia on aerosol formation in the ozonolysis of styrene: roles of Criegee intermediate reactions

PubMed Central

Ma, Qiao; Lin, Xiaoxiao; Yang, Chengqiang; Long, Bo; Zhang, Weijun

2018-01-01

The influences of ammonia (NH3) on secondary organic aerosol (SOA) formation from ozonolysis of styrene have been investigated using chamber experiments and quantum chemical calculations. With the value of [O3]0/[styrene]0 ratios between 2 and 4, chamber experiments were carried out without NH3 or under different [NH3]/[styrene]0 ratios. The chamber experiments reveal that the addition of NH3 led to significant decrease of SOA yield. The overall SOA yield decreased with the [NH3]0/[styrene]0 increasing. In addition, the addition of NH3 at the beginning of the reaction or several hours after the reaction occurs had obviously different influence on the yield of SOA. Gas phase reactions of Criegee intermediates (CIs) with aldehydes and NH3 were studied in detail by theoretical methods to probe into the mechanisms behind these phenomena. The calculated results showed that 3,5-diphenyl-1,2,4-trioxolane, a secondary ozonide formed through the reactions of C6H5ĊHOO· with C6H5CHO, could make important contribution to the aerosol composition. The addition of excess NH3 may compete with aldehydes, decreasing the secondary ozonide yield to some extent and thus affect the SOA formation. PMID:29892406

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

NASA Astrophysics Data System (ADS)

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

2010-11-01

We report simultaneous measurements of volatile organic compound (VOC) mixing ratios including C6 to C8 aromatics, isoprene, monoterpenes, acetone and organic aerosol mass loadings at a rural location in Southwestern Ontario, Canada by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) and Aerosol Mass Spectrometry (AMS), respectively. During the three-week-long Border Air Quality and Meteorology Study in June-July 2007, air was sampled from a range of sources, including aged air from the polluted US Midwest, direct outflow from Detroit 50 km away, and clean air with higher biogenic input. After normalization to the diurnal profile of CO, a long-lived tracer, diurnal analyses show clear photochemical loss of reactive aromatics and production of oxygenated VOCs and secondary organic aerosol (SOA) during the daytime. Biogenic VOC mixing ratios increase during the daytime in accord with their light- and temperature-dependent sources. Long-lived species, such as hydrocarbon-like organic aerosol and benzene show little to no photochemical reactivity on this timescale. From the normalized diurnal profiles of VOCs, an estimate of OH concentrations during the daytime, measured O3 concentrations, and laboratory SOA yields, we calculate integrated organic aerosol production amounts associated with each measured SOA precursor. Depending on whether the SOA formation is occurring in a low- or high-NOx regime, we estimate that the biogenic gases contribute between 10 to 36 times as much SOA as do the aromatic precursors, making this a highly biogenically dominated region for SOA formation. The conclusion that biogenic SOA formation is of significance to air quality in this region is supported by detailed air quality modeling during this period (Stroud et al., 2010).

Effect of secondary organic aerosol from isoprene-derived hydroxyhydroperoxides on the expression of oxidative stress response genes in human bronchial epithelial cells.

PubMed

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

2018-02-21

Isoprene-derived secondary organic aerosol (SOA), which comprise a large portion of atmospheric fine particulate matter (PM 2.5 ), can be formed through various gaseous precursors, including isoprene epoxydiols (IEPOX), methacrylic acid epoxide (MAE), and isoprene hydroxyhydroperoxides (ISOPOOH). The composition of the isoprene-derived SOA affects its reactive oxygen species (ROS) generation potential and its ability to alter oxidative stress-related gene expression. In this study we assess effects of isoprene SOA derived solely from ISOPOOH oxidation on human bronchial epithelial cells by measuring the gene expression changes in 84 oxidative stress-related genes. In addition, the thiol reactivity of ISOPOOH-derived SOA was measured through the dithiothreitol (DTT) assay. Our findings show that ISOPOOH-derived SOA alter more oxidative-stress related genes than IEPOX-derived SOA but not as many as MAE-derived SOA on a mass basis exposure. More importantly, we found that the different types of SOA derived from the various gaseous precursors (MAE, IEPOX, and ISOPOOH) have unique contributions to changes in oxidative stress-related genes that do not total all gene expression changes seen in exposures to atmospherically relevant compositions of total isoprene-derived SOA mixtures. This study suggests that amongst the different types of known isoprene-derived SOA, MAE-derived SOA are the most potent inducer of oxidative stress-related gene changes but highlights the importance of considering isoprene-derived SOA as a total mixture for pollution controls and exposure studies.

Assessment of the impacts of aromatic VOC emissions and yields of SOA on SOA concentrations with the air quality model RAMS-CMAQ

NASA Astrophysics Data System (ADS)

Li, Jialin; Zhang, Meigen; Wu, Fangkun; Sun, Yele; Tang, Guiqian

2017-06-01

The secondary organic aerosol (SOA) concentration is generally underestimated by models. Recent studies suggest that the underprediction is related to underestimations of aromatic volatile organic compound (VOC) emissions and SOA yields in current models. Here, the impacts of these two factors in China were investigated with the regional air quality modeling system RAMS-CMAQ, referring to field observations during the episode from October 14 to November 14, 2014. Comparisons between the observed and modeled SOA of four sensitivity simulation cases indicated the significant impacts of the two underestimated factors on the SOA output. By considering these two aspects, the simulated mean SOA concentrations significantly increased by nearly 4 times with a good representation of the intensively temporal variations of concentrations, which were largely controlled by photochemical processes rather than meteorological conditions. The improvement in SOA compensated for the underestimations by approximately 23.5% and contributed to the mean fraction of SOA to organic aerosol (OA) by increasing the fraction from less than 7% to more than 25%, which was closer to the observed result. These results suggested a more reasonable and more realistic representation of SOA formation in the model after allowing for the two factors. Due to the better simulation of SOA, predictions of OA were correspondingly improved when the correlation coefficient increased from 0.57 to 0.73 and other bias parameters were reduced, which indicated the improved ability of our model to trace the temporal variations of OA. Based on the improved simulation throughout the episode, the mean SOA concentration was obviously higher in eastern China than in the west. The highest concentration appeared in the Sichuan Basin and Pearl River Delta (PRD) areas, with values of 6-11 μg/m3 and 8-17 μg/m3, respectively. Over the wide regions of central and eastern China, the dominant component in SOA was formed from anthropogenic sources (ASOA), generally accounting for more than 60%.

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

EPA Science Inventory

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

Estimated effects of temperature on secondary organic aerosol concentrations.

PubMed

Sheehan, P E; Bowman, F M

2001-06-01

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

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

DOE PAGES

Zanca, Nicola; Lambe, Andrew T.; Massoli, Paola; ...

2017-09-06

The study of secondary organic aerosol (SOA) in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM) oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescalesmore » that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization – proton nuclear magnetic resonance ( 1H-NMR) spectroscopy and HPLC determination of humic-like substances (HULIS). Results were compared with previous Aerodyne aerosol mass spectrometer (AMS) measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1×10 12 molec OH cm -3 × s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC), providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zanca, Nicola; Lambe, Andrew T.; Massoli, Paola

The study of secondary organic aerosol (SOA) in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM) oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescalesmore » that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization – proton nuclear magnetic resonance ( 1H-NMR) spectroscopy and HPLC determination of humic-like substances (HULIS). Results were compared with previous Aerodyne aerosol mass spectrometer (AMS) measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1×10 12 molec OH cm -3 × s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC), providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.« less

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: Competition among oligomerization, functionalization, and fragmentation

DOE PAGES

Yu, Lu; Smith, Jeremy; Laskin, Alexander; ...

2016-04-13

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl ( 3C *) and hydroxyl radical ( • OH). Changes in themore » molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OS C) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ~2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OS C values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers ( n C) below 6. The average n C of phenolic aqSOA decreases while average OS C increases over the course of photochemical aging. In addition, the saturation vapor pressures ( C *) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C * values is observed, varying from < 10 –20 µg m –3 for functionalized phenolic oligomers to > 10 µg m –3 for small open-ring species. Furthermore, the detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.« less

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: Competition among oligomerization, functionalization, and fragmentation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Lu; Smith, Jeremy; Laskin, Alexander

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl ( 3C *) and hydroxyl radical ( • OH). Changes in themore » molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OS C) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ~2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OS C values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers ( n C) below 6. The average n C of phenolic aqSOA decreases while average OS C increases over the course of photochemical aging. In addition, the saturation vapor pressures ( C *) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C * values is observed, varying from < 10 –20 µg m –3 for functionalized phenolic oligomers to > 10 µg m –3 for small open-ring species. Furthermore, the detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.« less

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

NASA Astrophysics Data System (ADS)

Yu, L.; Smith, J.; Laskin, A.; George, K. M.; Anastasio, C.; Laskin, J.; Dillner, A. M.; Zhang, Q.

2015-10-01

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants - the triplet excited state of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼ 2 h irradiation under midday, winter solstice sunlight in northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated open-ring molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures C*) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C* values is observed, varying from < 10-20 μg m-3 for functionalized phenolic oligomers to > 10 μg m-3 for small open-ring species. The detection of abundant extremely low volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

NASA Astrophysics Data System (ADS)

Yu, Lu; Smith, Jeremy; Laskin, Alexander; George, Katheryn M.; Anastasio, Cort; Laskin, Julia; Dillner, Ann M.; Zhang, Qi

2016-04-01

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants - the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ˜ 2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed, varying from < 10-20 µg m-3 for functionalized phenolic oligomers to > 10 µg m-3 for small open-ring species. The detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.

Influence of local production and vertical transport on the organic aerosol budget over Paris

NASA Astrophysics Data System (ADS)

Janssen, R. H. H.; Tsimpidi, A. P.; Karydis, V. A.; Pozzer, A.; Lelieveld, J.; Crippa, M.; Prévôt, A. S. H.; Ait-Helal, W.; Borbon, A.; Sauvage, S.; Locoge, N.

2017-08-01

We performed a case study of the organic aerosol (OA) budget during the MEGAPOLI campaign during summer 2009 in Paris. We combined aerosol mass spectrometer, gas phase chemistry, and atmospheric boundary layer (ABL) data and applied the MXL/MESSy column model. We find that during daytime, vertical mixing due to ABL growth has opposing effects on secondary organic aerosol (SOA) and primary organic aerosol (POA) concentrations. POA concentrations are mainly governed by dilution due to boundary layer expansion and transport of POA-depleted air from aloft, while SOA concentrations are enhanced by entrainment of SOA-rich air from the residual layer (RL). Further, local emissions and photochemical production control the diurnal cycle of SOA. SOA from intermediate volatility organic compounds constitutes about half of the locally formed SOA mass. Other processes that previously have been shown to influence the urban OA budget, such as aging of semivolatile and intermediate volatility organic compounds (S/IVOC), dry deposition of S/IVOCs, and IVOC emissions, are found to have minor influences on OA. Our model results show that the modern carbon content of the OA is driven by vertical and long-range transport, with a minor contribution from local cooking emissions. SOA from regional sources and resulting from aging and long-lived precursors can lead to high SOA concentrations above the ABL, which can strongly influence ground-based observations through downward transport. Sensitivity analysis shows that modeled SOA concentrations in the ABL are equally sensitive to ABL dynamics as to SOA concentrations transported from the RL.

Oil Sands Operations in Alberta, Canada: A large source of secondary organic aerosol

NASA Astrophysics Data System (ADS)

Liggio, J.; Li, S. M.; Hayden, K.; Taha, Y. M.; Stroud, C.; Darlington, A. L.; Drollette, B.; Gordon, M.; Lee, P.; Liu, P.; Leithead, A.; Moussa, S.; Wang, D.; O'Brien, J.; Mittermeier, R. L.; Brook, J.; Lu, G.; Staebler, R. M.; Han, Y.; Tokarek, T. W.; Osthoff, H. D.; Makar, P.; Zhang, J.; Plata, D.; Gentner, D. R.

2015-12-01

Little is known of the reaction products of emissions to the atmosphere from extraction of oil from unconventional sources in the oil sands (OS) region of Alberta, Canada. This study examines these reaction products, and in particular, the extent to which they form secondary organic aerosol (SOA), which can significantly contribute to regional particulate matter formation. An aircraft measurement campaign was conducted over the Athabasca oil sands region between August 13 and September 7, 2013. A broad suite of measurements were made during 22 flights, including organic aerosol mass and composition with a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and organic aerosol gas-phase precursors by Proton Transfer Reaction (PTR) and off-line gas chromatography mass spectrometry. Large concentrations of organic aerosol were measured downwind of the OS region, which we show to be entirely secondary in nature. Laboratory experiments demonstrated that bitumen (the mined product) contains semi-volatile vapours in the C12-C18 range that will be emitted at ambient temperatures. When oxidized, these vapours form SOA with highly similar HR-ToF-AMS spectra to the SOA measured in the flights. Box modelling of the OS plume evolution indicated that the measured levels of traditional volatile organic compounds (VOCs) are not capable of accounting for the amount of SOA formed in OS plumes. This discrepancy is only reconciled in the model by including bitumen vapours along with their oxidation and condensation into the model. The concentration of bitumen vapours required to produce SOA matching observations is similar to that of traditional VOC precursors of SOA. It was further estimated that the cumulative SOA mass formation approximately 100 km downwind of the OS during these flights, and under these meteorological conditions was up to 82 tonnes/day. The combination of airborne measurements, laboratory experiments and box modelling indicated that semi-volatile organic compounds (SVOC) are emitted from OS operations which accounted for >85% of the formed SOA mass in these plumes. Implications of this SOA formation will be discussed.

Aerosol formation by ozonolysis of α- and β-pinene with initial concentrations below 1 ppb

NASA Astrophysics Data System (ADS)

Saathoff, Harald; Naumann, Karl-Heinz; Möhler, Ottmar

2014-05-01

Secondary organic aerosols (SOA) from the oxidation of biogenic volatile organic compounds (BVOC) are a large fraction of the tropospheric aerosol especially over tropical continental regions. The dominant SOA forming compounds are monoterpenes of which pinene is the most abundant. The reactions of monoterpenes with OH radicals, NO3 radicals, and ozone yield secondary organic aerosol mass in highly variable yields. Despite the various studies on SOA formation the influence of temperature and precursor concentrations on SOA yields are still major uncertainties in tropospheric aerosol models. In previous studies we observed a negative temperature dependence of SOA yields for SOA from ozonolysis α-pinene and limonene (Saathoff et al., 2009). However, this study as well as most of the literature data for measured SOA yields is limited to terpene concentrations of several ppb and higher (e.g. Bernard et al., 2012), hence about an order of magnitude higher than terpene concentrations even near their sources. Monoterpene concentrations in and above tropical or boral forests reach values up to a few tenth of a ppb during daytime decreasing rapidly with altitude in the boundary layer (Kesselmeier et al. 2000; Boy et al., 2004). Therefore we investigated the yield of SOA material from the ozonolysis of α- and β-pinene under simulated tropospheric conditions in the large aerosol chamber AIDA on time scales of several hours and for terpene concentrations between 0.1 and 1 ppb. The temperatures investigated were 243, 274, and 296 K with relative humidities ranging from 25% to 41%. The organic aerosol was generated by controlled oxidation with an excess of ozone (220-930 ppb) and the aerosol yield is calculated from size distributions measured with differential mobility analysers (SMPS, TSI, 3071 & 3080N) in the size range between 2 and 820 nm. On the basis of the measured initial particle size distribution, particle number concentration (CPC, TSI, 3775, 3776, 3022), and trace gas evolution model calculations were done using the aerosol model COSIMA (Naumann, 2003; Saathoff et al., 2009) supplemented by an improved SOA module in combination with the master chemical mechanism (MCM 3.2). As previously reported for higher SOA concentrations the overall SOA yields from ozonolysis of α- and β-pinene increase significantly with decreasing temperature. However, compared to the yields extrapolated from experiments done with higher terpene concentrations the SOA yields at ambient like concentrations are surprisingly high. They reach values of up to 20% at 243 K for organic aerosol mass concentrations of about 0.5 µg m-3 even without additional seed aerosol. This paper discusses the temperature dependent SOA yields from the ozonolysis of α-pinene and β-pinene in comparison with data from literature. Bernard et al., (2012) J. Aerosol Sci. 43, 14-30. Boy et al., (2004) Atmos. Chem. Phys. 4, 657-678. Kesselmeier et al., (2000) Atmos. Environ. 34, 4063-4072 Naumann (2003) J. Aerosol Sci. 34 (10), 1371-1397. Saathoff et al., (2009) Atmos. Chem. Phys. 9 (5), 1551-1577.

Nighttime aqueous-phase secondary organic aerosols in Los Angeles and its implication for fine particulate matter composition and oxidative potential

NASA Astrophysics Data System (ADS)

Saffari, Arian; Hasheminassab, Sina; Shafer, Martin M.; Schauer, James J.; Chatila, Talal A.; Sioutas, Constantinos

2016-05-01

Recent investigations suggest that aqueous phase oxidation of hydrophilic organic compounds can be a significant source of secondary organic aerosols (SOA) in the atmosphere. Here we investigate the possibility of nighttime aqueous phase formation of SOA in Los Angeles during winter, through examination of trends in fine particulate matter (PM2.5) carbonaceous content during two contrasting seasons. Distinctive winter and summer trends were observed for the diurnal variation of organic carbon (OC) and secondary organic carbon (SOC), with elevated levels during the nighttime in winter, suggesting an enhanced formation of SOA during that period. The nighttime ratio of SOC to OC was positively associated with the relative humidity (RH) at high RH levels (above 70%), which is when the liquid water content of the ambient aerosol would be high and could facilitate dissolution of hydrophilic primary organic compounds into the aqueous phase. Time-integrated collection and analysis of wintertime particles at three time periods of the day (morning, 6:00 a.m.-9:00 a.m.; afternoon, 11:00 a.m.-3:00 p.m.; night, 8:00 p.m.-4:00 a.m.) revealed higher levels of water soluble organic carbon (WSOC) and organic acids during the night and afternoon periods compared to the morning period, indicating that the SOA formation in winter continues throughout the nighttime. Furthermore, diurnal trends in concentrations of semi-volatile organic compounds (SVOCs) from primary emissions showed that partitioning of SVOCs from the gas to the particle phase due to the decreased nighttime temperatures cannot explain the substantial OC and SOC increase at night. The oxidative potential of the collected particles (quantified using a biological macrophage-based reactive oxygen species assay, in addition to the dithiothreitol assay) was comparable during afternoon and nighttime periods, but higher (by at least ∼30%) compared to the morning period, suggesting that SOA formation processes possibly enhance the toxicity of the ambient particles compared to mobile-source dominated primary emissions in the Los Angeles area.

Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, ground site

NASA Astrophysics Data System (ADS)

Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

2015-03-01

A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~9% (up to 26%) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~97% of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2>0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~25% (up to 47%) of the IEPOX-OA factor mass, which accounted for 32% of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO~0.03ppb), carbon monoxide (CO~116 ppb), and black carbon (BC~0.2 μg m-3). Particle-phase sulfate is fairly correlated (r2~0.3) with both MAE- and IEPOX-derived SOA tracers, and more strongly correlated (r2~0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the methacrylic acid epoxide (MAE)-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2=0.38) and nitrate (r2=0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a~clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2~0.5 and ~0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning

DOE PAGES

Murphy, Benjamin N.; Woody, Matthew C.; Jimenez, Jose L.; ...

2017-09-20

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustionmore » sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds–water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May–June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m -3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m -3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.« less

Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murphy, Benjamin N.; Woody, Matthew C.; Jimenez, Jose L.

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustionmore » sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds–water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May–June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m -3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m -3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.« less

Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning

NASA Astrophysics Data System (ADS)

Murphy, Benjamin N.; Woody, Matthew C.; Jimenez, Jose L.; Carlton, Ann Marie G.; Hayes, Patrick L.; Liu, Shang; Ng, Nga L.; Russell, Lynn M.; Setyan, Ari; Xu, Lu; Young, Jeff; Zaveri, Rahul A.; Zhang, Qi; Pye, Havala O. T.

2017-09-01

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds-water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May-June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m-3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m-3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plume of megacities can affect regional air quality. In the framework of the FP7/EU MEGAPOLI project, an intensive campaign was launched in the Greater Paris Region in July 2009. The major objective was to quantify different sources of organic aerosol (OA) within a megacity and in its plume. In this study, we use airborne measurements aboard the French ATR-42 aircraft to evaluate the regional chemistry-transport model CHIMERE within and downwind the Paris region. Slopes of the plume OA levels vs. Ox (= O3 + NO2) show secondary OA (SOA) formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. Simulated and observed slopes are in good agreement, when the most realistic "high-NOx" yields are used in the Volatility-Basis-Set scheme implemented into the model. In addition, these slopes are relatively stable from one day to another, which suggest that they are characteristic for the given megacity plume environment. Since OA within the plume is mainly formed from anthropogenic precursors (VOC and primary OA, POA), this work allows a specific evaluation of anthropogenic SOA and SOA formed from primary semi-volatile and intermediate volatile VOCs (SI-SOA) formation scheme in a model. For specific plumes, this anthropogenic OA build-up can reach about 10 μg m-3. For the average of the month of July 2009, maximum increases occur close to the agglomeration for primary OA are noticed at several tens (for POA) to hundred (for SI-SOA) kilometers of distance from the Paris agglomeration.

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

NASA Astrophysics Data System (ADS)

Hayes, P. L.; Ortega, A. M.; Cubison, M. J.; Froyd, K. D.; Zhao, Y.; Cliff, S. S.; Hu, W. W.; Toohey, D. W.; Flynn, J. H.; Lefer, B. L.; Grossberg, N.; Alvarez, S.; Rappenglück, B.; Taylor, J. W.; Allan, J. D.; Holloway, J. S.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; Massoli, P.; Zhang, X.; Liu, J.; Weber, R. J.; Corrigan, A. L.; Russell, L. M.; Isaacman, G.; Worton, D. R.; Kreisberg, N. M.; Goldstein, A. H.; Thalman, R.; Waxman, E. M.; Volkamer, R.; Lin, Y. H.; Surratt, J. D.; Kleindienst, T. E.; Offenberg, J. H.; Dusanter, S.; Griffith, S.; Stevens, P. S.; Brioude, J.; Angevine, W. M.; Jimenez, J. L.

2013-08-01

Organic aerosols (OA) in Pasadena are characterized using multiple measurements from the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign. Five OA components are identified using positive matrix factorization including hydrocarbon-like OA (HOA) and two types of oxygenated OA (OOA). The Pasadena OA elemental composition when plotted as H : C versus O : C follows a line less steep than that observed for Riverside, CA. The OOA components from both locations follow a common line, however, indicating similar secondary organic aerosol (SOA) oxidation chemistry at the two sites such as fragmentation reactions leading to acid formation. In addition to the similar evolution of elemental composition, the dependence of SOA concentration on photochemical age displays quantitatively the same trends across several North American urban sites. First, the OA/ΔCO values for Pasadena increase with photochemical age exhibiting a slope identical to or slightly higher than those for Mexico City and the northeastern United States. Second, the ratios of OOA to odd-oxygen (a photochemical oxidation marker) for Pasadena, Mexico City, and Riverside are similar, suggesting a proportional relationship between SOA and odd-oxygen formation rates. Weekly cycles of the OA components are examined as well. HOA exhibits lower concentrations on Sundays versus weekdays, and the decrease in HOA matches that predicted for primary vehicle emissions using fuel sales data, traffic counts, and vehicle emission ratios. OOA does not display a weekly cycle—after accounting for differences in photochemical aging —which suggests the dominance of gasoline emissions in SOA formation under the assumption that most urban SOA precursors are from motor vehicles.

Oxidation flow reactors (OFRs): overview of recent field and modeling studies

NASA Astrophysics Data System (ADS)

Jimenez, Jose-Luis; Palm, Brett B.; Peng, Zhe; Hu, Weiwei; Ortega, Amber M.; Li, Rui; Campuzano-Jost, Pedro; Day, Douglas A.; Stark, Harald; Brune, William H.; de Gouw, Joost; Schroder, Jason

2016-04-01

Oxidation flow reactors (OFRs) are popular tools for studying SOA formation and aging in both laboratory and field experiments. In an OFR, the concentration of an oxidant (OH, O3, or NO3) can be increased, leading to hours-months of equivalent atmospheric oxidation during the several-minute OFR residence time. Using gas- and particle-phase measurements from several recent field campaigns, we demonstrate SOA formation after oxidation of ambient air in an OFR. Typically, more SOA formation is observed from nighttime air than daytime air. This indicates that the concentration of SOA-forming gases in ambient air is relatively higher at night. Measured ambient VOCs are not able to explain the magnitude of SOA formation in the OFR, suggesting that typically unmeasured S/IVOCs (possibly VOC oxidation products or direct emissions) play a substantial intermediary role in ambient SOA formation. We also present highlights from recent OFR oxidant chemistry modeling studies. HOx, Ox, and photolysis chemistry was modeled for two common OH production methods (utilizing 185+254 nm UV light, or 254 nm only). OH exposure (OHexp) can be estimated within a factor of ~2 using model-derived equations, and can be verified in situ using VOC decay measurements. OHexp is strongly dependent on external OH reactivity, which may cause significant OH suppression in some circumstances (e.g., lab/source studies with high precursor concentrations). UV light photolysis and reaction with oxygen atoms are typically not major reaction pathways. Modeling the fate of condensable low-volatility organic gases (LVOCs) formed in an OFR suggests that LVOC fate is dependent on particle condensational sink. E.g., for the range of particle condensational sink at a remote pine forest, anywhere from 20-80% of produced LVOCs were predicted to condense onto aerosols for an OHexp of ~1 day, with the remainder lost to OFR or sampling line walls. Similar to large chamber wall loss corrections, a correction is needed to relate OFR sampling to the atmosphere, where condensation onto aerosols is the dominant LVOC fate. At high OHexp (>20 days) in an OFR, LVOCs are predicted to be oxidized many times before they can condense onto particles, leading to formation of volatile fragmentation products that can no longer condense to form SOA. Changes to preexisting OA at high OHexp should be predominantly a result of heterogeneous oxidation. SOA yields specific to OFR oxidation were investigated using standard addition of individual VOCs into ambient air in an OFR. SOA yields in the OFR were consistent with laboratory large chamber yields.

Considering the future of anthropogenic gas-phase organic compound emissions and the increasing influence of non-combustion sources on urban air quality

NASA Astrophysics Data System (ADS)

Khare, Peeyush; Gentner, Drew R.

2018-04-01

Decades of policy in developed regions has successfully reduced total anthropogenic emissions of gas-phase organic compounds, especially volatile organic compounds (VOCs), with an intentional, sustained focus on motor vehicles and other combustion-related sources. We examine potential secondary organic aerosol (SOA) and ozone formation in our case study megacity (Los Angeles) and demonstrate that non-combustion-related sources now contribute a major fraction of SOA and ozone precursors. Thus, they warrant greater attention beyond indoor environments to resolve large uncertainties in their emissions, oxidation chemistry, and outdoor air quality impacts in cities worldwide. We constrain the magnitude and chemical composition of emissions via several bottom-up approaches using chemical analyses of products, emissions inventory assessments, theoretical calculations of emission timescales, and a survey of consumer product material safety datasheets. We demonstrate that the chemical composition of emissions from consumer products as well as commercial and industrial products, processes, and materials is diverse across and within source subcategories. This leads to wide ranges of SOA and ozone formation potentials that rival other prominent sources, such as motor vehicles. With emission timescales from minutes to years, emission rates and source profiles need to be included, updated, and/or validated in emissions inventories with expected regional and national variability. In particular, intermediate-volatility and semi-volatile organic compounds (IVOCs and SVOCs) are key precursors to SOA, but are excluded or poorly represented in emissions inventories and exempt from emissions targets. We present an expanded framework for classifying VOC, IVOC, and SVOC emissions from this diverse array of sources that emphasizes a life cycle approach over longer timescales and three emission pathways that extend beyond the short-term evaporation of VOCs: (1) solvent evaporation, (2) solute off-gassing, and (3) volatilization of degradation by-products. Furthermore, we find that ambient SOA formed from these non-combustion-related emissions could be misattributed to fossil fuel combustion due to the isotopic signature of their petroleum-based feedstocks.

[Social Cognition and the Sense of Agency in Autism: From Action to Interaction].

PubMed

Lafleur, Alexis; Soulières, Isabelle; Forgeot d'Arc, Baudoin

The sense of agency (SoA) refers to the ability for one to detect that she is the cause of an action (Gallagher, 2000). The SoA is linked to motor control but also to self-awareness and could play an important role in social interactions. Autism spectrum disorder (ASD) is characterized by an alteration of social interactions and communication (DSM-5; APA, 2013) and is often seen as a primary deficit of functions specific to social cognition. However, motor control is also altered in ASD. We hypothesize that motor symptoms and social impairments could both arise from the same alteration of SoA. We first introduce theoretical models of implicit and explicit SoA (Synofzik et al., 2008) and present their neurofunctional basis. Then, we assess the clinical expressions of a disrupted SoA in different neuropsychiatric disorders such as schizophrenia. In ASD, the atypical formation of internal models of action during motor acquisition (Haswell et al., 2009) could be at the source of an altered implicit SoA. A lack of fidelity of sensorimotor agency cues (Zalla et al., 2015) could also entail an alteration of explicit SoA. We discuss the main clinical expressions of ASD that may ensue from a disrupted SoA (difficulties in theory of mind and imitation, deficits in motor coordination and praxis, etc.).

Significant Contributions of Isoprene to Summertime Secondary Organic Aerosol in Eastern United States.

PubMed

Ying, Qi; Li, Jingyi; Kota, Sri Harsha

2015-07-07

A modified SAPRC-11 (S11) photochemical mechanism with more detailed treatment of isoprene oxidation chemistry and additional secondary organic aerosol (SOA) formation through surface-controlled reactive uptake of dicarbonyls, isoprene epoxydiol and methacrylic acid epoxide was incorporated in the Community Multiscale Air Quality Model (CMAQ) to quantitatively determine contributions of isoprene to summertime ambient SOA concentrations in the eastern United States. The modified model utilizes a precursor-origin resolved approach to determine secondary glyoxal and methylglyoxal produced by oxidation of isoprene and other major volatile organic compounds (VOCs). Predicted OC concentrations show good agreement with field measurements without significant bias (MFB ∼ 0.07 and MFE ∼ 0.50), and predicted SOA reproduces observed day-to-day and diurnal variation of Oxygenated Organic Aerosol (OOA) determined by an aerosol mass spectrometer (AMS) at two locations in Houston, Texas. On average, isoprene SOA accounts for 55.5% of total predicted near-surface SOA in the eastern U.S., followed by aromatic compounds (13.2%), sesquiterpenes (13.0%) and monoterpenes (10.9%). Aerosol surface uptake of isoprene-generated glyoxal, methylglyoxal and epoxydiol accounts for approximately 83% of total isoprene SOA or more than 45% of total SOA. A domain wide reduction of NOx emissions by 40% leads to a slight decrease of domain average SOA by 3.6% and isoprene SOA by approximately 2.6%. Although most of the isoprene SOA component concentrations are decreased, SOA from isoprene epoxydiol is increased by ∼16%.

S – C – L triple wavelength superluminescent source based on an ultra-wideband SOA and FBGs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmad, H; Zulkifli, M Z; Hassan, N A

2013-10-31

We propose and demonstrate a wide-band semiconductor optical amplifier (SOA) based triple-wavelength superluminescent source with the output in the S-, C- and L-band regions. The proposed systems uses an ultra-wideband SOA with an amplification range from 1440 to 1620 nm as the linear gain medium. Three fibre Bragg gratings (FBGs) with centre wavelengths of 1500, 1540 and 1580 nm are used to generate the lasing wavelengths in the S-, Cand L-bands respectively, while a variable optical attenuator is used to finely balance the optical powers of the lasing wavelengths. The ultra-wideband SOA generates an amplified spontaneous emission (ASE) spectrum withmore » a peak power of -33 dBm at the highest SOA drive current, and also demonstrates a down-shift in the centre wavelength of the generated spectrum due to the spatial distribution of the carrier densities. The S-band wavelength is the dominant wavelength at high drive currents, with an output power of -6 dBm as compared to the C- and L-bands, which only have powers of -11 and -10 dBm, respectively. All wavelengths have a high average signal-to-noise ratio more than 60 dB at the highest drive current of 390 mA, and the system also shows a high degree of stability, with power fluctuations of less than 3 dB within 70 min. The proposed system can find many applications where a wide-band and stable laser source is crucial, such as in communications and sensing. (control of laser radiation parameters)« less

UNDERSTANDING REGIONAL OXIDATION CAPACITY BY COMPREHENSIVE OBSERVATIONS TO CONSTRAIN HYDROXYL RADICAL SOURCES AND SINKS DURING THE SOUTHERN OXIDANT AEROSOL STUDY (SOAS)

EPA Science Inventory

The proposed field measurements and data analysis will provide an important constraint to understand oxidation capacity in the Southeastern U.S. that determines SOA and photochemical ozone formation. Unexpectedly high levels of OH determining oxidation capacity have been co...

An upstream burst-mode equalization scheme for 40 Gb/s TWDM PON based on optimized SOA cascade

NASA Astrophysics Data System (ADS)

Sun, Xiao; Chang, Qingjiang; Gao, Zhensen; Ye, Chenhui; Xiao, Simiao; Huang, Xiaoan; Hu, Xiaofeng; Zhang, Kaibin

2016-02-01

We present a novel upstream burst-mode equalization scheme based on optimized SOA cascade for 40 Gb/s TWDMPON. The power equalizer is placed at the OLT which consists of two SOAs, two circulators, an optical NOT gate, and a variable optical attenuator. The first SOA operates in the linear region which acts as a pre-amplifier to let the second SOA operate in the saturation region. The upstream burst signals are equalized through the second SOA via nonlinear amplification. From theoretical analysis, this scheme gives sufficient dynamic range suppression up to 16.7 dB without any dynamic control or signal degradation. In addition, a total power budget extension of 9.3 dB for loud packets and 26 dB for soft packets has been achieved to allow longer transmission distance and increased splitting ratio.

Improving Secondary Organic Aerosol (SOA) Models using Global Sensitivity Analysis and by Comparison to Chamber Data.

NASA Astrophysics Data System (ADS)

Miller, D. O.; Brune, W. H.

2017-12-01

Accurate estimates of secondary organic aerosol (SOA) from atmospheric models is a major research challenge due to the complexity of the chemical and physical processes involved in the SOA formation and continuous aging. The primary uncertainties of SOA models include those associated with the formation of gas-phase products, the conversion between gas phase and particle phase, the aging mechanisms of SOA, and other processes related to the heterogeneous and particle-phase reactions. To address this challenge, we us a modular modeling framework that combines both simple and near-explicit gas-phase reactions and a two-dimensional volatility basis set (2D-VBS) to simulate the formation and evolution of SOA. Global sensitivity analysis is used to assess the relative importance of the model input parameters. In addition, the model is compared to the measurements from the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT).

Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate

DOE PAGES

Rastak, N.; Pajunoja, A.; Acosta Navarro, J. C.; ...

2017-04-28

A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient datamore » with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.« less

Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate

NASA Astrophysics Data System (ADS)

Rastak, N.; Pajunoja, A.; Acosta Navarro, J. C.; Ma, J.; Song, M.; Partridge, D. G.; Kirkevâg, A.; Leong, Y.; Hu, W. W.; Taylor, N. F.; Lambe, A.; Cerully, K.; Bougiatioti, A.; Liu, P.; Krejci, R.; Petäjä, T.; Percival, C.; Davidovits, P.; Worsnop, D. R.; Ekman, A. M. L.; Nenes, A.; Martin, S.; Jimenez, J. L.; Collins, D. R.; Topping, D. O.; Bertram, A. K.; Zuend, A.; Virtanen, A.; Riipinen, I.

2017-05-01

A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.

Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate.

PubMed

Rastak, N; Pajunoja, A; Acosta Navarro, J C; Ma, J; Song, M; Partridge, D G; Kirkevåg, A; Leong, Y; Hu, W W; Taylor, N F; Lambe, A; Cerully, K; Bougiatioti, A; Liu, P; Krejci, R; Petäjä, T; Percival, C; Davidovits, P; Worsnop, D R; Ekman, A M L; Nenes, A; Martin, S; Jimenez, J L; Collins, D R; Topping, D O; Bertram, A K; Zuend, A; Virtanen, A; Riipinen, I

2017-05-28

A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.

Microphysical explanation of the RH‐dependent water affinity of biogenic organic aerosol and its importance for climate

PubMed Central

Rastak, N.; Pajunoja, A.; Acosta Navarro, J. C.; Ma, J.; Song, M.; Partridge, D. G.; Kirkevåg, A.; Leong, Y.; Hu, W. W.; Taylor, N. F.; Lambe, A.; Cerully, K.; Bougiatioti, A.; Liu, P.; Krejci, R.; Petäjä, T.; Percival, C.; Davidovits, P.; Worsnop, D. R.; Ekman, A. M. L.; Nenes, A.; Martin, S.; Jimenez, J. L.; Collins, D. R.; Topping, D.O.; Bertram, A. K.; Zuend, A.; Virtanen, A.

2017-01-01

Abstract A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH‐dependent SOA water‐uptake with solubility and phase separation; (2) show that laboratory data on IP‐ and MT‐SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single‐parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources. PMID:28781391

Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rastak, N.; Pajunoja, A.; Acosta Navarro, J. C.

A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient datamore » with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.« less

The Dyad-Adaptive Paced Auditory Serial Addition Test (DA-PASAT): Normative data and the effects of repeated testing, simulated malingering, and traumatic brain injury

PubMed Central

Wyma, John M.; Herron, Timothy J.; Yund, E. William; Reed, Bruce

2018-01-01

The Paced Auditory Serial Addition Test (PASAT) is widely used to evaluate processing speed and executive function in patients with multiple sclerosis, traumatic brain injury, and other neurological disorders. In the PASAT, subjects listen to sequences of digits while continuously reporting the sum of the last two digits presented. Four different stimulus onset asynchronies (SOAs) are usually tested, with difficulty increasing as SOAs are reduced. Ceiling effects are common at long SOAs, while the digit delivery rate often exceeds the subject’s processing capacity at short SOAs, causing some subjects to stop performing altogether. In addition, subjects may adopt an “alternate answer” strategy at short SOAs, which reduces the test’s demands on working-memory and processing speed. Consequently, studies have shown that the number of dyads (consecutive correct answers) is a more sensitive measure of PASAT performance than the overall number of correct sums. Here, we describe a 2.5-minute computerized test, the Dyad-Adaptive PASAT (DA-PASAT), where SOAs are adjusted with a 2:1 staircase, decreasing after each pair of correct responses and increasing after misses. Processing capacity is reflected in the minimum SOA (minSOA) achieved in 54 trials. Experiment 1 gathered normative data in two large populations: 1617 subjects in New Zealand ranging in age from 18 to 65 years, and 214 Californians ranging in age from 18 to 82 years. Minimum SOAs were influenced by age, education, and daily hours of computer-use. Minimum SOA z-scores, calculated after factoring out the influence of these factors, were virtually identical in the two control groups, as were response times (RTs) and dyad ratios (the proportion of hits occurring in dyads). Experiment 2 measured the test-retest reliability of the DA-PASAT in 44 young subjects who underwent three test sessions at weekly intervals. High intraclass correlation coefficients (ICCs) were found for minSOAs (0.87), response times (0.76), and dyad ratios (0.87). Performance improved across test sessions for all measures. Experiment 3 investigated the effects of simulated malingering in 50 subjects: 42% of simulated malingerers produced abnormal (p< 0.05) minSOA z-scores. Simulated malingerers with abnormal scores were distinguished with 87% sensitivity and 69% specificity from control subjects with abnormal scores by excessive differences between training performance and the actual test. Experiment 4 investigated patients with traumatic brain injury (TBI): patients with mild TBI performed within the normal range while patients with severe TBI showed deficits. The DA-PASAT reduces the time and stress of PASAT assessment while gathering sensitive measures of dyad processing that reveal the effects of aging, malingering, and traumatic brain injury on performance. PMID:29677192

Secondary organic aerosol formation from in situ OH, O 3, and NO 3 oxidation of ambient forest air in an oxidation flow reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.

Ambient pine forest air was oxidized by OH, O 3, or NO 3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio–hydro–atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics and Nitrogen – Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O 3 and NO 3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20–30 min, in order to determine how the availability of SOAmore » precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O 3 or NO 3 oxidation. This is likely because O 3 and NO 3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O 3 and NO 3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O 3 and NO 3 oxidation produced SOA with elemental O : C and H : C similar to the least-oxidized OA observed in local ambient air, and neither oxidant led to net mass loss at the highest exposures, in contrast to OH oxidation. An OH exposure in the OFR equivalent to several hours of atmospheric aging also produced SOA with O : C and H : C values similar to ambient OA, while higher aging (days–weeks) led to formation of SOA with progressively higher O : C and lower H : C (and net mass loss at the highest exposures). NO 3 oxidation led to the production of particulate organic nitrates (pRONO 2), while OH and O 3 oxidation (under low NO) did not, as expected. As a result, these measurements of SOA formation provide the first direct comparison of SOA formation potential and chemical evolution from OH, O 3, and NO 3 oxidation in the real atmosphere and help to clarify the oxidation processes that lead to SOA formation from biogenic hydrocarbons.« less

Secondary organic aerosol formation from in situ OH, O 3, and NO 3 oxidation of ambient forest air in an oxidation flow reactor

DOE PAGES

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.; ...

2017-04-25

Ambient pine forest air was oxidized by OH, O 3, or NO 3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio–hydro–atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics and Nitrogen – Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O 3 and NO 3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20–30 min, in order to determine how the availability of SOAmore » precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O 3 or NO 3 oxidation. This is likely because O 3 and NO 3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O 3 and NO 3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O 3 and NO 3 oxidation produced SOA with elemental O : C and H : C similar to the least-oxidized OA observed in local ambient air, and neither oxidant led to net mass loss at the highest exposures, in contrast to OH oxidation. An OH exposure in the OFR equivalent to several hours of atmospheric aging also produced SOA with O : C and H : C values similar to ambient OA, while higher aging (days–weeks) led to formation of SOA with progressively higher O : C and lower H : C (and net mass loss at the highest exposures). NO 3 oxidation led to the production of particulate organic nitrates (pRONO 2), while OH and O 3 oxidation (under low NO) did not, as expected. As a result, these measurements of SOA formation provide the first direct comparison of SOA formation potential and chemical evolution from OH, O 3, and NO 3 oxidation in the real atmosphere and help to clarify the oxidation processes that lead to SOA formation from biogenic hydrocarbons.« less

Source apportionment of organic aerosol across Houston, TX during DISCOVER-AQ

NASA Astrophysics Data System (ADS)

Yoon, S.; Clark, A. E.; Ortiz, S. M.; Usenko, S.; Sheesley, R. J.

2015-12-01

As part of the ground-based sampling efforts during DISCOVER-AQ's Houston month-long campaign in September 2013, atmospheric particulate matter (PM) samples were collected at four sites: Moody Tower (urban), Manvel Croix (southern suburb), Conroe (northern suburb), and La Porte (urban industrial). The Houston metropolitan area, especially the Houston Ship Channel, is a densely industrialized urban city with large concentrations of petroleum refining, petrochemical manufacturing, and heavy traffic during peak hours. Due to these and other emission sources, the area is heavily impacted by ambient PM. This study will be looking at fine PM (diameter less than 2.5µm, PM2.5) from all four sites. PM2.5fraction is relevant for understanding fate and transport of organic contaminants and is widely known to negatively impact human health. Chemical analysis including radiocarbon (14C) and organic tracer measurements (polycyclic aromatic hydrocarbons, alkanes, hopanes, steranes, and levoglucosan) were used for source apportionment. The 14C measurements constrained CMB results to estimate both primary and secondary contributions to total organic carbon (TOC). Results indicate that Moody Tower had consistent primary motor vehicle exhaust contribution (18-27%) and a fossil secondary organic aerosol (SOA) contribution from 5-33% depending on atmospheric conditions. Conroe had a lower contribution of motor vehicle exhaust (5-10%) and similarly variable fraction of fossil SOA (4-25%). Manvel Croix had an interim motor vehicle contribution (9-15%) with a variable fossil SOA (5-30%). For contemporary OC, there was minimal contribution of wood smoke during examined weeks (0-9%) but larger contributor of biogenic SOA ranging from 40-75% at Moody Tower, 56-81% at Manvel Croix and 60-79% at Conroe. Overall, the motor vehicle contribution was consistent at each site during the analysis week, biogenic SOA was consistently high, while fossil SOA showed the most variability.

Aging of plumes from emission sources based on chamber simulation

NASA Astrophysics Data System (ADS)

Wang, X.; Deng, W.; Fang, Z.; Bernard, F.; Zhang, Y.; Yu, J.; Mellouki, A.; George, C.

2017-12-01

Study on atmospheric aging of plumes from emission sources is essential to understand their contribution to both secondary and primary pollutants occurring in the ambient air. Here we directly introduced vehicle exhaust, biomass burning plume, industrial solvents and cooking plumes into a smog chamber with 30 m3 fluorinated ethylene propylene (FEP) Teflon film reactor housed in a temperature-controlled enclosure, for characterizing primarily emitted air pollutants and for investigating secondarily formed products during photo-oxidation. Moreover, we also initiated study on the formation of secondary aerosols when gasoline vehicle exhaust is mixed with typical coal combustion pollutant SO2 or typical agricultural-related pollutant NH3. Formation of secondary organic aerosols (SOA) from typical solvent toluene was also investigated in ambient air matrix in comparison with purified air matrix. Main findings include: 1) Except for exhaust from idling gasoline vehicles, traditional precursor volatile organic compounds could only explain a very small fraction of SOA formed from vehicle exhaust, biomass burning or cooking plumes, suggesting knowledge gap in SOA precursors; 2) There is the need to re-think vehicle emission standards with a combined primary and/or secondary contribution of vehicle exhaust to PM2.5 or other secondary pollutants such as ozone; 3) When mixed with SO2, the gasoline vehicle exhaust revealed an increase of SOA production factor by 60-200% and meanwhile SO2 oxidation rates increased about a factor of 2.7; when the aged gasoline vehicle exhaust were mixing with NH3, both particle number and mass concentrations were increasing explosively. These phenomenons implied the complex interaction during aging of co-existing source emissions. 4) For typical combination of "tolune+SO2+NOx", when compared to chamber simulation with purified air as matrix, both SOA formation and SO2 oxidation were greatly enhanced under ambient air matrix, and the enhancement of SO2 oxidation was found be largely heterogonous and the enhancement of SOA formation seemed to be acid-catalyzed.

Primary emissions and chemical oxidation of volatile organic compounds emitted from laboratory biomass burning sources during the 2016 FIREX FireLab campaign: measurements from a H3O+ chemical ionization mass spectrometer

NASA Astrophysics Data System (ADS)

Coggon, M. M.; Warneke, C.; Koss, A.; Sekimoto, K.; Yuan, B.; Lim, C. Y.; Hagan, D. H.; Kroll, J. H.; Cappa, C. D.; Gilman, J.; Lerner, B. M.; Jimenez, J. L.; Yokelson, R. J.; Roberts, J. M.; De Gouw, J. A.

2017-12-01

Non-methane organic gases (NMOG) emitted by biomass burning constitute a large source of reactive carbon in the atmosphere. Once emitted, these compounds may undergo series of reactions with the OH radical and nitrogen oxides to form secondary organic aerosol (SOA), ozone, or other health-impacting products. The complex emission profile and strong variability of biomass burning NMOG play an important, yet understudied, role in the variability of air quality outcomes such as SOA and ozone. In this study, we summarize measurements of biomass burning volatile organic compounds (VOCs) conducted using a H3O+ chemical ionization mass spectrometer (H3O+-CIMS) during the 2016 FIREX laboratory campaign in Missoula, MT. Specifically, we will present data demonstrating the chemical evolution of biomass burning VOCs artificially aged in a field-deployable photooxidation chamber and an oxidation flow reactor. More than 50 OH-oxidation experiments were conducted with biomass types representing a range of North American fuels. Across many fuel types, VOCs with high SOA and ozone formation potential, such as aromatics and furans, were observed to quickly react with the OH radical while oxidized species were generated. We compare the calculated OH reactivity of the primary emissions to the calculated OH reactivity used in many photochemical models and highlight areas requiring additional research in order to improve model/measurement comparisons.

Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

NASA Astrophysics Data System (ADS)

Badali, K. M.; Zhou, S.; Aljawhary, D.; Antiñolo, M.; Chen, W. J.; Lok, A.; Mungall, E.; Wong, J. P. S.; Zhao, R.; Abbatt, J. P. D.

2015-07-01

This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are 5 times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions, assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloud water and aerosol chemistry.

Effect of Organic Coatings, Humidity and Aerosol Acidity on Multiphase Chemistry of Isoprene Epoxydiols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riva, Matthieu; Bell, David M.; Hansen, Anne-Maria Kaldal

2016-06-07

Multiphase chemistry of isomeric isoprene epoxydiols (IEPOX) has been shown to be the dominant source of isoprene-derived secondary organic aerosol (SOA). Recent studies have reported particles composed of ammonium bisulfate (ABS) mixed with model organics exhibit slower rates of IEPOX uptake. In the present study, we investigate the effect of atmospherically-relevant organic coatings of α-pinene (AP) SOA on the reactive uptake of trans-β-IEPOX onto ABS particles under different conditions and coating thicknesses. Single particle mass spectrometry was used to characterize in real-time particle size, shape, density, and quantitative composition before and after reaction with IEPOX. We find that IEPOX uptakemore » by pure sulfate particles is a volume-controlled process, which results in particles with uniform concentration of IEPOX-derived SOA across a wide range of sizes. Aerosol acidity was shown to enhance IEPOX-derived SOA formation, consistent with recent studies. The presence of water has a weaker impact on IEPOX-derived SOA yield, but significantly enhanced formation of 2-methyltetrols, consistent with offline filter analysis. In contrast, IEPOX uptake by ABS particles coated by AP-derived SOA is strongly dependent on particle size and composition. IEPOX uptake occurred only when weight fraction of AP-derived SOA dropped below 50 %, effectively limiting IEPOX uptake to larger particles.« less

Mixing of secondary organic aerosols versus relative humidity

PubMed Central

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.

PubMed

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.

The Optical Properties of Limonene Secondary Organic Aerosols: The Role of NO3, OH, and O3 in the Oxidation Processes

NASA Astrophysics Data System (ADS)

Peng, Chao; Wang, Weigang; Li, Kun; Li, Junling; Zhou, Li; Wang, Lingshu; Ge, Maofa

2018-03-01

Limonene, a typical proxy of monoterpenes emitted from biogenic sources, plays an important role in secondary organic aerosol (SOA) formation. However, the optical properties of SOA generated from limonene under various oxidation pathways remain poorly understood. In this study, we investigate the refractive index (RI) of limonene SOA produced from four oxidation conditions with cavity ring-down spectrometer (CRDS) and photoacoustic extinctiometer operated at 532 and 375 nm. Our results show that there is a significant difference in RI values of SOA produced from NO3 oxidation compared to other oxidation pathways. The mean values of RI of SOA produced from NO3 oxidation, NOx oxidation, OH oxidation with NOx-free, and O3 oxidation experiments are 1.578, 1.469, 1.495, and 1.494 at 532 nm; and 1.591, 1.527, 1.513, and 1.537 at 375 nm, respectively, while no detectable absorption is found in all oxidation conditions. We attribute the high RI values of SOA by NO3 oxidation to two factors: a large proportion of organic nitrates and high-molecular-weight dimers/oligomers in the SOA. Our study results indicate that the nighttime chemistry may significantly influence the optical properties of limonene oxidation products. The RI values of limonene SOA generated under various oxidation conditions at different wavelengths retrieved in our laboratory experiments could help improve the model predictions for evaluating the effect of biogenic SOA on the global radiative forcing as well as climate change.

Hydroxyl radicals from secondary organic aerosol decomposition in water

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

Hydroxyl radicals from secondary organic aerosol decomposition in water

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2012-03-01

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

Effect of SO2 and Photolysis on Photooxidized Diesel Fuel Secondary Organic Aerosol Composition

NASA Astrophysics Data System (ADS)

MacMillan, A. C.; Blair, S. L.; Lin, P.; Laskin, A.; Laskin, J.; Nizkorodov, S.

2014-12-01

Diesel fuel (DSL) and sulfur dioxide (SO2) are important precursors to secondary organic aerosol (SOA) formation. DSL is often co-emitted with SO2 and NO2, thus it is important to understand the possible effects of SO2 on DSL SOA composition. Additionally, DSL SOA composition can be affected by photochemical aging processes such as photolysis. In this study, DSL SOA was first prepared under dry, high-NOx conditions with various concentrations of SO2 by photooxidation in a smog chamber. The SOA was then stripped of excess oxidants and gaseous organics with a denuder train and the resulting particles were photolyzed at various photolysis times in a quartz flow tube. The SOA composition, photochemical aging, properties, and mass concentration, before and after direct photolysis in the flow tube, were examined using several techniques. High-resolution mass spectrometry (HR-MS) was performed on DSL SOA samples to investigate the effect of SO2 on molecular level composition. SOA composition as a function of photolysis time was measured with an aerosol mass spectrometer (AMS). HR-MS results show that organosulfates are produced in DSL SOA. Both AMS and HR-MS results show that photolysis also has an effect on composition; though, this is more apparent in the HR-MS results than in the AMS results. In summary, both the presence of SO2 and solar radiation has an effect on DSL SOA composition.

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

PubMed

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

2011-09-01

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

Effect of solar radiation on the optical properties and molecular composition of laboratory proxies of atmospheric brown carbon.

PubMed

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

2014-09-02

Sources, optical properties, and chemical composition of atmospheric brown carbon (BrC) aerosol are uncertain, making it challenging to estimate its contribution to radiative forcing. Furthermore, optical properties of BrC may change significantly during its atmospheric aging. We examined the effect of photolysis on the molecular composition, mass absorption coefficient, and fluorescence of secondary organic aerosol (SOA) prepared by high-NOx photooxidation of naphthalene (NAP SOA). Our experiments were designed to model photolysis processes of NAP SOA compounds dissolved in cloud or fog droplets. Aqueous solutions of NAP SOA were observed to photobleach (i.e., lose their ability to absorb visible radiation) with an effective half-life of ∼15 h (with sun in its zenith) for the loss of near-UV (300-400 nm) absorbance. The molecular composition of NAP SOA was significantly modified by photolysis, with the average SOA formula changing from C14.1H14.5O5.1N0.085 to C11.8H14.9O4.5N0.023 after 4 h of irradiation. However, the average O/C ratio did not change significantly, suggesting that it is not a good metric for assessing the extent of photolysis-driven aging in NAP SOA (and in BrC in general). In contrast to NAP SOA, the photobleaching of BrC material produced by the reaction of limonene + ozone SOA with ammonia vapor (aged LIM/O3 SOA) was much faster, but it did not result in a significant change in average molecular composition. The characteristic absorbance of the aged LIM/O3 SOA in the 450-600 nm range decayed with an effective half-life of <0.5 h. These results emphasize the highly variable and dynamic nature of different types of atmospheric BrC.

Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

NASA Astrophysics Data System (ADS)

Woody, M. C.; Baker, K. R.; Hayes, P. L.; Jimenez, J. L.; Koo, B.; Pye, H. O. T.

2015-10-01

Community Multiscale Air Quality (CMAQ) model simulations utilizing the volatility basis set (VBS) treatment for organic aerosols (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of organic aerosol (OA) in southern California. CMAQ-VBS (OA lumped by volatility, semivolatile POA) underpredicted total organic carbon (OC) at CSN (-25.5 % Normalized Median Bias (NMdnB)) and IMPROVE (-63.9 % NMdnB) locations and total OC was underpredicted to a greater degree compared to the CMAQ-AE6 (9.9 and -55.7 % NMdnB, respectively; semi-explicit OA treatment, SOA lumped by parent hydrocarbon, nonvolatile POA). However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA indicated that CMAQ-VBS better represented the diurnal profile and the primary/secondary split of OA. CMAQ-VBS secondary organic aerosol (SOA) underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate of SOA) concentration by a factor of 5.2 (4.7 μg m-3 measured vs. 0.9 μg m-3 modeled), a considerable improvement to CMAQ-AE6 SOA predictions, which were approximately 24× lower than the average AMS OOA concentration. We use two new methods, based on species ratios and on a simplified SOA parameterization from the observations, to apportion the SOA underprediction for CMAQ-VBS to too slow photochemical oxidation (estimated as 1.5× lower than observed at Pasadena using - log (NOx: NOy)), low intrinsic SOA formation efficiency (low by 1.6 to 2× for Pasadena), and too low emissions or too high dispersion for the Pasadena site (estimated to be 1.6 to 2.3× too low/high). The first and third factors will be similar for CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7×. For CMAQ-VBS, 90 % of the anthropogenic SOA mass formed was attributed to aged secondary semivolatile vapors (70 % originating from volatile organic compounds (VOCs) and 20 % from intermediate volatility compounds (IVOCs)). From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, and consistent with a substantial fraction of cooking OA in the observations), compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g. industrial/point sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 (1.16 μg m-3 modeled vs. 2.05 μg m-3 observed) compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but did well to capture the AMS diurnal profile of HOA and CIOA, with the exception of the midday peak. We estimated that using the National Emission Inventory (NEI) POA emissions without scaling to represent SVOCs underestimates SVOCs by ~1.7×.

Uptake of Semivolatile Secondary Organic Aerosol Formed from α-Pinene into Nonvolatile Polyethylene Glycol Probe Particles.

PubMed

Ye, Penglin; Ding, Xiang; Ye, Qing; Robinson, Ellis S; Donahue, Neil M

2016-03-10

Semivolatile organic compounds (SVOCs) play an essential role in secondary organic aerosol (SOA) formation, chemical aging, and mixing of organic aerosol (OA) from different sources. Polyethylene glycol (PEG400) particles are liquid, polar, and nearly nonvolatile; they provide a new vehicle to study the interaction between SVOCs with OA. With a unique fragment ion C4H9O2(+) (m/z 89), PEG400 can be easily separated from α-pinene SOA in aerosol mass spectra. By injecting separately prepared PEG probe particles into a chamber containing SOA coated on ammonium sulfate seeds, we show that a substantial pool of SVOCs exists in equilibrium with the original SOA particles. Quantitative findings are based on bulk mass spectra, size-dependent composition, and the evolution of individual particle mass spectra, which we use to separate the two particle populations. We observed a larger fraction of SVOC vapors with increased amounts of reacted α-pinene. For the same amount of reacted α-pinene, the SOA formed from α-pinene oxidized by OH radicals had a higher fraction of SOA vapors than SOA formed by α-pinene ozonolysis. Compared to the PEG400 probe particles, we observed a lower mass fraction of SVOCs in poly(ethylene glycol) dimethyl ether (MePEG500) probe particles under otherwise identical conditions; this may be due to the lower polarity of the MePEG500 or caused by esterification reactions between the PEG400 and organic acids in the SOA.

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

Chemical composition of aerosol particles and light extinction apportionment before and during the heating season in Beijing, China

NASA Astrophysics Data System (ADS)

Wang, Qingqing; Sun, Yele; Jiang, Qi; Du, Wei; Sun, Chengzhu; Fu, Pingqing; Wang, Zifa

2015-12-01

Despite extensive efforts into characterization of the sources and formation mechanisms of severe haze pollution in the megacity of Beijing, the response of aerosol composition and optical properties to coal combustion emissions in the heating season remain poorly understood. Here we conducted a 3 month real-time measurement of submicron aerosol (PM1) composition by an Aerosol Chemical Speciation Monitor and particle light extinction by a Cavity Attenuated Phase Shift extinction monitor in Beijing, China, from 1 October to 31 December 2012. The average (±σ) PM1 concentration was 82.4 (±73.1) µg/m3 during the heating period (HP, 15 November to 31 December), which was nearly 50% higher than that before HP (1 October to 14 November). While nitrate and secondary organic aerosol (SOA) showed relatively small changes, organics, sulfate, and chloride were observed to have significant increases during HP, indicating the dominant impacts of coal combustion sources on these three species. The relative humidity-dependent composition further illustrated an important role of aqueous-phase processing for the sulfate enhancement during HP. We also observed great increases of hydrocarbon-like OA (HOA) and coal combustion OA (CCOA) during HP, which was attributed to higher emissions at lower temperatures and coal combustion emissions, respectively. The relationship between light extinction and chemical composition was investigated using a multiple linear regression model. Our results showed that the largest contributors to particle extinction were ammonium nitrate (32%) and ammonium sulfate (28%) before and during HP, respectively. In addition, the contributions of SOA and primary OA to particle light extinction were quantified. The results showed that the OA extinction was mainly caused by SOA before HP and by SOA and CCOA during HP, yet with small contributions from HOA and cooking aerosol for the entire study period. Our results elucidate substantial changes of aerosol composition, formation mechanisms, and optical properties due to coal combustion emissions and meteorological changes in the heating season.

Aqueous SOA formation from radical oligomerization of methyl vinyl ketone (MVK) and methacrolein (MACR)

NASA Astrophysics Data System (ADS)

Renard, P.; Siekmann, F.; Ravier, S.; Temime-Roussel, B.; Clément, J.; Ervens, B.; Monod, A.

2013-12-01

It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from α-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. We have investigated the aqueous phase photooxidation of MACR and MVK, which are biogenic organic compounds derived from isoprene. Aqueous phase photooxidation of MVK and MACR was investigated in a photoreactor using photolysis of H2O2 as OH radical source. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature (T = 298 K) and highest precursor initial concentrations ([MVK]0 = 20 mM). A radical mechanism of oligomerization is proposed to explain the formation of the high molecular weight products. Furthermore, we quantified the total amount of carbon present in oligomers. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the atmospheric multiphase system as compared to other aqueous phase as well as traditional SOA sources. MVK time profile (as measured by UV Spectroscopy) and mass spectra (obtained using UPLC-ESI-MS for the retention time range 0-5 min in the positive mode) at 5, 10 and 50 min of reaction (MVK 20 mM, 25° C, under supersaturated O2 initial conditions).

Sense of agency is related to gamma band coupling in an inferior parietal-preSMA circuitry

PubMed Central

Ritterband-Rosenbaum, Anina; Nielsen, Jens B.; Christensen, Mark S.

2014-01-01

In the present study we tested whether sense of agency (SoA) is reflected by changes in coupling between right medio-frontal/supplementary motor area (SMA) and inferior parietal cortex (IPC). Twelve healthy adult volunteers participated in the study. They performed a variation of a line-drawing task (Nielsen, 1963; Fourneret and Jeannerod, 1998), in which they moved a cursor on a digital tablet with their right hand without seeing the hand. Visual feedback displayed on a computer monitor was either in correspondence with or deviated from the actual movement. This made participants uncertain as to the agent of the movement and they reported SoA in approximately 50% of trials when the movement was computer-generated. We tested whether IPC-preSMA coupling was associated with SoA, using dynamic causal modeling (DCM) for induced responses (Chen et al., 2008; Herz et al., 2012). Nine different DCMs were constructed for the early and late phases of the task, respectively. All models included two regions: a superior medial gyrus (preSMA) region and a right supramarginal gyrus (IPC) region. Bayesian models selection (Stephan et al., 2009) favored a model with input to IPC and modulation of the forward connection to SMA in the late task phase, and a model with input to preSMA and modulation of the backward connection was favored for the early task phase. The analysis shows that IPC source activity in the 50–60 Hz range modulated preSMA source activity in the 40–70 Hz range in the presence of SoA compared with no SoA in the late task phase, but the test of the early task phase did not reveal any differences between presence and absence of SoA. We show that SoA is associated with a directionally specific between frequencies coupling from IPC to preSMA in the higher gamma (ɣ) band in the late task phase. This suggests that SoA is a retrospective perception, which is highly dependent on interpretation of the outcome of the performed action. PMID:25076883

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

During the 2013 Southern Oxidant and Aerosol Study, Fourier Transform Infrared Spectroscopy (FTIR) and Aerosol Mass Spectrometer (AMS) measurements of submicron mass were collected at Look Rock, Tennessee, and Centreville, Alabama. The low NOx, low wind, little rain, and increased daytime isoprene emissions led to multi-day stagnation events at Look Rock that provided clear evidence of particle-phase sulfate enhancing biogenic secondary organic aerosol (bSOA) by selective uptake. Organic mass (OM) sources were apportioned as 42% "vehicle-related" and 54% bSOA, with the latter including "sulfate-related bSOA" that correlated to sulfate (r=0.72) and "nitrate-related bSOA" that correlated to nitrate (r=0.65). Single-particle mass spectra showed three composition types that corresponded to the mass-based factors with spectra cosine similarity of 0.93 and time series correlations of r>0.4. The vehicle-related OM with m/z 44 was correlated to black carbon, "sulfate-related bSOA" was on particles with high sulfate, and "nitrate-related bSOA" was on all particles. The similarity of the m/z spectra (cosine similarity=0.97) and the time series correlation (r=0.80) of the "sulfate-related bSOA" to the sulfate-containing single-particle type provide evidence for particle composition contributing to selective uptake of isoprene oxidation products onto particles that contain sulfate from power plants. Since Look Rock had much less NOx than Centreville, comparing the bSOA at the two sites provides an evaluation of the role of NOx for bSOA. CO and submicron sulfate and OM concentrations were 15-60 % higher at Centreville than at Look Rock but their time series had moderate correlations of r= 0.51, 0.54, and 0.47, respectively. However, NOx had no correlation (r=0.08) between the two sites. OM correlated with the higher NOx levels at Centreville but with O3 at Look Rock. OM sources identified by Positive Matrix Factorization had three very similar factors at both sites from FTIR, one of which was Biological Organic Aerosols. The FTIR spectrum for this factor is similar (cosine similarity > 0.6) to that of lab-generated particle mass from both isoprene and monoterpene with high NOx conditions from chamber experiments, providing verification of the reactions relevant to atmospheric conditions.

Model Representation of Secondary Organic Aerosol in CMAQ v4.7

EPA Science Inventory

Numerous scientific upgrades to the representation of secondary organic aerosol (SOA) are incorporated into the Community Multiscale Air Quality (CMAQ) modeling system. Additions include several recently identified SOA precursors: benzene, isoprene, and sesquiterpenes; and pathwa...

Characterization of secondary organic aerosol generated from ozonolysis of α-pinene mixtures

NASA Astrophysics Data System (ADS)

Amin, Hardik S.; Hatfield, Meagan L.; Huff Hartz, Kara E.

2013-03-01

In the atmosphere, multiple volatile organic compounds (VOCs) co-exist, and they can be oxidized concurrently and generate secondary organic aerosol (SOA). In this work, SOA is formed by the oxidation (in presence of excess ozone) of mixtures containing α-pinene and other VOCs. The VOC mixtures were made so their composition approached a commercially-available α-pinene-based essential oil, Siberian fir needle oil. The SOA products were sampled using filters, solvent extracted and analyzed by gas chromatography/mass spectrometry with trimethylsilyl derivatization. The individual product yields for SOA generated from α-pinene changed upon the addition of other VOCs. An increase in concentration of non-reactive VOCs (bornyl acetate, camphene, and borneol) lead to a decrease in individual product yields of characteristic α-pinene SOA products. Although these experiments were carried out under higher VOC and ozone concentrations in comparison to the atmosphere, this work suggests that the role of non-reactive VOCs should be explored in SOA products formation.

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

NASA Astrophysics Data System (ADS)

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).

Best Practices for Artifact Versioning in Service-Oriented Systems

DTIC Science & Technology

2012-01-01

and endpoint [OASIS 2004]. But as Peltz and Anagol- Subbarao warn, “[I]t can be appealing to version down to the very lowest levels in accordance...Schemes There are multiple sources for typical naming schemes in SOA environments: • Anagol- Subbarao and Peltz provide service naming schemes, including...service versioning. 3. Extensions must not use the targetNamespace value. Peltz and Anagol- Subbarao provide additional guidance on how to implement

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

NASA Astrophysics Data System (ADS)

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

2015-08-01

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

Characterization of a real-time tracer for Isoprene Epoxydiols-derived Secondary Organic Aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

NASA Astrophysics Data System (ADS)

Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

2015-04-01

Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene low-NO oxidation pathways, was quantified by applying Positive Matrix Factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of OA in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the SOAS study, 78% of IEPOX-SOA is accounted for the measured molecular tracers, making it the highest level of molecular identification of an ambient SOA component to our knowledge. Enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O ( fC5H6O = C5H6O+/OA) across multiple field, chamber and source datasets. A background of ~ 1.7 ± 0.1‰ is observed in studies strongly influenced by urban, biomass-burning and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.8‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7‰). Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3‰) observed in non IEPOX-derived isoprene-SOA indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a "triangle plot" of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2 if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass resolution data is available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Effect of Solar Radiation on the Optical Properties and Molecular Composition of Laboratory Proxies of Atmospheric Brown Carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Hyun Ji; Aiona, Paige K.; Laskin, Alexander

2014-09-02

Sources, optical properties, and chemical composition of atmospheric brown carbon (BrC) aerosol are uncertain, making it challenging to estimate its contribution to radiative forcing. Furthermore, optical properties of BrC may change significantly during its atmospheric aging. We examined the effect of solar photolysis on the molecular composition, mass absorption coefficient, and fluorescence of secondary organic aerosol prepared by high-NO x photooxidation of naphthalene (NAP SOA). The aqueous solutions of NAP SOA was observed to photobleach with an effective half-time of ~15 hours (with sun in its zenith) for the loss of the near-UV (300 -400 nm) absorbance. The molecular compositionmore » of NAP SOA was significantly modified by photolysis, with the average SOA formula changing from C 14.1H 14.5O 5.1N 0.08 to C 11.8H 14.9O 4.5N 0.02 after 4 hours of irradiation. The average O/C ratio did not change significantly, however, suggesting that it is not a good metric for assessing the extent of photolysis-driven aging in NAP SOA (and in BrC in general). In contrast to NAP SOA, the photolysis of BrC material produced by aqueous reaction of limonene+O 3 SOA (LIM/O 3 SOA) with ammonium sulfate was much faster, but it did not result in a significant change in the molecular level composition. The characteristic absorbance of the aged LIM/O 3 SOA in the 450-600 nm range decayed with an effective half-time of <0.5 hour. This result emphasizes the highly variable and dynamic nature of different types of atmospheric BrC.« less

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

NASA Astrophysics Data System (ADS)

Tasoglou, A.; Pandis, S. N.

2015-06-01

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

"Do You Feel in Control?": Towards Novel Approaches to Characterise, Manipulate and Measure the Sense of Agency in Virtual Environments.

PubMed

Jeunet, Camille; Albert, Louis; Argelaguet, Ferran; Lecuyer, Anatole

2018-04-01

While the Sense of Agency (SoA) has so far been predominantly characterised in VR as a component of the Sense of Embodiment, other communities (e.g., in psychology or neurosciences) have investigated the SoA from a different perspective proposing complementary theories. Yet, despite the acknowledged potential benefits of catching up with these theories a gap remains. This paper first aims to contribute to fill this gap by introducing a theory according to which the SoA can be divided into two components, the feeling and the judgment of agency, and relies on three principles, namely the principles of priority, exclusivity and consistency. We argue that this theory could provide insights on the factors influencing the SoA in VR systems. Second, we propose novel approaches to manipulate the SoA in controlled VR experiments (based on these three principles) as well as to measure the SoA, and more specifically its two components based on neurophysiological markers, using ElectroEncephaloGraphy (EEG). We claim that these approaches would enable us to deepen our understanding of the SoA in VR contexts. Finally, we validate these approaches in an experiment. Our results (N=24) suggest that our approach was successful in manipulating the SoA as the modulation of each of the three principles induced significant decreases of the SoA (measured using questionnaires). In addition, we recorded participants' EEG signals during the VR experiment, and neurophysiological markers of the SoA, potentially reflecting the feeling and judgment of agency specifically, were revealed. Our results also suggest that users' profile, more precisely their Locus of Control (LoC), influences their level of immersion and SoA.

A perspective on SOA generated in aerosol water from glyoxal and methylglyoxal and its impacts on climate-relevant aerosol properties

NASA Astrophysics Data System (ADS)

Sareen, N.; McNeill, V. F.

2011-12-01

In recent years, glyoxal and methylglyoxal have emerged to be potentially important SOA precursors with significant implications for climate-related aerosol properties. Here we will discuss how the chemistry of these and similar organic compounds in aerosol water can affect the aerosol optical and cloud formation properties. Aqueous-phase SOA production from glyoxal and methylglyoxal is a potential source of strongly light-absorbing organics, or "brown carbon". We characterized the kinetics of brown carbon formation from these precursors in mixtures of ammonium sulfate and water using UV-Vis spectrophotometry. This mechanism has been incorporated into a photochemical box model with coupled gas phase-aqueous aerosol chemistry. Methylglyoxal and related compounds also may impact an aerosol's ability to act as a cloud condensation nucleus. We recently showed via pendant drop tensiometry and aerosol chamber studies that uptake of methylglyoxal from the gas phase driven by aqueous-phase oligomerization chemistry is a potentially significant, previously unidentified source of surface-active organic material in aerosols. Results from pendant drop tensiometry showed significantly depressed surface tension in methylglyoxal-ammonium sulfate solutions. We further found that ammonium sulfate particles exposed to gas-phase methylglyoxal in a 3.5 m3 aerosol reaction chamber activate into cloud droplets at sizes up to 15% lower at a given supersaturation than do pure ammonium sulfate particles. The observed enhancement exceeds that predicted based on Henry's Law and our measurements of surface tension depression in bulk solutions, suggesting that surface adsorption of methylglyoxal plays a role in determining CCN activity. Methylglyoxal and similar gas-phase surfactants may be an important and overlooked source of enhanced CCN activity in the atmosphere. To characterize the SOA products formed in these solutions, an Aerosol Chemical Ionization Mass Spectrometer (CIMS) was used. These compounds included (hemi)acetals, aldol condensation products, and oligomeric species up to 759 amu. Since these products are vulnerable to oxidants such as O3 and OH in the atmosphere, kinetic studies were conducted to study their affect upon exposure to O3 and OH. Custom-designed flow tube reactors were coupled with the Aerosol-CIMS to monitor aerosol composition, and consequently this data was used to determine reactive uptake coefficients (γO3~10-8 and γOH~ 10-6). Additionally, the lifetime of these SOA species in the atmosphere can be estimated and if these time scales are sufficiently long, they may affect aerosol optical properties. The effect of oxidation on the optical properties is also currently being tested by collecting aerosol particles before and after oxidation on a quartz window and testing changes in absorption using the UV-Vis spectrophotometer. The results of all these studies will be integrated to understand the role of methylglyoxal as a SOA precursor and the effect on various aerosol properties, and this will be used as a model system to predict the fate of similar organics in the atmosphere.

Identifying organic aerosol sources by comparing functional group composition in chamber and atmospheric particles

PubMed Central

Russell, Lynn M.; Bahadur, Ranjit; Ziemann, Paul J.

2011-01-01

Measurements of submicron particles by Fourier transform infrared spectroscopy in 14 campaigns in North America, Asia, South America, and Europe were used to identify characteristic organic functional group compositions of fuel combustion, terrestrial vegetation, and ocean bubble bursting sources, each of which often accounts for more than a third of organic mass (OM), and some of which is secondary organic aerosol (SOA) from gas-phase precursors. The majority of the OM consists of alkane, carboxylic acid, hydroxyl, and carbonyl groups. The organic functional groups formed from combustion and vegetation emissions are similar to the secondary products identified in chamber studies. The near absence of carbonyl groups in the observed SOA associated with combustion is consistent with alkane rather than aromatic precursors, and the absence of organonitrate groups can be explained by their hydrolysis in humid ambient conditions. The remote forest observations have ratios of carboxylic acid, organic hydroxyl, and nonacid carbonyl groups similar to those observed for isoprene and monoterpene chamber studies, but in biogenic aerosols transported downwind of urban areas the formation of esters replaces the acid and hydroxyl groups and leaves only nonacid carbonyl groups. The carbonyl groups in SOA associated with vegetation emissions provides striking evidence for the mechanism of esterification as the pathway for possible oligomerization reactions in the atmosphere. Forest fires include biogenic emissions that produce SOA with organic components similar to isoprene and monoterpene chamber studies, also resulting in nonacid carbonyl groups in SOA. PMID:21317360

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

NASA Astrophysics Data System (ADS)

Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; McKinney, K.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Brito, J.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Alexander, M. L.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

2015-10-01

Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accountedmore » by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C 5H 6O + ( m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine f C5H6O ( f C5H6O= C 5H 6O +/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher f C5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. f C5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low f C5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of f CO2 vs. f C5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the f C5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.« less

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

DOE PAGES

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

2015-10-23

Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accountedmore » by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C 5H 6O + ( m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine f C5H6O ( f C5H6O= C 5H 6O +/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher f C5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. f C5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low f C5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of f CO2 vs. f C5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the f C5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.« less

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

SOA-dependent N400 and P300 semantic priming effects using pseudoword primes and a delayed lexical decision.

PubMed

Hill, Holger; Ott, Friederike; Weisbrod, Matthias

2005-06-01

In a previous semantic priming study, we found a semantic distance effect on the lexical-decision-related P300 when SOA was short (150 ms) only, but no different RT and N400 priming effects between short and long (700 ms) SOAs. To investigate this further, we separated priming from lexical decision, using a delayed lexical decision in the present study. In the short SOA only, primed targets evoked an early peaking (approximately 480 ms) P300-like component, probably because the subject detected the semantic relationship implicitly. We hypothesize that in tasks requiring an immediate lexical decision, this early P300 and the later lexical decision P300 (approximately 600 ms) are additive. Secondly, we found both a direct and an indirect priming effect for both SOAs for the ERP amplitude of the N400 time window. However the N400 component itself was considerably larger in the long SOA than in the short SOA. We interpreted this finding as an ERP correlate for deeper semantic processing in the long SOA, due to increased attention that was provoked by the use of pseudoword primes. In contrast, in the short SOA, subjects might have used a shallowed semantic processing. N400, P300, and RTs are sensitive to semantic priming-but the modulation patterns are not consistent. This raises the question as to which variable reflects an immediate physiological correlate of semantic priming, and which variable reflects co-occurring processes associated with semantic priming.

Formation kinetics and abundance of organic nitrates in α-pinene ozonolysis

NASA Astrophysics Data System (ADS)

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

2016-04-01

Formation of organic nitrates affects the total atmospheric budget of oxidized nitrogen (NOy) and alters the total aerosol mass yield from secondary sources. We investigated the formation of organic nitrate species during ozonolysis of α-pinene and subsequent formation of secondary organic aerosols (SOA) using the short-lived radioactive tracer 13N inside an aerosol flow reactor (Ammann et al., 2001). The results represent direct measurements of the organic nitrate content of α-pinene secondary aerosol and give insight into the kinetics of organic nitrate formation. Organic nitrates constituted up to 40 % of aerosol mass with a pronounced influence during the initial period of particle growth. Kinetic modelling, as well as additional experiments using OH scavengers and UV irradiation, suggests that organic peroxy radicals (RO2) from the reaction of α-pinene with secondarily produced OH are important intermediates in the organic nitrate formation process. Direct oxidation of α-pinene by NO3 was found to be a less efficient pathway for formation of particle phase nitrate. The organic nitrate content decreased very slightly with an increase of relative humidity on the experimental time scale. The experiments show a tight correlation between organic nitrate content and SOA number concentrations, implying that organic nitrates play an important role in nucleation and growth of nanoparticles. Since present in large amounts in organic aerosol, organic nitrates deposited in the lung might have implications for human health as they release nitric acid upon hydrolysis, especially in regions influenced by urban pollution and large sources of monoterpene SOA precursors. References Ammann et al. (2001) Radiochimica Acta 89, 831.

The Influence of Chemical Composition and Relative Humidity on the Optical Properties of Aerosols During the Southern Oxidant and Aerosol Study (SOAS)

NASA Astrophysics Data System (ADS)

Attwood, A. R.; Washenfelder, R. A.; Brock, C. A.; Brown, S. S.; Hu, W.; Campuzano Jost, P.; Day, D. A.; Palm, B. B.; Simoes de Sa, S.; Jimenez, J. L.

2013-12-01

Atmospheric particles are produced from a wide variety of both anthropogenic and natural sources and play an important role in the Earth's radiative budget by direct scattering and absorption of radiation. To address this impact, in situ measurements of aerosol optical, chemical and hygroscopic properties were performed during the Southern Oxidant and Aerosol Study (SOAS), which took place in the summer of 2013. Ground based measurements of sub-micron aerosol in the southeastern United States were made to investigate the influence of chemical composition and hygroscopicity on aerosol optical properties. We report the wavelength dependence of aerosol extinction cross sections measured with a novel broadband cavity enhanced spectrometer covering a wavelength range of 360-420 nm using two light emitting diodes (LED) and a separate cavity ring down (CRDS) channel. The sensitivity of the relative humidity dependence of extinction based on the type of aerosol present is examined and we show that the optical properties and hygroscopicity of aerosols are greatly influenced by the fraction of sulfate and organics within the particles. Additional data analysis from the SOAS campaign will be presented. The results, thus far, illustrate that the variability in aerosol chemical composition can impact visibility and climate forcing in this region.

Secondary organic aerosol formation through cloud processing of aromatic VOCs

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

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

PubMed

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

2013-01-01

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

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

PubMed

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

2017-02-07

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

SOA genes encode proteins controlling lipase expression in response to triacylglycerol utilization in the yeast Yarrowia lipolytica.

PubMed

Desfougères, Thomas; Haddouche, Ramdane; Fudalej, Franck; Neuvéglise, Cécile; Nicaud, Jean-Marc

2010-02-01

The oleaginous yeast Yarrowia lipolytica efficiently metabolizes hydrophobic substrates such as alkanes, fatty acids or triacylglycerol. This yeast has been identified in oil-polluted water and in lipid-rich food. The enzymes involved in lipid breakdown, for use as a carbon source, are known, but the molecular mechanisms controlling the expression of the genes encoding these enzymes are still poorly understood. The study of mRNAs obtained from cells grown on oleic acid identified a new group of genes called SOA genes (specific for oleic acid). SOA1 and SOA2 are two small genes coding for proteins with no known homologs. Single- and double-disrupted strains were constructed. Wild-type and mutant strains were grown on dextrose, oleic acid and triacylglycerols. The double mutant presents a clear phenotype consisting of a growth defect on tributyrin and triolein, but not on dextrose or oleic acid media. Lipase activity was 50-fold lower in this mutant than in the wild-type strain. The impact of SOA deletion on the expression of the main extracellular lipase gene (LIP2) was monitored using a LIP2-beta-galactosidase promoter fusion protein. These data suggest that Soa proteins are components of a molecular mechanism controlling lipase gene expression in response to extracellular triacylglycerol.

Biogenic-Anthropogenic Interactions in Secondary Organic Aerosol Formation and Health Effects of Atmospheric Organic Aerosol

NASA Astrophysics Data System (ADS)

Ye, Jianhuai

Secondary organic aerosol (SOA) formed from oxidation of volatile organic compounds (VOCs), comprises a major fraction of atmospheric submicron particulate matter, which is crucial for global climate change and human health. While biogenic VOCs are naturally emitted and cannot be directly controlled, field measurements and satellite observations have shown that biogenic SOA (BSOA) formation correlates well with anthropogenic pollutants and may be anthropogenically controlled. In this work, the formation of the "anthropogenically controllable BSOA" was examined. BSOA from alpha-pinene ozonolysis was investigated in the presence of laboratory-generated or ambient organic aerosol such as Toronto ambient particles. It is shown that SOA was not equally miscible with all organic species. Aerosol mixing thermodynamics in the atmosphere is composition dependent. Based on laboratory observations, an empirical framework using bulk elemental ratios was developed to predict atmospheric organic miscibility and SOA yield enhancements. Besides organic aerosol, interactions between BSOA formation and SO2 was also examined. Synergistic effects were observed between BSOA formation and SO2 oxidation through Criegee and peroxide chemistry under atmospherically relevant RH conditions. In addition to the physicochemical properties of SOA, health impacts of SOA were examined. An atmospheric simulation reactor (ASR) was developed to investigate the health effects of air pollutants by permitting controlled chronic in vivo exposure of mice to combine particulate and gaseous pollutants at 'real-life' concentrations. Results show that daily exposure to SOA from naphthalene photooxidation led to increased airway hyperresponsiveness (AHR) to methacholine in a dose-dependent manner. Multi-pollutant exposures with ozone and/or NO2 in conjunction with a sub-toxic concentration of SOA resulted in additive effects on AHR to methacholine. Inflammatory cell recruitment to the airways was not observed in any of the exposure conditions, indicating the increased AHR was not associated with airway inflammation and may occur through other mechanisms.

Performance and Challenges of Service-Oriented Architecture for Wireless Sensor Networks.

PubMed

Alshinina, Remah; Elleithy, Khaled

2017-03-08

Wireless Sensor Networks (WSNs) have become essential components for a variety of environmental, surveillance, military, traffic control, and healthcare applications. These applications face critical challenges such as communication, security, power consumption, data aggregation, heterogeneities of sensor hardware, and Quality of Service (QoS) issues. Service-Oriented Architecture (SOA) is a software architecture that can be integrated with WSN applications to address those challenges. The SOA middleware bridges the gap between the high-level requirements of different applications and the hardware constraints of WSNs. This survey explores state-of-the-art approaches based on SOA and Service-Oriented Middleware (SOM) architecture that provide solutions for WSN challenges. The categories of this paper are based on approaches of SOA with and without middleware for WSNs. Additionally, features of SOA and middleware architectures for WSNs are compared to achieve more robust and efficient network performance. Design issues of SOA middleware for WSNs and its characteristics are also highlighted. The paper concludes with future research directions in SOM architecture to meet all requirements of emerging application of WSNs.

Performance and Challenges of Service-Oriented Architecture for Wireless Sensor Networks

PubMed Central

Alshinina, Remah; Elleithy, Khaled

2017-01-01

Wireless Sensor Networks (WSNs) have become essential components for a variety of environmental, surveillance, military, traffic control, and healthcare applications. These applications face critical challenges such as communication, security, power consumption, data aggregation, heterogeneities of sensor hardware, and Quality of Service (QoS) issues. Service-Oriented Architecture (SOA) is a software architecture that can be integrated with WSN applications to address those challenges. The SOA middleware bridges the gap between the high-level requirements of different applications and the hardware constraints of WSNs. This survey explores state-of-the-art approaches based on SOA and Service-Oriented Middleware (SOM) architecture that provide solutions for WSN challenges. The categories of this paper are based on approaches of SOA with and without middleware for WSNs. Additionally, features of SOA and middleware architectures for WSNs are compared to achieve more robust and efficient network performance. Design issues of SOA middleware for WSNs and its characteristics are also highlighted. The paper concludes with future research directions in SOM architecture to meet all requirements of emerging application of WSNs. PMID:28282896

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

A series of smog chamber experiments were conducted to investigate the transformation of primary organic aerosol (POA) and formation of secondary organic aerosol (SOA) during the photooxidation of dilute exhaust from a fleet of gasoline and diesel motor vehicles and two gas-turbine engines. In experiments where POA was present in the chamber at the onset of photooxidation, positive matrix factorization (PMF) was used to determine separate POA and SOA factors from aerosol mass spectrometer data. A 2-factor solution, with one POA factor and one SOA factor, was sufficient to describe the organic aerosol for gasoline vehicles, diesel vehicles, and one of the gas-turbine engines. Experiments with the second gas-turbine engine required a 3-factor PMF solution with a POA factor and two SOA factors. Results from the PMF analysis were compared to the residual method for determining SOA and POA mass concentrations. The residual method apportioned a larger fraction of the organic aerosol mass as POA because it assumes that all mass at m / z 57 is associated with POA. The POA mass spectrum for the gasoline and diesel vehicles exhibited high abundances of the CnH2n+1 series of ions (m / z 43, 57, etc.) and was similar to the mass spectra of the hydrocarbon-like organic aerosol factor determined from ambient data sets with one exception, a diesel vehicle equipped with a diesel oxidation catalyst. POA mass spectra for the gas-turbine engines are enriched in the CnH2n-1 series of ions (m / z 41, 55, etc.), consistent with the composition of the lubricating oil used in these engines. The SOA formed from the three sources exhibits high abundances of m / z 44 and 43, indicative of mild oxidation. The SOA mass spectra are consistent with less-oxidized ambient SV-OOA (semivolatile oxygenated organic aerosols) and fall within the triangular region of f44 versus f43 defined by ambient measurements. However there is poor absolute agreement between the experimentally derived SOA mass spectra and ambient OOA factors, though this poor agreement should be expected based on the variability of ambient OOA factors. Van Krevelen analysis of the POA and SOA factors for gasoline and diesel experiments reveal slopes of -0.50 and -0.40, respectively. This suggests that the oxidation chemistry in these experiments is a combination of carboxylic acid and alcohol/peroxide formation, consistent with ambient oxidation chemistry.

Photolysis of α-KETO Acids in Model Atmospheric Water

NASA Astrophysics Data System (ADS)

Eugene, A. J.; Guzman, M. I.

2017-12-01

Recent work has reported the potential of aqueous-phase photochemistry to promote secondary organic aerosol (SOA) formation. New aqueous photochemical SOA sources may contribute to bridging the gap between field measurements of SOA and models of SOA formation. The ubiquitous α-ketocarboxylic acids pyruvic and glyoxylic acid are known products of the atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) as well as of biogenic volatile organic compounds (VOCs). The combination of a carbonyl chromophore (absorbing at wavelengths λ ≥ 300 nm) and hydrophilic functional groups makes these acids likely candidates for forming aqueous SOA by direct sunlight photolysis. We use a variety of analytical techniques including: 2,4-dinitrophenylhydrazine (DNPH) derivatization; ultra-high performance liquid chromatography (UHPLC) and ion chromatography (IC) coupled to mass spectrometry;1H and 13C NMR; and 13C gCOSY NMR to probe the kinetics and mechanisms of the direct photolysis of model solutions of pyruvic acid and glyoxylic acid. The results indicate that despite the structural similarity between the two acids, they each react via very different primary photochemical pathways. Pyruvic acid undergoes a proton-coupled electron transfer (PCET) mechanism with radical recombination, resulting in CO2 and 6-8 carbon organic acids. In contrast, glyoxylic acid primarily undergoes α-cleavage to generate CO, CO2, and glyoxal which is a key species in SOA formation. This work demonstrates that aqueous photolysis is a very competitive atmospheric sink for both pyruvic and glyoxylic acid, indicating that these photoreactions are capable of contributing substantially to SOA formation.

Terahertz Schottky Multiplier Sources

NASA Technical Reports Server (NTRS)

Schlecht, Erich T.

2007-01-01

This viewgraph presentation reviews the multiplier source technologies and the status/Performance of THz multiplier sources. An example of a THz application is imaging radar. The presentation reviews areas of requirements for THz sources: (1) Figures of merit, (i.e., Frequency Terahertz for high resolution Bandwidth of at least 15 GHz for high range resolution Efficiency (i.e., minimize power supply requirements) (2) Output power: (i.e., Milliwatts below 800 GHz, 10s of microwatts above 1 THz, 1-2 microwatts near 2 THz (3) Mechanical--stability, compact, low mass (4) Environmental -- radiation, vibration, thermal. Several sources for 0.3 - 2 THz are reviewed: FIR lasers, quantum cascade lasers (QCL), backward-wave oscillator (BWO), and Multiplier sources. The current state of the art (SoA) is shown as Substrateless Technology. It also shows where the SoA is for devices beyond 1 THz. The presentation concludes by reviewing the options for future development, and 2 technology roadmaps

Microspectroscopic Analysis of Anthropogenic- and Biogenic-Influenced Aerosol Particles during the SOAS Field Campaign

NASA Astrophysics Data System (ADS)

Ault, A. P.; Bondy, A. L.; Nhliziyo, M. V.; Bertman, S. B.; Pratt, K.; Shepson, P. B.

2013-12-01

During the summer, the southeastern United States experiences a cooling haze due to the interaction of anthropogenic and biogenic aerosol sources. An objective of the summer 2013 Southern Oxidant and Aerosol Study (SOAS) was to improve our understanding of how trace gases and aerosols are contributing to this relative cooling through light scattering and absorption. To improve understanding of biogenic-anthropogenic interactions through secondary organic aerosol (SOA) formation on primary aerosol cores requires detailed physicochemical characterization of the particles after uptake and processing. Our measurements focus on single particle analysis of aerosols in the accumulation mode (300-1000 nm) collected using a multi orifice uniform deposition impactor (MOUDI) at the Centreville, Alabama SEARCH site. Particles were characterized using an array of microscopic and spectroscopic techniques, including: scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and Raman microspectroscopy. These analyses provide detailed information on particle size, morphology, elemental composition, and functional groups. This information is combined with mapping capabilities to explore individual particle spatial patterns and how that impacts structural characteristics. The improved understanding will be used to explore how sources and processing (such as SOA coating of soot) change particle structure (i.e. core shell) and how the altered optical properties impact air quality/climate effects on a regional scale.

Formation of Organic Tracers for Isoprene SOA under Acidic Conditions

EPA Science Inventory

The chemical compositions of a series of secondary organic aerosol (SOA) samples, formed by irradiating mixtures of isoprene and NO in a smog chamber in the absence or presence of acidic aerosols, were analyzed using derivatization-based GC-MS methods. In addition to the known is...

Modeling the formation and properties of traditional and non-traditional secondary organic aerosol: problem formulation and application to aircraft exhaust

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Miracolo, M. A.; Presto, A. A.; Donahue, N. M.; Adams, P. J.; Robinson, A. L.

2012-10-01

We present a methodology to model secondary organic aerosol (SOA) formation from the photo-oxidation of unspeciated low-volatility organics (semi-volatile and intermediate volatile organic compounds) emitted by combustion systems. It is formulated using the volatility basis-set approach. Unspeciated low-volatility organics are classified by volatility and then allowed to react with the hydroxyl radical. The new methodology allows for larger reductions in volatility with each oxidation step than previous volatility basis set models, which is more consistent with the addition of common functional groups and similar to those used by traditional SOA models. The methodology is illustrated using data collected during two field campaigns that characterized the atmospheric evolution of dilute gas-turbine engine emissions using a smog chamber. In those experiments, photo-oxidation formed a significant amount of SOA, much of which could not be explained based on the emissions of traditional speciated precursors; we refer to the unexplained SOA as non-traditional SOA (NT-SOA). The NT-SOA can be explained by emissions of unspeciated low-volatility organics measured using sorbents. We show that the parameterization proposed by Robinson et al. (2007) is unable to explain the timing of the NT-SOA formation in the aircraft experiments because it assumes a very modest reduction in volatility of the precursors with every oxidation reaction. In contrast the new method better reproduces the NT-SOA formation. The NT-SOA yields estimated for the unspeciated low-volatility organic emissions in aircraft exhaust are similar to literature data for large n-alkanes and other low-volatility organics. The estimated yields vary with fuel composition (Jet Propellent-8 versus Fischer-Tropsch) and engine load (ground idle versus non-ground idle). The framework developed here is suitable for modeling SOA formation from emissions from other combustion systems.

Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

NASA Astrophysics Data System (ADS)

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

2011-12-01

Reactive halogen species are released by various sources like photo-activated sea-salt aerosol or salt pans and salt lakes. These heterogeneous release mechanisms have been overlooked so far, although their potential of interaction with organic aerosols like Secondary Organic Aerosol (SOA), Biomass Burning Organic Aerosol (BBOA) or Atmospheric Humic LIke Substances (HULIS) is completely unknown. Such reactions can constitute sources of gaseous organo-halogen compounds or halogenated organic particles in the atmospheric boundary layer. To study the interaction of organic aerosols with reactive halogen species (RHS), SOA was produced from α-pinene, catechol and guaiacol using an aerosol smog-chamber. The model SOAs were characterized in detail using a variety of physico-chemical methods (Ofner et al., 2011). Those aerosols were exposed to molecular halogens in the presence of UV/VIS irradiation and to halogens, released from simulated natural halogen sources like salt pans, in order to study the complex aerosol-halogen interaction. The heterogeneous reaction of RHS with those model aerosols leads to different gaseous species like CO2, CO and small reactive/toxic molecules like phosgene (COCl2). Hydrogen containing groups on the aerosol particles are destroyed to form HCl or HBr, and a significant formation of C-Br bonds could be verified in the particle phase. Carbonyl containing functional groups of the aerosol are strongly affected by the halogenation process. While changes of functional groups and gaseous species were visible using FTIR spectroscopy, optical properties were studied using Diffuse Reflectance UV/VIS spectroscopy. Overall, the optical properties of the processed organic aerosols are significantly changed. While chlorine causes a "bleaching" of the aerosol particles, bromine shifts the maximum of UV/VIS absorption to the red end of the UV/VIS spectrum. Further physico-chemical changes were recognized according to the aerosol size-distributions or the averaged carbon oxidation state (OSc). The heterogeneous reaction of SOA with molecular halogens released from the simulated salt-pan at different simulated environmental conditions leads to changes of several physico-chemical features of the aerosol. However, the halogen release mechanisms are also affected by the presence of organic aerosols. One order of magnitude less BrO was detected by an active Differential Optical Absorption Spectroscopy (DOAS) instrument in the presence of SOA compared to experiments without SOA. This work was supported by the German Research Foundation within the HALOPROC project. Ofner, J., Krüger, H.-U., Grothe, H., Schmitt-Kopplin, P., Whitmore, K., and Zetzsch, C. (2011), Atmos. Chem. Phys., 11, 1-15.

Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene.

PubMed

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

2017-08-24

Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (<3) conditions. ROS formation can be explained by the decomposition of organic hydroperoxides, which are a prominent fraction of SOA, through interactions with water and Fenton-like reactions with dissolved transition metal ions. Our findings imply that the chemical reactivity and aging of SOA particles can be enhanced upon interaction with mineral dust in deliquesced particles or cloud/fog droplets. SOA decomposition could be comparably important to the classical Fenton reaction of H 2 O 2 with Fe 2+ and that SOA can be the main source of OH radicals in aqueous droplets at low concentrations of H 2 O 2 and Fe 2+ . In the human respiratory tract, the inhalation and deposition of SOA and mineral dust can also lead to the release of ROS, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols in the Anthropocene.

Chemical transport model simulations of organic aerosol in ...

EPA Pesticide Factsheets

Gasoline- and diesel-fueled engines are ubiquitous sources of air pollution in urban environments. They emit both primary particulate matter and precursor gases that react to form secondary particulate matter in the atmosphere. In this work, we updated the organic aerosol module and organic emissions inventory of a three-dimensional chemical transport model, the Community Multiscale Air Quality Model (CMAQ), using recent, experimentally derived inputs and parameterizations for mobile sources. The updated model included a revised volatile organic compound (VOC) speciation for mobile sources and secondary organic aerosol (SOA) formation from unspeciated intermediate volatility organic compounds (IVOCs). The updated model was used to simulate air quality in southern California during May and June 2010, when the California Research at the Nexus of Air Quality and Climate Change (CalNex) study was conducted. Compared to the Traditional version of CMAQ, which is commonly used for regulatory applications, the updated model did not significantly alter the predicted organic aerosol (OA) mass concentrations but did substantially improve predictions of OA sources and composition (e.g., POA–SOA split), as well as ambient IVOC concentrations. The updated model, despite substantial differences in emissions and chemistry, performed similar to a recently released research version of CMAQ (Woody et al., 2016) that did not include the updated VOC and IVOC emissions and SOA data

Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3D model

NASA Astrophysics Data System (ADS)

Knote, C. J.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J. F.; Fast, J. D.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R. M.; Tyndall, G. S.; Washenfelder, R. A.; Waxman, E.; Zhang, Q.

2013-12-01

Formation of secondary organic aerosols (SOA) through multi-phase processing of glyoxal has been proposed recently as a relevant contributor to SOA mass. Glyoxal has both anthropogenic and biogenic sources, and readily partitions into the aqueous-phase of cloud droplets and aerosols. Both reversible and irreversible chemistry in the liquid-phase has been observed. A recent laboratory study indicates that the presence of salts in the liquid-phase strongly enhances the Henry';s law constant of glyoxal, allowing for much more effective multi-phase processing. In our work we investigate the contribution of glyoxal to SOA formation on the regional scale. We employ the regional chemistry transport model WRF-chem with MOZART gas-phase chemistry and MOSAIC aerosols, which we both extended to improve the description of glyoxal formation in the gas-phase, and its interactions with aerosols. The detailed description of aerosols in our setup allows us to compare very simple (uptake coefficient) parameterizations of SOA formation from glyoxal, as has been used in previous modeling studies, with much more detailed descriptions of the various pathways postulated based on laboratory studies. Measurements taken during the CARES and CalNex campaigns in California in summer 2010 allowed us to constrain the model, including the major direct precursors of glyoxal. Simulations at convection-permitting resolution over a 2 week period in June 2010 have been conducted to assess the effect of the different ways to parameterize SOA formation from glyoxal and investigate its regional variability. We find that depending on the parameterization used the contribution of glyoxal to SOA is between 1 and 15% in the LA basin during this period, and that simple parameterizations based on uptake coefficients derived from box model studies lead to higher contributions (15%) than parameterizations based on lab experiments (1%). A kinetic limitation found in experiments hinders substantial contribution of volume-based pathways to total SOA formation from glyoxal. Once removed, 5% of total SOA can be formed from glyoxal through these channels. Results from a year-long simulation over the continental US will give a broader picture of the contribution of glyoxal to SOA formation.

Similarities in STXM-NEXAFS Spectra of Atmospheric Particles and Secondary Organic Aerosol Generated from Glyoxal, α-Pinene, Isoprene, 1,2,4-Trimethylbenzene, and d-Limonene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shakya, Kabindra M.; Liu, Shang; Takahama, Satoshi

2013-02-06

Functional group composition of particles produced in smog chambers are examined using scanning transmission X-ray microscopy (STXM) with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in order to identify characteristic spectral signatures for secondary organic aerosol (SOA). Glyoxal uptake studies showed absorption for mainly alkyl, carbon-nitrogen (C-N), and carboxylic carbonyl groups. The SOA formed from the photooxidation of α-pinene (with and without isoprene) showed stronger absorptions for alkyl and carbonyl groups than the glyoxal studies. The mass ratio of carbonyl to acid group was larger in α-pinene-only experiments relative to the mixed α-pinene-isoprene experiments. The chamber particle spectra were comparedmore » with the ambient particle spectra from multiple field campaigns to understand the potential SOA sources. One hundred nineteen particles from six field campaigns had spectral features that were considered similar to the chamber-SOA particles: MILAGRO-2006 (9 particles), VOCALS-2008 (42 particles), Whistler-2008 (22 particles), Scripps Pier-2009 (9 particles), Bakersfield-2010 (25 particles), and Whistler-2010 (12 particles). These similarities with SOA formed from glyoxal, α-pinene (with and without isoprene), 1,2,4-trimethylbenzene, and limonene provide spectroscopic evidence of SOA products from these precursors in ambient particles.« less

Known and Newly Identified Semi-Volatile Organic Compounds from Biomass Burning in Amazonia: Variability and Relationship to Aerosol Physical Properties

NASA Astrophysics Data System (ADS)

Wernis, R. A.; Yee, L.; Isaacman-VanWertz, G. A.; Kreisberg, N. M.; de Sá, S. S.; Liu, Y.; Martin, S. T.; Alexander, M. L. L.; Palm, B. B.; Hu, W.; Campuzano-Jost, P.; Day, D. A.; Jimenez, J. L.; Artaxo, P.; Viegas, J.; Manzi, A. O.; Souza, R. A. F. D.; Hering, S. V.; Goldstein, A. H.

2016-12-01

Aerosols are a source of great uncertainty in radiative forcing predictions and have poorly understood impacts on human health. In many environments, biomass burning contributes a significant source of primary aerosol as well as reactive gas-phase precursors that can form secondary organic aerosol (SOA). One class of these precursors, semi-volatile organic compounds (SVOCs), has been shown to have a large contribution to the amount of SOA formed from fire emissions. At present, SVOC emissions from biomass burning are poorly constrained and understanding their contributions to SOA formation is an important research challenge. In the Amazonian dry season, biomass burning is a major source of gases and aerosols reducing regional air quality. As part of the GoAmazon 2014/5 field campaign, we deployed the Semi-Volatile Thermal desorption Aerosol Gas Chromatograph (SV-TAG) instrument at the rural T3 site, 60 km to the west of Manaus, Brazil to measure hourly concentrations of SVOCs in the gas and particle phases. This comprehensive technique detects thousands of compounds, enabling the discovery of previously unidentified compounds. In this work we explore compounds for which a correlation with well-known biomass burning tracers is observed to discover the identities of new markers. We discuss contributions to the total organic aerosol from over 30 well-known, rarely reported and newly identified biomass burning markers. We examine the relationship between biomass burning aerosol composition and aerosol physical properties as measured at the T3 site. Additionally, we report gas-particle partitioning of all identified compounds with comparison to theoretical predictions. We find that the commonly used biomass burning tracer levoglucosan existed entirely in the particle phase and contributed 0.6% and 0.3% of total organic aerosol mass in the dry and wet seasons, respectively.

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

DOE PAGES

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

2014-07-03

Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for several days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (∼50%) and of shorter duration (1–2 days). The production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction products ofmore » both aromatics and alkanes. In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

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

PubMed

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).

Observational Constraints on Glyoxal Production from Isoprene Oxidation and Its Contribution to Organic Aerosol over the Southeast United States

NASA Technical Reports Server (NTRS)

Li, Jingyi; Mao, Jingqiu; Min, Kyung-Eun; Washenfelder, Rebecca A.; Brown, Steven S.; Kaiser, Jennifer; Keutsch, Frank N.; Volkamer, Rainer; Wolfe, Glenn M.; Hanisco, Thomas F.

2016-01-01

We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and Master Chemical Mechanism (MCM) v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient gamma(sub glyx) of 2 x 10(exp -3) and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0-0.8micrograms m(exp -3) secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde (RGF[GLYX]/[HCHO]), resulting from the suppression of delta-isoprene peroxy radicals (delta-ISOPO2). We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of isoprene epoxydiol (IEPOX) peroxy radicals with HO2. Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA.

Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States

NASA Astrophysics Data System (ADS)

Li, Jingyi; Mao, Jingqiu; Min, Kyung-Eun; Washenfelder, Rebecca A.; Brown, Steven S.; Kaiser, Jennifer; Keutsch, Frank N.; Volkamer, Rainer; Wolfe, Glenn M.; Hanisco, Thomas F.; Pollack, Ilana B.; Ryerson, Thomas B.; Graus, Martin; Gilman, Jessica B.; Lerner, Brian M.; Warneke, Carsten; de Gouw, Joost A.; Middlebrook, Ann M.; Liao, Jin; Welti, André; Henderson, Barron H.; McNeill, V. Faye; Hall, Samuel R.; Ullmann, Kirk; Donner, Leo J.; Paulot, Fabien; Horowitz, Larry W.

2016-08-01

We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and Master Chemical Mechanism (MCM) v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient γglyx of 2 × 10-3 and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0-0.8 µg m-3 secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde (RGF = [GLYX]/[HCHO]), resulting from the suppression of δ-isoprene peroxy radicals. We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of isoprene epoxydiol (IEPOX) peroxy radicals with HO2. Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA.

Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States

PubMed Central

Li, Jingyi; Mao, Jingqiu; Min, Kyung-Eun; Washenfelder, Rebecca A.; Brown, Steven S.; Kaiser, Jennifer; Keutsch, Frank N.; Volkamer, Rainer; Wolfe, Glenn M.; Hanisco, Thomas F.; Pollack, Ilana B.; Ryerson, Thomas B.; Graus, Martin; Gilman, Jessica B.; Lerner, Brian M.; Warneke, Carsten; de Gouw, Joost A.; Middlebrook, Ann M.; Liao, Jin; Welti, André; Henderson, Barron H.; McNeill, V. Faye; Hall, Samuel R.; Ullmann, Kirk; Donner, Leo J.; Paulot, Fabien; Horowitz, Larry W.

2018-01-01

We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and MCM v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient γglyx of 2 × 10−3, and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0–0.8 μg m−3 secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde (RGF = [GLYX]/[HCHO]), resulting from the suppression of δ-isoprene peroxy radicals (δ-ISOPO2). We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of IEPOX peroxy radicals (IEPOXOO) with HO2. Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA. PMID:29619286

Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States.

PubMed

Li, Jingyi; Mao, Jingqiu; Min, Kyung-Eun; Washenfelder, Rebecca A; Brown, Steven S; Kaiser, Jennifer; Keutsch, Frank N; Volkamer, Rainer; Wolfe, Glenn M; Hanisco, Thomas F; Pollack, Ilana B; Ryerson, Thomas B; Graus, Martin; Gilman, Jessica B; Lerner, Brian M; Warneke, Carsten; de Gouw, Joost A; Middlebrook, Ann M; Liao, Jin; Welti, André; Henderson, Barron H; McNeill, V Faye; Hall, Samuel R; Ullmann, Kirk; Donner, Leo J; Paulot, Fabien; Horowitz, Larry W

2016-08-27

We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and MCM v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient γ glyx of 2 × 10 -3 , and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0-0.8 μg m -3 secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde ( R GF = [GLYX]/[HCHO]), resulting from the suppression of δ-isoprene peroxy radicals (δ-ISOPO 2 ). We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of IEPOX peroxy radicals (IEPOXOO) with HO 2 . Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA.

Characteristics and sources of carbonaceous aerosols from Shanghai, China

NASA Astrophysics Data System (ADS)

Cao, J.-J.; Zhu, C.-S.; Tie, X.-X.; Geng, F.-H.; Xu, H.-M.; Ho, S. S. H.; Wang, G.-H.; Han, Y.-M.; Ho, K.-F.

2013-01-01

An intensive investigation of carbonaceous PM2.5 and TSP (total suspended particles) from Pudong (China) was conducted as part of the MIRAGE-Shanghai (Megacities Impact on Regional and Global Environment) experiment in 2009. Data for organic and elemental carbon (OC and EC), organic species, including C17 to C40 n-alkanes and 17 polycyclic aromatic hydrocarbons (PAHs), and stable carbon isotopes OC (δ13COC) and EC (δ13CEC) were used to evaluate the aerosols' temporal variations and identify presumptive sources. High OC/EC ratios indicated a large fraction of secondary organic aerosol (SOA); high char/soot ratios indicated stronger contributions to EC from motor vehicles and coal combustion than biomass burning. Diagnostic ratios of PAHs indicated that much of the SOA was produced via coal combustion. Isotope abundances (δ13COC = -24.5 ± 0.8‰ and δ13CEC = -25.1 ± 0.6‰) indicated that fossil fuels were the most important source for carbonaceous PM2.5 (particulate matter less than 2.5 micrometers in diameter), with lesser impacts from biomass burning and natural sources. An EC tracer system and isotope mass balance calculations showed that the relative contributions to total carbon from coal combustion, motor vehicle exhaust, and SOA were 41%, 21%, and 31%; other primary sources such as marine, soil and biogenic emissions contributed 7%. Combined analyses of OC and EC, n-alkanes and PAHs, and stable carbon isotopes provide a new way to apportion the sources of carbonaceous particles.

Correlations between water-soluble organic aerosol and water vapor: a synergistic effect from biogenic emissions?

PubMed

Hennigan, Christopher J; Bergin, Michael H; Weber, Rodney J

2008-12-15

Ground-based measurements of meteorological parameters and water-soluble organic carbon in the gas(WSOCg) and particle (WSOCp) phases were carried out in Atlanta, Georgia, from May to September 2007. Fourteen separate events were observed throughout the summer in which WSOCp and water vapor concentrations were highly correlated (average WSOCp-water vapor r = 0.92); however, for the entire summer, no well-defined relationship existed between the two. The correlation events, which lasted on average 19 h, were characterized by a wide range of WSOCp and water vapor concentrations. Several hypotheses for the correlation are explored, including heterogeneous liquid phase SOA formation and the co-emission of biogenic VOCs and water vapor. The data provide supporting evidence for contributions from both and suggest the possibility of a synergistic effect between the co-emission of water vapor and VOCs from biogenic sources on SOA formation. Median WSOCp concentrations were also correlated with elemental carbon (EC), although this correlation extended over the entire summer. Despite the emission of water vapor from anthropogenic mobile sources and the WSOCp-EC correlation, mobile sources were not considered a potential cause for the WSOCp-water vapor correlations because of their low contribution to the water vapor budget. Meteorology could perhaps have influenced the WSOCp-EC correlation, but other factors are implicated as well. Overall, the results suggest that the temperature-dependent co-emission of water vapor through evapotranspiration and SOA precursor-VOCs by vegetation may be an important process contributing to SOA in some environments.

Reprint of "How do components of real cloud water affect aqueous pyruvate oxidation?"

NASA Astrophysics Data System (ADS)

Boris, Alexandra J.; Desyaterik, Yury; Collett, Jeffrey L.

2015-01-01

Chemical oxidation of dissolved volatile or semi-volatile organic compounds within fog and cloud droplets in the atmosphere could be a major pathway for secondary organic aerosol (SOA) formation. This proposed pathway consists of: (1) dissolution of organic chemicals from the gas phase into a droplet; (2) reaction with an aqueous phase oxidant to yield low volatility products; and (3) formation of particle phase organic matter as the droplet evaporates. The common approach to simulating aqueous SOA (aqSOA) reactions is photo-oxidation of laboratory standards in pure water. Reactions leading to aqSOA formation should be studied within real cloud and fog water to determine whether additional competing processes might alter apparent rates of reaction as indicated by rates of reactant loss or product formation. To evaluate and identify the origin of any cloud water matrix effects on one example of observed aqSOA production, pyruvate oxidation experiments simulating aqSOA formation were monitored within pure water, real cloud water samples, and an aqueous solution of inorganic salts. Two analysis methods were used: online electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR-ToF-MS), and offline anion exchange chromatography (IC) with quantitative conductivity and qualitative ESI-HR-ToF-MS detection. The apparent rate of oxidation of pyruvate was slowed in cloud water matrices: overall measured degradation rates of pyruvate were lower than in pure water. This can be at least partially accounted for by the observed formation of pyruvate from reactions of other cloud water components. Organic constituents of cloud water also compete for oxidants and/or UV light, contributing to the observed slowed degradation rates of pyruvate. The oxidation of pyruvate was not significantly affected by the presence of inorganic anions (nitrate and sulfate) at cloud-relevant concentrations. Future bulk studies of aqSOA formation reactions using simplified simulated cloud solutions and model estimates of generated aqSOA mass should take into account possible generation of, or competition for, oxidant molecules by organic components found in the complex matrices typically associated with real atmospheric water droplets. Additionally, it is likely that some components of real atmospheric waters have not yet been identified as aqSOA precursors, but could be distinguished through further simplified bulk oxidations of known atmospheric water components.

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

PubMed Central

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

2013-01-01

Isoprene and monoterpenes are important precursors of secondary organic aerosols (SOA) in continents. However, their contributions to aerosols over oceans are still inconclusive. Here we analyzed SOA tracers from isoprene and monoterpenes in aerosol samples collected over oceans during the Chinese Arctic and Antarctic Research Expeditions. Combined with literature reports elsewhere, we found that the dominant tracers are the oxidation products of isoprene. The concentrations of tracers varied considerably. The mean average values were approximately one order of magnitude higher in the Northern Hemisphere than in the Southern Hemisphere. High values were generally observed in coastal regions. This phenomenon was ascribed to the outflow influence from continental sources. High levels of isoprene could emit from oceans and consequently have a significant impact on marine SOA as inferred from isoprene SOA during phytoplankton blooms, which may abruptly increase up to 95 ng/m3 in the boundary layer over remote oceans. PMID:23880782

Quantification of Terpenes by 1DGC-MS and 2DGC-TOF-MS

NASA Astrophysics Data System (ADS)

Flores, R. M.; Perlinger, J. A.; Doskey, P. V.

2009-12-01

Biogenic emissions are the primary source of volatile organic compounds in the global troposphere. Deciduous and coniferous forests are the principal emitters of a complex mixture of isoprene (C5H8), monoterpenes (C10H16), and sesquiterpenes (C15H24). Sesquiterpenes are readily oxidized in the atmosphere producing secondary organic aerosols (SOA) with 100% yields. The SOA are hydrophilic and scatter light, and thus, increase albedo and lead to a cooling effect. In addition, both monoterpene and sesquiterpene generated SOA are effective cloud condensation nuclei leading to an increase in the particle number concentration and to the formation of clouds that also increase albedo. To quantify the complex mixture of terpenes and their oxidation products requires development of on-line extraction and comprehensive two-dimensional gas chromatographic techniques. One objective of this work was to compare one-dimensional gas chromatography-mass spectrometry (1DGC-MS) and two-dimensional gas chromatography time-of-flight mass spectrometry (2DGC-TOFMS) for quantifying eight monoterpenes (alpha- and beta-pinene, limonene, 3-carene, linalool, terpinolene, myrcene and ocimene) and eight sesquiterpenes (beta-caryophyllene, humulene, alpha-cedrene, cis-nerolidol, trans-nerolidol, cedrol, camphene and farnesene) in air samples collected in Northern Michigan. Future research involves coupling thermal desorption and supercritical fluid extraction devices to a GC×2GC for routine quantification of the complex mixture of terpenes and their oxidation products in rural and urban air.

Investigating the role of chemical and physical processes on organic aerosol modelling with CAMx in the Po Valley during a winter episode

NASA Astrophysics Data System (ADS)

Meroni, A.; Pirovano, G.; Gilardoni, S.; Lonati, G.; Colombi, C.; Gianelle, V.; Paglione, M.; Poluzzi, V.; Riva, G. M.; Toppetti, A.

2017-12-01

Traditional aerosol mechanisms underestimate the observed organic aerosol concentration, especially due to the lack of information on secondary organic aerosol (SOA) formation and processing. In this study we evaluate the chemical and transport model CAMx during a one-month in winter (February 2013) over a 5 km resolution domain, covering the whole Po valley (Northern Italy). This works aims at investigating the effects of chemical and physical atmospheric processing on modelling results and, in particular, to evaluate the CAMx sensitivity to organic aerosol (OA) modelling schemes: we will compare the recent 1.5D-VBS algorithm (CAMx-VBS) with the traditional Odum 2-product model (CAMx-SOAP). Additionally, the thorough diagnostic analysis of the reproduction of meteorology, precursors and aerosol components was intended to point put strength and weaknesses of the modelling system and address its improvement. Firstly, we evaluate model performance for criteria PM concentration. PM10 concentration was underestimated both by CAMx-SOAP and even more by CAMx-VBS, with the latter showing a bias ranging between -4.7 and -7.1 μg m-3. PM2.5 model performance was to some extent better than PM10, showing a mean bias ranging between -0.5 μg m-3 at rural sites and -5.5 μg m-3 at urban and suburban sites. CAMx performance for OA was clearly worse than for the other PM compounds (negative bias ranging between -40% and -75%). The comparisons of model results with OA sources (identified by PMF analysis) shows that the VBS scheme underestimates freshly emitted organic aerosol while SOAP overestimates. The VBS scheme correctly reproduces biomass burning (BBOA) contributions to primary OA concentrations (POA). In contrast VBS slightly underestimates the contribution from fossil-fuel combustion (HOA), indicating that POA emissions related to road transport are either underestimated or associated to higher volatility classes. The VBS scheme under-predictes the SOA too, but to a lesser extent than CAMx-SOAP. SOA underestimation can be related to corresponding underestimation of either aging processes or precursor emissions. This indicates that improvements in the emission inventories for semi- and intermediate-volatility organic compounds are needed for further progress in this area. Finally, the comparison between modelled and observed SOA sources points out the urgency to include processing of OA in particle water phase into SOA formation mechanisms, to reconcile model results and observations.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Molecular formula composition of β-caryophyllene ozonolysis SOA formed in humid and dry conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kundu, Shuvashish; Fisseha, Rebeka; Putman, Annie L.

Here, we studied the molecular formula composition of six β-caryophyllene SOA samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry under various reaction conditions. The SOA samples were generated in dry or low relative humidity (RH) chamber conditions with or without cyclohexane. All of the studied SOA mass spectra have three distinct clusters of hundreds of negative ions referred to as Group I (100 < m/z < 400), Group II (400 < m/z < 700) and Group III (700 < m/z < 1 000) compounds. C 14-16H 22-28O 2-11, C 28-29H 42-48O 6-16 and C 42-43H 68-70O 14-16more » were observed as highly abundant organic compounds in the compound class of Group I, II and III, respectively. The relative intensities of most analytes were higher in humid conditions compared to those in dry conditions, indicating the importance of water-dependent reactions and the catalytic role of water both in the presence and absence of cyclohexane. In addition, molecular formulas with higher average carbon numbers were observed in humid SOA than in dry SOA in the absence of cyclohexane, suggesting a decrease of cleavage reactions in humid condition. This study characterizes β-caryophyllene ozonolysis SOA based on ultrahigh mass resolution and demonstrates the significance of humidity in terms of the molecular distributions and relative abundances of the analytes. We also discuss the possible mechanism for the formation of Group I-III compounds based on the current understanding of SOA formation in the atmosphere.« less

Molecular formula composition of β-caryophyllene ozonolysis SOA formed in humid and dry conditions

DOE PAGES

Kundu, Shuvashish; Fisseha, Rebeka; Putman, Annie L.; ...

2016-12-22

Here, we studied the molecular formula composition of six β-caryophyllene SOA samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry under various reaction conditions. The SOA samples were generated in dry or low relative humidity (RH) chamber conditions with or without cyclohexane. All of the studied SOA mass spectra have three distinct clusters of hundreds of negative ions referred to as Group I (100 < m/z < 400), Group II (400 < m/z < 700) and Group III (700 < m/z < 1 000) compounds. C 14-16H 22-28O 2-11, C 28-29H 42-48O 6-16 and C 42-43H 68-70O 14-16more » were observed as highly abundant organic compounds in the compound class of Group I, II and III, respectively. The relative intensities of most analytes were higher in humid conditions compared to those in dry conditions, indicating the importance of water-dependent reactions and the catalytic role of water both in the presence and absence of cyclohexane. In addition, molecular formulas with higher average carbon numbers were observed in humid SOA than in dry SOA in the absence of cyclohexane, suggesting a decrease of cleavage reactions in humid condition. This study characterizes β-caryophyllene ozonolysis SOA based on ultrahigh mass resolution and demonstrates the significance of humidity in terms of the molecular distributions and relative abundances of the analytes. We also discuss the possible mechanism for the formation of Group I-III compounds based on the current understanding of SOA formation in the atmosphere.« less

Airborne observations of IEPOX-derived isoprene SOA in the Amazon during SAMBBA

NASA Astrophysics Data System (ADS)

Allan, J. D.; Morgan, W. T.; Darbyshire, E.; Flynn, M. J.; Williams, P. I.; Oram, D. E.; Artaxo, P.; Brito, J.; Lee, J. D.; Coe, H.

2014-10-01

Isoprene is a potentially highly significant but currently poorly quantified source of secondary organic aerosols (SOA). This is especially important in the tropics, where large rainforests act as significant sources of isoprene. Methylfuran, produced through thermal decomposition during analysis, has recently been suggested as a marker for isoprene SOA formation through the isoprene epoxydiol (IEPOX) route, which mostly occurs under low NOx conditions. This is manifested as a peak at m/z=82 in Aerodyne Aerosol Mass Spectrometer (AMS) data. Here we present a study of this marker measured during five flights over the Amazon rainforest on board the UK Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft during the South American Biomass Burning Analysis (SAMBBA) campaign. Cases where this marker is and is not present are contrasted and linked to the presence of acidic seed particles, lower NOx concentrations and higher humidities. There are also data to suggest a role of organic nitrogen in the particulate composition. Furthermore, an inspection of the vertical trends of the marker indicates that concentrations are highest at the top of the boundary layer (possibly due to semivolatile repartitioning) and that upwards through the free troposphere, the mass spectral profile evolves towards that of low volatility oxygenated aerosol. These observations offer insights into the behaviour of IEPOX-derived SOA formation above the Amazon rainforest and the suitability of methylfuran as a marker for this process.

Simulation of semi-explicit mechanisms of SOA formation from glyoxal in aerosol in a 3-D model

NASA Astrophysics Data System (ADS)

Knote, C.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J.; Fast, J.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R.; Tyndall, G.; Washenfelder, R.; Waxman, E.; Zhang, Q.

2014-06-01

New pathways to form secondary organic aerosol (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous phase of cloud droplets and deliquesced particles where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aerosol aqueous-phase. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. A month-long simulation over the continental United States (US) enables us to extend our results to the continental scale. In all simulations over California, the Los Angeles (LA) basin was found to be the hot spot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a reactive (surface limited) uptake coefficient leads to higher SOA yields from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to give the highest SOA mass yields compared to a volume process and reversible formation. We find that the yields of the latter are limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A time dependence in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute > 20% of glyoxal-SOA mass, and the total mass formed (5.8% of total SOA in the LA basin) is about a third of the simple uptake coefficient formulation without consideration of aerosol phase state and composition. Results from the continental US simulation reveal the much larger potential to form glyoxal-SOA over the eastern continental US. Interestingly, the low concentrations of glyoxal-SOA over the western continental US are not due to the lack of a potential to form glyoxal-SOA here. Rather these small glyoxal-SOA concentrations reflect dry conditions and high salt concentrations, and the potential to form SOA mass here will strongly depend on the water associated with particles.

Service oriented architecture for clinical decision support: a systematic review and future directions.

PubMed

Loya, Salvador Rodriguez; Kawamoto, Kensaku; Chatwin, Chris; Huser, Vojtech

2014-12-01

The use of a service-oriented architecture (SOA) has been identified as a promising approach for improving health care by facilitating reliable clinical decision support (CDS). A review of the literature through October 2013 identified 44 articles on this topic. The review suggests that SOA related technologies such as Business Process Model and Notation (BPMN) and Service Component Architecture (SCA) have not been generally adopted to impact health IT systems' performance for better care solutions. Additionally, technologies such as Enterprise Service Bus (ESB) and architectural approaches like Service Choreography have not been generally exploited among researchers and developers. Based on the experience of other industries and our observation of the evolution of SOA, we found that the greater use of these approaches have the potential to significantly impact SOA implementations for CDS.

Service Oriented Architecture for Clinical Decision Support: A Systematic Review and Future Directions

PubMed Central

Loya, Salvador Rodriguez; Kawamoto, Kensaku; Chatwin, Chris; Huser, Vojtech

2017-01-01

The use of a service-oriented architecture (SOA) has been identified as a promising approach for improving health care by facilitating reliable clinical decision support (CDS). A review of the literature through October 2013 identified 44 articles on this topic. The review suggests that SOA related technologies such as Business Process Model and Notation (BPMN) and Service Component Architecture (SCA) have not been generally adopted to impact health IT systems’ performance for better care solutions. Additionally, technologies such as Enterprise Service Bus (ESB) and architectural approaches like Service Choreography have not been generally exploited among researchers and developers. Based on the experience of other industries and our observation of the evolution of SOA, we found that the greater use of these approaches have the potential to significantly impact SOA implementations for CDS PMID:25325996

Observational Constraints on Modeling Growth and Evaporation Kinetics of Isoprene SOA

NASA Astrophysics Data System (ADS)

Zaveri, R. A.; Shilling, J. E.; Zelenyuk, A.; Liu, J.; Wilson, J. M.; Laskin, A.; Wang, B.; Fast, J. D.; Easter, R. C.; Wang, J.; Kuang, C.; Thornton, J. A.; Setyan, A.; Zhang, Q.; Onasch, T. B.; Worsnop, D. R.

2014-12-01

Isoprene is thought to be a major contributor to the global secondary organic aerosol (SOA) budget, and therefore has the potential to exert a significant influence on earth's climate via aerosol direct and indirect radiative effects. Both aerosol optical and cloud condensation nuclei properties are quite sensitive to aerosol number size distribution, as opposed to the total aerosol mass concentration. Recent studies suggest that SOA particles can be highly viscous, which can affect the kinetics of SOA partitioning and size distribution evolution when the condensing organic vapors are semi-volatile. In this study, we examine the growth kinetics of SOA formed from isoprene photooxidation in the presence of pre-existing Aitken and accumulation mode aerosols in: (a) the ambient atmosphere during the CARES field campaign, and (b) the environmental chamber at PNNL. Each growth episode is analyzed and interpreted with the updated MOSAIC aerosol box model, which performs kinetic gas-particle partitioning of SOA and takes into account diffusion and chemical reaction within the particle phase. The model is initialized with the observed aerosol size distribution and composition at the beginning of the experiment, and the total amount of SOA formed in the model at any given time is constrained by the observed total amount of SOA formed. The variable model parameters include the number of condensing organic species, their gas-phase formation rates, their effective volatilities, and their bulk diffusivities in the Aitken and accumulation modes. The objective of the constrained modeling exercise is then to determine which model configuration is able to best reproduce the observed size distribution evolution, thus providing valuable insights into the possible mechanism of SOA formation. We also examine the evaporation kinetics of size-selected particles formed in the environmental chamber to provide additional constraints on the effective volatility and bulk diffusivity of the organic species. Our results suggest that SOA formed from isoprene photooxidation is semi-volatile, and the resulting size distribution evolution is highly sensitive to the phase state (bulk diffusivity) of the pre-existing aerosol. Implications of these findings on further SOA model development and evaluation strategy will be discussed.

Sources and formation mechanisms of carbonaceous aerosol at a regional background site in the Netherlands: insights from a year-long radiocarbon study

NASA Astrophysics Data System (ADS)

Dusek, Ulrike; Hitzenberger, Regina; Kasper-Giebl, Anne; Kistler, Magdalena; Meijer, Harro A. J.; Szidat, Sönke; Wacker, Lukas; Holzinger, Rupert; Röckmann, Thomas

2017-03-01

We measured the radioactive carbon isotope 14C (radiocarbon) in various fractions of the carbonaceous aerosol sampled between February 2011 and March 2012 at the Cesar Observatory in the Netherlands. Based on the radiocarbon content in total carbon (TC), organic carbon (OC), water-insoluble organic carbon (WIOC), and elemental carbon (EC), we estimated the contribution of major sources to the carbonaceous aerosol. The main source categories were fossil fuel combustion, biomass burning, and other contemporary carbon, which is mainly biogenic secondary organic aerosol material (SOA). A clear seasonal variation is seen in EC from biomass burning (ECbb), with lowest values in summer and highest values in winter, but ECbb is a minor fraction of EC in all seasons. WIOC from contemporary sources is highly correlated with ECbb, indicating that biomass burning is a dominant source of contemporary WIOC. This suggests that most biogenic SOA is water soluble and that water-insoluble carbon stems mainly from primary sources. Seasonal variations in other carbon fractions are less clear and hardly distinguishable from variations related to air mass history. Air masses originating from the ocean sector presumably contain little carbonaceous aerosol from outside the Netherlands, and during these conditions measured carbon concentrations reflect regional sources. In these situations absolute TC concentrations are usually rather low, around 1.5 µg m-3, and ECbb is always very low ( ˜ 0.05 µg m-3), even in winter, indicating that biomass burning is not a strong source of carbonaceous aerosol in the Netherlands. In continental air masses, which usually arrive from the east or south and have spent several days over land, TC concentrations are on average by a factor of 3.5 higher. ECbb increases more strongly than TC to 0.2 µg m-3. Fossil EC and fossil WIOC, which are indicative of primary emissions, show a more moderate increase by a factor of 2.5 on average. An interesting case is fossil water-soluble organic carbon (WSOC, calculated as OC-WIOC), which can be regarded as a proxy for SOA from fossil precursors. Fossil WSOC has low concentrations when regional sources are sampled and increases by more than a factor of 5 in continental air masses. A longer residence time of air masses over land seems to result in increased SOA concentrations from fossil origin.

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

NASA Astrophysics Data System (ADS)

Mahmud, A.; Barsanti, K. C.

2012-12-01

The secondary organic aerosol (SOA) module in the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4) has been updated by replacing existing two-product (2p) parameters with those obtained from two-product volatility basis set (2p-VBS) fits, and by treating SOA formation from the following volatile organic compounds (VOCs): isoprene, propene and lumped alkenes. Strong seasonal and spatial variations in global SOA distributions were demonstrated, with significant differences in the predicted concentrations between the base-case and updated model versions. The base-case MOZART-4 predicted annual average SOA of 0.36 ± 0.50 μg m-3 in South America, 0.31 ± 0.38 μg m-3 in Indonesia, 0.09 ± 0.05 μg m-3 in the USA, and 0.12 ± 0.07 μg m-3 in Europe. Concentrations from the updated versions of the model showed a~marked increase in annual average SOA. Using the updated set of parameters alone (MZ4-v1) increased annual average SOA by ~8%, ~16%, ~56%, and ~108% from the base-case in South America, Indonesia, USA, and Europe, respectively. Treatment of additional parent VOCs (MZ4-v2) resulted in an even more dramatic increase of ~178-406% in annual average SOA for these regions over the base-case. The increases in predicted SOA concentrations further resulted in increases in corresponding SOA contributions to annual average total aerosol optical depth (AOD) by <1% for MZ4-v1 and ~1-6% for MZ4-v2. Estimated global SOA production was ~6.6 Tg yr-1 and ~19.1 Tg yr-1 with corresponding burdens of ~0.24 Tg and ~0.59 Tg using MZ4-v1 and MZ4-v2, respectively. The SOA budgets predicted in the current study fall well within reported ranges for similar modeling studies, 6.7 to 96 Tg yr-1, but are lower than recently reported observationally-constrained values, 50 to 380 Tg yr-1. With MZ4-v2, simulated SOA concentrations at the surface were also in reasonable agreement with comparable modeling studies and observations. Concentrations of estimated organic aerosol (OA) at the surface, however, showed under-prediction in Europe and over-prediction in the Amazonian regions and Malaysian Borneo during certain months of the year. Overall, the updated version of MOZART-4, MZ4-v2, showed consistently better skill in predicting SOA and OA levels and spatial distributions as compared with unmodified MOZART-4. The MZ4-v2 updates may be particularly important when MOZART-4 output is used to generate boundary conditions for regional air quality simulations that require more accurate representation of SOA concentrations and distributions.

Sources and production of organic aerosol in Mexico City: insights from the combination of a chemical transport model (PMCAMx-2008) and measurements during MILAGRO

NASA Astrophysics Data System (ADS)

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

2011-06-01

Urban areas are large sources of organic aerosols and their precursors. Nevertheless, the contributions of primary (POA) and secondary organic aerosol (SOA) to the observed particulate matter levels have been difficult to quantify. In this study the three-dimensional chemical transport model PMCAMx-2008 is used to investigate the temporal and geographic variability of organic aerosol in the Mexico City Metropolitan Area (MCMA) during the MILAGRO campaign that took place in the spring of 2006. The organic module of PMCAMx-2008 includes the recently developed volatility basis-set framework in which both primary and secondary organic components are assumed to be semi-volatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The MCMA emission inventory is modified and the POA emissions are distributed by volatility based on dilution experiments. The model predictions are compared with observations from four different types of sites, an urban (T0), a suburban (T1), a rural (T2), and an elevated site in Pico de Tres Padres (PTP). The performance of the model in reproducing organic mass concentrations in these sites is encouraging. The average predicted PM1 organic aerosol (OA) concentration in T0, T1, and T2 is 18 μg m-3, 11.7 μg m-3, and 10.5 μg m-3 respectively, while the corresponding measured values are 17.2 μg m-3, 11 μg m-3, and 9 μg m-3. The average predicted locally-emitted primary OA concentrations, 4.4 μg m-3 at T0, 1.2 μg m-3 at T1 and 1.7 μg m-3 at PTP, are in reasonably good agreement with the corresponding PMF analysis estimates based on the Aerosol Mass Spectrometer (AMS) observations of 4.5, 1.3, and 2.9 μg m-3 respectively. The model reproduces reasonably well the average oxygenated OA (OOA) levels in T0 (7.5 μg m-3 predicted versus 7.5 μg m-3 measured), in T1 (6.3 μg m-3 predicted versus 4.6 μg m-3 measured) and in PTP (6.6 μg m-3 predicted versus 5.9 μg m-3 measured). The rest of the OA mass (6.1 μg m-3 and 4.2 μg m-3 in T0 and T1 respectively) is assumed to originate from biomass burning activities and is introduced to the model as part of the boundary conditions. Inside Mexico City (at T0), the locally-produced OA is predicted to be on average 60 % locally-emitted primary (POA), 6 % semi-volatile (S-SOA) and intermediate volatile (I-SOA) organic aerosol, and 34 % traditional SOA from the oxidation of VOCs (V-SOA). The average contributions of the OA components to the locally-produced OA for the entire modelling domain are predicted to be 32 % POA, 10 % S-SOA and I-SOA, and 58 % V-SOA. The long range transport from biomass burning activities and other sources in Mexico is predicted to contribute on average almost as much as the local sources during the MILAGRO period.

Light-absorbing oligomer formation in secondary organic aerosol from reactive uptake of isoprene epoxydiols.

PubMed

Lin, Ying-Hsuan; Budisulistiorini, Sri Hapsari; Chu, Kevin; Siejack, Richard A; Zhang, Haofei; Riva, Matthieu; Zhang, Zhenfa; Gold, Avram; Kautzman, Kathryn E; Surratt, Jason D

2014-10-21

Secondary organic aerosol (SOA) produced from reactive uptake and multiphase chemistry of isoprene epoxydiols (IEPOX) has been found to contribute substantially (upward of 33%) to the fine organic aerosol mass over the Southeastern U.S. Brown carbon (BrC) in rural areas of this region has been linked to secondary sources in the summer when the influence of biomass burning is low. We demonstrate the formation of light-absorbing (290 < λ < 700 nm) SOA constituents from reactive uptake of trans-β-IEPOX onto preexisting sulfate aerosols as a potential source of secondary BrC. IEPOX-derived BrC generated in controlled chamber experiments under dry, acidic conditions has an average mass absorption coefficient of ∼ 300 cm(2) g(-1). Chemical analyses of SOA constituents using UV-visible spectroscopy and high-resolution mass spectrometry indicate the presence of highly unsaturated oligomeric species with molecular weights separated by mass units of 100 (C5H8O2) and 82 (C5H6O) coincident with the observations of enhanced light absorption, suggesting such oligomers as chromophores, and potentially explaining one source of humic-like substances (HULIS) ubiquitously present in atmospheric aerosol. Similar light-absorbing oligomers were identified in fine aerosol collected in the rural Southeastern U.S., supporting their atmospheric relevance and revealing a previously unrecognized source of oligomers derived from isoprene that contributes to ambient fine aerosol mass.

Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents

NASA Astrophysics Data System (ADS)

Kahnt, A.; Iinuma, Y.; Mutzel, A.; Böge, O.; Claeys, M.; Herrmann, H.

2014-01-01

In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon α-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger, leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised by 2,4-dinitrophenylhydrazine (DNPH) followed by liquid chromatography/negative ion electrospray ionisation time-of-flight mass spectrometry analysis and were compared to the gas-phase compounds detected by online proton-transfer-reaction mass spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and additional mass spectrometry (MS2 and MS3 fragmentation studies). Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving α-pinene, α-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. m / z 201, C9H14O5 and m / z 215, C10H16O5), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The m / z 201 and 215 compounds were tentatively identified as a C9- and C10-carbonyl-dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, as well as detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH derivatives.

Doing Your Science While You're in Orbit

NASA Astrophysics Data System (ADS)

Green, Mark L.; Miller, Stephen D.; Vazhkudai, Sudharshan S.; Trater, James R.

2010-11-01

Large-scale neutron facilities such as the Spallation Neutron Source (SNS) located at Oak Ridge National Laboratory need easy-to-use access to Department of Energy Leadership Computing Facilities and experiment repository data. The Orbiter thick- and thin-client and its supporting Service Oriented Architecture (SOA) based services (available at https://orbiter.sns.gov) consist of standards-based components that are reusable and extensible for accessing high performance computing, data and computational grid infrastructure, and cluster-based resources easily from a user configurable interface. The primary Orbiter system goals consist of (1) developing infrastructure for the creation and automation of virtual instrumentation experiment optimization, (2) developing user interfaces for thin- and thick-client access, (3) provide a prototype incorporating major instrument simulation packages, and (4) facilitate neutron science community access and collaboration. The secure Orbiter SOA authentication and authorization is achieved through the developed Virtual File System (VFS) services, which use Role-Based Access Control (RBAC) for data repository file access, thin-and thick-client functionality and application access, and computational job workflow management. The VFS Relational Database Management System (RDMS) consists of approximately 45 database tables describing 498 user accounts with 495 groups over 432,000 directories with 904,077 repository files. Over 59 million NeXus file metadata records are associated to the 12,800 unique NeXus file field/class names generated from the 52,824 repository NeXus files. Services that enable (a) summary dashboards of data repository status with Quality of Service (QoS) metrics, (b) data repository NeXus file field/class name full text search capabilities within a Google like interface, (c) fully functional RBAC browser for the read-only data repository and shared areas, (d) user/group defined and shared metadata for data repository files, (e) user, group, repository, and web 2.0 based global positioning with additional service capabilities are currently available. The SNS based Orbiter SOA integration progress with the Distributed Data Analysis for Neutron Scattering Experiments (DANSE) software development project is summarized with an emphasis on DANSE Central Services and the Virtual Neutron Facility (VNF). Additionally, the DANSE utilization of the Orbiter SOA authentication, authorization, and data transfer services best practice implementations are presented.

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

NASA Astrophysics Data System (ADS)

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

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jiumeng; D’Ambro, Emma L.; Lee, Ben H.

2016-09-20

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

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

NASA Astrophysics Data System (ADS)

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.

SSA Building Blocks - Transforming Your Data and Applications into Operational Capability

NASA Astrophysics Data System (ADS)

Buell, D.; Hawthorne, Shayn, L.; Higgins, J.

The Electronic System Center's 850 Electronic Systems Group (ELSG) is currently using a Service Oriented Architecture (SOA) to rapidly create net-centric experimental prototypes. This SOA has been utilized effectively across diverse mission areas, such as global air operations and rapid sensor tasking for improved space event management. The 850 ELSG has deployed a working, accredited, SOA on the SIPRNET and provided real-time space information to five separate distributed operations centers. The 850 ELSG has learned first-hand the power of SOAs for integrating DoD and non-DoD SSA data in a rapid and agile manner, allowing capabilities to be fielded and sensors to be integrated in weeks instead of months. This opens a world of opportunity to integrate University data and experimental or proof-of-concept data with sensitive sensors and sources to support developing an array of SSA products for approved users in and outside of the space community. This paper will identify how new capabilities can be proactively developed to rapidly answer critical needs when SOA methodologies are employed and identifies the operational utility and the far-reaching benefits realized by implementing a service-oriented architecture. We offer a new paradigm for how data and application producer's contributions are presented for the rest of the community to leverage.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2015-01-16

Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for multiple days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (~50%) and of shorter duration (1–2 days). The multiday production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction productsmore » of both aromatics and alkanes, especially those with relatively low carbon numbers (C4–15). In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions and different vapor pressure schemes, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

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

DOE PAGES

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

2015-01-16

Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for multiple days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (~50%) and of shorter duration (1–2 days). The multiday production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction productsmore » of both aromatics and alkanes, especially those with relatively low carbon numbers (C4–15). In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions and different vapor pressure schemes, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. Here, the results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments

NASA Astrophysics Data System (ADS)

Chirico, R.; Decarlo, P. F.; Heringa, M. F.; Tritscher, T.; Richter, R.; Prévôt, A. S. H.; Dommen, J.; Weingartner, E.; Wehrle, G.; Gysel, M.; Laborde, M.; Baltensperger, U.

2010-12-01

Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the third vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC < 0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23-0.56 g/kg fuel burned. In presence of both a DOC and a DPF, only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.10 to 0.19. Five hours of oxidation led to a more oxidized OA with an O/C range of 0.21 to 0.37.

Chemical and isotopic composition of secondary organic aerosol generated by α-pinene ozonolysis

NASA Astrophysics Data System (ADS)

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

2017-05-01

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 it is difficult to apply because neither the isotopic composition of aerosol precursors nor the fractionation of aerosol forming processes is well characterised. In this paper, SOA formation from ozonolysis of α-pinene - an important precursor and perhaps the best-known model system used in laboratory studies - was investigated using position-dependent and average determinations of 13C in α-pinene and advanced analysis of reaction products using thermal-desorption proton-transfer-reaction mass spectrometry (PTR-MS). The total carbon (TC) isotopic composition δ13C of the initial α-pinene was measured, and the δ13C of the specific carbon atom sites was determined using position-specific isotope analysis (PSIA). The PSIA analysis showed variations at individual positions from -6.9 to +10. 5 ‰ relative to the bulk composition. SOA was formed from α-pinene and ozone in a constant-flow chamber under dark, dry, and low-NOx conditions, with OH scavengers and in the absence of seed particles. The excess of ozone and long residence time in the flow chamber ensured that virtually all α-pinene had reacted. Product SOA was collected on two sequential quartz filters. The filters were analysed offline by heating them stepwise from 100 to 400 °C to desorb organic compounds that were (i) detected using PTR-MS for chemical analysis and to determine the O : C ratio, and (ii) converted to CO2 for 13C analysis. More than 400 ions in the mass range 39-800 Da were detected from the desorbed material and quantified using a PTR-MS. The largest amount desorbed at 150 °C. The O : C ratio of material from the front filter increased from 0.18 to 0.25 as the desorption temperature was raised from 100 to 250 °C. At temperatures above 250 °C, the O : C ratio of thermally desorbed material, presumably from oligomeric precursors, was constant. The observation of a number of components that occurred across the full range of desorption temperatures suggests that they are generated by thermal decomposition of oligomers. The isotopic composition of SOA was more or less independent of desorption temperature above 100 °C. TC analysis showed that SOA was enriched in 13C by 0.6-1.2 ‰ relative to the initial α-pinene. According to mass balance, gas-phase products will be depleted relative to the initial α-pinene. Accordingly, organic material on the back filters, which contain adsorbed gas-phase compounds, is depleted in 13C in TC by 0.7 ‰ relative to the initial α-pinene, and by 1.3 ‰ compared to SOA collected on the front filter. The observed difference in 13C between the gas and particle phases may arise from isotope-dependent changes in the branching ratios in the α-pinene + O3 reaction. Alternatively, some gas-phase products involve carbon atoms from highly enriched and depleted sites, as shown in the PSIA analysis, giving a non-kinetic origin to the observed fractionations. In either case, the present study suggests that the site-specific distribution of 13C in the source material itself governs the abundance of 13C in SOA.

Molecular marker characterization and source appointment of particulate matter and its organic aerosols.

PubMed

Choi, Jong-Kyu; Ban, Soo-Jin; Kim, Yong-Pyo; Kim, Yong-Hee; Yi, Seung-Muk; Zoh, Kyung-Duk

2015-09-01

This study was carried out to identify possible sources and to estimate their contribution to total suspended particle (TSP) organic aerosol (OA) contents. A total of 120 TSP and PM2.5 samples were collected simultaneously every third day over a one-year period in urban area of Incheon, Korea. High concentration in particulate matters (PM) and its components (NO3(-), water soluble organic compounds (WSOCs), and n-alkanoic acids) were observed during the winter season. Among the organics, n-alkanes, n-alkanoic acids, levoglucosan, and phthalates were major components. Positive matrix factorization (PMF) analysis identified seven sources of organic aerosols including combustion 1 (low molecular weight (LMW)-polycyclic aromatic hydrocarbons (PAHs)), combustion 2 (high molecular weight (HMW)-PAHs), biomass burning, vegetative detritus (n-alkane), secondary organic aerosol 1 (SOA1), secondary organic aerosol 2 (SOA2), and motor vehicles. Vegetative detritus increased during the summer season through an increase in biogenic/photochemical activity, while most of the organic sources were prominent in the winter season due to the increases in air pollutant emissions and atmospheric stability. The correlation factors were high among the main components of the organic carbon (OC) in the TSP and PM2.5. The results showed that TSP OAs had very similar characteristics to the PM2.5 OAs. SOA, combustion (PAHs), and motor vehicle were found to be important sources of carbonaceous PM in this region. Our results imply that molecular markers (MMs)-PMF model can provide useful information on the source and characteristics of PM. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chemical characterization of biogenic secondary organic aerosol generated from plant emissions under baseline and stressed conditions: Inter- and intra-species variability for six coniferous species

DOE PAGES

Faiola, C. L.; Wen, M.; VanReken, T. M.

2015-04-01

The largest global source of secondary organic aerosol (SOA) in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic volatile organic compound (BVOC) profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate (MeJA), a proxy compound. Experiments were repeated under pre- andmore » post-treatment conditions for six different coniferous plant types. Volatile organic compounds (VOCs) emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA chemical composition was measured using a Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS). The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH 3O +), m/z 58 (C 2H 2O 2 +, C 3H 6O +), m/z 29 (C 2H 5 +), m/z 57 (C 3H 5O +), m/z 59 (C 2H 3O 2 +, C 3H 7O +), m/z 71 (C 3H 3O 2 +, C 4H 7O +), and m/z 83 (C 5H 7O +). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, MeJA, is also presented. Elemental analysis results demonstrated an O : C range of baseline biogenic SOA between 0.3 and 0.47. The O : C of standard MeJA SOA was 0.52. Furthermore the results presented here could be used to help identify a biogenic plant stress marker in ambient data sets collected in forest environments.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Flores, J. M.; Washenfelder, Rebecca; Adler, Gabriela

2014-05-14

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

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

PubMed

Flores, J M; Washenfelder, R A; Adler, G; Lee, H J; Segev, L; Laskin, J; Laskin, A; Nizkorodov, S A; Brown, S S; Rudich, Y

2014-06-14

Atmospheric absorption by brown carbon aerosol may play an important role in global radiative forcing. Brown carbon arises from both primary and secondary sources, but the mechanisms and reactions of the latter are highly uncertain. One proposed mechanism is the reaction of ammonia or amino acids with carbonyl products in secondary organic aerosol (SOA). We generated SOA in situ by reacting biogenic alkenes (α-pinene, limonene, and α-humulene) with excess ozone, humidifying the resulting aerosol, and reacting the humidified aerosol with gaseous ammonia. We determined the complex refractive indices (RI) in the 360-420 nm range for these aerosols using broadband cavity enhanced spectroscopy (BBCES). The average real part (n) of the measured spectral range of the NH3-aged α-pinene SOA increased from n = 1.50 (±0.01) for the unreacted SOA to n = 1.57 (±0.01) after 1.5 h of exposure to 1.9 ppm NH3, whereas the imaginary component (k) remained below k < 0.001((+0.002)(-0.001)). For the limonene and α-humulene SOA the real part did not change significantly, and we observed a small change in the imaginary component of the RI. The imaginary component increased from k = 0.000 to an average k = 0.029 (±0.021) for α-humulene SOA, and from k < 0.001((+0.002)(-0.001)) to an average k = 0.032 (±0.019) for limonene SOA after 1.5 h of exposure to 1.3 and 1.9 ppm of NH3, respectively. Collected filter samples of the aged and unreacted α-pinene SOA and limonene SOA were analyzed off-line by nanospray desorption electrospray ionization high resolution mass spectrometry (nano-DESI/HR-MS), and in situ using a Time-of-Flight Aerosol Mass Spectrometer (ToF-AMS), confirming that the SOA reacted and that various nitrogen-containing reaction products formed. If we assume that NH3 aging reactions scale linearly with time and concentration, which will not necessarily be the case in the atmosphere, then a 1.5 h reaction with 1 ppm NH3 in the laboratory is equivalent to 24 h reaction with 63 ppbv NH3, indicating that the observed aerosol absorption will be limited to atmospheric regions with high NH3 concentrations.

Chemical characterization of biogenic SOA generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

NASA Astrophysics Data System (ADS)

Faiola, C. L.; Wen, M.; VanReken, T. M.

2014-10-01

The largest global source of secondary organic aerosol in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic VOC profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate, a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six different coniferous plant types. VOCs emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA particle size distribution and chemical composition were measured using a scanning mobility particle sizer (SMPS) and Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS), respectively. The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+) m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, methyl jasmonate, is also presented. Elemental analysis results demonstrated an O:C range of baseline biogenic SOA between 0.3-0.47. The O:C of standard methyl jasmonate SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient datasets collected in forest environments.

Chemical characterization of biogenic secondary organic aerosol generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

NASA Astrophysics Data System (ADS)

Faiola, C. L.; Wen, M.; VanReken, T. M.

2015-04-01

The largest global source of secondary organic aerosol (SOA) in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic volatile organic compound (BVOC) profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate (MeJA), a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six different coniferous plant types. Volatile organic compounds (VOCs) emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA chemical composition was measured using a Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS). The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+), m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, MeJA, is also presented. Elemental analysis results demonstrated an O : C range of baseline biogenic SOA between 0.3 and 0.47. The O : C of standard MeJA SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient data sets collected in forest environments.

Aqueous aerosol SOA formation: impact on aerosol physical properties.

PubMed

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

2013-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-06-01

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

Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of α-pinene

NASA Astrophysics Data System (ADS)

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

2014-04-01

Secondary Organic Aerosol (SOA) were generated from the ozonolysis of α-pinene in the CESAM simulation chamber. The formation and ageing of the SOA were studied by following their optical, hygroscopic and chemical properties. The optical properties investigated by determining the particle Complex Refractive Index (CRI). The hygroscopicity was quantified by measuring the effect of RH on particle size (Growth Factor, GF) and scattering coefficient (f(RH)). The oxygen to carbon (O : C) atomic ratio of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition in CESAM. The real CRI at 525 nm wavelength decreased from 1.43-1.60 (±0.02) to 1.32-1.38 (±0.02) during the SOA formation. The decrease in real CRI correlates with a decrease in the O : C ratio of SOA from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF stayed roughly constant over the reaction time, with values of 1.02-1.07 (±0.02) at 90% (±4.2) RH. Simultaneous measurements of O : C ratio of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but with less oxidised species at the surface which would limit the water adsorption onto particle. In addition, an apparent change of both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 16 h reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state.

Secondary Organic Aerosol Formation from the Photooxidation of Naphthalene

NASA Astrophysics Data System (ADS)

Zhou, S.; Chen, Y.; Wenger, J.

2009-04-01

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous air pollutants that are released into the atmosphere as a by-product of combustion processes. The gas-phase PAHs can be chemically transformed via reaction with the hydroxyl radical to produce a range of oxidised organic compounds and other pollutants such as ozone and secondary organic aerosol (SOA). Epidemiological studies have established that exposure to this type of air pollution is associated with damaging effects on the respiratory and cardiovascular systems, and can lead to asthma, oxidative stress, health deterioration and even death. The major anthropogenic source of SOA in urban areas is believed to be aromatic hydrocarbons, which are present in automobile fuels and are used as solvents. As a result, research is currently being performed on the characterisation of SOA produced from aromatic hydrocarbons such as toluene, the xylenes and trimethylbenzenes. However, significant amounts of PAHs are also released into urban areas from automobile emissions and the combustion of fossil fuels for home heating. Naphthalene is regularly cited as the most abundant PAH in polluted urban air, with typical ambient air concentrations of 0.05 - 0.20 parts per billion (ppbV) in European cities, comparable to the xylenes. Since naphthalene reacts in an analogous manner to monocyclic aromatic compounds then it is also expected to make a significant contribution to ambient SOA. However, the yield and chemical composition of SOA produced from the atmospheric degradation of naphthalene is not well known. In this presentation, the effects of NOx level and relative humidity on the SOA formation from the phootooixdation of naphthalene will be presented. A series of experiments has been performed in a large atmospheric simulation chamber equipped with a gas chromatograph and analyzers for monitoring nitrogen oxides (NOx) and ozone. SOA formation from the photooxidation of naphthalene was measured using a scanning mobility particle sizer. The effect of NOx concentration on SOA formation was evaluated by varying the initial naphthalene and NOx concentrations. The results clearly show that a higher hydrocarbon to NOx ratio produces a higher yield of SOA. The SOA mass yields were also found to increase as the relative humidity was raised from 0 to 50%. A recently developed denuder-filter sampling technique was used to investigate the gas/particle partitioning behavior of the photooxidation products. This work is the first study of the formation of SOA from naphthalene and the results will be compared to those obtained from other aromatic compounds.

Environmental conditions regulate the impact of plants on cloud formation

PubMed Central

Zhao, D. F.; Buchholz, A.; Tillmann, R.; Kleist, E.; Wu, C.; Rubach, F.; Kiendler-Scharr, A.; Rudich, Y.; Wildt, J.; Mentel, Th. F.

2017-01-01

The terrestrial vegetation emits large amounts of volatile organic compounds (VOC) into the atmosphere, which on oxidation produce secondary organic aerosol (SOA). By acting as cloud condensation nuclei (CCN), SOA influences cloud formation and climate. In a warming climate, changes in environmental factors can cause stresses to plants, inducing changes of the emitted VOC. These can modify particle size and composition. Here we report how induced emissions eventually affect CCN activity of SOA, a key parameter in cloud formation. For boreal forest tree species, insect infestation by aphids causes additional VOC emissions which modifies SOA composition thus hygroscopicity and CCN activity. Moderate heat increases the total amount of constitutive VOC, which has a minor effect on hygroscopicity, but affects CCN activity by increasing the particles' size. The coupling of plant stresses, VOC composition and CCN activity points to an important impact of induced plant emissions on cloud formation and climate. PMID:28218253

Environmental conditions regulate the impact of plants on cloud formation.

PubMed

Zhao, D F; Buchholz, A; Tillmann, R; Kleist, E; Wu, C; Rubach, F; Kiendler-Scharr, A; Rudich, Y; Wildt, J; Mentel, Th F

2017-02-20

The terrestrial vegetation emits large amounts of volatile organic compounds (VOC) into the atmosphere, which on oxidation produce secondary organic aerosol (SOA). By acting as cloud condensation nuclei (CCN), SOA influences cloud formation and climate. In a warming climate, changes in environmental factors can cause stresses to plants, inducing changes of the emitted VOC. These can modify particle size and composition. Here we report how induced emissions eventually affect CCN activity of SOA, a key parameter in cloud formation. For boreal forest tree species, insect infestation by aphids causes additional VOC emissions which modifies SOA composition thus hygroscopicity and CCN activity. Moderate heat increases the total amount of constitutive VOC, which has a minor effect on hygroscopicity, but affects CCN activity by increasing the particles' size. The coupling of plant stresses, VOC composition and CCN activity points to an important impact of induced plant emissions on cloud formation and climate.

SOA precursors at the T0 site during the 2010 CARES campaign

NASA Astrophysics Data System (ADS)

Wallace, H. W.; Jobson, B. T.; Erickson, M. H.

2010-12-01

Continuous measurements of C5 to C12 Volatile Organic Compounds (VOC) have been made using the Washington State University Mobile Atmospheric Chemistry Laboratory (MACL), at the T0 site during the month of June 2010 Carbonaceous Aerosol Carbonaceous Aerosols and Radiative Effects Study (CARES). These measurements were made to better understand aerosol formation and growth in Sacramento, CA and the surrounding areas. Using a sorbent based preconcentration sampling technique for our quadrupole ion trap gas chromatography mass spectrometer (GCMS), we have measured anthropogenic and biogenic secondary organic aerosol (SOA) precursors. Major biogenic VOCs identified include: α-pinene, limonene, isoprene, phellanderene and β-pinene. Diurnal profiles of the concentrations will be presented. Monoterpenes were highest in the mornings while isoprene was highest in the afternoon. In addition to understanding the diurnal profiles the SOA precursors at the T0 site, the relative contributions of biogenic and anthropogenic compounds to SOA formation will be presented.

Chemically-resolved volatility measurements of organic aerosol fom different sources.

PubMed

Huffman, J A; Docherty, K S; Mohr, C; Cubison, M J; Ulbrich, I M; Ziemann, P J; Onasch, T B; Jimenez, J L

2009-07-15

A newly modified fast temperature-stepping thermodenuder (TD) was coupled to a High Resolution Time-of-Flight Aerosol Mass Spectrometer for rapid determination of chemically resolved volatility of organic aerosols (OA) emitted from individual sources. The TD-AMS system was used to characterize primary OA (POA) from biomass burning, trash burning surrogates (paper and plastic), and meat cooking as well as chamber-generated secondary OA (SOA) from alpha-pinene and gasoline vapor. Almost all atmospheric models represent POA as nonvolatile, with no allowance for evaporation upon heating or dilution, or condensation upon cooling. Our results indicate that all OAs observed show semivolatile behavior and that most POAs characterized here were at least as volatile as SOA measured in urban environments. Biomass-burning OA (BBOA) exhibited a wide range of volatilities, but more often showed volatility similar to urban OA. Paper-burning resembles some types of BBOA because of its relatively high volatility and intermediate atomic oxygen-to-carbon (O/C) ratio, while meat-cooking OAs (MCOA) have consistently lower volatility than ambient OA. Chamber-generated SOA under the relatively high concentrations used intraditional experiments was significantly more volatile than urban SOA, challenging extrapolation of traditional laboratory volatility measurements to the atmosphere. Most OAs sampled show increasing O/C ratio and decreasing H/C (hydrogen-to-carbon) ratio with temperature, further indicating that more oxygenated OA components are typically less volatile. Future experiments should systematically explore a wider range of mass concentrations to more fully characterize the volatility distributions of these OAs.

Formation and fate of alkyl nitrates from chlorine-initiated oxidation of alkanes

NASA Astrophysics Data System (ADS)

Wang, D. S.; Hildebrandt Ruiz, L.

2017-12-01

Alkanes are a main source of anthropogenic volatile organic compounds (VOCs). Studies suggest that large alkanes, despite having high carbon mass, often do not significantly contribute to secondary organic aerosol (SOA) formation due to their low reactivity towards hydroxyl radicals. Chlorine radicals react much more quickly with alkanes; for example, the reaction of Cl with n-decane is about 50 times faster than the reaction of OH with n-decane. High reactive chlorine concentrations have been reported within continental regions as well as near coastal regions. The rapid oxidation of alkanes by chlorine radicals can therefore be a potentially significant, and overlooked source of alkylperoxy radicals and SOA formation. We present results from environmental chamber experiments on chlorine-initiated oxidation of C8, C10, and C12 linear and branched alkanes. Experiments were conducted under high NOx conditions to simulate highly polluted industrial environments. Formation of multigenerational gas-phase oxidation products were monitored using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (CIMS). High SOA formation was observed using an Aerosol Chemical Speciation Monitor (ACSM). Aerosol volatility was determined using a thermodenuder and a kinetic aerosol evaporation model. Particle-phase composition was investigated using a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to the CIMS, where dimer and oligomer formation were observed. Results from this study can be used to more accurately represent the fate of anthropogenic alkanes and SOA loadings in the atmosphere.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

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

PubMed

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

2016-03-01

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

Towards mechanistic representations of SOA from BVOC + NO3 reactions

EPA Science Inventory

Monoterpene reaction with nitrate radicals is a significant source of organic aerosol in the southeast United States. This source of organic aerosol represents an anthropogenic control on biogenic organic aerosol since nitrate radicals result from NOx emissions and are generally ...

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

PubMed Central

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

2016-01-01

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

Modeling Adaptable Business Service for Enterprise Collaboration

NASA Astrophysics Data System (ADS)

Boukadi, Khouloud; Vincent, Lucien; Burlat, Patrick

Nowadays, a Service Oriented Architecture (SOA) seems to be one of the most promising paradigms for leveraging enterprise information systems. SOA creates opportunities for enterprises to provide value added service tailored for on demand enterprise collaboration. With the emergence and rapid development of Web services technologies, SOA is being paid increasing attention and has become widespread. In spite of the popularity of SOA, a standardized framework for modeling and implementing business services are still in progress. For the purpose of supporting these service-oriented solutions, we adopt a model driven development approach. This paper outlines the Contextual Service Oriented Modeling and Analysis (CSOMA) methodology and presents UML profiles for the PIM level service-oriented architectural modeling, as well as its corresponding meta-models. The proposed PIM (Platform Independent Model) describes the business SOA at a high level of abstraction regardless of techniques involved in the application employment. In addition, all essential service-specific concerns required for delivering quality and context-aware service are covered. Some of the advantages of this approach are that it is generic and thus not closely allied with Web service technology as well as specifically treating the service adaptability during the design stage.

Impact of Propene on Secondary Organic Aerosol Formation from m-Xylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Chen; Na, Kwangsam; Warren, Bethany

2007-10-15

Propene is widely used in smog chamber experiments to increase the hydroxyl radical (OH) level based on the assumption that the formation of secondary organic aerosol (SOA) from parent hydrocarbon is unaffected. A series ofm-xylene/NOx photooxidation experiments were conducted in the presence of propene in the University of California CECERT atmospheric chamber facility. The experimental data are compared with previousm-xylene/NOx photooxidation work performed in the same chamber facility in the absence of propene (Song et al. Environ. Sci. Technol. 2005, 39, 3143-3149). The result shows that, for similar initial conditions, experiments with propene have lower reaction rates of m-xylene thanmore » those without propene, which indicates that propene reduces OH in the system. Furthermore, experiments with propene showed more than 15% reduction in SOA yield compared to experiments in the absence of propene. Additional experiments ofm-xylene/NOx with CO showed similar trends of suppressing OH and SOA formation. These results indicate that SOA from m-xylene/NOx photooxidation is strongly dependent on the OH level present, which provides evidence for the critical role of OH in SOA formation from aromatic hydrocarbons.« less

Infrared spectroscopy of secondary organic aerosol precursors and investigation of the hygroscopicity of SOA formed from the OH reaction with guaiacol and syringol.

PubMed

Ahmad, Waed; Coeur, Cecile; Tomas, Alexandre; Fagniez, Thomas; Brubach, Jean-Blaise; Cuisset, Arnaud

2017-04-10

Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) synchrotron analyses supplemented by density functional theory (DFT) anharmonic calculations have been undertaken to study the fundamental vibrational signatures of guaiacol and syringol, two methoxyphenol compounds found at the highest concentrations in fresh wood smoke and precursors of secondary organic aerosols (SOA) affecting the radiative balance and chemistry of the atmosphere. Nitroderivatives of these two compounds have also been studied experimentally for nitroguaiacol and theoretically for nitrosyringol. All the active fundamental vibrational bands have been assigned and compared to available gas phase measurements, providing a vibrational database of the main precursors for the analysis of SOA produced by atmospheric oxidation of methoxyphenols. In addition, the SOA formed in an atmospheric simulation chamber from the OH reaction with guaiacol and syringol were analyzed using the ATR-FTIR synchrotron spectroscopy and their hygroscopic properties were also investigated. The vibrational study confirms that nitroguaiacol and nitrosyringol are the main oxidation products of methoxyphenols by OH and are key intermediates in SOA production. The hydration experiments highlight the hydrophilic and hydrophobic characters of nitrosyringol and nitroguaiacol, respectively.

Sources of primary and secondary organic aerosol and their diurnal variations.

PubMed

Zheng, Mei; Zhao, Xiuying; Cheng, Yuan; Yan, Caiqing; Shi, Wenyan; Zhang, Xiaolu; Weber, Rodney J; Schauer, James J; Wang, Xinming; Edgerton, Eric S

2014-01-15

PM(2.5), as one of the criteria pollutants regulated in the U.S. and other countries due to its adverse health impacts, contains more than hundreds of organic pollutants with different sources and formation mechanisms. Daytime and nighttime PM2.5 samples from the August Mini-Intensive Gas and Aerosol Campaign (AMIGAS) in the southeastern U.S. were collected during summer 2008 at one urban site and one rural site, and were analyzed for organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC), and various individual organic compounds including some important tracers for carbonaceous aerosol sources by gas chromatography-mass spectrometry. Most samples exhibited higher daytime OC concentration, while higher nighttime OC was found in a few events at the urban site. Sources, formation mechanisms and composition of organic aerosol are complicated and results of this study showed that it exhibited distinct diurnal variations. With detailed organic tracer information, sources contributing to particulate OC were identified: higher nighttime OC concentration occurring in several occasions was mainly contributed by the increasing primary emissions at night, especially diesel exhaust and biomass burning; whereas sources responsible for higher daytime OC concentration included secondary organic aerosol (SOA) formation (e.g., cis-pinonic acid and non-biomass burning WSOC) together with traffic emissions especially gasoline engine exhaust. Primary tracers from combustion related sources such as EC, polycyclic aromatic hydrocarbons, and hopanes and steranes were significantly higher at the urban site with an urban to rural ratio between 5 and 8. However, this urban-rural difference for secondary components was less significant, indicating a relatively homogeneous distribution of SOA spatially. We found cholesterol concentrations, a typical tracer for meat cooking, were consistently higher at the rural site especially during the daytime, suggesting the likely additional sources for this tracer at rural site and that it should be used with caution as meat cooking tracer in rural areas in the future. Copyright © 2013 Elsevier B.V. All rights reserved.

TOXICOLOGICAL EVALUATION OF REALISTIC EMISSIONS OF SOURCE AEROSOLS (TERESA): APPLICATION TO POWER PLANT-DERIVED PM2.5

DOE Office of Scientific and Technical Information (OSTI.GOV)

Annette Rohr

2005-09-30

This report documents progress made on the subject project during the period of March 1, 2005 through August 31, 2005. The TERESA Study is designed to investigate the role played by specific emissions sources and components in the induction of adverse health effects by examining the relative toxicity of coal combustion and mobile source (gasoline and/or diesel engine) emissions and their oxidative products. The study involves on-site sampling, dilution, and aging of coal combustion emissions at three coal-fired power plants, as well as mobile source emissions, followed by animal exposures incorporating a number of toxicological endpoints. The DOE-EPRI Cooperative Agreementmore » (henceforth referred to as ''the Agreement'') for which this technical progress report has been prepared covers the performance and analysis of field experiments at the first TERESA plant, located in the Upper Midwest and henceforth referred to as Plant 0, and at two additional coal-fired power plants (Plants 1 and 2) utilizing different coal types and with different plant configurations. During this reporting period, fieldwork was completed at Plant 1, located in the Southeast. Stage I toxicological assessments were carried out in normal Sprague-Dawley rats, and Stage II assessments were carried out in a compromised model (myocardial infarction-MI-model). Normal rats were exposed to the following atmospheric scenarios: (1) primary particles; (2) oxidized emissions; (3) oxidized emissions + secondary organic aerosol (SOA)--this scenario was repeated; and (4) oxidized emissions + ammonia + SOA. Compromised animals were exposed to oxidized emissions + SOA (this scenario was also conducted in replicate). Stage I assessment endpoints included breathing pattern/pulmonary function; in vivo chemiluminescence (an indicator of oxidative stress); blood cytology; bronchoalveolar lavage (BAL) fluid analysis; and histopathology. Stage II assessments included continuous ECG monitoring via implanted telemeters and blood chemistry (complete blood count, circulating cytokines (interleukins-1 and -6), C-reactive protein (CRP), tumor necrosis factor alpha (TNF-{alpha}), and endothelin-1). Only a subset of exposure data was available at the time of preparation of this report. Continuous PM{sub 2.5} mass (TEOM) results indicate a mass concentration of 14 {micro}g/m{sup 3} for the primary particle scenario, and a range of 151 to 385 {micro}g/m{sup 3} for the oxidized emissions scenarios. Toxicological results obtained to date from Plant 1 indicate subtle biological responses to some of the exposure scenarios. We observed statistically significant changes in several breathing pattern parameters, including tidal volume and frequency. For one scenario (oxidized emissions + SOA), we observed a significant increase in Enhanced Pause (Penh), a parameter that may reflect airflow restriction. However, the respiratory changes are very subtle and do not present a clear picture of a particular respiratory effect (e.g., airway restriction, sensory irritation, or pulmonary irritation). A significant increase in lung chemiluminescence (a marker of oxidative stress in lung tissue) in exposed animals (vs. air-exposed controls) was observed in animals exposed to oxidized emissions + SOA. No changes were observed in heart tissue, nor in any other scenario. Stage II assessments were conducted to the secondary + SOA scenario; ECG and blood analysis data are pending. Planning was initiated for Plant 2, located in the Midwest. Because of the requirement for both the FGD and the SCR to be concurrently operational for appropriate reaction conditions, fieldwork at Plant 2 is scheduled for Summer 2006. During the next reporting period, we will complete all remaining exposure and toxicological analyses for Plant 1, and the next semiannual report will include a detailed description of these data and their interpretation. We are also in the process of preparing a topical report for Plant 0.« less

Studies on the Effect of Sub-zero Temperatures on the Formation of Extremely Low Volatility Dimer Esters in Secondary Organic Aerosol from Alpha-Pinene

NASA Astrophysics Data System (ADS)

Kristensen, Kasper; Normann Jensen, Louise; Bilde, Merete

2016-04-01

The oxidation of volatile organic compounds (VOC) is considered a major source of secondary organic aerosols (SOA) in the atmosphere. Recently, extremely low volatility organic compounds, or ELVOC, formed from the oxidation of VOCs have been shown to play a crucial role in new particle formation (Ehn et al., 2014). In addition, higher molecular weight dimer esters originating from the oxidation of the biogenic VOC alpha-pinene have been observed in both laboratory-generated and ambient SOA (Kristensen et al., 2013). The low volatility of the dimer esters along with an observed rapid formation makes these high molecular weight compounds likely candidates involved in new particle formation from the oxidation of alpha-pinene. Furthermore, laboratory experiments show that the dimer esters only form in the presence of ozone, thus may be used as tracers for the ozone-initiated oxidation of alpha-pinene, and are therefore indicative of enhanced anthropogenic activities. In this work, we present the results of a series of oxidation experiments performed in the newly constructed cold-room smog chamber at Aarhus University. This unique and state-of-the-art Teflon chamber allows for atmospheric simulations of the oxidation VOCs and subsequent SOA formation at temperatures down to -16 °C. In this study, ozonolysis and photochemical oxidations of alpha-pinene are performed at temperatures ranging from +20 to -16 °C. Chemical characterization of the formed SOA is performed using liquid chromatography coupled to quadrupole time-of-flight mass spectrometry. The results show significant differences in the chemical composition related to the experiment temperature. In particularly, the concentration of the high molecular weight dimer esters showed to be highly affected by temperature. Interestingly, preliminary results show higher formation of dimer esters related to increased SOA formation rate, thus indicating that these particle-phase ELVOCs may be linked with new particle formation. Ehn, M., Thornton, J. A., Kleist, E., Sipila, M., Junninen, H., Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F., Andres, S., Acir, I. H., Rissanen, M., Jokinen, T., Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurten, T., Nielsen, L. B., Jorgensen, S., Kjaergaard, H. G., Canagaratna, M., Dal Maso, M., Berndt, T., Petaja, T., Wahner, A., Kerminen, V. M., Kulmala, M., Worsnop, D. R., Wildt, J., and Mentel, T. F.: A large source of low-volatility secondary organic aerosol, Nature, 506, 476-+, 10.1038/nature13032, 2014. Kristensen, K., Enggrob, K. L., King, S. M., Worton, D. R., Platt, S. M., Mortensen, R., Rosenoern, T., Surratt, J. D., Bilde, M., Goldstein, A. H., and Glasius, M.: Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols, Atmospheric Chemistry and Physics, 13, 3763-3776, 2013.

Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3-D model

NASA Astrophysics Data System (ADS)

Knote, C.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J.; Fast, J.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R.; Tyndall, G.; Washenfelder, R.; Waxman, E.; Zhang, Q.

2013-10-01

New pathways to form secondary organic aerosols (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous-phase of cloud droplets and deliquesced aerosols where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include a detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aqueous-phase of aerosols. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. In all simulations the LA basin was found to be the hotspot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a simple uptake coefficient, as frequently employed in global modeling studies, leads to higher SOA contributions from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to be the main contributor to SOA mass compared to a volume process and reversible formation. We find that contribution of the latter is limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A kinetic limitation in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute >20% of glyoxal SOA mass, and the total mass formed (5.8% of total SOA in the LA basin) is about a third of the simple uptake coefficient formulation without consideration of aerosol phase state and composition. All these model formulations are based on very limited and recent field or laboratory data and we conclude that the current uncertainty on glyoxal SOA formation spans a factor of 10 in this domain and time period.

Can scooter emissions dominate urban organic aerosol?

NASA Astrophysics Data System (ADS)

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

2014-05-01

In urban areas, where the health impact of pollutants increases due to higher population density, traffic is a major source of ambient organic aerosol (OA). A significant fraction of OA from traffic is secondary, produced via the reaction of exhaust volatile organic compounds (VOCs) with atmospheric oxidants. Secondary OA (SOA) has not been systematically assessed for different vehicles and driving conditions and thus its relative importance compared to directly emitted, primary OA (POA) is unknown, hindering the design of effective vehicle emissions regulations. 2-stroke (2S) scooters are inexpensive and convenient and as such a popular means of transportation globally, particularly in Asia. European regulations for scooters are less stringent than for other vehicles and thus primary particulate emissions and SOA precursor VOCs from 2S engines are estimated to be much higher. Assessing the effects of scooters on public health requires consideration of both POA, and SOA production. Here, we quantify POA emission factors and potential SOA EFs from 2S scooters, and the effect of using aromatic free fuel instead of standard gasoline thereon. During the tests, Euro 1 and Euro 2 2S scooters were run in idle or simulated low power conditions. Emissions from a Euro 2 2S scooter were also sampled during regulatory driving cycles on a chassis dynamometer. Vehicle exhaust was introduced into smog chambers, where POA emission and SOA production were quantified using a high-resolution time-of-flight aerosol mass spectrometer. A high resolution proton transfer time-of-flight mass spectrometer was used to investigate volatile organic compounds and a suite of instruments was utilized to quantify CO, CO2, O3, NOX and total hydrocarbons. We show that the oxidation of VOCs in the exhaust emissions of 2S scooters produce significant SOA, exceeding by up to an order of magnitude POA emissions. By monitoring the decay of VOC precursors, we show that SOA formation from 2S scooter emissions essentially stems from the condensation of aromatic oxidation products. Further, we demonstrate that replacing the standard gasoline with an aromatic-free fuel mitigates SOA production, underlining the major role of aromatic compounds from 2S exhaust on SOA production. POA and potential SOA EFs determined here from 2S scooters will be presented and compared with EF from other vehicles, including 4-stroke scooters, gasoline cars and diesel cars to assess the contributions of 2S scooters in urban atmospheres.

Characterization of the limonene oxidation products with liquid chromatography coupled to the tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Witkowski, Bartłomiej; Gierczak, Tomasz

2017-04-01

Composition of the secondary organic aerosol (SOA) generated during ozonolysis of limonene was investigated with liquid chromatography coupled to the negative electrospray ionization (ESI), quadrupole tandem mass spectrometry (MS/MS) as well as high resolution Time-of-Flight mass spectrometry. Aerosol was generated in the flow-tube reactor. HR-MS/MS analysis allowed for proposing structures for the several up-to-date unknown limonene oxidation products. In addition to the low MW limonene oxidation products, significant quantities of oligomers characterized by elemental compositions: C19H30O5, C18H28O6, C19H28O7, C19H30O7 and C20H34O9 were detected in the SOA samples. It was concluded that these compounds are most likely esters, aldol reaction products and/or hemiacetals. In addition to detailed study of the limonene oxidation products, the reaction time as well as initial ozone concentration impact on the limonene SOA composition was investigated. The relative intensities of the two esters of the limonic acid and 7-hydroxy limononic acid increased as a result of lowering the initial ozone concentration and shortening the reaction time, indicating that esterification may be an important oligomerization pathway during limonene SOA formation.

Broadband optical extinction measurements and complex refractive indices in the ultraviolet spectral region for biogenic secondary organic aerosol exposed to ammonia

NASA Astrophysics Data System (ADS)

Flores, J.; Washenfelder, R. A.; Lee, H.; Segev, L.; Nizkorodov, S.; Brown, S. S.; Rudich, Y.

2013-12-01

The interaction between aerosols and sunlight plays an important role in the radiative balance of Earth's atmosphere. Aerosols can both scatter and absorb solar radiation causing surface cooling and heating of the atmosphere. These interactions depend on the optical properties of the aerosols (i.e., complex refractive index). Secondary organic aerosol (SOA) account for a significant fraction of the tropospheric aerosol. However, their chemical, physical, and optical properties, especially as they are processed in the atmosphere (aging), are still poorly understood. In this study, SOA formed by the ozonolysis of various biogenic volatile organic compound (BVOC) precursors (α-pinene, limonene, and α-humulene) were exposed to humid air containing various concentrations of gaseous ammonia which has been shown to cause the biogenic SOA to ';brown' on filters. The extent of absorption of the SOA in the aerosol phase cause by the exposure to gaseous ammonia was measured by a newly developed instrument to measure aerosol extinction as a function of wavelength using Broadband Cavity Enhanced Spectroscopy (BBCES) with a broadband light source. Size-selected measurements of the humid SOA exposed to NH3 for about 1.5 hours were used to derive complex refractive indices (RI) as a function of wavelength in the UV spectral region (from 360 - 420nm). The imaginary part of the refractive index did not exceed 0.05 in the 360 - 420 nm range for SOA formed from the three BVOCs even at high concentrations of NH3 (>1ppm), allowing to place an upper limit of k = 0.05. Furthermore, the small k values are consistent with bulk UV-VIS measurements. However, for the α-pinene SOA, the real part of the RI slightly increased from n = 1.49 to n = 1.55 with negligible spectral dependence. For limonene and α-humulene the real part remind constant within error calculations. Based on these observations, reactive uptake of gaseous ammonia is not expected to significantly affect absorption and scattering properties of SOA particles.

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOAAQ.

Observational insights into aerosol formation from isoprene.

PubMed

Worton, David R; Surratt, Jason D; Lafranchi, Brian W; Chan, Arthur W H; Zhao, Yunliang; Weber, Robin J; Park, Jeong-Hoo; Gilman, Jessica B; de Gouw, Joost; Park, Changhyoun; Schade, Gunnar; Beaver, Melinda; Clair, Jason M St; Crounse, John; Wennberg, Paul; Wolfe, Glenn M; Harrold, Sara; Thornton, Joel A; Farmer, Delphine K; Docherty, Kenneth S; Cubison, Michael J; Jimenez, Jose-Luis; Frossard, Amanda A; Russell, Lynn M; Kristensen, Kasper; Glasius, Marianne; Mao, Jingqiu; Ren, Xinrong; Brune, William; Browne, Eleanor C; Pusede, Sally E; Cohen, Ronald C; Seinfeld, John H; Goldstein, Allen H

2013-10-15

Atmospheric photooxidation of isoprene is an important source of secondary organic aerosol (SOA) and there is increasing evidence that anthropogenic oxidant emissions can enhance this SOA formation. In this work, we use ambient observations of organosulfates formed from isoprene epoxydiols (IEPOX) and methacrylic acid epoxide (MAE) and a broad suite of chemical measurements to investigate the relative importance of nitrogen oxide (NO/NO2) and hydroperoxyl (HO2) SOA formation pathways from isoprene at a forested site in California. In contrast to IEPOX, the calculated production rate of MAE was observed to be independent of temperature. This is the result of the very fast thermolysis of MPAN at high temperatures that affects the distribution of the MPAN reservoir (MPAN / MPA radical) reducing the fraction that can react with OH to form MAE and subsequently SOA (F(MAE formation)). The strong temperature dependence of F(MAE formation) helps to explain our observations of similar concentrations of IEPOX-derived organosulfates (IEPOX-OS; ~1 ng m(-3)) and MAE-derived organosulfates (MAE-OS; ~1 ng m(-3)) under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OS (~20 ng m(-3)) relative to MAE-OS (<0.0005 ng m(-3)) at higher temperatures (higher isoprene concentrations). A kinetic model of IEPOX and MAE loss showed that MAE forms 10-100 times more ring-opening products than IEPOX and that both are strongly dependent on aerosol water content when aerosol pH is constant. However, the higher fraction of MAE ring opening products does not compensate for the lower MAE production under warmer conditions (higher isoprene concentrations) resulting in lower formation of MAE-derived products relative to IEPOX at the surface. In regions of high NOx, high isoprene emissions and strong vertical mixing the slower MPAN thermolysis rate aloft could increase the fraction of MPAN that forms MAE resulting in a vertically varying isoprene SOA source.

Quantifying Volatile Organic Compound Emissions from Solvents and their Impacts on Urban Air Quality

NASA Astrophysics Data System (ADS)

Mcdonald, B. C.; De Gouw, J. A.; Gilman, J.; Ahmadov, R.; Cappa, C. D.; Frost, G. J.; Goldstein, A. H.; Jathar, S.; Jimenez, J. L.; Kim, S. W.; McKeen, S. A.; Roberts, J. M.; Trainer, M.

2016-12-01

Solvents, which consist of personal care products, paints, degreasing agents, and other chemical products, are an important anthropogenic source of volatile organic compound (VOC) emissions. Yet there are many unresolved questions related to their emission rates, chemical composition, and relative importance on urban air quality problems. Using atmospheric measurements of speciated VOCs collected at a ground site located in the Los Angeles basin during the California Nexus (CalNex) Study in 2010, and utilizing data on the composition of solvent emissions from the California Air Resources Board (CARB), we are able to reconcile solvent emissions with ambient observations. Our analysis indicates that solvent emissions are underestimated by a factor of 2-3 in the CARB inventory. We then estimate the reactivity of solvent emissions with the hydroxyl (OH) radical, and also estimate the propensity of solvent emissions to form secondary organic aerosol (SOA). Solvents contain significant fractions of oxygenated compounds, including intermediate volatility compounds, which if released to the atmosphere are potentially reactive and can lead to the formation of SOA. Overall, our results suggest that in the Los Angeles basin, solvents are now the largest anthropogenic source of VOC emissions, OH reactivity, and SOA formation, and larger than the contribution from motor vehicles. This suggests that more research is needed in better constraining this potentially important source of urban VOC emissions.

Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

2015-09-01

Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data; and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the Statistical Oxidation Model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional UCD/CIT air quality model and applied to air quality episodes in California and the eastern US. The mass, composition and properties of SOA predicted using SOM are compared to SOA predictions generated by a traditional "two-product" model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation. Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields perturbs SOA concentrations by a factor of two and are probably a much stronger determinant in 3-D models than constrained multi-generational oxidation. While total predicted SOA mass is similar for the SOM and two-product models, the SOM model predicts increased SOA contributions from anthropogenic (alkane, aromatic) and sesquiterpenes and decreased SOA contributions from isoprene and monoterpene relative to the two-product model calculations. The SOA predicted by SOM has a much lower volatility than that predicted by the traditional model resulting in better qualitative agreement with volatility measurements of ambient OA. On account of its lower-volatility, the SOA mass produced by SOM does not appear to be as strongly influenced by the inclusion of oligomerization reactions, whereas the two-product model relies heavily on oligomerization to form low volatility SOA products. Finally, an unconstrained contemporary hybrid scheme to model multi-generational oxidation within the framework of a two-product model in which "ageing" reactions are added on top of the existing two-product parameterization is considered. This hybrid scheme formed at least three times more SOA than the SOM during regional simulations as a result of excessive transformation of semi-volatile vapors into lower volatility material that strongly partitions to the particle phase. This finding suggests that these "hybrid" multi-generational schemes should be used with great caution in regional models.

Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

2016-02-01

Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the statistical oxidation model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional University of California at Davis / California Institute of Technology (UCD/CIT) air quality model and applied to air quality episodes in California and the eastern USA. The mass, composition and properties of SOA predicted using SOM were compared to SOA predictions generated by a traditional two-product model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation.Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields perturbs SOA concentrations by a factor of two and are probably a much stronger determinant in 3-D models than multi-generational oxidation. While total predicted SOA mass is similar for the SOM and two-product models, the SOM model predicts increased SOA contributions from anthropogenic (alkane, aromatic) and sesquiterpenes and decreased SOA contributions from isoprene and monoterpene relative to the two-product model calculations. The SOA predicted by SOM has a much lower volatility than that predicted by the traditional model, resulting in better qualitative agreement with volatility measurements of ambient OA. On account of its lower-volatility, the SOA mass produced by SOM does not appear to be as strongly influenced by the inclusion of oligomerization reactions, whereas the two-product model relies heavily on oligomerization to form low-volatility SOA products. Finally, an unconstrained contemporary hybrid scheme to model multi-generational oxidation within the framework of a two-product model in which ageing reactions are added on top of the existing two-product parameterization is considered. This hybrid scheme formed at least 3 times more SOA than the SOM during regional simulations as a result of excessive transformation of semi-volatile vapors into lower volatility material that strongly partitions to the particle phase. This finding suggests that these hybrid multi-generational schemes should be used with great caution in regional models.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

The oxidation of volatile organic compounds (VOCs) leads to the formation of low volatile organic compounds that can form secondary organic aerosol (SOA). Studies in the past showed that laboratory generated and ambient SOA are made of polar molecules with O/C ratios generally greater than 0.5. More recent studies have shown that SOA compounds can contain heteroatoms mainly sulfur and nitrogen atoms. Offline chemical analysis with high-resolution mass spectrometers and fragmentation experiments has shown that sulphur containing compounds are mainly organosulfates and nitrogen containing species are aromatic heterocyclic compounds such as imidazole and nitrated aromatic compounds such as nitrophenols. In addition to these, SOA compounds containing both sulfur and nitrogen have been reported from the analysis of ambient organic aerosol, rainwater, fog and cloud samples. Based on the mass spectrometric evidence these compounds are attributed to nitrooxy-organosulfates originating from isoprene and monoterpenes. Although these compounds are ubiquitously detected in the ambient samples, reports about their detection in laboratory generated SOA are scares and their formation mechanisms are not well understood. In the present study, we investigated the formation of sulfur and nitrogen containing SOA species in the oxidation of biogenic VOCs. Photooxidation and night-time oxidation experiments were performed in a smog chamber to produce SOA samples. The laboratory generated SOA samples were analysed with UPLC-IMS-TOFMS (Ultra Performance Liquid Chromatography coupled to Ion Mobility Spectrometry and Time of Flight Mass Spectrometry). The presence of highly acidic sulphate seed particles (pH0) did not promote the formation of compounds with chemical formula of C10H17NO7S- and m/z value of 294.0653, indicating that the formation mechanisms of these compounds unlikely involve the ring opening reactions of epoxides and subsequent sulfation reactions. On the other hand, their formation was significantly enhanced when the night-time oxidation was performed in the presence of both neutral seed particle and gas-phase SO2, suggesting that the presence of gas-phase SO2 is a key for their formation.

Exposure of BALB/c Mice to Diesel Engine Exhaust Origin Secondary Organic Aerosol (DE-SOA) during the Developmental Stages Impairs the Social Behavior in Adult Life of the Males.

PubMed

Win-Shwe, Tin-Tin; Kyi-Tha-Thu, Chaw; Moe, Yadanar; Fujitani, Yuji; Tsukahara, Shinji; Hirano, Seishiro

2015-01-01

Secondary organic aerosol (SOA) is a component of particulate matter (PM) 2.5 and formed in the atmosphere by oxidation of volatile organic compounds. Recently, we have reported that inhalation exposure to diesel engine exhaust (DE) originated SOA (DE-SOA) affect novel object recognition ability and impair maternal behavior in adult mice. However, it is not clear whether early life exposure to SOA during the developmental stages affect social behavior in adult life or not. In the present study, to investigate the effects of early life exposure to DE-SOA during the gestational and lactation stages on the social behavior in the adult life, BALB/c mice were exposed to clean air (control), DE, DE-SOA and gas without any PM in the inhalation chambers from gestational day 14 to postnatal day 21 for 5 h a day and 5 days per week. Then adult mice were examined for changes in their social behavior at the age of 13 week by a sociability and social novelty preference, social interaction with a juvenile mouse and light-dark transition test, hypothalamic mRNA expression levels of social behavior-related genes, estrogen receptor-alpha and oxytocin receptor as well as of the oxidative stress marker gene, heme oxygenase (HO)-1 by real-time RT-PCR method. In addition, hypothalamic level of neuronal excitatory marker, glutamate was determined by ELISA method. We observed that sociability and social novelty preference as well as social interaction were remarkably impaired, expression levels of estrogen receptor-alpha, oxytocin receptor mRNAs were significantly decreased, expression levels of HO-1 mRNAs and glutamate levels were significantly increased in adult male mice exposed to DE-SOA compared to the control ones. Findings of this study indicate early life exposure of BALB/c mice to DE-SOA may affect their late-onset hypothalamic expression of social behavior related genes, trigger neurotoxicity and impair social behavior in the males.

Exposure of BALB/c Mice to Diesel Engine Exhaust Origin Secondary Organic Aerosol (DE-SOA) during the Developmental Stages Impairs the Social Behavior in Adult Life of the Males

PubMed Central

Win-Shwe, Tin-Tin; Kyi-Tha-Thu, Chaw; Moe, Yadanar; Fujitani, Yuji; Tsukahara, Shinji; Hirano, Seishiro

2016-01-01

Secondary organic aerosol (SOA) is a component of particulate matter (PM) 2.5 and formed in the atmosphere by oxidation of volatile organic compounds. Recently, we have reported that inhalation exposure to diesel engine exhaust (DE) originated SOA (DE-SOA) affect novel object recognition ability and impair maternal behavior in adult mice. However, it is not clear whether early life exposure to SOA during the developmental stages affect social behavior in adult life or not. In the present study, to investigate the effects of early life exposure to DE-SOA during the gestational and lactation stages on the social behavior in the adult life, BALB/c mice were exposed to clean air (control), DE, DE-SOA and gas without any PM in the inhalation chambers from gestational day 14 to postnatal day 21 for 5 h a day and 5 days per week. Then adult mice were examined for changes in their social behavior at the age of 13 week by a sociability and social novelty preference, social interaction with a juvenile mouse and light-dark transition test, hypothalamic mRNA expression levels of social behavior-related genes, estrogen receptor-alpha and oxytocin receptor as well as of the oxidative stress marker gene, heme oxygenase (HO)-1 by real-time RT-PCR method. In addition, hypothalamic level of neuronal excitatory marker, glutamate was determined by ELISA method. We observed that sociability and social novelty preference as well as social interaction were remarkably impaired, expression levels of estrogen receptor-alpha, oxytocin receptor mRNAs were significantly decreased, expression levels of HO-1 mRNAs and glutamate levels were significantly increased in adult male mice exposed to DE-SOA compared to the control ones. Findings of this study indicate early life exposure of BALB/c mice to DE-SOA may affect their late-onset hypothalamic expression of social behavior related genes, trigger neurotoxicity and impair social behavior in the males. PMID:26834549

Violation of expectations about movement and goal achievement leads to Sense of Agency reduction.

PubMed

Villa, Riccardo; Tidoni, Emmanuele; Porciello, Giuseppina; Aglioti, Salvatore Maria

2018-05-16

The control of one's own movements and of their impact on the external world generates a feeling of control referred to as Sense of Agency (SoA). SoA is experienced when actions match predictions and is reduced by unpredicted events. The present study investigated the contribution of monitoring two fundamental components of action-movement execution and goal achievement-that have been most often explored separately in previous research. We have devised a new paradigm in which participants performed goal-directed actions while viewing an avatar's hand in a mixed-reality scenario. The hand performed either the same action or a different one, simultaneously or after various delays. Movement of the virtual finger and goal attainment were manipulated, so that they could match or conflict with the participants' expectations. We collected judgments of correspondence (an explicit index of SoA that overcomes the tendency to over-attribute actions to oneself) by asking participants if the observed action was synchronous or not with their action. In keeping with previous studies, we found that monitoring both movement execution and goal attainment is relevant for SoA. Moreover, we expanded previous findings by showing that movement information may be a more constant source of SoA modulation than goal information. Indeed, an incongruent movement impaired SoA irrespective of delay duration, while a missed goal did so only when delays were short. Our novel paradigm allowed us to simultaneously manipulate multiple action features, a characteristic that makes it suitable for investigating the contribution of different sub-components of action in modulating SoA in healthy and clinical populations.

VOC species and emission inventory from vehicles and their SOA formation potentials estimation in Shanghai, China

NASA Astrophysics Data System (ADS)

Huang, C.; Wang, H. L.; Li, L.; Wang, Q.; Lu, Q.; de Gouw, J. A.; Zhou, M.; Jing, S. A.; Lu, J.; Chen, C. H.

2015-10-01

Volatile organic compound (VOC) species from vehicle exhausts and gas evaporation were investigated by chassis dynamometer and on-road measurements of nine gasoline vehicles, seven diesel vehicles, five motorcycles, and four gas evaporation samples. The secondary organic aerosol (SOA) mass yields of gasoline, diesel, motorcycle exhausts, and gas evaporation were estimated based on the mixing ratio of measured C2-C12 VOC species and inferred carbon number distributions. High aromatic contents were measured in gasoline exhausts and contributed comparatively more SOA yield. A vehicular emission inventory was compiled based on a local survey of on-road traffic in Shanghai and real-world measurements of vehicle emission factors from previous studies in the cities of China. The inventory-based vehicular organic aerosol (OA) productions to total CO emissions were compared with the observed OA to CO concentrations (ΔOA / ΔCO) in the urban atmosphere. The results indicate that vehicles dominate the primary organic aerosol (POA) emissions and OA production, which contributed about 40 and 60 % of OA mass in the urban atmosphere of Shanghai. Diesel vehicles, which accounted for less than 20 % of vehicle kilometers of travel (VKT), contribute more than 90 % of vehicular POA emissions and 80-90 % of OA mass derived by vehicles in urban Shanghai. Gasoline exhaust could be an important source of SOA formation. Tightening the limit of aromatic content in gasoline fuel will be helpful to reduce its SOA contribution. Intermediate-volatile organic compounds (IVOCs) in vehicle exhausts greatly contribute to SOA formation in the urban atmosphere of China. However, more experiments need to be conducted to determine the contributions of IVOCs to OA pollution in China.

Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning

EPA Science Inventory

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to amb...

Assessing and evaluating urban VOC emissions in mid-latitude megacities from intensive observations in Paris and Los Angeles

NASA Astrophysics Data System (ADS)

Borbon, A.; Gilman, J. B.; Kuster, W. C.; McKeen, S. A.; Holloway, J. S.; Gros, V.; Gaimoz, C.; Beekmann, M.; De Gouw, J. A.

2011-12-01

Volatile Organic Compounds (VOC) affect urban air quality and regional climate change by contributing to ozone formation and the build-up of Secondary Organic Aerosols (SOA). Quantification of VOC emissions is a first critical step to predict VOC environmental impacts and to design effective abatement strategies. Indeed, the quality of ozone and SOA forecasts strongly depends on an accurate knowledge of the primary VOC emissions. However, commonly used bottom-up approaches are highly uncertain due to source multiplicity (combustion processes, storage and distribution of fossil fuels, solvent use, etc.) because of numerous controlling factors (driving conditions, fuel type, temperature, radiation, etc.), and their great variability in time and space. Field observations of VOC and other trace gases can provide valuable top-down constraints to evaluate VOC emission inventories at urban scales. In addition, the implementation of emission reduction measures raises the question of the increasing importance of VOC sources other than traffic. Here, we will evaluate VOC emissions of two mid-latitude megacities in the Northern Hemisphere: the Greater Paris area (Europe) and Los Angeles (USA). In 2009 and 2010, three intensive field campaigns took place in Paris and Los Angeles in the framework of the MEGAPOLI (EU FP7) and CalNex-2010 projects, respectively. Very detailed measurements of aerosol composition and properties, and their gaseous VOC precursors were carried out at ground-based sites (urban center and suburban) and on various mobile platforms. This contribution uses a comprehensive suite of VOC measurements collected by GC-MS/FID techniques at ground-based sites in both cities by a source-receptor methodology. First, emission ratios were estimated from the observations (uncertainty of ± 20%) and compared regarding regional characteristics and European vs. Californian control policies. Then, determined emission ratios were used to assess the accuracy of up-to-date emission inventories. While emission ratios agree within the uncertainties for many VOCs, remarkable differences are observed for aromatic VOCs (C7-C9) depending on the season. Moreover, the evaluation of emission inventories shows large discrepancies for VOCs for which traffic is not the dominant source. Commonalities and/or differences are also discussed in term of implication for urban atmospheric chemistry (ozone and SOA formation potential) in both megacities.

Assessing the role of anthropogenic and biogenic sources on PM1 over southern West Africa using aircraft measurements

NASA Astrophysics Data System (ADS)

Brito, Joel; Freney, Evelyn; Dominutti, Pamela; Borbon, Agnes; Haslett, Sophie L.; Batenburg, Anneke M.; Colomb, Aurelie; Dupuy, Regis; Denjean, Cyrielle; Burnet, Frederic; Bourriane, Thierry; Deroubaix, Adrien; Sellegri, Karine; Borrmann, Stephan; Coe, Hugh; Flamant, Cyrille; Knippertz, Peter; Schwarzenboeck, Alfons

2018-01-01

As part of the Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa (DACCIWA) project, an airborne campaign was designed to measure a large range of atmospheric constituents, focusing on the effect of anthropogenic emissions on regional climate. The presented study details results of the French ATR42 research aircraft, which aimed to characterize gas-phase, aerosol and cloud properties in the region during the field campaign carried out in June/July 2016 in combination with the German Falcon 20 and the British Twin Otter aircraft. The aircraft flight paths covered large areas of Benin, Togo, Ghana and Côte d'Ivoire, focusing on emissions from large urban conurbations such as Abidjan, Accra and Lomé, as well as remote continental areas and the Gulf of Guinea. This paper focuses on aerosol particle measurements within the boundary layer (< 2000 m), in particular their sources and chemical composition in view of the complex mix of both biogenic and anthropogenic emissions, based on measurements from a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS) and ancillary instrumentation. Background concentrations (i.e. outside urban plumes) observed from the ATR42 indicate a fairly polluted region during the time of the campaign, with average concentrations of carbon monoxide of 131 ppb, ozone of 32 ppb, and aerosol particle number concentration ( > 15 nm) of 735 cm-3 stp. Regarding submicron aerosol composition (considering non-refractory species and black carbon, BC), organic aerosol (OA) is the most abundant species contributing 53 %, followed by SO4 (27 %), NH4 (11 %), BC (6 %), NO3 (2 %) and minor contribution of Cl (< 0.5 %). Average background PM1 in the region was 5.9 µg m-3 stp. During measurements of urban pollution plumes, mainly focusing on the outflow of Abidjan, Accra and Lomé, pollutants are significantly enhanced (e.g. average concentration of CO of 176 ppb, and aerosol particle number concentration of 6500 cm-3 stp), as well as PM1 concentration (11.9 µg m-3 stp). Two classes of organic aerosols were estimated based on C-ToF-AMS: particulate organic nitrates (pONs) and isoprene epoxydiols secondary organic aerosols (IEPOX-SOA). Both classes are usually associated with the formation of particulate matter through complex interactions of anthropogenic and biogenic sources. During DACCIWA, pONs have a fairly small contribution to OA (around 5 %) and are more associated with long-range transport from central Africa than local formation. Conversely, IEPOX-SOA provides a significant contribution to OA (around 24 and 28 % under background and in-plume conditions). Furthermore, the fractional contribution of IEPOX-SOA is largely unaffected by changes in the aerosol composition (particularly the SO4 concentration), which suggests that IEPOX-SOA concentration is mainly driven by pre-existing aerosol surface, instead of aerosol chemical properties. At times of large in-plume SO4 enhancements (above 5 µg m-3), the fractional contribution of IEPOX-SOA to OA increases above 50 %, suggesting only then a change in the IEPOX-SOA-controlling mechanism. It is important to note that IEPOX-SOA constitutes a lower limit to the contribution of biogenic OA, given that other processes (e.g. non-IEPOX isoprene, monoterpene SOA) are likely in the region. Given the significant contribution to aerosol concentration, it is crucial that such complex biogenic-anthropogenic interactions are taken into account in both present-day and future scenario models of this fast-changing, highly sensitive region.

Volatile organic compound mixing ratios above Beijing in November and December 2016

NASA Astrophysics Data System (ADS)

Acton, William; Shaw, Marvin; Huang, Zhonghui; Wang, Zhaoyi; Wang, Xinming; Zhang, Yanli; Davison, Brian; Langford, Ben; Mullinger, Neil; Nemitz, Eiko; Fu, Pingqing; Squires, Freya; Carpenter, Lucy; Lewis, Alastair; Hewitt, Nick

2017-04-01

Volatile organic compounds (VOCs) are emitted into the atmosphere from vegetation and anthropogenic sources such as fossil fuel combustion, biomass burning and the evaporation of petroleum products. These compounds play an important role in the chemistry of the lower atmosphere through secondary organic aerosol (SOA) formation and facilitating the formation of tropospheric ozone. As well as their indirect impact on human health via the formation of ozone and SOA, some VOCs, including benzene, directly affect human health adversely. Here we report VOC mixing ratios measured in Beijing during a 5 week intensive field campaign from the 7th November to the 10th December 2016. This work was carried out as part of the Sources and Emissions of Air Pollutants in Beijing (AIRPOLL-Beijing) work project within the Air Pollution and Human Health in a Developing Megacity (APHH-Beijing) research programme. APHH is a large multi-institutional study which aims to record the concentrations and identify the sources of urban air pollutants in Beijing, determine exposure, understand their effects on human health, and to identify solutions. VOC mixing ratios were recorded using a Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS, Ionicon Analytik) and a Selected Ion Flow Tube-Mass Spectrometer (SIFT-MS, SYFT Technologies). During the measurement period Beijing was subject to multiple pollution events that alternated with periods of relatively good air quality, allowing the VOCs within the polluted air masses to be identified and quantified. VOCs were sampled at 102 m with additional gradient measurements made at 3, 15, 32 and 64 m providing a vertical profile of VOC mixing ratios. Mixing ratios of methanol, acetonitrile, acetaldehyde, acetone, isoprene and aromatics species will be reported together with a discussion of potential sources. Comparisons will then be drawn with other large cities.

Analysis of Glyoxal and Methylglyoxal in atmospheric particulate matter - Qualification and Quantification using a derivatisation method for HPLC-ESI-MS

NASA Astrophysics Data System (ADS)

Kampf, Christopher; Hoffmann, Thorsten

2010-05-01

In recent years much effort has been put into the analysis of so called secondary organic aerosols (SOA). SOA is produced through gas phase oxidation of volatile organic compounds (VOC's) by atmospheric oxidants like OH- or NO3-radicals or ozone with subsequent gas-particle partitioning of the low volatility products. VOC's are emitted by both biogenic and anthropogenic sources in large amounts into the atmosphere. However, it is found that gas to particle partitioning alone cannot explain the complete amount of SOA produced in the atmosphere. It is therefore proposed that heterogeneous reactions on the particle surface or in the particles themselves could lead to the formation of additional SOA mass from semi-volatile compounds such as the reactive dialdehydes glyoxal and methylglyoxal[1]. Global glyoxal and methylglyoxal emissions are estimated to be 45 Tg a-1 and 140 Tg a-1, respectively. The oxidation of biogenic isoprene contributes to about 47% of the total glyoxal mass formed and even to about 79% for methylglyoxal[2]. Due to their high solubility in water (hydration of aldehyde functions), glyoxal and methylglyoxal have a high potential to form SOA via heterogeneous reactions in the particle phase although their volatility is relatively high. Several studies propose oligomerisation or formation of imidazole derivatives as potential reaction pathways to reduce their volatility[1,3,4,5]. Here we present a method for the qualification and quantification of both glyoxal and methylglyoxal in atmospheric PM2.5 filter samples via derivatisation with phenylhydrazine. Reproducibility, recovery and limits of detection and quantification are given. The method is found to be easily suitable for measurements at atmospheric concentration levels for both substances. First results of a measurement campaign in Mainz, Germany in August 2009 are shown for a proof of principle. Initial problems of the method development due to the chemical nature of the analytes und future enhancements of the sampling procedure are discussed. References 1. Kalberer, M., et al. (2004). Science, 303(5664), 1659-1662 2. Fu, T.-M., et al. (2008). Journal of Geophysical Research, 113, D15303 3. Iinuma, Y., et al. (2004). Atmospheric Environment, 38(5), 761-773 4. Galloway, M. M., et al. (2009), Atmos. Chem. Phys., 9, 3331-3345 5. Nozière, B., et al. (2009), J. Phys. Chem. A, 113, 231-237

Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments

NASA Astrophysics Data System (ADS)

Chirico, R.; Decarlo, P. F.; Heringa, M. F.; Tritscher, T.; Richter, R.; Prevot, A. S. H.; Dommen, J.; Weingartner, E.; Wehrle, G.; Gysel, M.; Laborde, M.; Baltensperger, U.

2010-06-01

Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the final vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC<0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23-0.56 g/kg fuel burned. In presence of both a DOC and a DPF, primary particles with a mobility diameter above 5 nm were 300±19 cm-3, and only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.097 to 0.190. Five hours of oxidation led to a more oxidized OA with an O/C range of 0.208 to 0.369.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

Aksoyoglu, Sebnem; Ciarelli, Giancarlo; El-Haddad, Imad; Baltensperger, Urs; Prévôt, André S. H.

2017-06-01

Contributions of various anthropogenic sources to the secondary inorganic aerosol (SIA) in Europe as well as the role of biogenic emissions on SIA formation were investigated using the three-dimensional regional model CAMx (comprehensive air quality model with extensions). Simulations were carried out for two periods of EMEP field campaigns, February-March 2009 and June 2006, which are representative of cold and warm seasons, respectively. Biogenic volatile organic compounds (BVOCs) are known mainly as precursors of ozone and secondary organic aerosol (SOA), but their role on inorganic aerosol formation has not attracted much attention so far. In this study, we showed the importance of the chemical reactions of BVOCs and how they affect the oxidant concentrations, leading to significant changes, especially in the formation of ammonium nitrate. A sensitivity test with doubled BVOC emissions in Europe during the warm season showed a large increase in secondary organic aerosol (SOA) concentrations (by about a factor of two), while particulate inorganic nitrate concentrations decreased by up to 35 %, leading to a better agreement between the model results and measurements. Sulfate concentrations decreased as well; the change, however, was smaller. The changes in inorganic nitrate and sulfate concentrations occurred at different locations in Europe, indicating the importance of precursor gases and biogenic emission types for the negative correlation between BVOCs and SIA. Further analysis of the data suggested that reactions of the additional terpenes with nitrate radicals at night were responsible for the decline in inorganic nitrate formation, whereas oxidation of BVOCs with OH radicals led to a decrease in sulfate. Source apportionment results suggest that the main anthropogenic source of precursors leading to formation of particulate inorganic nitrate is road transport (SNAP7; see Table 1 for a description of the categories), whereas combustion in energy and transformation industries (SNAP1) was the most important contributor to sulfate particulate mass. Emissions from international shipping were also found to be very important for both nitrate and sulfate formation in Europe. In addition, we also examined contributions from the geographical source regions to SIA concentrations in the most densely populated region of Switzerland, the Swiss Plateau.

Evaluating the impact of new observational constraints on P-S/IVOC emissions, multi-generation oxidation, and chamber wall losses on SOA modeling for Los Angeles, CA

NASA Astrophysics Data System (ADS)

Ma, Prettiny K.; Zhao, Yunliang; Robinson, Allen L.; Worton, David R.; Goldstein, Allen H.; Ortega, Amber M.; Jimenez, Jose L.; Zotter, Peter; Prévôt, André S. H.; Szidat, Sönke; Hayes, Patrick L.

2017-08-01

Secondary organic aerosol (SOA) is an important contributor to fine particulate matter (PM) mass in polluted regions, and its modeling remains poorly constrained. A box model is developed that uses recently published literature parameterizations and data sets to better constrain and evaluate the formation pathways and precursors of urban SOA during the CalNex 2010 campaign in Los Angeles. When using the measurements of intermediate-volatility organic compounds (IVOCs) reported in Zhao et al. (2014) and of semi-volatile organic compounds (SVOCs) reported in Worton et al. (2014) the model is biased high at longer photochemical ages, whereas at shorter photochemical ages it is biased low, if the yields for VOC oxidation are not updated. The parameterizations using an updated version of the yields, which takes into account the effect of gas-phase wall losses in environmental chambers, show model-measurement agreement at longer photochemical ages, even though some low bias at short photochemical ages still remains. Furthermore, the fossil and non-fossil carbon split of urban SOA simulated by the model is consistent with measurements at the Pasadena ground site. Multi-generation oxidation mechanisms are often employed in SOA models to increase the SOA yields derived from environmental chamber experiments in order to obtain better model-measurement agreement. However, there are many uncertainties associated with these aging mechanisms. Thus, SOA formation in the model is compared to data from an oxidation flow reactor (OFR) in order to constrain SOA formation at longer photochemical ages than observed in urban air. The model predicts similar SOA mass at short to moderate photochemical ages when the aging mechanisms or the updated version of the yields for VOC oxidation are implemented. The latter case has SOA formation rates that are more consistent with observations from the OFR though. Aging mechanisms may still play an important role in SOA chemistry, but the additional mass formed by functionalization reactions during aging would need to be offset by gas-phase fragmentation of SVOCs. All the model cases evaluated in this work show a large majority of the urban SOA (70-83 %) at Pasadena coming from the oxidation of primary SVOCs (P-SVOCs) and primary IVOCs (P-IVOCs). The importance of these two types of precursors is further supported by analyzing the percentage of SOA formed at long photochemical ages (1.5 days) as a function of the precursor rate constant. The P-SVOCs and P-IVOCs have rate constants that are similar to highly reactive VOCs that have been previously found to strongly correlate with SOA formation potential measured by the OFR. Finally, the volatility distribution of the total organic mass (gas and particle phase) in the model is compared against measurements. The total SVOC mass simulated is similar to the measurements, but there are important differences in the measured and modeled volatility distributions. A likely reason for the difference is the lack of particle-phase reactions in the model that can oligomerize and/or continue to oxidize organic compounds even after they partition to the particle phase.

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

EPA Science Inventory

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

Source apportionment of organic compounds in Berlin using positive matrix factorization - assessing the impact of biogenic aerosol and biomass burning on urban particulate matter.

PubMed

Wagener, Sandra; Langner, Marcel; Hansen, Ute; Moriske, Heinz-Jörn; Endlicher, Wilfried R

2012-10-01

Source apportionment of 13 organic compounds, elemental carbon and organic carbon of ambient PM(10) and PM(1) was performed with positive matrix factorization (PMF). Samples were collected at three sites characterized by different vegetation influences in Berlin, Germany in 2010. The aim was to determine organic, mainly biogenic sources and their impact on urban aerosol collected in a densely populated region. A 6-factor solution provided the best data fit for both PM-fractions, allowing the sources isoprene- and α-pinene-derived secondary organic aerosol (SOA), bio primary, primarily attributable to fungal spores, bio/urban primary including plant fragments in PM(10) and cooking and traffic emissions in PM(1), biomass burning and combustion fossil to be identified. With mean concentrations up to 2.6 μg Cm(-3), biomass burning dominated the organic fraction in cooler months. Concentrations for α-pinene-derived SOA exceeded isoprene-derived concentrations. Estimated secondary organic carbon contributions to total organic carbon (OC) were between 7% and 42% in PM(10) and between 11% and 60% in PM(1), which is slightly lower than observed for US- or Asian cities. Primary biogenic emissions reached up to 33% of OC in the PM(10)-fraction in the late summer and autumn months. Temperature-dependence was found for both SOA-factors, correlations with ozone and mix depth only for the α-pinene-derived SOA-factor. Latter indicated input of α-pinene from the borders, highlighting differences in the origin of the precursors of both factors. Most factors were regionally distributed. High regional distribution was found to be associated with stronger influence of ambient parameters and higher concentrations at the background station. A significant contribution of biogenic emissions and biomass burning to urban organic aerosol could be stated. This indicates a considerable impact on PM concentrations also in cities in a densely populated area, and should draw the attention concerning health aspects not only to cardio-vascular diseases but also to allergy issues. Copyright © 2012 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Ots, Riinu; Young, Dominique E.; Vieno, Massimo; Xu, Lu; Dunmore, Rachel E.; Allan, James D.; Coe, Hugh; Williams, Leah R.; Herndon, Scott C.; Ng, Nga L.; Hamilton, Jacqueline F.; Bergström, Robert; Di Marco, Chiara; Nemitz, Eiko; Mackenzie, Ian A.; Kuenen, Jeroen J. P.; Green, David C.; Reis, Stefan; Heal, Mathew R.

2016-05-01

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

Aerosol composition and the contribution of SOA formation over Mediterranean forests

NASA Astrophysics Data System (ADS)

Freney, Evelyn; Sellegri, Karine; Chrit, Mounir; Adachi, Kouji; Brito, Joel; Waked, Antoine; Borbon, Agnès; Colomb, Aurélie; Dupuy, Régis; Pichon, Jean-Marc; Bouvier, Laetitia; Delon, Claire; Jambert, Corinne; Durand, Pierre; Bourianne, Thierry; Gaimoz, Cécile; Triquet, Sylvain; Féron, Anaïs; Beekmann, Matthias; Dulac, François; Sartelet, Karine

2018-05-01

As part of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx), a series of aerosol and gas-phase measurements were deployed aboard the SAFIRE ATR42 research aircraft in summer 2014. The present study focuses on the four flights performed in late June early July over two forested regions in the south of France. We combine in situ observations and model simulations to aid in the understanding of secondary organic aerosol (SOA) formation over these forested areas in the Mediterranean and to highlight the role of different gas-phase precursors. The non-refractory particulate species measured by a compact aerosol time-of-flight mass spectrometer (cToF-AMS) were dominated by organics (60 to 72 %) followed by a combined contribution of 25 % by ammonia and sulfate aerosols. The contribution from nitrate and black carbon (BC) particles was less than 5 % of the total PM1 mass concentration. Measurements of non-refractory species from off-line transmission electron microscopy (TEM) showed that particles have different mixing states and that large fractions (35 %) of the measured particles were organic aerosol containing C, O, and S but without inclusions of crystalline sulfate particles. The organic aerosol measured using the cToF-AMS contained only evidence of oxidized organic aerosol (OOA), without a contribution of fresh primary organic aerosol. Positive matrix factorization (PMF) on the combined organic-inorganic matrices separated the oxidized organic aerosol into a more-oxidized organic aerosol (MOOA), and a less-oxidized organic aerosol (LOOA). The MOOA component is associated with inorganic species and had higher contributions of m/z 44 than the LOOA factor. The LOOA factor is not associated with inorganic species and correlates well with biogenic volatile organic species measured with a proton-transfer-reaction mass spectrometer, such as isoprene and its oxidation products (methyl vinyl ketone, MVK; methacroleine, MACR; and isoprene hydroxyhydroperoxides, ISOPOOH). Despite a significantly high mixing ratio of isoprene (0.4 to 1.2 ppbV) and its oxidation products (0.2 and 0.8 ppbV), the contribution of specific signatures for isoprene epoxydiols SOA (IEPOX-SOA) within the aerosol organic mass spectrum (m/z 53 and m/z 82) were very weak, suggesting that the presence of isoprene-derived SOA was either too low to be detected by the cToF-AMS, or that SOA was not formed through IEPOX. This was corroborated through simulations performed with the Polyphemus model showing that although 60 to 80 % of SOA originated from biogenic precursors, only about 15 to 32 % was related to isoprene (non-IEPOX) SOA; the remainder was 10 % sesquiterpene SOA and 35 to 40 % monoterpene SOA. The model results show that despite the zone of sampling being far from industrial or urban sources, a total contribution of 20 to 34 % of the SOA was attributed to purely anthropogenic precursors (aromatics and intermediate or semi-volatile compounds). The measurements obtained during this study allow us to evaluate how biogenic emissions contribute to increasing SOA concentrations over Mediterranean forested areas. Directly comparing these measurements with the Polyphemus model provides insight into the SOA formation pathways that are prevailing in these forested areas as well as processes that need to be implemented in future simulations.

Secondary organic aerosol formation from road vehicle emissions

NASA Astrophysics Data System (ADS)

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

2014-05-01

Organic aerosol particles (OA) are a major fraction of the submicron particulate matter. OA consists of directly emitted primary (POA) and secondary OA (SOA). SOA is formed in-situ in the atmosphere via the reaction of volatile organic precursors. The partitioning of SOA species depends not only on the exposure to oxidants, but for instance also on temperature, relative humidity (RH), and the absorptive mass chemical composition (presence of inorganics) and concentration. Vehicle exhaust is a known source of POA and likely contributes to SOA formation in urban areas [1;2]. This has recently been estimated by (i) analyzing ambient data from urban areas combined with fuel consumption data [3], (ii) by examining the chemical composition of raw fuels [4], or (iii) smog chamber studies [5, 6]. Contradictory and thus somewhat controversial results in the relative quantity of SOA from diesel vs. gasoline vehicle exhaust were observed. In order to elucidate the impact of variable ambient conditions on the potential SOA formation of vehicle exhaust, and its relation to the emitted gas phase species, we studied SOA formed from the exhaust of passenger cars and trucks as a function of fuel and engine type (gasoline, diesel) at different temperatures (T 22 vs. -7oC) and RH (40 vs. 90%), as well as with different levels of inorganic salt concentrations. The exhaust was sampled at the tailpipe during regulatory driving cycles on chassis dynamometers, diluted (200 - 400x) and introduced into the PSI mobile smog chamber [6], where the emissions were subjected to simulated atmospheric ageing. Particle phase instruments (HR-ToF-AMS, aethalometers, CPC, SMPS) and gas phase instruments (PTR-TOF-MS, CO, CO2, CH4, THC, NH3 and other gases) were used online during the experiments. We found that gasoline emissions, because of cold starts, were generally larger than diesel, especially during cold temperatures driving cycles. Gasoline vehicles also showed the highest SOA formation. Furthermore, we observed that vehicle emissions and SOA are significantly affected by temperature and RH: doubling the RH in the chamber resulted in significantly increased SOA formation. Primary emissions and secondary aerosol formation from diesel and gasoline vehicles will be compared at different temperature and RH. Also the interaction and influence of inorganics on organics will be discussed. References: [1] Robinson, A.L., et al. (2007) Science 315, 1259. [2] Weitkamp, E.A., et al. (2007) Environ. Sci. Technol. 41, 6969. [3] Bahreini, R., et al. (2012) Geophys. Res. Lett. 39, L06805. [4] Gentner, D.R. et al. (2012) PNAS 109, 18318. [5] Gordon, T.D. et al. (2013) Atmos. Chem. Phys. Discuss 13, 23173. [6] Platt, S.M., et al. (2013) Atmos. Chem. Phys. Discuss. 12, 28343.

Volatility Properties of Internally- and Externally-Mixed Ambient Aerosols at an Anthropogenically-influenced Forest Site in Southeastern USA

NASA Astrophysics Data System (ADS)

Khlystov, A.; Subramanian, R.

2015-12-01

Secondary organic aerosol (SOA) from biogenic sources has a significant contribution to ambient aerosol loadings in Southeastern USA and thus contributes to adverse health effects of air pollution and influences regional and global climate. Volatility properties of biogenic SOA determine its concentration, reactivity, and lifetime, but are still largely unknown. As part of a larger study to assess the effect of biogenic SOA on aerosol optical properties, a set of instruments, including scanning mobility sizers (SMPS), single particle soot photometer (SP2), and a thermodenuder, was deployed during June 2015 at a Duke Forest site near Chapel Hill, NC. The site is characterized by a significant contribution of both biogenic and urban (mostly traffic) sources. Measurements of changes in aerosol volume and optical size upon heating in the thermodenuder at different temperatures are used to derive volatility properties of the ambient aerosol. A limited set of experiments was carried out using the tandem differential mobility analysis (TDMA) approach to investigate whether the ambient aerosol at the Duke Forest site is internally mixed with respect to its volatility properties. In this presentation we will discuss equilibrium and kinetic aspects of aerosol volatility observed during this study and implications of external vs. internal mixing for derivation of bulk volatility properties of ambient aerosol.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer

NASA Astrophysics Data System (ADS)

Mungall, Emma L.; Abbatt, Jonathan P. D.; Wentzell, Jeremy J. B.; Lee, Alex K. Y.; Thomas, Jennie L.; Blais, Marjolaine; Gosselin, Michel; Miller, Lisa A.; Papakyriakou, Tim; Willis, Megan D.; Liggio, John

2017-06-01

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer.

PubMed

Mungall, Emma L; Abbatt, Jonathan P D; Wentzell, Jeremy J B; Lee, Alex K Y; Thomas, Jennie L; Blais, Marjolaine; Gosselin, Michel; Miller, Lisa A; Papakyriakou, Tim; Willis, Megan D; Liggio, John

2017-06-13

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Photooxidation of farnesene mixtures in the presence of NOx: Analysis of reaction products and their implication to ambient PM2.5

EPA Pesticide Factsheets

Chemical analysis of SOA produced from the irradiation of a mixture of 03b1/03b2-farnesene/NOx was conducted in a 14.5 cubic meter smog chamber. SOA collected on glass-fiber filters was solvent extracted, derivatized using BSTFA, and analyzed by GC-MS. Gas-phase products were analyzed using a combination of GC-FID and GC-MS. This analysis showed the occurrence of more than 30 SOA oxygenated species and more than 20 in the gas phase. The major SOA components measured include conjugated 03b1 farnesene trienols, C3??C7 linear dicarboxylic acids, carbonyl compounds, and hydroxy/carbonyl/carboxylic compounds. In the gas phase, the main species identified were formaldehyde, glyoxal, methylglyoxal, acetone, 2,3-dimethyl-oxirane, 2(3H)-furanone, 2-butenedioic acid, 4 oxopentanal, 4-methylenehex-5-enal, and 6-methylhept-5-en-2-one. Proposed reaction schemes are provided for selected compounds. H-atom abstraction and OH addition in 03b1/03b2-farnesene oxidation seem to play an important role via the formation of unsaturated radicals containing different numbers of delocalized electrons. Allylic hydrogen abstraction and hydroperoxyalkyl radical channels might play a key role in the oxidation of 03b1/03b2-farnesene. The contribution of farnesene SOA products to ambient PM2.5 was investigated by analyzing PM2.5 samples collected during SOAS 2013 field study at a site in Research Triangle Park (RTP), NC. The importance of these findings was supported by the occurrence of seve

Lions, tigers, and bears, oh sh!t: Semantics versus tabooness in speech production.

PubMed

White, Katherine K; Abrams, Lise; Koehler, Sarah M; Collins, Richard J

2017-04-01

While both semantic and highly emotional (i.e., taboo) words can interfere with speech production, different theoretical mechanisms have been proposed to explain why interference occurs. Two experiments investigated these theoretical approaches by comparing the magnitude of these two types of interference and the stages at which they occur during picture naming. Participants named target pictures superimposed with semantic, taboo, or unrelated distractor words that were presented at three different stimulus-onset asynchronies (SOA): -150 ms, 0 ms, or +150 ms. In addition, the duration of distractor presentation was manipulated across experiments, with distractors appearing for the duration of the picture (Experiment 1) or for 350 ms (Experiment 2). Taboo distractors interfered more than semantic distractors, i.e., slowed target naming times, at all SOAs. While distractor duration had no effect on type of interference at -150 or 0 SOAs, briefly presented distractors eliminated semantic interference but not taboo interference at +150 SOA. Discussion focuses on how existing speech production theories can explain interference from emotional distractors and the unique role that attention may play in taboo interference.

The effects of associative and semantic priming in the lexical decision task.

PubMed

Perea, Manuel; Rosa, Eva

2002-08-01

Four lexical decision experiments were conducted to examine under which conditions automatic semantic priming effects can be obtained. Experiments 1 and 2 analyzed associative/semantic effects at several very short stimulus-onset asynchronies (SOAs), whereas Experiments 3 and 4 used a single-presentation paradigm at two response-stimulus intervals (RSIs). Experiment 1 tested associatively related pairs from three semantic categories (synonyms, antonyms, and category coordinates). The results showed reliable associative priming effects at all SOAs. In addition, the correlation between associative strength and magnitude of priming was significant only at the shortest SOA (66 ms). When prime-target pairs were semantically but not associatively related (Experiment 2), reliable priming effects were obtained at SOAs of 83 ms and longer. Using the single-presentation paradigm with a short RSI (200 ms, Experiment 3), the priming effect was equal in size for associative + semantic and for semantic-only pairs (a 21-ms effect). When the RSI was set much longer (1,750 ms, Experiment 4), only the associative + semantic pairs showed a reliable priming effect (23 ms). The results are interpreted in the context of models of semantic memory.

Multi-generation chemical aging of α-pinene ozonolysis products by reactions with OH

NASA Astrophysics Data System (ADS)

Wang, Ningxin; Kostenidou, Evangelia; Donahue, Neil M.; Pandis, Spyros N.

2018-03-01

Secondary organic aerosol (SOA) formation from volatile organic compounds (VOCs) in the atmosphere can be thought of as a succession of oxidation steps. The production of later-generation SOA via continued oxidation of the first-generation products is defined as chemical aging. This study investigates aging in the α-pinene ozonolysis system with hydroxyl radicals (OH) through smog chamber experiments. The first-generation α-pinene ozonolysis products were allowed to react further with OH formed via HONO photolysis. After an equivalent of 2-4 days of typical atmospheric oxidation conditions, homogeneous OH oxidation of the α-pinene ozonolysis products resulted in a 20-40 % net increase in the SOA for the experimental conditions used in this work. A more oxygenated product distribution was observed after aging based on the increase in aerosol atomic oxygen-to-carbon ratio (O : C) by up to 0.04. Experiments performed at intermediate relative humidity (RH) of 50 % showed no significant difference in additional SOA formation during aging compared to those performed at a low RH of less than 20 %.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen

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 combinationmore » 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 mass and number with knowledge of particle properties such as volatility and viscosity are crucial for improving understanding of non-linear SOA-related processes. For example, useful insights can be attained by combining bottom-up information related to the molecular speciation of gas- and particle-phase precursors with top-down insights on size evolution dynamics of SOA. Continuing efforts are also needed to rank the most influential processes affecting SOA lifecycle, so that these processes can be accurately represented in atmospheric chemistry-climate models.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrivastava, Manish; Zhao, Chun; Easter, Richard C.

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

Soa genotype selectively affects mouse gustatory neural responses to sucrose octaacetate

PubMed Central

INOUE, MASASHI; LI, XIA; McCAUGHEY, STUART A.; BEAUCHAMP, GARY K.; BACHMANOV, ALEXANDER A.

2013-01-01

In mice, behavioral acceptance of the bitter compound sucrose octaacetate (SOA) depends on allelic variation of a single gene, Soa. The SW.B6-Soab congenic mouse strain has the genetic background of an “SOA taster” SWR/J strain and an Soa-containing donor chromosome fragment from an “SOA nontaster” C57BL/6J strain. Using microsatellite markers polymorphic between the two parental strains, we determined that the donor fragment spans 5–10 cM of distal chromosome 6. The SWR/J mice avoided SOA in two-bottle tests with water and had strong responses to SOA in two gustatory nerves, the chorda tympani (CT) and glossopharyngeal (GL). In contrast, the SW.B6-Soab mice were indifferent to SOA in two-bottle tests and had very weak responses to SOA in both of these nerves. The SWR/J and SW.B6-Soab mice did not differ in responses of either nerve to sucrose, NaCl, HCl, or the bitter-tasting stimuli quinine, denatonium, strychnine, 6-n-propylthiouracil, phenylthiocarbamide, and MgSO4. Thus the effect of the Soa genotype on SOA avoidance is mediated by peripheral taste responsiveness to SOA, involving taste receptor cells innervated by both the CT and GL nerves. PMID:11328963

Molecular Characterization of Organosulfur Compounds in Biodiesel and Diesel Fuel Secondary Organic Aerosol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blair, Sandra L.; MacMillan, Amanda C.; Drozd, Greg T.

Secondary organic aerosol (SOA), formed in a process of photooxidization of diesel fuel, biodiesel fuel, and 20% biodiesel fuel/80% diesel fuel mixture, are prepared under high-NOx conditions in the presence and absence of sulfur dioxide (SO2), ammonia (NH3), and relative humidity (RH). The composition of condensed-phase organic compounds in SOA is measured using several analytical techniques including aerosol mass spectrometry (AMS), high-resolution nanospray desorption electrospray ionization mass spectrometry (nano-DESI/HRMS), and ultra high resolution and mass accuracy 21T Fourier transform ion cyclotron resonance mass spectrometry (21T FT-ICR MS). Results demonstrate that sulfuric acid and condensed organosulfur species formed in photooxidation experimentsmore » with SO2 are present in the SOA particles. Fewer organosulfur species are formed in the high humidity experiments, performed at RH 90%, in comparison with experiments done under dry conditions. There is a strong overlap of organosulfur species observed in this study with previous field and chamber studies of SOA. Many mass spectrometry peaks of organosulfates (R–OS(O)2OH) in field studies previously designated as biogenic or of unknown origin might have originated from anthropogenic sources, such as photooxidation of hydrocarbons present in diesel and biodiesel fuel.« less

Molecular Markers of Secondary Organic Aerosol in Mumbai, India.

PubMed

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

2016-05-03

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Ben H.; Mohr, Claudia; Lopez-Hilfiker, Felipe D.

Organic nitrates (ON = RONO2 + RO2NO2) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NOx=NO+NO2). ON formed from isoprene oxidation alone are responsible for the export of 8 to 30% of anthropogenic NOx out of the U.S. continental boundary layer [Horowitz et al., 1998; Liang et al., 1998]. Regional NOx budgets and tropospheric ozone (O3) production, are therefore particularly sensitive to uncertainties in the yields and fates of ON [Beaver et al., 2012; Browne et al., 2013]. The yields implemented in modeling studies are determined from laboratory experiments in which only a few of the firstmore » generation gaseous ON or the total gas and particle-phase ON have been quantified [Perring et al., 2013 and references therein], while production of highly functionalized ON capable of strongly partitioning to the particle-phase have been inferred [Farmer et al., 2010; Ng et al., 2007; Nguyen et al., 2011; Perraud et al., 2012; Rollins et al., 2012], or directly measured [Ehn et al., 2014]. Addition of a nitrate (–ONO2) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5 to 3 orders of magnitude [e.g. Capouet and Muller, 2006]. Thus, organic nitrate formation can potentially enhance particle-phase partitioning of hydrocarbons in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) formation [Ng et al., 2007]. There has, however, been no high time-resolved measurements of speciated ON in the particle-phase. We utilize a newly developed high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adduct ionization [B H Lee et al., 2014a] with a filter inlet for gases and aerosols (FIGAERO) [Lopez-Hilfiker et al., 2014] that allows alternating in situ measurement of the molecular composition of gas and particle phases. We present observations of speciated ON in the particle-phase obtained during the 2013 Southern Oxidant and Aerosol Study (SOAS). We compare these speciated measurements to total unspeciated particulate organic nitrate measured by three independent methods, and analyze using a zero-dimensional box model the diel cycles of individual components to elucidate differential source and sink terms. Biogenic volatile organic compounds (VOCs), including isoprene, monoterpenes, and sesquiterpenes appear to dominate the ON sources during SOAS. We show that the molecular compositions that dominate the particle-phase are significantly more oxygenated than the most abundant gas-phase counterparts, consistent with volatility and solubility driven partitioning requirements. However, the detailed mechanisms by which most of these ON arise are not yet clear. These speciated measurements put a strong constraint on the extent to which ON directly contribute to SOA in regions with high biogenic hydrocarbon emissions, and illustrate that the fate of particulate ON can have significant implications for SOA and the reactive nitrogen budget.« less

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

DOE PAGES

Lee, Ben H.; Mohr, Claudia; Lopez-Hilfiker, Felipe D.; ...

2016-01-25

Organic nitrates (ON = RONO2 + RO2NO2) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NOx=NO+NO2). ON formed from isoprene oxidation alone are responsible for the export of 8 to 30% of anthropogenic NOx out of the U.S. continental boundary layer [Horowitz et al., 1998; Liang et al., 1998]. Regional NOx budgets and tropospheric ozone (O3) production, are therefore particularly sensitive to uncertainties in the yields and fates of ON [Beaver et al., 2012; Browne et al., 2013]. The yields implemented in modeling studies are determined from laboratory experiments in which only a few of the firstmore » generation gaseous ON or the total gas and particle-phase ON have been quantified [Perring et al., 2013 and references therein], while production of highly functionalized ON capable of strongly partitioning to the particle-phase have been inferred [Farmer et al., 2010; Ng et al., 2007; Nguyen et al., 2011; Perraud et al., 2012; Rollins et al., 2012], or directly measured [Ehn et al., 2014]. Addition of a nitrate (–ONO2) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5 to 3 orders of magnitude [e.g. Capouet and Muller, 2006]. Thus, organic nitrate formation can potentially enhance particle-phase partitioning of hydrocarbons in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) formation [Ng et al., 2007]. There has, however, been no high time-resolved measurements of speciated ON in the particle-phase. We utilize a newly developed high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adduct ionization [B H Lee et al., 2014a] with a filter inlet for gases and aerosols (FIGAERO) [Lopez-Hilfiker et al., 2014] that allows alternating in situ measurement of the molecular composition of gas and particle phases. We present observations of speciated ON in the particle-phase obtained during the 2013 Southern Oxidant and Aerosol Study (SOAS). We compare these speciated measurements to total unspeciated particulate organic nitrate measured by three independent methods, and analyze using a zero-dimensional box model the diel cycles of individual components to elucidate differential source and sink terms. Biogenic volatile organic compounds (VOCs), including isoprene, monoterpenes, and sesquiterpenes appear to dominate the ON sources during SOAS. We show that the molecular compositions that dominate the particle-phase are significantly more oxygenated than the most abundant gas-phase counterparts, consistent with volatility and solubility driven partitioning requirements. However, the detailed mechanisms by which most of these ON arise are not yet clear. These speciated measurements put a strong constraint on the extent to which ON directly contribute to SOA in regions with high biogenic hydrocarbon emissions, and illustrate that the fate of particulate ON can have significant implications for SOA and the reactive nitrogen budget.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charnawskas, Joseph C.; Alpert, Peter A.; Lambe, Andrew

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil-fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without presence of sulfate or soot particles. Corresponding particle glass transition (T g) and full deliquescence relative humidity (FDRH) were estimated by a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibitmore » a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation in agreement with respective T g and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid inducing ice nucleation. Naphthalene SOA coated soot particles acted as IN above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate further renders this even less likely. Furthermore, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during preindustrial times or in pristine areas.« less

Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation

DOE PAGES

Charnawskas, Joseph C.; Alpert, Peter A.; Lambe, Andrew; ...

2017-01-24

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil-fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without presence of sulfate or soot particles. Corresponding particle glass transition (T g) and full deliquescence relative humidity (FDRH) were estimated by a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibitmore » a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation in agreement with respective T g and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid inducing ice nucleation. Naphthalene SOA coated soot particles acted as IN above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate further renders this even less likely. Furthermore, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during preindustrial times or in pristine areas.« less

Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation.

PubMed

Charnawskas, Joseph C; Alpert, Peter A; Lambe, Andrew T; Berkemeier, Thomas; O'Brien, Rachel E; Massoli, Paola; Onasch, Timothy B; Shiraiwa, Manabu; Moffet, Ryan C; Gilles, Mary K; Davidovits, Paul; Worsnop, Douglas R; Knopf, Daniel A

2017-08-24

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles' organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (T g ) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibit a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respective T g and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.

On the mixing and evaporation of secondary organic aerosol components.

PubMed

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

2013-06-18

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

SOA Formation Potential of Emissions from Soil and Leaf Litter

NASA Astrophysics Data System (ADS)

Faiola, C. L.; Vanderschelden, G. S.; Wen, M.; Cobos, D. R.; Jobson, B. T.; VanReken, T. M.

2013-12-01

In the United States, emissions of volatile organic compounds (VOCs) from natural sources exceed all anthropogenic sources combined. VOCs participate in oxidative chemistry in the atmosphere and impact the concentrations of ozone and particulate material. The formation of secondary organic aerosol (SOA) is particularly complex and is frequently underestimated using state-of-the-art modeling techniques. We present findings that suggest emissions of important SOA precursors from soil and leaf litter are higher than current inventories would suggest, particularly under conditions typical of Fall and Spring. Soil and leaf litter samples were collected at Big Meadow Creek from the University of Idaho Experimental Forest. The dominant tree species in this area of the forest are ponderosa pine, Douglas-fir, and western larch. Samples were transported to the laboratory and housed within a 0.9 cubic meter Teflon dynamic chamber where VOC emissions were continuously monitored with a GC-FID-MS and PTR-MS. Aerosol was generated from soil and leaf litter emissions by pumping the emissions into a 7 cubic meter Teflon aerosol growth chamber where they were oxidized with ozone in the absence of light. The evolution of particle microphysical and chemical characteristics was monitored over the following eight hours. Particle size distribution and chemical composition were measured with a SMPS and HR-ToF-AMS respectively. Monoterpenes dominated the emission profile with emission rates up to 283 micrograms carbon per meter squared per hour. The dominant monoterpenes emitted were beta-pinene, alpha-pinene, and delta-3-carene in descending order. The composition of the SOA produced was similar to biogenic SOA formed from oxidation of ponderosa pine emissions and alpha-pinene. Measured soil/litter monoterpene emission rates were compared with modeled canopy emissions. Results suggest that during fall and spring when tree emissions are lower, monoterpene emissions within forests may be dominated by soil/litter emissions--soil/litter monoterpene emissions in spring could contribute up to 63% of total forest emissions. If this is the case, a significant portion of total forest monoterpene emission rates would be controlled by factors that affect soil/litter emissions rather than factors that affect plant emissions.

VOC species and emission inventory from vehicles and their SOA formation potentials estimation in Shanghai, China

NASA Astrophysics Data System (ADS)

Huang, C.; Wang, H. L.; Li, L.; Wang, Q.; Lu, Q.; de Gouw, J. A.; Zhou, M.; Jing, S. A.; Lu, J.; Chen, C. H.

2015-03-01

VOC species from vehicle exhaust and gas evaporation were investigated by chassis dynamometer and on-road measurements of 9 gasoline vehicles, 7 diesel vehicles, 5 motorcycles, and 4 gas evaporation samples. The SOA mass yields of gasoline, diesel, motorcycle exhausts, and gas evaporation were calculated based on the mixing ratio of individual VOC species. The SOA mass yields of gasoline and motorcycle exhaust were similar to the results of the published smog chamber study with the exception of that of diesel exhaust was 20% lower than experimental data (Gordon et al., 2013, 2014a, b). This suggests the requirement for further research on SVOC or LVOC emissions. A vehicular emission inventory was compiled based on a local survey of vehicle mileage traveled and real-world measurements of vehicle emission factors. The inventory-based vehicular initial emission ratio of OA to CO was 15.6 μg m-3 ppmv-1. The OA production rate reached 22.3 and 42.7 μg m-3 ppmv-1 under high-NOx and low-NOx conditions, respectively. To determine the vehicular contribution to OA pollution, the inventory-based OA formation ratios for vehicles were calculated with a photochemical-age-based parameterization method and compared with the observation-based OA formation ratios in the urban atmosphere of Shanghai. The results indicated that VOC emissions from vehicle exhaust and gas evaporation only explained 15 and 22% of the total organic aerosols observed in summer and winter, respectively. SOA production only accounted for 25 and 18% of the total vehicular OA formation in summer and winter. VOC emissions from gasoline vehicles contribute 21-38% of vehicular OA formation after 6-24 h of photochemical aging. The results suggest that vehicle emissions are an important contributor to OA pollution in the urban atmosphere of Shanghai. However, a large number of OA mass in the atmosphere still cannot be explained in this study. SOA formation contributions from other sources (e.g. coal burning, biomass burning, cooking, dust, etc.) as well as IVOCs and SVOCs from the combustion sources need to be considered in future studies.

Mapping SOA Artefacts onto an Enterprise Reference Architecture Framework

NASA Astrophysics Data System (ADS)

Noran, Ovidiu

Currently, there is still no common agreement on the service-Oriented architecture (SOA) definition, or the types and meaning of the artefacts involved in the creation and maintenance of an SOA. Furthermore, the SOA image shift from an infrastructure solution to a business-wide change project may have promoted a perception that SOA is a parallel initiative, a competitor and perhaps a successor of enterprise architecture (EA). This chapter attempts to map several typical SOA artefacts onto an enterprise reference framework commonly used in EA. This is done in order to show that the EA framework can express and structure most of the SOA artefacts and therefore, a framework for SOA could in fact be derived from an EA framework with the ensuing SOA-EA integration benefits.

Development of a Novel Simulation Reactor for Chronic Exposure to Atmospheric Particulate Matter

NASA Astrophysics Data System (ADS)

Ye, Jianhuai; Salehi, Sepehr; North, Michelle L.; Portelli, Anjelica M.; Chow, Chung-Wai; Chan, Arthur W. H.

2017-02-01

Epidemiological studies have shown that air pollution is associated with the morbidity and mortality from cardiopulmonary diseases. Currently, limited experimental models are available to evaluate the physiological and cellular pathways activated by chronic multi-pollutant exposures. This manuscript describes an atmospheric simulation reactor (ASR) that was developed to investigate the health effects of air pollutants by permitting controlled chronic in vivo exposure of mice to combined particulate and gaseous pollutants. BALB/c mice were exposed for 1 hr/day for 3 consecutive days to secondary organic aerosol (SOA, a common particulate air pollutant) at 10-150 μg/m3, SOA (30 μg/m3) + ozone (65 ppb) or SOA + ozone (65 ppb) + nitrogen dioxide (NO2; 100 ppb). Daily exposure to SOA alone led to increased airway hyperresponsiveness (AHR) to methacholine with increasing SOA concentrations. Multi-pollutant exposure with ozone and/or NO2 in conjunction with a sub-toxic concentration of SOA resulted in additive effects on AHR to methacholine. Inflammatory cell recruitment to the airways was not observed in any of the exposure conditions. The ASR developed in this study allows us to evaluate the chronic health effects of relevant multi-pollutant exposures at ‘real-life’ levels under controlled conditions and permits repeated-exposure studies.

Electrophysiology reveals semantic priming at a short SOA irrespective of depth of prime processing.

PubMed

Küper, Kristina; Heil, Martin

2009-04-03

The otherwise robust behavioral semantic priming effect is reduced to the point of being absent when a letter search has to be performed on the prime word. As a result the automaticity of semantic activation has been called into question. It is unclear, however, in how far automatic processes are even measurable in the letter search priming paradigm as the prime task necessitates a long prime-probe stimulus-onset asynchrony (SOA). In a modified procedure, a short SOA can be realized by delaying the prime task response until after participants have made a lexical decision on the probe. While the absence of lexical decision priming has already been demonstrated in this design it seems premature to draw any definite conclusions from this purely behavioral result since event related potential (ERP) measures have been shown to be a more sensitive index of semantic activation. Using the modified paradigm we thus recorded ERP in addition to lexical decision times. Stimuli were presented at two different SOAs (240 ms vs. 840 ms) and participants performed either a grammatical discrimination (Experiment 1) or a letter search (Experiment 2) on the prime. Irrespective of prime task, the modulation of the N400, the ERP correlate of semantic activation, provided clear-cut evidence of semantic processing at the short SOA. Implications for theories of semantic activation as well as the constraints of the delayed prime task procedure are discussed.

High abundances of oxalic, azelaic, and glyoxylic acids and methylglyoxal in the open ocean with high biological activity: Implication for secondary OA formation from isoprene

NASA Astrophysics Data System (ADS)

Bikkina, Srinivas; Kawamura, Kimitaka; Miyazaki, Yuzo; Fu, Pingqing

2014-05-01

Atmospheric dicarboxylic acids (DCA) are a ubiquitous water-soluble component of secondary organic aerosols (SOA), which can act as cloud condensation nuclei (CCN), affecting the Earth's climate. Despite the high abundances of oxalic acid and related compounds in the marine aerosols, there is no consensus on what controls their distributions over the open ocean. Marine biological productivity could play a role in the production of DCA, but there is no substantial evidence to support this hypothesis. Here we present latitudinal distributions of DCA, oxoacids and α-dicarbonyls in the marine aerosols from the remote Pacific. Their concentrations were found several times higher in more biologically influenced aerosols (MBA) than less biologically influenced aerosols. We propose isoprene and unsaturated fatty acids as sources of DCA as inferred from significantly higher abundances of isoprene-SOA tracers and azelaic acid in MBA. These results have implications toward the reassessment of climate forcing feedbacks of marine-derived SOA.

Effects of diesel exhaust-derived secondary organic aerosol (SOA) on oocytes: Potential risks to meiotic maturation.

PubMed

Udagawa, Osamu; Furuyama, Akiko; Imai, Koji; Fujitani, Yuji; Hirano, Seishiro

2018-01-01

Particulate air pollution (PM 2.5) is a worldwide concern. Growing epidemiological evidence has shown pathophysiological effects of PM 2.5, not only on cardiovascular system but also on reproductive performance. The composition and physicochemical properties of PM 2.5 vary depending on the emission sources, climate conditions, and complex chemical reactions in the air. These factors make it difficult to understand the cause and mechanistic details of the adverse health effects of PM 2.5. Here, we show potential impacts of PM 2.5 on oocyte maturation in mice by utilizing diesel exhaust-derived secondary organic aerosol (SOA), a major component of urban PM 2.5. We found that the SOA destabilized microtubules of mouse oocytes and p-benzoquinone is one of the candidates for the microtubule-destabilizing compounds. We propose that some biologically reactive components of PM 2.5 should be prioritized for the regulation of atmospheric quality. Copyright © 2017 Elsevier Inc. All rights reserved.

Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of α-pinene

NASA Astrophysics Data System (ADS)

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

2015-03-01

Secondary organic aerosol (SOA) were generated from the ozonolysis of α-pinene in the CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) simulation chamber. The SOA formation and aging were studied by following their optical, hygroscopic and chemical properties. The optical properties were investigated by determining the particle complex refractive index (CRI). The hygroscopicity was quantified by measuring the effect of relative humidity (RH) on the particle size (size growth factor, GF) and on the scattering coefficient (scattering growth factor, f(RH)). The oxygen to carbon atomic ratios (O : C) of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition during their formation and aging in CESAM. The real CRI at 525 nm wavelength decreased from 1.43-1.60 (±0.02) to 1.32-1.38 (±0.02) during the SOA formation. The decrease in the real CRI correlated to the O : C decrease from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF remained roughly constant over the reaction time, with values of 1.02-1.07 (±0.02) at 90% (±4.2%) RH. Simultaneous measurements of O : C of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but contained less oxidised species at the surface which may limit water absorption. In addition, an apparent change in both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 14 h of reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state.

Sources and production of organic aerosol in Mexico City: insights from the combination of a chemical transport model (PMCAMx-2008) and measurements during MILAGRO

NASA Astrophysics Data System (ADS)

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

2010-11-01

Urban areas are large sources of organic aerosols and their precursors. Nevertheless, the contributions of primary (POA) and secondary organic aerosol (SOA) to the observed particulate matter levels have been difficult to quantify. In this study the three-dimensional chemical transport model PMCAMx-2008 is used to investigate the temporal and geographic variability of organic aerosol in the Mexico City Metropolitan Area (MCMA) during the MILAGRO campaign that took place in the spring of 2006. The organic module of PMCAMx-2008 is based on the volatility basis-set approach: both primary and secondary organic components are assumed to be semi-volatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The MCMA emission inventory is modified and the POA emissions are distributed by volatility based on dilution experiments. The model predictions are compared with observations from four different types of sites, an urban (T0), a suburban (T1), a rural (T2), and an elevated site in Pico Tres Padres (PTP). The performance of the model in reproducing organic mass concentrations in these sites was encouraging. The average predicted PM1 OA concentration in T0, T1, and T2 was 18 μg m-3, 11.7 μg m-3, and 10.5 μg m-3 respectively, while the corresponding measured values were 17.2 μg m-3, 11 μg m-3, and 9 μg m-3. The average predicted fresh primary OA concentrations were 4.4 μg m-3 at T0, 1.2 μg m-3 at T1 and 1.7 μg m-3 at PTP in reasonably good agreement with the corresponding PMF analysis estimates based on the AMS observations of 4.5, 1.3, and 2.9 μg m-3 respectively. The model reproduced reasonably well the average oxygenated OA (OOA) levels in T0 (7.5 μg m-3 predicted versus 7.5 μg m-3 measured), in T1 (6.3 μg m-3 predicted versus 4.6 μg m-3 measured) and in PTP (6.6 μg m-3 predicted versus 5.9 μg m-3 measured). Inside Mexico City, the locally produced OA is predicted to be on average 53% fresh primary (POA), 11% semi-volatile (S-SOA) and intermediate volatile (I-SOA) organic aerosol, and 36% traditional SOA from the oxidation of VOCs (V-SOA). The long range transport from biomass burning activities and other sources in Mexico is predicted to contribute on average almost as much as the local sources during the MILAGRO period.

Simulation of SOA formation and composition from oxidation of toluene and m-xylene in chamber experiments

NASA Astrophysics Data System (ADS)

Xu, J.; Liu, Y.; Nakao, S.; Cocker, D.; Griffin, R. J.

2013-12-01

Aromatic hydrocarbons contribute an important fraction of anthropogenic reactive volatile organic compounds (VOCs) in the urban atmosphere. Photo-oxidation of aromatic hydrocarbons leads to secondary organic products that have decreased volatilities or increased solubilities and can form secondary organic aerosol (SOA). Despite the crucial role of aromatic-derived SOA in deteriorating air quality and harming human health, its formation mechanism is not well understood and model simulation of SOA formation still remains difficult. The dependence of aromatic SOA formation on nitrogen oxides (NOx) is not captured fully by most SOA formation models. Most models predict SOA formation under high NOx levels well but underestimate SOA formation under low NOx levels more representative of the ambient atmosphere. Thus, it is crucial to investigate the NOx-dependent chemistry in aromatic photo-oxidation systems and correspondingly update SOA formation models. In this study, NOx-dependent mechanisms of toluene and m-xylene SOA formation are updated using the gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) coupled to a gas/aerosol partitioning model. The updated models were optimized by comparing to eighteen University of California, Riverside United States Environmental Protection Agency (EPA) chamber experiment runs under both high and low NOx conditions. Correction factors for vapor pressures imply uncharacterized aerosol-phase association chemistry. Simulated SOA speciation implies the importance of ring-opening products in governing SOA formation (up to 40%~60% for both aromatics). The newly developed model can predict strong decreases of m-xylene SOA yield with increasing NOx. Speciation distributions under varied NOx levels implies that the well-known competition between RO2 + HO2 and RO2 + NO (RO2 = peroxide bicyclic radical) may not be the only factor influencing SOA formation. The reaction of aromatic peroxy radicals with NO competing with its self-cyclization also affects NOx-dependence of SOA formation. Comparison of SOA formation yield and composition between two aromatics implies aldehyde/ketone chemistry from ring-opening route and chemistry for phenolic route play important roles in governing SOA formation and that ring-opening aldehydes and phenolic nitrates are produced to a greater extent in the toluene system, leading to higher SOA yields for toluene than for m-xylene.

Simulating Aqueous-Phase Isoprene-Epoxydiol (IEPOX) ...

EPA Pesticide Factsheets

The lack of statistically robust relationships between IEPOX (isoprene epoxydiol)-derived SOA (IEPOX SOA) and aerosol liquid water and pH observed during the 2013 Southern Oxidant and Aerosol Study (SOAS) emphasizes the importance of modeling the whole system to understand the controlling factors governing IEPOX SOA formation. We present a mechanistic modeling investigation predicting IEPOX SOA based on Community Multiscale Air Quality (CMAQ) model algorithms and a recently introduced photochemical box model, simpleGAMMA. We aim to (1) simulate IEPOX SOA tracers from the SOAS Look Rock ground site, (2) compare the two model formulations, (3) determine the limiting factors in IEPOX SOA formation, and (4) test the impact of a hypothetical sulfate reduction scenario on IEPOX SOA. The estimated IEPOX SOA mass variability is in similar agreement (r2 ∼ 0.6) with measurements. Correlations of the estimated and measured IEPOX SOA tracers with observed aerosol surface area (r2 ∼ 0.5–0.7), rate of particle-phase reaction (r2 ∼ 0.4–0.7), and sulfate (r2 ∼ 0.4–0.5) suggest an important role of sulfate in tracer formation via both physical and chemical mechanisms. A hypothetical 25% reduction of sulfate results in ∼70% reduction of IEPOX SOA formation, reaffirming the importance of aqueous phase chemistry in IEPOX SOA production. The National Exposure Research Laboratory (NERL) Computational Exposure Division (CED) develops and evaluates data, decision-suppor

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

NASA Astrophysics Data System (ADS)

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.

Effect of secondary organic aerosol coating thickness on the real-time detection and characterization of biomass-burning soot by two particle mass spectrometers

DOE PAGES

Ahern, Adam T.; Subramanian, Ramachandran; Saliba, Georges; ...

2016-12-22

Biomass burning is a large source of light-absorbing refractory black carbon (rBC) particles with a wide range of morphologies and sizes. The net radiative forcing from these particles is strongly dependent on the amount and composition of non-light-absorbing material internally mixed with the rBC and on the morphology of the mixed particles. Understanding how the mixing state and morphology of biomass-burning aerosol evolves in the atmosphere is critical for constraining the influence of these particles on radiative forcing and climate. We investigated the response of two commercial laser-based particle mass spectrometers, the vacuum ultraviolet (VUV) ablation LAAPTOF and the IRmore » vaporization SP-AMS, to monodisperse biomass-burning particles as we sequentially coated the particles with secondary organic aerosol (SOA) from α-pinene ozonolysis. We studied three mobility-selected soot core sizes, each with a number of successively thicker coatings of SOA applied. Using IR laser vaporization, the SP-AMS had different changes in sensitivity to rBC compared to potassium as a function of applied SOA coatings. We show that this is due to different effective beam widths for the IR laser vaporization region of potassium versus black carbon. The SP-AMS's sensitivity to black carbon (BC) mass was not observed to plateau following successive SOA coatings, despite achieving high OA : BC mass ratios greater than 9. We also measured the ion fragmentation pattern of biomass-burning rBC and found it changed only slightly with increasing SOA mass. The average organic matter ion signal measured by the LAAPTOF demonstrated a positive correlation with the condensed SOA mass on individual particles, despite the inhomogeneity of the particle core compositions. This demonstrates that the LAAPTOF can obtain quantitative mass measurements of aged soot-particle composition from realistic biomass-burning particles with complex morphologies and composition.« less

Effect of secondary organic aerosol coating thickness on the real-time detection and characterization of biomass-burning soot by two particle mass spectrometers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahern, Adam T.; Subramanian, Ramachandran; Saliba, Georges

Biomass burning is a large source of light-absorbing refractory black carbon (rBC) particles with a wide range of morphologies and sizes. The net radiative forcing from these particles is strongly dependent on the amount and composition of non-light-absorbing material internally mixed with the rBC and on the morphology of the mixed particles. Understanding how the mixing state and morphology of biomass-burning aerosol evolves in the atmosphere is critical for constraining the influence of these particles on radiative forcing and climate. We investigated the response of two commercial laser-based particle mass spectrometers, the vacuum ultraviolet (VUV) ablation LAAPTOF and the IRmore » vaporization SP-AMS, to monodisperse biomass-burning particles as we sequentially coated the particles with secondary organic aerosol (SOA) from α-pinene ozonolysis. We studied three mobility-selected soot core sizes, each with a number of successively thicker coatings of SOA applied. Using IR laser vaporization, the SP-AMS had different changes in sensitivity to rBC compared to potassium as a function of applied SOA coatings. We show that this is due to different effective beam widths for the IR laser vaporization region of potassium versus black carbon. The SP-AMS's sensitivity to black carbon (BC) mass was not observed to plateau following successive SOA coatings, despite achieving high OA : BC mass ratios greater than 9. We also measured the ion fragmentation pattern of biomass-burning rBC and found it changed only slightly with increasing SOA mass. The average organic matter ion signal measured by the LAAPTOF demonstrated a positive correlation with the condensed SOA mass on individual particles, despite the inhomogeneity of the particle core compositions. This demonstrates that the LAAPTOF can obtain quantitative mass measurements of aged soot-particle composition from realistic biomass-burning particles with complex morphologies and composition.« less

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2016-02-17

Secondary organic aerosol (SOA) plays a significant role in the Earth system by altering its radiative balance. Here we use an Earth system model coupled with an explicit SOA formation module to estimate the response of SOA concentrations to changes in climate, anthropogenic emissions, and human land use in the future. We find that climate change is the major driver for SOA change under the representative concentration pathways for the 8.5 future scenario. Climate change increases isoprene emission rate by 18% with the effect of temperature increases outweighing that of the CO2 inhibition effect. Annual mean global SOA mass ismore » increased by 25% as a result of climate change. However, anthropogenic emissions and land use change decrease SOA. The net effect is that future global SOA burden in 2100 is nearly the same as that of the present day. The SOA concentrations over the Northern Hemisphere are predicted to decline in the future due to the control of sulfur emissions.« less

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

PubMed

McNeill, V Faye

2015-02-03

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

Biomarkers as indicators of fungal biomass in the atmosphere of São Paulo, Brazil.

PubMed

Emygdio, Ana Paula Mendes; Andrade, Maria de Fátima; Gonçalves, Fabio Luiz Teixeira; Engling, Guenter; Zanetti, Rafael Henrique de Souza; Kumar, Prashant

2018-01-15

The biogenic aerosol contribution to atmospheric particulate matter (PM) mass concentration is usually neglected due to the difficulty in identifying its components, although it can be significant. In the Metropolitan Area of São Paulo (MASP)-Brazil, several studies have been performed to identify sources for PM, revealing vehicular emissions and soil re-suspension as the main identified sources. The organic fraction has been related primarily to biomass burning (BB) and fuel combustion, although there is significant presence of green areas in the city which render biogenic emissions as an additional source of organic carbon (OC). The objectives of this work are to (i) characterise the composition of the PM 10 (ii) estimate the relative mass contribution of fungal spores to PM concentrations with sizes smaller than 10μm (PM 10 ) in MASP and (iii) assess the main sources of PM 10 . To achieve these objectives, we measured markers of biogenic sources and BB, during the fall-winter transition, which along with other constituents, such as ions, organic/elemental carbon, elemental composition and fungal spore concentrations, help assess the PM 10 sources. We used receptor models to identify distinct source-related PM 10 fractions and conversion factors to convert biomarker concentrations to fungal mass. Our results show the mean contributions of fungal aerosol to PM 10 and OC mass were 2% and 8%, respectively, indicating the importance of fungal spores to the aerosol burden in the urban atmosphere. Using specific rotation factor analysis, we identified the following factors contributing to PM: soil re-suspension, biogenic aerosol, secondary inorganic aerosol, vehicular emissions and BB/isoprene-related secondary organic aerosol (I-SOA). BB/I-SOA was the main source representing 28% of the PM 10 mass, while biogenic aerosol explained a significant (11%) fraction of the PM 10 mass as well. Our findings suggest that primary biogenic aerosol is an important fraction of PM 10 mass, yet not considered in most studies. Copyright © 2017 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charnawskas, Joseph C.; Alpert, Peter A.; Lambe, Andrew T.

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA–soot biogenic–anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (T g) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfatemore » mixtures exhibit a core–shell configuration (i.e.a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respectiveT gand FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.« less

Condensed-phase biogenic–anthropogenic interactions with implications for cold cloud formation

DOE PAGES

Charnawskas, Joseph C.; Alpert, Peter A.; Lambe, Andrew T.; ...

2017-01-24

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA–soot biogenic–anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (T g) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfatemore » mixtures exhibit a core–shell configuration (i.e.a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respectiveT gand FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.« less

Campholenic aldehyde ozonolysis: a possible mechanism for the formation of specific biogenic secondary organic aerosol constituents

NASA Astrophysics Data System (ADS)

Kahnt, A.; Iinuma, Y.; Mutzel, A.; Böge, O.; Claeys, M.; Herrmann, H.

2013-08-01

In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon α-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised with 2,4-dinitrophenylhydrazine (DNPH) followed by Liquid Chromatography/negative ion Electrospray Ionisation Time-of-Flight Mass Spectrometry analysis and were compared to the gas-phase compounds detected by online Proton-Transfer-Reaction Mass Spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and MS2 and MS3 fragmentation studies. Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving α-pinene, α-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. m/z 201, C9H14O5 and m/z 215, C10H16O5), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The m/z 201 and 215 compounds were tentatively identified as a C9- and C10-carbonyl-dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH-derivatives.

Fine particulate matter (PM2.5) in Edmonton, Canada: Source apportionment and potential risk for human health.

PubMed

Bari, Md Aynul; Kindzierski, Warren B

2016-11-01

To design effective PM 2.5 control strategies in urban centers, there is a need to better understand local and remote sources influencing PM 2.5 levels and associated risk to public health. An investigation of PM 2.5 levels, sources and potential human health risk associated with trace elements in the PM 2.5 was undertaken in Edmonton over a 6-year period (September 2009-August 2015). The geometric mean PM 2.5 concentration of was 7.11 μg/m 3 (interquartile range, IQR = 4.83-10.08 μg/m 3 ). Positive matrix factorization (PMF) receptor modeling identified secondary organic aerosol (SOA) as the major contributor (2.2 μg/m 3 , 27%), followed by secondary nitrate (1.3 μg/m 3 , 17%) and secondary sulfate (1.2 μg/m 3 , 15%). Other local sources included transportation (1.1 μg/m 3 , 14%) and industry-related emissions (0.26 μg/m 3 , 3.4%), biomass burning (1.0 μg/m 3 , 13%) and soil (0.54 μg/m 3 , 6.8%). Five factors (i.e., SOA, secondary nitrate, secondary sulfate, transportation and biomass burning) contributed more than 85% to PM 2.5 for the 2009-2015 period. Geometric (arithmetic) mean and maximum ambient air concentrations for hazardous trace elements of public health concern in PM 2.5 during the study period were below United States regulatory agency chronic and acute health risk screening criteria. Carcinogenic and non-carcinogenic risk of trace elements and source-specific risk values were well below acceptable and safe levels of risks recommended by regulatory agencies. More work is needed to understand the origin of potential SOA and wintertime wood burning sources in Edmonton and the surrounding region and to apply source-risk apportionment using all available hazardous air pollutants (HAPs) including organic compounds to better interpret the potential health risk posed by various sources in urban areas. Copyright © 2016 Elsevier Ltd. All rights reserved.

The preparation effect in task switching: carryover of SOA.

PubMed

Altmann, Erik M

2004-01-01

A common finding in task-switching studies is switch preparation (commonly known as the preparation effect), in which a longer interval between task cue and trial stimulus (i.e., a longer stimulus onset asynchrony, or SOA) reduces the cost of switching to a different task. Three experiments link switch preparation to within-subjects manipulations of SOA. In Experiment 1, SOA was randomized within subjects, producing switch preparation that was more pronounced when the SOA switched from the previous trial than when the SOA repeated. In Experiment 2, SOA was blocked within subjects, producing switch preparation but not on the first block of trials. In Experiment 3, SOA was manipulated between subjects with sufficient statistical power to detect switch preparation, but the effect was absent. The results favor an encoding view of cognitive control, but show that any putative switching mechanism reacts lazily when exposed to only one SOA.

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

PubMed Central

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

2016-01-01

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

Role of methyl group number on SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions

NASA Astrophysics Data System (ADS)

Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker, D. R., III

2016-02-01

Substitution of methyl groups onto the aromatic ring determines the secondary organic aerosol (SOA) formation from the monocyclic aromatic hydrocarbon precursor (SOA yield and chemical composition). This study links the number of methyl groups on the aromatic ring to SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions (HC/NO > 10 ppbC : ppb). Monocyclic aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from monocyclic aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low-NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from monocyclic aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests that, as more methyl groups are attached on the aromatic ring, SOA products from these monocyclic aromatic hydrocarbons become less oxidized per mass/carbon on the basis of SOA yield or chemical composition.

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

PubMed

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

2007-06-01

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

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

PubMed

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

2012-07-07

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

Despite extensive efforts toward the characterization of submicron aerosols at ground level in the megacity of Beijing, our understanding of aerosol sources and processes at high altitudes remains low. Here we conducted a 3-month real-time measurement of non-refractory submicron aerosol (NR-PM1) species at a height of 260 m from 10 October 2014 to 18 January 2015 using an aerosol chemical speciation monitor. Our results showed a significant change in aerosol composition from the non-heating period (NHP) to the heating period (HP). Organics and chloride showed clear increases during HP due to coal combustion emissions, while nitrate showed substantial decreases from 28 to 15-18 %. We also found that NR-PM1 species in the heating season can have average mass differences of 30-44 % under similar emission sources yet different meteorological conditions. Multi-linear engine 2 (ME-2) using three primary organic aerosol (OA) factors as constraints, i.e., fossil-fuel-related OA (FFOA) dominantly from coal combustion emissions, cooking OA (COA), and biomass burning OA (BBOA) resolved from ground high-resolution aerosol mass spectrometer measurements, was applied to OA mass spectra of ACSM. Two types of secondary OA (SOA) that were well correlated with nitrate and chloride-CO, respectively, were identified. SOA played a dominant role in OA during all periods at 260 m although the contributions were decreased from 72 % during NHP to 58-64 % during HP. The SOA composition also changed significantly from NHP to HP. While the contribution of oxygenated OA (OOA) was decreased from 56-63 to 32-40 %, less oxidized OOA (LO-OOA) showed a large increase from 9-16 to 24-26 %. COA contributed a considerable fraction of OA at high altitude, and the contribution was relatively similar across different periods (10-13 %). In contrast, FFOA showed a large increase during HP due to the influences of coal combustion emissions. We also observed very different OA composition between ground level and 260 m. Particularly, the contributions of COA and BBOA at the ground site were nearly twice those at 260 m, while SOA at 260 m was ˜ 15-34 % higher than that at ground level. Bivariate polar plots and back-trajectory analysis further illustrated the different source regions of OA factors in different seasons.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer

PubMed Central

Abbatt, Jonathan P. D.; Wentzell, Jeremy J. B.; Lee, Alex K. Y.; Thomas, Jennie L.; Blais, Marjolaine; Miller, Lisa A.; Papakyriakou, Tim; Liggio, John

2017-01-01

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate. PMID:28559340

Seasonal cycles of secondary organic aerosol tracers in rural Guangzhou, Southern China: The importance of atmospheric oxidants.

PubMed

Yuan, Qi; Lai, Senchao; Song, Junwei; Ding, Xiang; Zheng, Lishan; Wang, Xinming; Zhao, Yan; Zheng, Junyu; Yue, Dingli; Zhong, Liuju; Niu, Xiaojun; Zhang, Yingyi

2018-05-21

Thirteen secondary organic aerosol (SOA) tracers of isoprene (SOA I ), monoterpenes (SOA M ), sesquiterpenes (SOA S ) and aromatics (SOA A ) in fine particulate matter (PM 2.5 ) were measured at a Pearl River Delta (PRD) regional site for one year. The characteristics including their seasonal cycles and the factors influencing their formation in this region were studied. The seasonal patterns of SOA I , SOA M and SOA S tracers were characterized over three enhancement periods in summer (I), autumn (II) and winter (III), while the elevations of SOA A tracer (i.e., 2,3-dihydroxy-4-oxopentanoic acid, DHOPA) were observed in Periods II and III. We found that SOA formed from different biogenic precursors could be driven by several factors during a one-year seasonal cycle. Isoprene emission controlled SOA I formation throughout the year, while monoterpene and sesquiterpene emissions facilitated SOA M and SOA S formation in summer rather than in other seasons. The influence of atmospheric oxidants (O x ) was found to be an important factor of the formation of SOA M tracers during the enhancement periods in autumn and winter. The formation of SOA S tracer was influenced by the precursor emissions in summer, atmospheric oxidation in autumn and probably also by biomass burning in both summer and winter. In this study, we could not see the strong contribution of biomass burning to DHOPA as suggested by previous studies in this region. Instead, good correlations between observed DHOPA and O x as well as [NO 2 ][O 3 ] suggest the involvement of both ozone (O 3 ) and nitrogen dioxide (NO 2 ) in the formation of DHOPA. The results showed that regional air pollution may not only increase the emissions of aromatic precursors but also can greatly promote the formation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

PubMed

Cleary, Ciaran S; Manning, Robert J

2012-06-18

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

Characterization of the sources and processes of organic and inorganic aerosols in New York City with a high-resolution time-of-flight aerosol mass spectrometer

NASA Astrophysics Data System (ADS)

Sun, Y.-L.; Zhang, Q.; Schwab, J. J.; Demerjian, K. L.; Chen, W.-N.; Bae, M.-S.; Hung, H.-M.; Hogrefe, O.; Frank, B.; Rattigan, O. V.; Lin, Y.-C.

2010-10-01

Submicron aerosol particles (PM1) were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during the summer 2009 Field Intensive Study at Queens College in New York City. Organic aerosol (OA) and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of total PM1 mass on average. The average mass size distribution of OA presents a small mode peaking at ~150 nm (Dva) in addition to an accumulation mode (~550 nm) that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of sulfate and OA both show pronounced peaks between 01:00-02:00 p.m. EST due to photochemical production. The average (±1σ) oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios of OA in NYC are 0.36 (±0.09), 1.49 (±0.08), and 0.012(±0.005), respectively, corresponding to an average organic mass-to-carbon (OM/OC) ratio of 1.62(±0.11). Positive matrix factorization (PMF) of the high resolution mass spectra identified five OA components: a hydrocarbon-like OA (HOA), two types of oxygenated OA (OOA) including a low-volatility OOA (LV-OOA) and a semi-volatile OOA (SV-OOA), a cooking-emission related OA (COA), and a unique nitrogen-enriched OA (NOA). HOA appears to represent primary OA (POA) from urban traffic emissions. It comprises primarily of reduced species (H/C=1.83; O/C=0.06) and shows a mass spectral pattern very similar to those of POA from fossil fuel combustion, and correlates tightly with traffic emission tracers including elemental carbon and NOx. LV-OOA, which is highly oxidized (O/C=0.63) and correlates well with sulfate, appears to be representative for regional, aged secondary OA (SOA). SV-OOA, which is less oxidized (O/C=0.38) and correlates well with non-refractory chloride, likely represents less photo-chemically aged, semi-volatile SOA. COA shows a similar spectral pattern to the reference spectra of POA from cooking emissions and a distinct diurnal pattern peaking around local lunch and dinner times. In addition, NOA is characterized with prominent CxH2x+2N+ peaks likely from amine compounds. Our results indicate that cooking-related activities are a major source of POA in NYC, releasing comparable amounts of POA as traffic emissions. POA=HOA+COA) on average accounts for ~30% of the total OA mass during this study while SOA dominates the OA composition with SV-OOA and LV-OOA on average accounting for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC involves a~continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed analysis of NOA (5.8% of OA) presents evidence that nitrogen-containing organic species such as amines might have played an important role in the atmospheric processing of OA in NYC, likely involving acid-base chemistry. Analysis of air mass trajectories and satellite imagery of aerosol optical depth (AOD) indicates that the high potential source regions of secondary sulfate and aged OA are mainly located in regions to the west and southwest of the city.

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

NASA Astrophysics Data System (ADS)

Waring, Michael S.

2016-11-01

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

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed Central

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

2017-01-01

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

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

PubMed

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

2017-01-06

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m 3 smog chamber. The presence of FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO 4 or (NH 4 ) 2 SO 4 . These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.

Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

DOE Office of Scientific and Technical Information (OSTI.GOV)

D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D.

2017-04-11

We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1.more » Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.« less

Temperature Effects on Secondary Organic Aerosol (SOA) from the Dark Ozonolysis and Photo-Oxidation of Isoprene.

PubMed

Clark, Christopher H; Kacarab, Mary; Nakao, Shunsuke; Asa-Awuku, Akua; Sato, Kei; Cocker, David R

2016-06-07

Isoprene is globally the most ubiquitous nonmethane hydrocarbon. The biogenic emission is found in abundance and has a propensity for SOA formation in diverse climates. It is important to characterize isoprene SOA formation with varying reaction temperature. In this work, the effect of temperature on SOA formation, physical properties, and chemical nature is probed. Three experimental systems are probed for temperature effects on SOA formation from isoprene, NO + H2O2 photo-oxidation, H2O2 only photo-oxidation, and dark ozonolysis. These experiments show that isoprene readily forms SOA in unseeded chamber experiments, even during dark ozonolysis, and also reveal that temperature affects SOA yield, volatility, and density formed from isoprene. As temperature increases SOA yield is shown to generally decrease, particle density is shown to be stable (or increase slightly), and formed SOA is shown to be less volatile. Chemical characterization is shown to have a complex trend with both temperature and oxidant, but extensive chemical speciation are provided.

Overview of surface measurements and spatial characterization of submicrometer particulate matter during the DISCOVER-AQ 2013 campaign in Houston, TX.

PubMed

Leong, Y J; Sanchez, N P; Wallace, H W; Karakurt Cevik, B; Hernandez, C S; Han, Y; Flynn, J H; Massoli, P; Floerchinger, C; Fortner, E C; Herndon, S; Bean, J K; Hildebrandt Ruiz, L; Jeon, W; Choi, Y; Lefer, B; Griffin, R J

2017-08-01

The sources of submicrometer particulate matter (PM 1 ) remain poorly characterized in the industrialized city of Houston, TX. A mobile sampling approach was used to characterize PM 1 composition and concentration across Houston based on high-time-resolution measurements of nonrefractory PM 1 and trace gases during the DISCOVER-AQ Texas 2013 campaign. Two pollution zones with marked differences in PM 1 levels, character, and dynamics were established based on cluster analysis of organic aerosol mass loadings sampled at 16 sites. The highest PM 1 mass concentrations (average 11.6 ± 5.7 µg/m 3 ) were observed to the northwest of Houston (zone 1), dominated by secondary organic aerosol (SOA) mass likely driven by nighttime biogenic organonitrate formation. Zone 2, an industrial/urban area south/east of Houston, exhibited lower concentrations of PM 1 (average 4.4 ± 3.3 µg/m 3 ), significant organic aerosol (OA) aging, and evidence of primary sulfate emissions. Diurnal patterns and backward-trajectory analyses enable the classification of airmass clusters characterized by distinct PM sources: biogenic SOA, photochemical aged SOA, and primary sulfate emissions from the Houston Ship Channel. Principal component analysis (PCA) indicates that secondary biogenic organonitrates primarily related with monoterpenes are predominant in zone 1 (accounting for 34% of the variability in the data set). The relevance of photochemical processes and industrial and traffic emission sources in zone 2 also is highlighted by PCA, which identifies three factors related with these processes/sources (~50% of the aerosol/trace gas concentration variability). PCA reveals a relatively minor contribution of isoprene to SOA formation in zone 1 and the absence of isoprene-derived aerosol in zone 2. The relevance of industrial amine emissions and the likely contribution of chloride-displaced sea salt aerosol to the observed variability in pollution levels in zone 2 also are captured by PCA. This article describes an urban-scale mobile study to characterize spatial variations in submicrometer particulate matter (PM 1 ) in greater Houston. The data set indicates substantial spatial variations in PM 1 sources/chemistry and elucidates the importance of photochemistry and nighttime oxidant chemistry in producing secondary PM 1 . These results emphasize the potential benefits of effective control strategies throughout the region, not only to reduce primary emissions of PM 1 from automobiles and industry but also to reduce the emissions of important secondary PM 1 precursors, including sulfur oxides, nitrogen oxides, ammonia, and volatile organic compounds. Such efforts also could aid in efforts to reduce mixing ratios of ozone.

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

PubMed

Cao, Gang; Jang, Myoseon

2010-01-15

A predictive model for secondary organic aerosol (SOA) formation including both partitioning and heterogeneous reactions is explored for the SOA produced from the oxidation of toluene in the presence of inorganic seed aerosols. The predictive SOA model comprises the explicit gas-phase chemistry of toluene, gas-particle partitioning, and heterogeneous chemistry. The resulting products from the explicit gas phase chemistry are lumped into several classes of chemical species based on their vapor pressure and reactivity for heterogeneous reactions. Both the gas-particle partitioning coefficient and the heterogeneous reaction rate constant of each lumped gas-phase product are theoretically determined using group contribution and molecular structure-reactivity. In the SOA model, the predictive SOA mass is decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). OM(P) is estimated from the SOA partitioning model developed by Schell et al. (J. Geophys. Res. 2001, 106, 28275-28293 ) that has been used in a regional air quality model (CMAQ 4.7). OM(H) is predicted from the heterogeneous SOA model developed by Jang et al. (Environ. Sci. Technol. 2006, 40, 3013-3022 ). The SOA model is evaluated using a number of the experimental SOA data that are generated in a 2 m(3) indoor Teflon film chamber under various experimental conditions (e.g., humidity, inorganic seed compositions, NO(x) concentrations). The SOA model reasonably predicts not only the gas-phase chemistry, such as the ozone formation, the conversion of NO to NO(2), and the toluene decay, but also the SOA production. The model predicted that the OM(H) fraction of the total toluene SOA mass increases as NO(x) concentrations decrease: 0.73-0.83 at low NO(x) levels and 0.17-0.47 at middle and high NO(x) levels for SOA experiments with high initial toluene concentrations. Our study also finds a significant increase in the OM(H) mass fraction in the SOA generated with low initial toluene concentrations, compared to those with high initial toluene concentrations. On average, more than a 1-fold increase in OM(H) fraction is observed when the comparison is made between SOA experiments with 40 ppb toluene to those with 630 ppb toluene. Such an observation implies that heterogeneous reactions of the second-generation products of toluene oxidation can contribute considerably to the total SOA mass under atmospheric relevant conditions.

Emission factors for open and domestic biomass burning for use in atmospheric models

Treesearch

S. K. Akagi; R. J. Yokelson; C. Wiedinmyer; M. J. Alvarado; J. S. Reid; T. Karl; J. D. Crounse; P. O. Wennberg

2010-01-01

Biomass burning (BB) is the second largest source of trace gases and the largest source of primary fine carbonaceous particles in the global troposphere. Many recent BB studies have provided new emission factor (EF) measurements. This is especially 5 true for non methane organic compounds (NMOC), which influence secondary organic aerosol (SOA) and ozone formation. New...

Mechanism of SOA formation determines magnitude of radiative effects

NASA Astrophysics Data System (ADS)

Zhu, Jialei; Penner, Joyce E.; Lin, Guangxing; Zhou, Cheng; Xu, Li; Zhuang, Bingliang

2017-11-01

Secondary organic aerosol (SOA) nearly always exists as an internal mixture, and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing state based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66% of SOA is internally mixed with sulfate, while 34% is internally mixed with primary soot. Compared with using an external mixture, the direct effect of SOA is decreased due to the decrease in total aerosol surface area and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced, and this is responsible for a large decrease in the cloud albedo effect. Internal mixing decreases the radiative effect of SOA by a factor of >4 compared with treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of ‑0.05 W m‑2. When the combined effects of changes in climate, anthropogenic emissions, and land use are included, the SOA forcing is ‑0.07 W m‑2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing.

Heating-Induced Evaporation of Nine Different Secondary Organic Aerosol Types

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kolesar, Katheryn R.; Li, Ziyue; Wilson, Kevin R.

The volatility of the compounds comprising organic aerosol (OA) determines their distribution between the gas and particle phases. However, there is a disconnect between volatility distributions as typically derived from secondary OA (SOA) growth experiments and the effective particle volatility as probed in evaporation experiments. Specifically, the evaporation experiments indicate an overall much less volatile SOA. This raises questions regarding the use of traditional volatility distributions in the simulation and prediction of atmospheric SOA concentrations. Here, we present results from measurements of thermally induced evaporation of SOA for nine different SOA types (i.e., distinct volatile organic compound and oxidant pairs)more » encompassing both anthropogenic and biogenic compounds and O 3 and OH to examine the extent to which the low effective volatility of SOA is a general phenomenon or specific to a subset of SOA types. The observed extents of evaporation with temperature were similar for all the SOA types and indicative of a low effective volatility. Furthermore, minimal variations in the composition of all the SOA types upon heating-induced evaporation were observed. These results suggest that oligomer decomposition likely plays a major role in controlling SOA evaporation, and since the SOA formation time scale in these measurements was less than a minute, the oligomer-forming reactions must be similarly rapid. Overall, these results emphasize the importance of accounting for the role of condensed phase reactions in altering the composition of SOA when assessing particle volatility.« less

Mechanism of SOA formation determines magnitude of radiative effects

DOE PAGES

Zhu, Jialei; Penner, Joyce E.; Lin, Guangxing; ...

2017-11-13

Secondary organic aerosol (SOA) nearly always exists as an internal mixture and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing states based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66 % of SOA is internally mixed with sulfate, while 34 % is internally mixed with primary soot. When compared with using an external mixture, the direct effect of SOA is decreased, due to the decrease of total aerosol surface areamore » and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced and this is responsible for a large decrease in the cloud albedo effect. In total, internal mixing suppresses the radiative effect of SOA by a factor of >4 compared to treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of -0.05 W m-2. When the combined effects of changes in climate, anthropogenic emissions and land use are included, the SOA forcing is -0.07 W m-2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing.« less

Mechanism of SOA formation determines magnitude of radiative effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jialei; Penner, Joyce E.; Lin, Guangxing

Secondary organic aerosol (SOA) nearly always exists as an internal mixture and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing states based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66 % of SOA is internally mixed with sulfate, while 34 % is internally mixed with primary soot. When compared with using an external mixture, the direct effect of SOA is decreased, due to the decrease of total aerosol surface areamore » and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced and this is responsible for a large decrease in the cloud albedo effect. In total, internal mixing suppresses the radiative effect of SOA by a factor of >4 compared to treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of -0.05 W m-2. When the combined effects of changes in climate, anthropogenic emissions and land use are included, the SOA forcing is -0.07 W m-2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing.« less

Mechanism of SOA Formation Determines Magnitude of Radiative Effects

NASA Astrophysics Data System (ADS)

Zhu, J.; Penner, J.; Lin, G.; Zhou, C.

2017-12-01

Secondary organic aerosol (SOA) nearly always exists as an internal mixture and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing states based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66 % of SOA is internally mixed with sulfate, while 34 % is internally mixed with primary soot. When compared with using an external mixture, the direct effect of SOA is decreased, due to the decrease of total aerosol surface area and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced and this is responsible for a large decrease in the cloud albedo effect. In total, internal mixing suppresses the radiative effect of SOA by a factor of >4 compared to treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of -0.05 W m-2. When the combined effects of changes in climate, anthropogenic emissions and land use are included, the SOA forcing is -0.07 W m-2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing.

Heating-Induced Evaporation of Nine Different Secondary Organic Aerosol Types

DOE PAGES

Kolesar, Katheryn R.; Li, Ziyue; Wilson, Kevin R.; ...

2015-09-22

The volatility of the compounds comprising organic aerosol (OA) determines their distribution between the gas and particle phases. However, there is a disconnect between volatility distributions as typically derived from secondary OA (SOA) growth experiments and the effective particle volatility as probed in evaporation experiments. Specifically, the evaporation experiments indicate an overall much less volatile SOA. This raises questions regarding the use of traditional volatility distributions in the simulation and prediction of atmospheric SOA concentrations. Here, we present results from measurements of thermally induced evaporation of SOA for nine different SOA types (i.e., distinct volatile organic compound and oxidant pairs)more » encompassing both anthropogenic and biogenic compounds and O 3 and OH to examine the extent to which the low effective volatility of SOA is a general phenomenon or specific to a subset of SOA types. The observed extents of evaporation with temperature were similar for all the SOA types and indicative of a low effective volatility. Furthermore, minimal variations in the composition of all the SOA types upon heating-induced evaporation were observed. These results suggest that oligomer decomposition likely plays a major role in controlling SOA evaporation, and since the SOA formation time scale in these measurements was less than a minute, the oligomer-forming reactions must be similarly rapid. Overall, these results emphasize the importance of accounting for the role of condensed phase reactions in altering the composition of SOA when assessing particle volatility.« less

Effects of inorganic seeds on secondary organic aerosol formation from photochemical oxidation of acetone in a chamber

NASA Astrophysics Data System (ADS)

Ge, Shuangshuang; Xu, Yongfu; Jia, Long

2017-12-01

Photochemical oxidations of acetone were studied under different inorganic seed (NaCl, (NH4)2SO4 and NaNO3) conditions in a self-made chamber. The results show that no secondary organic aerosol (SOA) can be formed in the experiments either in the absence of artificially added seed particles or in the presence of solid status of the added particles. Liquid water content is the key factor for the formation of SOA in the experiments with seeds. The amount of SOA was only about 4-7 μg m-3 in the experiments with the initial acetone of ∼15 ppm under different seed conditions. The analysis of SOA compositions by Exactive-Orbitrap mass spectrometer equipped with electro-spray interface (ESI-MS) shows that chlorine-containing and sulfur-containing compounds were detected in SOA formed from the experiments with NaCl and (NH4)2SO4 seeds, respectively, which were not identified in SOA from those with NaNO3. The compositions of SOA were mainly esters, organonitrates, hydroperoxides, etc. It is concluded that inorganic seed particles participated into the formation of SOA. Acetone SOA was mainly formed in the aqueous phase in which dissolved SOA precursors underwent further oxidation reactions, esterification reactions and/or radical-radical reactions. Our experiments further demonstrate that low-molecular-weight VOCs, such as acetone, can form SOA under certain conditions in the atmosphere, although their contributions to SOA may not be large.

Mechanism of SOA formation determines magnitude of radiative effects

PubMed Central

Penner, Joyce E.; Lin, Guangxing; Zhou, Cheng; Xu, Li; Zhuang, Bingliang

2017-01-01

Secondary organic aerosol (SOA) nearly always exists as an internal mixture, and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing state based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66% of SOA is internally mixed with sulfate, while 34% is internally mixed with primary soot. Compared with using an external mixture, the direct effect of SOA is decreased due to the decrease in total aerosol surface area and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced, and this is responsible for a large decrease in the cloud albedo effect. Internal mixing decreases the radiative effect of SOA by a factor of >4 compared with treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of −0.05 W m−2. When the combined effects of changes in climate, anthropogenic emissions, and land use are included, the SOA forcing is −0.07 W m−2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing. PMID:29133426

Mechanism of SOA formation determines magnitude of radiative effects.

PubMed

Zhu, Jialei; Penner, Joyce E; Lin, Guangxing; Zhou, Cheng; Xu, Li; Zhuang, Bingliang

2017-11-28

Secondary organic aerosol (SOA) nearly always exists as an internal mixture, and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing state based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66% of SOA is internally mixed with sulfate, while 34% is internally mixed with primary soot. Compared with using an external mixture, the direct effect of SOA is decreased due to the decrease in total aerosol surface area and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced, and this is responsible for a large decrease in the cloud albedo effect. Internal mixing decreases the radiative effect of SOA by a factor of >4 compared with treating SOA as an external mixture. The future SOA burden increases by 24% due to CO 2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of -0.05 W m -2 When the combined effects of changes in climate, anthropogenic emissions, and land use are included, the SOA forcing is -0.07 W m -2 , even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing. Copyright © 2017 the Author(s). Published by PNAS.

Observation of SOA tracers at a mountainous site in Hong Kong: Chemical characteristics, origins and implication on particle growth.

PubMed

Lyu, X P; Guo, H; Cheng, H R; Wang, X M; Ding, X; Lu, H X; Yao, D W; Xu, C

2017-12-15

Secondary organic aerosol (SOA) is an important constituent of airborne fine particles. PM 2.5 (particles with aerodynamic diameters≤2.5μm) samples were collected at a mountainous site in Hong Kong in autumn of 2010, and analyzed for SOA tracers. Results indicated that the concentrations of isoprene SOA tracers (54.7±22.7ng/m 3 ) and aromatics SOA tracers (2.1±1.6ng/m 3 ) were on relatively high levels in Hong Kong. Secondary organic carbon (SOC) derived from isoprene, monoterpenes, sesquiterpenes and aromatics was estimated with the SOA tracer based approach, which constituted 0.35±0.15μg/m 3 (40.6±5.7%), 0.20±0.03μg/m 3 (30.4±5.5%), 0.05±0.02μg/m 3 (5.6±1.7%) and 0.26±0.20μg/m 3 (21.3±8.2%) of the total estimated SOC. Biogenic SOC (0.60±0.18μg/m 3 ) dominated over anthropogenic SOC (0.26±0.20μg/m 3 ) at this site. In addition to the total estimated SOC (17.8±4.6% of organic carbon (OC) in PM 2.5 ), primary organic carbon (POC) emitted from biomass burning also accounted for a considerable proportion of OC (11.6±3.2%). Insight into the OC origins found that regional transport significantly (p<0.05) elevated SOC from 0.37±0.17 to 1.04±0.39μg/m 3 . Besides, SOC load could also increase significantly if there was influence from local ship emission. Biomass burning related POC in regional air masses (0.81±0.24μg/m 3 ) was also higher (p<0.05) than that in samples affected by local air (0.29±0.35μg/m 3 ). Evidences indicated that SOA formation was closely related to new particle formation and the growth of nucleation mode particles, while biomass burning was responsible for some particle burst events in Hong Kong. This is the first SOA study in afforested areas of Hong Kong. Copyright © 2017 Elsevier B.V. All rights reserved.

Role of methyl group number on SOA formation from aromatic hydrocarbons photooxidation under low NOx conditions

NASA Astrophysics Data System (ADS)

Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker, D. R., III

2015-11-01

Substitution of methyl groups onto the aromatic ring determines the SOA formation from the aromatic hydrocarbon precursor. This study links the number of methyl groups on the aromatic ring to SOA formation from aromatic hydrocarbons photooxidation under low NOx conditions (HC / NO > 10 ppb C : ppb). Aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests as more methyl groups are attached on the aromatic ring, SOA products from these aromatic hydrocarbons become less oxidized per mass/carbon.

Ozone and OH-induced oxidation of monoterpenes: Changes in the thermal properties of secondary organic aerosol (SOA)

NASA Astrophysics Data System (ADS)

Watne, Ågot K.; Westerlund, Jonathan; Hallquist, Åsa M.; Brune, William H.; Hallquist, Mattias

2017-12-01

The behaviour of secondary organic aerosols (SOA) in the atmosphere is highly dependent on their thermal properties. Here we investigate the volatility of SOA formed from alpha-pinene, beta-pinene and limonene upon ozone- and OH-induced oxidation, and the effect of OH-induced ageing on the initially produced SOA. For all three terpenes, the ozone-induced SOA was less volatile than the OH-induced SOA. The thermal properties of the SOA were described using three parameters extracted from the volatility measurements: the temperature at which 50 per cent of the volume has evaporated (TVFR0.5), which is used as a general volatility indicator; a slope factor (SVFR), which describes the volatility distribution; and TVFR0.1, which measures the volatility of the least volatile particle fraction. Limonene-derived SOA generally had higher TVFR0.5 values and shallower slopes than SOA derived from alpha- and beta-pinene. This was especially true for the ozone-induced SOA, partially because the ozonolysis of limonene has a strong tendency to cause SOA formation and to produce extremely low volatility VOCs (ELVOCs). Ageing by OH exposure did not reduce TVFR0.5 for any of the studied terpenes but did increase the breadth of the volatility distribution by increasing the aerosols heterogeneity and contents of substances with different vapour pressures, also leading to increases in TVFR0.1. This stands in contrast to previously reported results from smog chamber experiments, in which TVFR0.5 always increased with ageing. These results demonstrate that there are two opposing processes that influence the evolution of SOAs thermal properties as they age, and that results from both flow reactors and static chambers are needed to fully understand the temporal evolution of atmospheric SOA thermal properties.

Laboratory observations of artificial sand and oil agglomerates

USGS Publications Warehouse

Jenkins, Robert L.; Dalyander, P. Soupy; Penko, Allison; Long, Joseph W.

2018-04-27

Sand and oil agglomerates (SOAs) form when weathered oil reaches the surf zone and combines with suspended sediments. The presence of large SOAs in the form of thick mats (up to 10 centimeters [cm] in height and up to 10 square meters [m2] in area) and smaller SOAs, sometimes referred to as surface residual balls (SRBs), may lead to the re-oiling of beaches previously affected by an oil spill. A limited number of numerical modeling and field studies exist on the transport and dynamics of centimeter-scale SOAs and their interaction with the sea floor. Numerical models used to study SOAs have relied on shear-stress formulations to predict incipient motion. However, uncertainty exists as to the accuracy of applying these formulations, originally developed for sand grains in a uniformly sorted sediment bed, to larger, nonspherical SOAs. In the current effort, artificial sand and oil agglomerates (aSOAs) created with the size, density, and shape characteristics of SOAs were studied in a small-oscillatory flow tunnel. These experiments expanded the available data on SOA motion and interaction with the sea floor and were used to examine the applicability of shear-stress formulations to predict SOA mobility. Data collected during these two sets of experiments, including photographs, video, and flow velocity, are presented in this report, along with an analysis of shear-stress-based formulations for incipient motion. The results showed that shear-stress thresholds for typical quartz sand predicted the incipient motion of aSOAs with 0.5–1.0-cm diameters, but were inaccurate for aSOAs with larger diameters (>2.5 cm). This finding implies that modified parameterizations of incipient motion may be necessary under certain combinations of aSOA characteristics and environmental conditions.

Incipient Motion of Sand and Oil Agglomerates

NASA Astrophysics Data System (ADS)

Nelson, T. R.; Dalyander, S.; Jenkins, R. L., III; Penko, A.; Long, J.; Frank, D. P.; Braithwaite, E. F., III; Calantoni, J.

2016-12-01

Weathered oil mixed with sediment in the surf zone in the northern Gulf of Mexico after the 2010 Deepwater Horizon oil spill, forming large mats of sand and oil. Wave action fragmented the mats into sand and oil agglomerates (SOAs) with diameters of about 1 to 10 cm. These SOAs were transported by waves and currents along the Gulf Coast, and have been observed on beaches for years following the spill. SOAs are composed of 70%-95% sand by mass, with an approximate density of 2107 kg/m³. To measure the incipient motion of SOAs, experiments using artificial SOAs were conducted in the Small-Oscillatory Flow Tunnel at the U.S. Naval Research Laboratory under a range of hydrodynamic forcing. Spherical and ellipsoidal SOAs ranging in size from 0.5 to 10 cm were deployed on a fixed flat bed, a fixed rippled bed, and a movable sand bed. In the case of the movable sand bed, SOAs were placed both proud and partially buried. Motion was tracked with high-definition video and with inertial measurement units embedded in some of the SOAs. Shear stress and horizontal pressure gradients, estimated from velocity measurements made with a Nortek Vectrino Profiler, were compared with observed mobility to assess formulations for incipient motion. For SOAs smaller than 1 cm in diameter, incipient motion of spherical and ellipsoidal SOAs was consistent with predicted critical stress values. The measured shear stress at incipient motion of larger, spherical SOAs was lower than predicted, indicating an increased dependence on the horizontal pressure gradient. In contrast, the measured shear stress required to move ellipsoidal SOAs was higher than predicted, even compared to values modified for larger particles in mixed-grain riverine environments. The laboratory observations will be used to improve the prediction of incipient motion, transport, and seafloor interaction of SOAs.

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

PubMed

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

2014-05-01

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

Nearshore dynamics of artificial sand and oil agglomerates

USGS Publications Warehouse

Dalyander, P. Soupy; Plant, Nathaniel G.; Long, Joseph W.; McLaughlin, Molly R.

2015-01-01

Weathered oil can mix with sediment to form heavier-than-water sand and oil agglomerates (SOAs) that can cause beach re-oiling for years after a spill. Few studies have focused on the physical dynamics of SOAs. In this study, artificial SOAs (aSOAs) were created and deployed in the nearshore, and shear stress-based mobility formulations were assessed to predict SOA response. Prediction sensitivity to uncertainty in hydrodynamic conditions and shear stress parameterizations were explored. Critical stress estimates accounting for large particle exposure in a mixed bed gave the best predictions of mobility under shoaling and breaking waves. In the surf zone, the 10-cm aSOA was immobile and began to bury in the seafloor while smaller size classes dispersed alongshore. aSOAs up to 5 cm in diameter were frequently mobilized in the swash zone. The uncertainty in predicting aSOA dynamics reflects a broader uncertainty in applying mobility and transport formulations to cm-sized particles.

Constructing service-oriented architecture adoption maturity matrix using Kano model

NASA Astrophysics Data System (ADS)

Hamzah, Mohd Hamdi Irwan; Baharom, Fauziah; Mohd, Haslina

2017-10-01

Commonly, organizations adopted Service-Oriented Architecture (SOA) because it can provide a flexible reconfiguration and can reduce the development time and cost. In order to guide the SOA adoption, previous industry and academia have constructed SOA maturity model. However, there is a limited number of works on how to construct the matrix in the previous SOA maturity model. Therefore, this study is going to provide a method that can be used in order to construct the matrix in the SOA maturity model. This study adapts Kano Model to construct the cross evaluation matrix focused on SOA adoption IT and business benefits. This study found that Kano Model can provide a suitable and appropriate method for constructing the cross evaluation matrix in SOA maturity model. Kano model also can be used to plot, organize and better represent the evaluation dimension for evaluating the SOA adoption.

The AeroCom evaluation and intercomparison of organic aerosol in global models

DOE PAGES

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

2014-10-15

This paper evaluates the current status of global modeling of the organic aerosol (OA) in the troposphere and analyzes the differences between models as well as between models and observations. Thirty-one global chemistry transport models (CTMs) and general circulation models (GCMs) have participated in this intercomparison, in the framework of AeroCom phase II. The simulation of OA varies greatly between models in terms of the magnitude of primary emissions, secondary OA (SOA) formation, the number of OA species used (2 to 62), the complexity of OA parameterizations (gas-particle partitioning, chemical aging, multiphase chemistry, aerosol microphysics), and the OA physical, chemicalmore » and optical properties. The diversity of the global OA simulation results has increased since earlier AeroCom experiments, mainly due to the increasing complexity of the SOA parameterization in models, and the implementation of new, highly uncertain, OA sources. Diversity of over one order of magnitude exists in the modeled vertical distribution of OA concentrations that deserves a dedicated future study. Furthermore, although the OA / OC ratio depends on OA sources and atmospheric processing, and is important for model evaluation against OA and OC observations, it is resolved only by a few global models. The median global primary OA (POA) source strength is 56 Tg a –1 (range 34–144 Tg a −1) and the median SOA source strength (natural and anthropogenic) is 19 Tg a –1 (range 13–121 Tg a −1). Among the models that take into account the semi-volatile SOA nature, the median source is calculated to be 51 Tg a –1 (range 16–121 Tg a −1), much larger than the median value of the models that calculate SOA in a more simplistic way (19 Tg a –1; range 13–20 Tg a –1, with one model at 37 Tg a −1). The median atmospheric burden of OA is 1.4 Tg (24 models in the range of 0.6–2.0 Tg and 4 between 2.0 and 3.8 Tg), with a median OA lifetime of 5.4 days (range 3.8–9.6 days). In models that reported both OA and sulfate burdens, the median value of the OA/sulfate burden ratio is calculated to be 0.77; 13 models calculate a ratio lower than 1, and 9 models higher than 1. For 26 models that reported OA deposition fluxes, the median wet removal is 70 Tg a –1 (range 28–209 Tg a −1), which is on average 85% of the total OA deposition. Fine aerosol organic carbon (OC) and OA observations from continuous monitoring networks and individual field campaigns have been used for model evaluation. At urban locations, the model–observation comparison indicates missing knowledge on anthropogenic OA sources, both strength and seasonality. The combined model–measurements analysis suggests the existence of increased OA levels during summer due to biogenic SOA formation over large areas of the USA that can be of the same order of magnitude as the POA, even at urban locations, and contribute to the measured urban seasonal pattern. Global models are able to simulate the high secondary character of OA observed in the atmosphere as a result of SOA formation and POA aging, although the amount of OA present in the atmosphere remains largely underestimated, with a mean normalized bias (MNB) equal to –0.62 (–0.51) based on the comparison against OC (OA) urban data of all models at the surface, –0.15 (+0.51) when compared with remote measurements, and –0.30 for marine locations with OC data. The mean temporal correlations across all stations are low when compared with OC (OA) measurements: 0.47 (0.52) for urban stations, 0.39 (0.37) for remote stations, and 0.25 for marine stations with OC data. The combination of high (negative) MNB and higher correlation at urban stations when compared with the low MNB and lower correlation at remote sites suggests that knowledge about the processes that govern aerosol processing, transport and removal, on top of their sources, is important at the remote stations. There is no clear change in model skill with increasing model complexity with regard to OC or OA mass concentration. As a result, the complexity is needed in models in order to distinguish between anthropogenic and natural OA as needed for climate mitigation, and to calculate the impact of OA on climate accurately.« less

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Modulations of the executive control network by stimulus onset asynchrony in a Stroop task

PubMed Central

2013-01-01

Background Manipulating task difficulty is a useful way of elucidating the functional recruitment of the brain’s executive control network. In a Stroop task, pre-exposing the irrelevant word using varying stimulus onset asynchronies (‘negative’ SOAs) modulates the amount of behavioural interference and facilitation, suggesting disparate mechanisms of cognitive processing in each SOA. The current study employed a Stroop task with three SOAs (−400, -200, 0 ms), using functional magnetic resonance imaging to investigate for the first time the neural effects of SOA manipulation. Of specific interest were 1) how SOA affects the neural representation of interference and facilitation; 2) response priming effects in negative SOAs; and 3) attentional effects of blocked SOA presentation. Results The results revealed three regions of the executive control network that were sensitive to SOA during Stroop interference; the 0 ms SOA elicited the greatest activation of these areas but experienced relatively smaller behavioural interference, suggesting that the enhanced recruitment led to more efficient conflict processing. Response priming effects were localized to the right inferior frontal gyrus, which is consistent with the idea that this region performed response inhibition in incongruent conditions to overcome the incorrectly-primed response, as well as more general action updating and response preparation. Finally, the right superior parietal lobe was sensitive to blocked SOA presentation and was most active for the 0 ms SOA, suggesting that this region is involved in attentional control. Conclusions SOA exerted both trial-specific and block-wide effects on executive processing, providing a unique paradigm for functional investigations of the cognitive control network. PMID:23902451

Partitioning phase preference for secondary organic aerosol in an urban atmosphere

NASA Astrophysics Data System (ADS)

Chang, Wayne Li-Wen

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

Integration of decentralized clinical data in a data warehouse: a service-oriented design and realization.

PubMed

Hanss, Sabine; Schaaf, T; Wetzel, T; Hahn, C; Schrader, T; Tolxdorff, T

2009-01-01

In this paper we present a general concept and describe the difficulties for the integration of data from various clinical partners in one data warehouse using the Open European Nephrology Science Center (OpEN.SC) as an example. This includes a requirements analysis of the data integration process and also the design according to these requirements. This conceptual approach based on the Rational Unified Process (RUP) and paradigm of Service-Oriented Architecture (SOA). Because we have to enhance the confidence of our partners in the OpEN.SC system and with this the willingness of them to participate, important requirements are controllability, transparency and security for all partners. Reusable and fine-grained components were found to be necessary when working with diverse data sources. With SOA the requested reusability is implemented easily. A key step in the development of a data integration process within such a health information system like OpEN.SC is to analyze the requirements. And to show that this is not only a theoretical work, we present a design - developed with RUP and SOA - which fulfills these requirements.

Characterizing oxidative flow reactor SOA production and OH radical exposure from laboratory experiments of complex mixtures (engine exhaust) and simple precursors (monoterpenes)

NASA Astrophysics Data System (ADS)

Michael Link, M. L.; Friedman, B.; Ortega, J. V.; Son, J.; Kim, J.; Park, G.; Park, T.; Kim, K.; Lee, T.; Farmer, D.

2016-12-01

Recent commercialization of the Oxidative Flow Reactor (OFR, occasionally described in the literature as a "Potential Aerosol Mass") has created the opportunity for many researchers to explore the mechanisms behind OH-driven aerosol formation on a wide range of oxidative timescales (hours to weeks) in both laboratory and field measurements. These experiments have been conducted in both laboratory and field settings, including simple (i.e. single component) and complex (multi-component) precursors. Standard practices for performing OFR experiments, and interpreting data from the measurements, are still being developed. Measurement of gas and particle phase chemistry, from oxidation products generated in the OFR, through laboratory studies on single precursors and the measurement of SOA from vehicle emissions on short atmospheric timescales represent two very different experiments in which careful experimental design is essential for exploring reaction mechanisms and SOA yields. Two parameters essential in experimental design are (1) the role of seed aerosol in controlling gas-particle partitioning and SOA yields, and (2) the accurate determination of OH exposure during any one experiment. We investigated the role of seed aerosol surface area in controlling the observed SOA yields and gas/particle composition from the OH-initiated oxidation of four monoterpenes using an aerosol chemical ionization time-of-flight mass spectrometer and scanning mobility particle sizer. While the OH exposure during laboratory experiments is simple to constrain, complex mixtures such as diesel exhaust have high estimated OH reactivity values, and thus require careful consideration. We developed methods for constraining OH radical exposure in the OFR during vehicle exhaust oxidation experiments. We observe changes in O/C ratios and highly functionalized species over the temperature gradient employed in the aerosol-CIMS measurement. We relate this observed, speciated chemistry to the volatility of the aerosol, and compare observed SOA yields to other OFR and smog chamber SOA generation methods. Additionally, estimates of OH radical exposure in the OFR during different vehicle experiments of varying fuel type and speed were observed to vary as determined from a high-NOx and variable humidity calibration set.

Comparison of secondary organic aerosol formation from toluene on initially wet and dry ammonium sulfate particles at moderate relative humidity

NASA Astrophysics Data System (ADS)

Liu, Tengyu; Huang, Dan Dan; Li, Zijun; Liu, Qianyun; Chan, ManNin; Chan, Chak K.

2018-04-01

The formation of secondary organic aerosol (SOA) has been widely studied in the presence of dry seed particles at low relative humidity (RH). At higher RH, initially dry seed particles can exist as wet particles due to water uptake by the seeds as well as the SOA. Here, we investigated the formation of SOA from the photooxidation of toluene using an oxidation flow reactor in the absence of NOx under a range of OH exposures on initially wet or dry ammonium sulfate (AS) seed particles at an RH of 68 %. The ratio of the SOA yield on wet AS seeds to that on dry AS seeds, the relative SOA yield, decreased from 1.31 ± 0.02 at an OH exposure of 4.66 × 1010 molecules cm-3 s to 1.01 ± 0.01 at an OH exposure of 5.28 × 1011 molecules cm-3 s. This decrease may be due to the early deliquescence of initially dry AS seeds after being coated by highly oxidized toluene-derived SOA. SOA formation lowered the deliquescence RH of AS and resulted in the uptake of water by both AS and SOA. Hence the initially dry AS seeds contained aerosol liquid water (ALW) soon after SOA formed, and the SOA yield and ALW approached those of the initially wet AS seeds as OH exposure and ALW increased, especially at high OH exposure. However, a higher oxidation state of the SOA on initially wet AS seeds than that on dry AS seeds was observed at all levels of OH exposure. The difference in mass fractions of m / z 29, 43 and 44 of SOA mass spectra, obtained using an aerosol mass spectrometer (AMS), indicated that SOA formed on initially wet seeds may be enriched in earlier-generation products containing carbonyl functional groups at low OH exposures and later-generation products containing acidic functional groups at high exposures. Our results suggest that inorganic dry seeds become at least partially deliquesced particles during SOA formation and hence that ALW is inevitably involved in the SOA formation at moderate RH. More laboratory experiments conducted with a wide variety of SOA precursors and inorganic seeds under different NOx and RH conditions are warranted.

High-resolution genetic mapping of the sucrose octaacetate taste aversion (Soa) locus on mouse Chromosome 6

PubMed Central

Bachmanov, Alexander A.; Li, Xia; Li, Shanru; Neira, Mauricio; Beauchamp, Gary K.; Azen, Edwin A.

2013-01-01

An acetylated sugar, sucrose octaacetate (SOA), tastes bitter to humans and has an aversive taste to at least some mice and other animals. In mice, taste aversion to SOA depends on allelic variation of a single locus, Soa. Three Soa alleles determine ‘taster’ (Soaa), ‘nontaster’ (Soab), and ‘demitaster’ (Soac) phenotypes of taste sensitivity to SOA. Although Soa has been mapped to distal Chromosome (Chr) 6, the limits of the Soa region have not been defined. In this study, mice from congenic strains SW.B6-Soab, B6.SW-Soaa, and C3.SW-Soaa/c and from an outbred CFW strain were genotyped with polymorphic markers on Chr 6. In the congenic strains, the limits of introgressed donor fragments were determined. In the outbred mice, linkage disequilibrium and haplotype analyses were conducted. Positions of the markers were further resolved by using radiation hybrid mapping. The results show that the Soa locus is contained in a ~1-cM (3.3–4.9 Mb) region including the Prp locus. PMID:11641717

Spatial and temporal EEG dynamics of dual-task driving performance

PubMed Central

2011-01-01

Background Driver distraction is a significant cause of traffic accidents. The aim of this study is to investigate Electroencephalography (EEG) dynamics in relation to distraction during driving. To study human cognition under a specific driving task, simulated real driving using virtual reality (VR)-based simulation and designed dual-task events are built, which include unexpected car deviations and mathematics questions. Methods We designed five cases with different stimulus onset asynchrony (SOA) to investigate the distraction effects between the deviations and equations. The EEG channel signals are first converted into separated brain sources by independent component analysis (ICA). Then, event-related spectral perturbation (ERSP) changes of the EEG power spectrum are used to evaluate brain dynamics in time-frequency domains. Results Power increases in the theta and beta bands are observed in relation with distraction effects in the frontal cortex. In the motor area, alpha and beta power suppressions are also observed. All of the above results are consistently observed across 15 subjects. Additionally, further analysis demonstrates that response time and multiple cortical EEG power both changed significantly with different SOA. Conclusions This study suggests that theta power increases in the frontal area is related to driver distraction and represents the strength of distraction in real-life situations. PMID:21332977

Functional group composition of organic aerosol from combustion emissions and secondary processes at two contrasted urban environments

NASA Astrophysics Data System (ADS)

El Haddad, Imad; Marchand, Nicolas; D'Anna, Barbara; Jaffrezo, Jean Luc; Wortham, Henri

2013-08-01

The quantification of major functional groups in atmospheric organic aerosol (OA) provides a constraint on the types of compounds emitted and formed in atmospheric conditions. This paper presents functional group composition of organic aerosol from two contrasted urban environments: Marseille during summer and Grenoble during winter. Functional groups were determined using a tandem mass spectrometry approach, enabling the quantification of carboxylic (RCOOH), carbonyl (RCOR‧), and nitro (RNO2) functional groups. Using a multiple regression analysis, absolute concentrations of functional groups were combined with those of organic carbon derived from different sources in order to infer the functional group contents of different organic aerosol fractions. These fractions include fossil fuel combustion emissions, biomass burning emissions and secondary organic aerosol (SOA). Results clearly highlight the differences between functional group fingerprints of primary and secondary OA fractions. OA emitted from primary sources is found to be moderately functionalized, as about 20 carbons per 1000 bear one of the functional groups determined here, whereas SOA is much more functionalized, as in average 94 carbons per 1000 bear a functional group under study. Aging processes appear to increase both RCOOH and RCOR‧ functional group contents by nearly one order of magnitude. Conversely, RNO2 content is found to decrease with photochemical processes. Finally, our results also suggest that other functional groups significantly contribute to biomass smoke and SOA. In particular, for SOA, the overall oxygen content, assessed using aerosol mass spectrometer measurements by an O:C ratio of 0.63, is significantly higher than the apparent O:C* ratio of 0.17 estimated based on functional groups measured here. A thorough examination of our data suggests that this remaining unexplained oxygen content can be most probably assigned to alcohol (ROH), organic peroxides (ROOH), organonitrates (RONO2) and/or organosulfates (ROSO3H).

On-road vehicle emissions of glyoxal and methylglyoxal from tunnel tests in urban Guangzhou, China

NASA Astrophysics Data System (ADS)

Zhang, Yanli; Wang, Xinming; Wen, Sheng; Herrmann, Hartmut; Yang, Weiqiang; Huang, Xinyu; Zhang, Zhou; Huang, Zhonghui; He, Quanfu; George, Christian

2016-02-01

Glyoxal and methylglyoxal, the two smallest yet most abundant dicarbonyls, play vital roles in forming secondary organic aerosols (SOA) in the ambient air. The direct sources for glyoxal and methylglyoxal from vehicles are still unclear because of only a few investigations in the USA. Here we carried out tests in the Zhujiang tunnel in urban Guangzhou in south China to obtain emission factors (EFs) of glyoxal and methylglyoxal for on-road vehicles. Measured EFs for glyoxal and methylglyoxal averaged 1.18 ± 0.43 and 0.52 ± 0.26 mg km-1 veh-1, and were about 6.6 and 2.3 times those measured in the Tuscarora Mountain Tunnel in 1999 (Grosjean et al., 2001), respectively. Multiple linear regressions further resolved glyoxal EFs of 1.64 ± 1.03, 0.10 ± 3.49 and 0.58 ± 2.37 mg km-1 and methylglyoxal EFs of 0.17 ± 0.33, 1.68 ± 1.20 and 0.70 ± 0.66 mg km-1, respectively, for gasoline, diesel and liquefied petroleum gas (LPG) vehicles. The fuel-based EFs for glyoxal and methylglyoxal were estimated to be 28.1 and 2.9 mg kg-1 for gasoline vehicles, and 1.5 and 26.3 mg kg-1 for diesel vehicles, respectively. Based on available SOA yields, SOA formed from vehicle-emitted glyoxal and methylglyoxal could attain 25-50% of that formed from vehicle-emitted toluene. With the EFs from this study, the vehicle emission of the two dicarbonyls in China and in the world were roughly estimated. Either the CO-tracer-based or the fuel-based global estimates are below 0.1 Tg a-1 and therefore vehicle emission could be negligible in their global total sources, yet they might play vital roles in urban areas in forming SOA, particularly in the early chemical evolution of vehicle exhausts in the ambient.

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

PubMed

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

2010-03-29

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

All-optical noise reduction of fiber laser via intracavity SOA structure.

PubMed

Ying, Kang; Chen, Dijun; Pan, Zhengqing; Zhang, Xi; Cai, Haiwen; Qu, Ronghui

2016-10-10

We have designed a unique intracavity semiconductor optical amplifier (SOA) structure to suppress the relative intensity noise (RIN) for a fiber DFB laser. By exploiting the gain saturation effect of the SOA, a maximum noise suppression of 30 dB around the relaxation oscillation frequency is achieved, and the whole resonance relaxation oscillation peak completely disappears. Moreover, via a specially designed intracavity SOA structure, the optical intensity inside the SOA will be in a balanced state via the oscillation in the laser cavity, and the frequency noise of the laser will not be degraded with the SOA.

To what extent can biogenic SOA be controlled?

PubMed

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

2010-05-01

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

Aqueous Photochemistry of Secondary Organic Aerosol of α-Pinene and α-Humulene Oxidized with Ozone, Hydroxyl Radical, and Nitrate Radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romonosky, Dian E.; Li, Ying; Shiraiwa, Manabu

Formation of secondary organic aerosols (SOA) from biogenic volatile organic compounds 13 (BVOC) occurs via O 3 - and OH-initiated reactions during the day and reactions with NO 3 during the 14 night. We explored the effect of these three oxidation conditions on the molecular composition and 15 aqueous photochemistry of model SOA prepared from two common BVOC. A common monoterpene, α- 16 pinene, and sesquiterpene, α-humulene, were used to form SOA in a smog chamber via BVOC + O3, 17 BVOC + NO3, and BVOC + OH + NOx oxidation. Samples of SOA were collected, extracted in water,more » 18 and photolyzed in an aqueous solution in order to simulate the photochemical cloud processing of SOA. 19 The extent of change in the molecular level composition of SOA over 4 hours of photolysis (roughly 20 equivalent to 64 hours of photolysis under ambient conditions) was assessed with high-resolution 21 electrospray ionization mass spectrometry. The analysis revealed significant differences in the molecular 22 composition between monoterpene and sesquiterpene SOA formed by the different oxidation pathways. 23 The composition further evolved during photolysis with the most notable change corresponding to the 24 nearly-complete removal of nitrogen-containing organic compounds. Hydrolysis of SOA compounds also 25 occurred in parallel with photolysis. The preferential loss of larger SOA compounds during photolysis 26 and hydrolysis made the SOA compounds more volatile on average. This study suggests that cloud- and 27 fog-processing may under certain conditions lead to a reduction in the SOA loading as opposed to an 28 increase in SOA loading commonly assumed in the literature.« less

Modeling the formation and properties of traditional and non-traditional secondary organic aerosol: problem formulation and application to aircraft exhaust

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Miracolo, M. A.; Presto, A. A.; Adams, P. J.; Robinson, A. L.

2012-04-01

We present a methodology to model secondary organic aerosol (SOA) formation from the photo-oxidation of low-volatility organics (semi-volatile and intermediate volatility organic compounds). The model is parameterized and tested using SOA data collected during two field campaigns that characterized the atmospheric evolution of dilute gas-turbine engine emissions using a smog chamber. Photo-oxidation formed a significant amount of SOA, much of which cannot be explained based on the emissions of traditional, speciated precursors; we refer to this as non-traditional SOA (NT-SOA). The NT-SOA can be explained by emissions of low-volatility organic vapors measured using sorbents. Since these vapors could not be speciated, we employ a volatility-based approach to model NT-SOA formation. We show that the method proposed by Robinson et al. (2007) is unable to explain the timing of NT-SOA formation because it assumes a very modest reduction in volatility of the precursors with every oxidation reaction. In contrast, a Hybrid method, similar to models of traditional SOA formation, assumes a larger reduction in volatility with each oxidation step and results in a better reproduction of NT-SOA formation. The NT-SOA yields estimated for the low-volatility organic vapor emissions are similar to literature data for large n-alkanes and other low-volatility organics. The yields vary with fuel composition (JP8 versus Fischer-Tropsch) and engine load (idle versus non-idle). These differences are consistent with the expected contribution of high (aromatics and n-alkanes) and low (branched alkanes and oxygenated species) SOA forming species to the exhaust.

Reaction Time Correlations during Eye–Hand Coordination:Behavior and Modeling

PubMed Central

Dean, Heather L.; Martí, Daniel; Tsui, Eva; Rinzel, John; Pesaran, Bijan

2011-01-01

During coordinated eye– hand movements, saccade reaction times (SRTs) and reach reaction times (RRTs) are correlated in humans and monkeys. Reaction times (RTs) measure the degree of movement preparation and can correlate with movement speed and accuracy. However, RTs can also reflect effector nonspecific influences, such as motivation and arousal. We use a combination of behavioral psychophysics and computational modeling to identify plausible mechanisms for correlations in SRTs and RRTs. To disambiguate nonspecific mechanisms from mechanisms specific to movement coordination, we introduce a dual-task paradigm in which a reach and a saccade are cued with a stimulus onset asynchrony (SOA). We then develop several variants of integrate-to-threshold models of RT, which postulate that responses are initiated when the neural activity encoding effector-specific movement preparation reaches a threshold. The integrator models formalize hypotheses about RT correlations and make predictions for how each RT should vary with SOA. To test these hypotheses, we trained three monkeys to perform the eye– hand SOA task and analyzed their SRTs and RRTs. In all three subjects, RT correlations decreased with increasing SOA duration. Additionally, mean SRT decreased with decreasing SOA, revealing facilitation of saccades with simultaneous reaches, as predicted by the model. These results are not consistent with the predictions of the models with common modulation or common input but are compatible with the predictions of a model with mutual excitation between two effector-specific integrators. We propose that RT correlations are not simply attributable to motivation and arousal and are a signature of coordination. PMID:21325507

The impact of SOA for achieving healthcare interoperability. An empirical investigation based on a hypothetical adoption.

PubMed

Daskalakis, S; Mantas, J

2009-01-01

The evaluation of a service-oriented prototype implementation for healthcare interoperability. A prototype framework was developed, aiming to exploit the use of service-oriented architecture (SOA) concepts for achieving healthcare interoperability and to move towards a virtual patient record (VPR) paradigm. The prototype implementation was evaluated for its hypothetical adoption. The evaluation strategy was based on the initial proposition of the DeLone and McLean model of information systems (IS) success [1], as modeled by Iivari [2]. A set of SOA and VPR characteristics were empirically encapsulated within the dimensions of IS success model, combined with measures from previous research works. The data gathered was analyzed using partial least squares (PLS). The results highlighted that system quality is a partial predictor of system use but not of user satisfaction. On the contrary, information quality proved to be a significant predictor of user satisfaction and partially a strong significant predictor of system use. Moreover, system use did not prove to be a significant predictor of individual impact whereas the bi-directional relation between use and user satisfaction did not confirm. Additionally, user satisfaction was found to be a strong significant predictor of individual impact. Finally, individual impact proved to be a strong significant predictor of organizational impact. The empirical study attempted to obtain hypothetical, but still useful beliefs and perceptions regarding the SOA prototype implementation. The deduced observations can form the basis for further investigation regarding the adaptability of SOA implementations with VPR characteristics in the healthcare domain.

Influence of humidity, temperature, and radicals on the formation and thermal properties of secondary organic aerosol (SOA) from ozonolysis of β-pinene.

PubMed

Emanuelsson, Eva U; Watne, Ågot K; Lutz, Anna; Ljungström, Evert; Hallquist, Mattias

2013-10-10

The influence of water and radicals on SOAs produced by β-pinene ozonolysis was investigated at 298 and 288 K using a laminar flow reactor. A volatility tandem differential mobility analyzer (VTDMA) was used to measure the evaporation of the SOA, enabling the parametrization of its volatility properties. The parameters extracted included the temperature at which 50% of the aerosol had evaporated (T(VFR0.5)) and the slope factor (S(VFR)). An increase in S(VFR) indicates a broader distribution of vapor pressures for the aerosol constituents. Reducing the reaction temperature increased S(VFR) and decreased T(VFR0.5) under humid conditions but had less effect on T(VFR0.5) under dry conditions. In general, higher water concentrations gave lower T(VFR0.5) values, more negative S(VFR) values, and a reduction in total SOA production. The radical conditions were changed by introducing OH scavengers to generate systems with and without OH radicals and with different [HO2]/[RO2] ratios. The presence of a scavenger and lower [HO2]/[RO2] ratio reduced SOA production. Observed changes in S(VFR) values could be linked to the more complex chemistry that occurs in the absence of a scavenger and indicated that additional HO2 chemistry gives products with a wider range of vapor pressures. Updates to existing ozonolysis mechanisms with routes that describe the observed responses to water and radical conditions for monoterpenes with endocyclic and exocyclic double bonds are discussed.

Development of Sensitivity to Audiovisual Temporal Asynchrony during Mid-Childhood

PubMed Central

Kaganovich, Natalya

2015-01-01

Temporal proximity is one of the key factors determining whether events in different modalities are integrated into a unified percept. Sensitivity to audiovisual temporal asynchrony has been studied in adults in great detail. However, how such sensitivity matures during childhood is poorly understood. We examined perception of audiovisual temporal asynchrony in 7-8-year-olds, 10-11-year-olds, and adults by using a simultaneity judgment task (SJT). Additionally, we evaluated whether non-verbal intelligence, verbal ability, attention skills, or age influenced children's performance. On each trial, participants saw an explosion-shaped figure and heard a 2 kHz pure tone. These occurred at the following stimulus onset asynchronies (SOAs) - 0, 100, 200, 300, 400, and 500 ms. In half of all trials, the visual stimulus appeared first (VA condition) while in another half, the auditory stimulus appeared first (AV condition). Both groups of children were significantly more likely than adults to perceive asynchronous events as synchronous at all SOAs exceeding 100 ms, in both VA and AV conditions. Furthermore, only adults exhibited a significant shortening of RT at long SOAs compared to medium SOAs. Sensitivities to the VA and AV temporal asynchronies showed different developmental trajectories, with 10-11-year-olds outperforming 7-8-year-olds at the 300-500 ms SOAs, but only in the AV condition. Lastly, age was the only predictor of children's performance on the SJT. These results provide an important baseline against which children with developmental disorders associated with impaired audiovisual temporal function, such as autism, specific language impairment, and dyslexia may be compared. PMID:26569563

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

NASA Astrophysics Data System (ADS)

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

2007-07-01

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

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

PubMed

Ervens, Barbara; Kreidenweis, Sonia M

2007-06-01

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

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

NASA Astrophysics Data System (ADS)

Jia, Long; Xu, YongFu

2018-06-01

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

An event-related brain potential study of schizotypal personality and associative semantic processing

PubMed Central

Kiang, Michael; Prugh, Jocelyn; Kutas, Marta

2009-01-01

To examine whether schizotypal personality is associated with the degree to which concepts activate each other in semantic memory, event-related brain potentials (ERPs) were recorded during a delayed lexical decision task from healthy volunteers rated for schizotypy. Each target word was directly, indirectly, or not at all related to a prime word preceding it at a 300- or 750-ms stimulus-onset asynchrony (SOA). Overall, N400 amplitudes were largest for unrelated targets, smallest for directly related targets, and intermediate for indirectly related targets. Higher total Schizotypal Personality Questionnaire (SPQ) scores correlated with smaller N400 indirect priming effects (i.e., smaller N400 amplitude differences between unrelated and indirectly related targets) at both SOAs. In addition, schizotypal subscale scores were differentially associated with N400 effects. Higher SPQ Cognitive-Perceptual scores correlated with smaller N400 direct priming effects (smaller N400 amplitude differences between unrelated and directly related targets) at both SOAs, and with smaller N400 indirect priming effects at the shorter SOA. These correlations are consistent with the hypothesis that decreased use of meaningful context to activate related concepts in general, and/or to inhibit unrelated concepts, may play some role in the development of unusual beliefs. PMID:19818815

Semicontinuous measurements of organic carbon and acidity during the Pittsburgh air quality study: implications for acid-catalyzed organic aerosol formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

S. Takahama; C.I. Davidson; S.N. Pandis

2006-04-01

Laboratory evidence suggests that inorganic acid seed particles may increase secondary organic aerosol yields secondary organic aerosol (SOA) through heterogeneous chemistry. Additional laboratory studies, however, report that organic acidity generated in the same photochemical process by which SOA is formed may be sufficient to catalyze these heterogeneous reactions. Understanding the interaction between inorganic acidity and SOA mass is important when evaluating emission controls to meet PM2.5 regulations. Semicontinuous measurements of organic carbon (OC), elemental carbon (EC), and inorganic species from the Pittsburgh Air Quality Study were examined to determine if coupling in the variations of inorganic acidity and OC couldmore » be detected. Significant enhancements of SOA production could not be detected due to inorganic acidity in Western Pennsylvania most of the time, but its signal might have been lost in the noise. If a causal relationship between inorganic acidity and OC is assumed, reductions in OC for Western Pennsylvania that might result from drastic reductions in inorganic acidity were estimated to be 2 {+-} 4% by a regression technique, and an upper bound for this geographic area was estimated to be 5 {+-} 8% based on calculations from laboratory measurements. 48 refs., 7 figs., 3 tabs.« less

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices, including diesel particulate filters (DPFs), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOCs). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle,~Urban Dynamometer Driving Schedule, and creep + idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photooxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary PM emissions and SOA production from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after 3 h of oxidation at typical urban VOC / NOx ratios (3 : 1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the nonmethane organic gas emissions that could not be speciated using traditional one-dimensional gas chromatography. The unspeciated organics - likely comprising less volatile species such as intermediate volatility organic compounds - appear to be important SOA precursors; we estimate that the effective SOA yield (defined as the ratio of SOA mass to reacted precursor mass) was 9 ± 6% if both speciated SOA precursors and unspeciated organics are included in the analysis. SOA production from creep + idle operation was 3-4 times larger than SOA production from the same vehicle operated over the Urban Dynamometer Driving Schedule (UDDS). Fuel properties had little or no effect on primary PM emissions or SOA formation.

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

NASA Astrophysics Data System (ADS)

Matsui, H.; Koike, M.; Kondo, Y.; Fast, J. D.; Takigawa, M.

2014-09-01

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

Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

DOE PAGES

Yu, L.; Smith, J.; Laskin, A.; ...

2014-12-23

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C 6H 5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl ( 3C *) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). Amore » large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C * are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

Landscape fires dominate terrestrial natural aerosol - climate feedbacks

NASA Astrophysics Data System (ADS)

Scott, C.; Arnold, S.; Monks, S. A.; Asmi, A.; Paasonen, P.; Spracklen, D. V.

2017-12-01

The terrestrial biosphere is an important source of natural aerosol including landscape fire emissions and secondary organic aerosol (SOA) formed from biogenic volatile organic compounds (BVOCs). Atmospheric aerosol alters the Earth's climate by absorbing and scattering radiation (direct radiative effect; DRE) and by perturbing the properties of clouds (aerosol indirect effect; AIE). Natural aerosol sources are strongly controlled by, and can influence, climate; giving rise to potential natural aerosol-climate feedbacks. Earth System Models (ESMs) include a description of some of these natural aerosol-climate feedbacks, predicting substantial changes in natural aerosol over the coming century with associated radiative perturbations. Despite this, the sensitivity of natural aerosols simulated by ESMs to changes in climate or emissions has not been robustly tested against observations. Here we combine long-term observations of aerosol number and a global aerosol microphysics model to assess terrestrial natural aerosol-climate feedbacks. We find a strong positive relationship between the summertime anomaly in observed concentration of particles greater than 100 nm diameter and the anomaly in local air temperature. This relationship is reproduced by the model and driven by variability in dynamics and meteorology, as well as natural sources of aerosol. We use an offline radiative transfer model to determine radiative effects due to changes in two natural aerosol sources: landscape fire and biogenic SOA. We find that interannual variability in the simulated global natural aerosol radiative effect (RE) is negatively related to the global temperature anomaly. The magnitude of global aerosol-climate feedback (sum of DRE and AIE) is estimated to be -0.15 Wm-2 K-1 for landscape fire aerosol and -0.06 Wm-2 K-1 for biogenic SOA. These feedbacks are comparable in magnitude, but opposite in sign to the snow albedo feedback, highlighting the need for natural aerosol feedbacks to be included in climate simulations.

Primary Emission and the Potential of Secondary Aerosol Formation from Chinese Gasoline Engine Exhaust

NASA Astrophysics Data System (ADS)

Hu, Min; Peng, Jianfei; Qin, Yanhong; Du, Zhuofei; Li, Mengjin; Zheng, Rong; Zheng, Jing; Shang, Dongjie; Lu, Sihua; Wu, Yusheng; Zeng, Limin; Guo, Song; Shao, Min; Wang, Yinhui; Shuai, Shijin

2017-04-01

Along with the urbanization and economic growth, vehicle population in China reached 269 million, ranked the second in the world in 2015. Gasoline vehicle is identified to be the main source for urban PM2.5 in China, accounting for 15%-31%. In this study the impact of fuel components on PM2.5 and volatile organic compounds (VOCs) emissions from a gasoline port fuel injection (PFI) engine and a gasoline direct injection (GDI) engine are discussed. Results show that, higher proportion of aromatics, alkenes or sulfur in gasoline fuel will lead to higher PM emissions. The PM from the PFI engine mainly consists of OC and a small amount of EC and inorganic ions, while the PM discharge from the GDI engine mainly consists of EC, OM and a small amount of inorganic ions. Since the GDI engines can reduce fuel consumption and CO2 emissions, and it would become more and more popular in the near future. The characteristics of POM component, emission factors and source profile were investigated from GDI engine, particularly focused on the effect of engine speed, load and the catalyst, which will be very much helpful for source identification as source indicators. Chamber experiments were conducted to quantify the potential of secondary aerosol formation from exhaust of a PFI gasoline engine and China V gasoline fuel. During 4-5 h simulation, equivalent to10 days of atmospheric photo-oxidation in Beijing, the extreme SOA production was 426 ± 85 mg/kg fuel, with high precursors and OH exposure. 14% of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatility organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reduction of emissions of aerosol precursor gases from vehicles is essential to mediate pollution in China.

Concentrations, sources and human health risk of inhalation exposure to air toxics in Edmonton, Canada.

PubMed

Bari, Md Aynul; Kindzierski, Warren B

2017-04-01

With concern about levels of air pollutants in recent years in the Capital Region of Alberta, an investigation of ambient concentrations, sources and potential human health risk of hazardous air pollutants (HAPs) or air toxics was undertaken in the City of Edmonton over a 5-year period (2009-2013). Mean concentrations of individual HAPs in ambient air including volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs) and trace metals ranged from 0.04 to 1.73 μg/m 3 , 0.01-0.54 ng/m 3 , and 0.05-3.58 ng/m 3 , respectively. Concentrations of benzene, naphthalene, benzo(a)pyrene (BaP), arsenic, manganese and nickel were far below respective annual Alberta Ambient Air Quality Objectives. Carcinogenic and non-carcinogenic risk of air toxics were also compared with risk levels recommended by regulatory agencies. Positive matrix factorization identified six air toxics sources with traffic as the dominant contributor to total HAPs (4.33 μg/m 3 , 42%), followed by background/secondary organic aerosol (SOA) (1.92 μg/m 3 , 25%), fossil fuel combustion (0.92 μg/m 3 , 11%). On high particulate air pollution event days, local traffic was identified as the major contributor to total HAPs compared to background/SOA and fossil fuel combustion. Carcinogenic risk values of traffic, background/SOA and metals industry emissions were above the USEPA acceptable level (1 × 10 -6 ), but below a tolerable risk (1 × 10 -4 ) and Alberta benchmark (1 × 10 -5 ). These findings offer useful preliminary information about current ambient air toxics levels, dominant sources and their potential risk to public health; and this information can support policy makers in the development of appropriate control strategies if required. Copyright © 2017 Elsevier Ltd. All rights reserved.

Observational Comparison of Hydroxynitrates from the Southeast United States and the Korean-US Air Quality (KORUS-AQ) Mission

NASA Astrophysics Data System (ADS)

Kim, M. J.; Teng, A.; Crounse, J.; Wennberg, P. O.

2016-12-01

Hydroxynitrates, a multifunctional product of alkene oxidation, can make significant impacts on regional ozone, SOA, and NOX budgets. A product of VOC oxidation and NOx, hydroxynitrates can be key markers of interactions between biogenic and anthropogenic sources, as well as aging of petrochemical emissions. This work compares observations from recent field campaigns across the globe including the Southeast United States (SEAC4RS, SOAS) as well as the recently concluded Korean US Air Quality mission (KORUS-AQ). The KORUS-AQ airborne campaign examined air quality around the Seoul Metropolitan Area (population 25 million) and immediate forested regions, as well as petrochemical processing facilities and shipping activities throughout the Korean peninsula.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seinfeld, John H.

This project addressed the following research need in the Atmospheric System Research (ASR) Science and Program Plan: "Measurements downwind of urban sources of aerosol particles and precursor gases have shown that the mass concentration of secondary organic aerosol (SOA) can be several-fold greater than can be explained on the basis of current model calculations using observed precursor concentrations. ASR will continue conducting laboratory experiments on both gas-phase and aqueous-phase SOA formation to characterize the particle formation and the organic gases that react to form new organic aerosol material on aerosol seeds. ASR will use these experiments to guide the developmentmore » of comprehensive chemical mechanisms... to guide the development of parameterizations that are simple enough to be applied to aerosol life cycle models."« less

Sources of particulate matter in China: Insights from source apportionment studies published in 1987-2017.

PubMed

Zhu, Yanhong; Huang, Lin; Li, Jingyi; Ying, Qi; Zhang, Hongliang; Liu, Xingang; Liao, Hong; Li, Nan; Liu, Zhenxin; Mao, Yuhao; Fang, Hao; Hu, Jianlin

2018-06-01

Particulate matter (PM) in the atmosphere has adverse effects on human health, ecosystems, and visibility. It also plays an important role in meteorology and climate change. A good understanding of its sources is essential for effective emission controls to reduce PM and to protect public health. In this study, a total of 239 PM source apportionment studies in China published during 1987-2017 were reviewed. The documents studied include peer-reviewed papers in international and Chinese journals, as well as degree dissertations. The methods applied in these studies were summarized and the main sources in various regions of China were identified. The trends of source contributions at two major cities with abundant studies over long-time periods were analyzed. The most frequently used methods for PM source apportionment in China are receptor models, including chemical mass balance (CMB), positive matrix factorization (PMF), and principle component analysis (PCA). Dust, fossil fuel combustion, transportation, biomass burning, industrial emission, secondary inorganic aerosol (SIA) and secondary organic aerosol (SOA) are the main source categories of fine PM identified in China. Even though the sources of PM vary among seven different geographical areas of China, SIA, industrial, and dust emissions are generally found to be the top three source categories in 2007-2016. A number of studies investigated the sources of SIA and SOA in China using air quality models and indicated that fossil fuel combustion and industrial emissions were the most important sources of SIA (total contributing 63.5%-88.1% of SO 4 2- , and 47.3%-70% NO 3 - ), and agriculture emissions were the dominant source of NH 4 + (contributing 53.9%-90%). Biogenic emissions were the most important source of SOA in China in summer, while residential and industrial emissions were important in winter. Long-term changes of PM sources at two megacities of Beijing and Nanjing indicated that the contributions of fossil fuel and industrial sources have been declining after stricter emission controls in recent years. In general, dust and industrial contributions decreased and transportation contributions increased after 2000. PM 2.5 emissions are predicted to decline in most regions during 2005-2030, even though the energy consumptions except biomass burning are predicted to continue to increase. Industrial, residential, and biomass burning sources will become more important in the future in the businuess-as-usual senarios. This review provides valuable information about main sources of PM and their trends in China. A few recommendations are suggested to further improve our understanding the sources and to develop effective PM control strategies in various regions of China. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

PubMed Central

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.

PubMed

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.

Ultrafine particles generated from coloring with scented markers in the presence of ozone.

PubMed

Fung, C-C D; Shu, S; Zhu, Y

2014-10-01

High concentrations of ultrafine particles (UFPs) have been previously reported during school art activities. This is possibly due to secondary organic aerosols (SOAs) formed from reactions between ozone and volatile organic compounds emitted from art products. Four brands of markers, three scented and one unscented, were tested inside a stainless steel chamber at eight different ozone concentrations between 0 and 300 ppb. Out of the 32 tested markers, only the lemon- and orange-scented markers from one brand reacted with ozone to form UFPs. Limonene, pinene, and several other terpenes were identified as ingredients of ink in SOA-forming markers. Coloring with one lemon-scented marker for 1 min without ozone generated on average approximately 26 ± 4 ppb of limonene inside the chamber. At 150 ppb ozone, using one lemon marker for 1 min formed on average 7.7 × 10(10) particles. The particle size distribution indicated an initial mode of 15 nm which grew to 40 nm. At 50 ppb ozone and below, no significant SOA formation occurred. The number of particles formed is moderately correlated with the mass of ink used (R(2)  = 0.68). Based on these data, scented markers are not likely a strong source of SOA under normal indoor ozone levels. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

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

NASA Astrophysics Data System (ADS)

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

2009-12-01

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

Organic aerosol evaporation and formation in biomass-burning plumes: The competition between dilution and chemistry

NASA Astrophysics Data System (ADS)

Pierce, J. R.; Kreidenweis, S. M.; Bian, Q.; Jathar, S.; Kodros, J.; Barsanti, K.; Hatch, L. E.; May, A.

2017-12-01

Secondary organic aerosol (SOA) has been shown to form in biomass-burning emissions in laboratory and field studies. However, there is significant variability among studies in mass enhancement, which could be due to differences in fuels, fire conditions, dilution, and/or limitations of laboratory experiments and observations. This study focuses on understanding processes affecting biomass-burning SOA formation in ambient plumes. The plume dilution rate impacts the organic partitioning between the gas and particle phases, which may impact the potential for SOA to form as well as the rate of SOA formation. We use an aerosol microphysics model that includes representations of volatility and oxidation chemistry to estimate SOA formation in the smoke emitted into the atmosphere. We add Gaussian dispersion to our aerosol microphysical model to estimate how SOA formation may vary under different ambient-plume conditions (e.g. fire size, emission mass flux, atmospheric stability). Smoke from small fires, such as typical prescribed burns, dilutes rapidly, which drives evaporation of organic vapor from the particle phase, leading to more effective SOA formation. Emissions from large fires, such as intense wildfires, dilute slowly, suppressing OA evaporation and subsequent SOA formation in the near field. We also demonstrate that different approaches to the calculation of OA enhancement in ambient plumes can lead to different conclusions regarding SOA formation. Normalized OA mass enhancement ratios of around 1 calculated using an inert tracer, such as black carbon or CO, have traditionally been interpreted as exhibiting little or no SOA formation; however, we show that SOA formation may have greatly contributed to the mass in these plumes.

Chemical and Physical Properties of Individual Aerosol Particles Characterized in Sacramento, CA during CARES Field Campaign

NASA Astrophysics Data System (ADS)

Zelenyuk, A.; Beranek, J.; Vaden, T.; Imre, D. G.; Zaveri, R. A.

2011-12-01

We present results of measurements conducted by our Single Particle Mass Spectrometer, SPLAT II, in Sacramento, CA over the month of June 2010. SPLAT II measured the size of 195 million particles, and compositions of 10 million particles. In addition to size and composition, SPLAT II simultaneously measured size, density and composition of 121,000 individual particles. These measurements were conducted 2 - 3 times per day, depending on conditions. The data show that throughout the day particles were relatively small (<200 nm), and the vast majority were composed of oxygenated organics mixed with various amounts of sulfate. In addition, we characterized fresh and processed soot, biomass burning aerosol, organic amines, fresh and processed sea salt, and few dust particles. The data show a reproducible diurnal pattern in aerosol size distributions, number concentrations, and compositions. Early in the day, number concentrations were low, particles were very small, and the size distributions peaked at ~70 nm. At this time of the day, 80 nm particles had a density of 1.3 g cm-3; while the density of 200 nm particles was 1.6 g cm-3, consistent with our mass spectra showing that smaller particles were composed of organics mixed with ~10% sulfates, while larger particles were composed mostly of sulfate mixed with a small amount of organics. Later in the day, secondary organic aerosols (SOA) formation led to a number of nucleation events that significantly increased the number concentrations of very small particles. By mid-afternoon, as more SOA formed and condensed, particles increased in size the number concentrations of particles larger than 70 nm increased and the densities of particles 80 to 200 nm particles was ~1.3 g cm-3. The vast majority of these particles were composed of oxygenated organics mixed with a ~10% sulfate. In other words they were SOA particles mixed with a small amount of sulfate. The mass spectra of these particles shows that there were two types of SOA particles, which we labeled Type 43 and Type 44, to indicate which of the two mass-spectral peaks caries higher intensity. We were also able to conduct room temperature evaporation studies of these particles on four separate occasions and found the evaporation kinetics to be reproducible. The data show that after 4 hours of evaporation, in an organic vapor free environment, particles lose only ~20% of their volume. Moreover, evaporation starts with a relatively fast phase and proceeds with a much slower stage about 2 hours after evaporation starts. It is important to keep in mind that these slow evaporating SOA particles were relatively fresh. Based on these studies and similar studies conducted in our laboratory we conclude that these atmospheric SOA particles are quasi-solids. Moreover the data indicate that to first order it is reasonable to approximate SOA particles as being non-volatile. Interestingly, we find that in both SOA particle types a large fraction of the intensity in peaks 44 and 73 was related to a small amount of surface compounds that evaporated within a few minutes.

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

EPA Science Inventory

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

More insight into the interplay of response selection and visual attention in dual-tasks: masked visual search and response selection are performed in parallel.

PubMed

Reimer, Christina B; Schubert, Torsten

2017-09-15

Both response selection and visual attention are limited in capacity. According to the central bottleneck model, the response selection processes of two tasks in a dual-task situation are performed sequentially. In conjunction search, visual attention is required to select the items and to bind their features (e.g., color and form), which results in a serial search process. Search time increases as items are added to the search display (i.e., set size effect). When the search display is masked, visual attention deployment is restricted to a brief period of time and target detection decreases as a function of set size. Here, we investigated whether response selection and visual attention (i.e., feature binding) rely on a common or on distinct capacity limitations. In four dual-task experiments, participants completed an auditory Task 1 and a conjunction search Task 2 that were presented with an experimentally modulated temporal interval between them (Stimulus Onset Asynchrony, SOA). In Experiment 1, Task 1 was a two-choice discrimination task and the conjunction search display was not masked. In Experiment 2, the response selection difficulty in Task 1 was increased to a four-choice discrimination and the search task was the same as in Experiment 1. We applied the locus-of-slack method in both experiments to analyze conjunction search time, that is, we compared the set size effects across SOAs. Similar set size effects across SOAs (i.e., additive effects of SOA and set size) would indicate sequential processing of response selection and visual attention. However, a significantly smaller set size effect at short SOA compared to long SOA (i.e., underadditive interaction of SOA and set size) would indicate parallel processing of response selection and visual attention. In both experiments, we found underadditive interactions of SOA and set size. In Experiments 3 and 4, the conjunction search display in Task 2 was masked. Task 1 was the same as in Experiments 1 and 2, respectively. In both experiments, the d' analysis revealed that response selection did not affect target detection. Overall, Experiments 1-4 indicated that neither the response selection difficulty in the auditory Task 1 (i.e., two-choice vs. four-choice) nor the type of presentation of the search display in Task 2 (i.e., not masked vs. masked) impaired parallel processing of response selection and conjunction search. We concluded that in general, response selection and visual attention (i.e., feature binding) rely on distinct capacity limitations.

Phoenix: SOA based information management services

NASA Astrophysics Data System (ADS)

Grant, Rob; Combs, Vaughn; Hanna, Jim; Lipa, Brian; Reilly, Jim

2009-05-01

The Air Force Research Laboratory (AFRL) has developed a reference set of Information Management (IM) Services that will provide an essential piece of the envisioned final Net-Centric IM solution for the Department of Defense (DoD). These IM Services will provide mission critical functionality to enable seamless interoperability between existing and future DoD systems and services while maintaining a highly available IM capability across the wide spectrum of differing scalability and performance requirements. AFRL designed this set of IM Services for integration with other DoD and commercial SOA environments. The services developed will provide capabilities for information submission, information brokering and discovery, repository, query, type management, dissemination, session management, authorization, service brokering and event notification. In addition, the IM services support common information models that facilitate the management and dissemination of information consistent with client needs and established policy. The services support flexible and extensible definitions of session, service, and channel contexts that enable the application of Quality of Service (QoS) and security policies at many levels within the SOA.

Associative and semantic priming effects occur at very short stimulus-onset asynchronies in lexical decision and naming.

PubMed

Perea, M; Gotor, A

1997-02-01

Prior research has found significant associative/semantic priming effects at very short stimulus-onset asynchronies (SOAs) in experimental tasks such as lexical decision, but not in naming tasks (however, see Lukatela and Turvey, 1994). In this paper, the time course of associative priming effects was analyzed a several very short SOAs (33, 50, and 67 ms), using the masked priming paradigm (Forster and Davis, 1984), both in lexical decision (Experiment 1) and naming (Experiment 2). The results show small--but significant--associative priming effects in both tasks. Additionally, using the masked priming procedure at the 67 ms SOA. Experiments 3 and 4, shows facilitatory priming effects for both associatively and semantically (unassociated) related pairs in lexical decision and naming tasks. That is, automatic priming can be semantic. Taken together our data appear to support interactive models of word recognition in which semantic activation may influence the early stages of word processing.

Pollution data analysis and characteristics of volatile organic compounds in the environment

NASA Astrophysics Data System (ADS)

Wang, Qi; Wang, Chěn; Hou, Lujian; Lv, Bo; WANG, Chén

2018-06-01

Volatile organic compounds (VOCs) have a wide range of sources and have a significant impact on the ecological environment and human health, which have attracted wide attention of many researchers. In this paper, the pollution characteristics of VOCs, the role of VOCs in atmospheric chemistry including OH reaction reactivity (LOH), Ozone Formation Potential (OFP) and SOA generation potential (SOAP), VOCs source apportionment were discussed and reviewed.

Simulating Aqueous-Phase Isoprene-Epoxydiol (IEPOX) Secondary Organic Aerosol Production During the 2013 Southern Oxidant and Aerosol Study (SOAS)

EPA Science Inventory

The lack of statistically robust relationships between IEPOX (isoprene epoxydiol)-derived SOA (IEPOX SOA) and aerosol liquid water and pH observed during the 2013 Southern Oxidant and Aerosol Study (SOAS) emphasizes the importance of modeling the whole system to understand the co...

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Lu; Kollman, Matthew S.; Song, Chen

2014-01-28

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

Secondary Organic Aerosol Formation from 2-Methyl-3-Buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Haofei; Zhang, Zhenfa; Cui, Tianqu

2014-04-08

Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to isoprene, MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide) was synthesized and tentatively proposed here to explain this enhancement. In the present study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosols. Major SOA constituents, 2,3-dihydroxyisopentanol (DHIP) and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and inmore » ambient fine aerosols collected from the BEACHON-RoMBAS field campaign during summer 2011, where MBO emissions are substantial. Our results support epoxides as potential products of MBO photooxidation leading to formation of atmospheric SOA and suggest that reactive uptake of epoxides may generally explain acid enhancement of SOA observed from other biogenic hydrocarbons.« less

Scalable and Resilient Middleware to Handle Information Exchange during Environment Crisis

NASA Astrophysics Data System (ADS)

Tao, R.; Poslad, S.; Moßgraber, J.; Middleton, S.; Hammitzsch, M.

2012-04-01

The EU FP7 TRIDEC project focuses on enabling real-time, intelligent, information management of collaborative, complex, critical decision processes for earth management. A key challenge is to promote a communication infrastructure to facilitate interoperable environment information services during environment events and crises such as tsunamis and drilling, during which increasing volumes and dimensionality of disparate information sources, including sensor-based and human-based ones, can result, and need to be managed. Such a system needs to support: scalable, distributed messaging; asynchronous messaging; open messaging to handling changing clients such as new and retired automated system and human information sources becoming online or offline; flexible data filtering, and heterogeneous access networks (e.g., GSM, WLAN and LAN). In addition, the system needs to be resilient to handle the ICT system failures, e.g. failure, degradation and overloads, during environment events. There are several system middleware choices for TRIDEC based upon a Service-oriented-architecture (SOA), Event-driven-Architecture (EDA), Cloud Computing, and Enterprise Service Bus (ESB). In an SOA, everything is a service (e.g. data access, processing and exchange); clients can request on demand or subscribe to services registered by providers; more often interaction is synchronous. In an EDA system, events that represent significant changes in state can be processed simply, or as streams or more complexly. Cloud computing is a virtualization, interoperable and elastic resource allocation model. An ESB, a fundamental component for enterprise messaging, supports synchronous and asynchronous message exchange models and has inbuilt resilience against ICT failure. Our middleware proposal is an ESB based hybrid architecture model: an SOA extension supports more synchronous workflows; EDA assists the ESB to handle more complex event processing; Cloud computing can be used to increase and decrease the ESB resources on demand. To reify this hybrid ESB centric architecture, we will adopt two complementary approaches: an open source one for scalability and resilience improvement while a commercial one can be used for ultra-speed messaging, whilst we can bridge between these two to support interoperability. In TRIDEC, to manage such a hybrid messaging system, overlay and underlay management techniques will be adopted. The managers (both global and local) will collect, store and update status information (e.g. CPU utilization, free space, number of clients) and balance the usage, throughput, and delays to improve resilience and scalability. The expected resilience improvement includes dynamic failover, self-healing, pre-emptive load balancing, and bottleneck prediction while the expected improvement for scalability includes capacity estimation, Http Bridge, and automatic configuration and reconfiguration (e.g. add or delete clients and servers).

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

PubMed

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

2018-02-06

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

Gas-phase kinetics modifies the CCN activity of a biogenic SOA.

PubMed

Vizenor, A E; Asa-Awuku, A A

2018-02-28

Our current knowledge of cloud condensation nuclei (CCN) activity and the hygroscopicity of secondary organic aerosol (SOA) depends on the particle size and composition, explicitly, the thermodynamic properties of the aerosol solute and subsequent interactions with water. Here, we examine the CCN activation of 3 SOA systems (2 biogenic single precursor and 1 mixed precursor SOA system) in relation to gas-phase decay. Specifically, the relationship between time, gas-phase precursor decay and CCN activity of 100 nm SOA is studied. The studied SOA systems exhibit a time-dependent growth of CCN activity at an instrument supersaturation of ∼0.2%. As such, we define a critical activation time, t 50 , above which a 100 nm SOA particle will activate. The critical activation time for isoprene, longifolene and a mixture of the two precursor SOA is 2.01 hours, 2.53 hours and 3.17 hours, respectively. The activation times are then predicted with gas-phase kinetic data inferred from measurements of precursor decay. The gas-phase prediction of t 50 agrees well with CCN measured t 50 (within 0.05 hours of the actual critical times) and suggests that the gas-to-particle phase partitioning may be more significant for SOA CCN prediction than previously thought.

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

PubMed

Chang, Wayne L; Griffin, Robert J; Dabdub, Donald

2010-04-13

Secondary organic aerosol (SOA) comprises a significant portion of atmospheric particular matter. The impact of particular matter on both human health and global climate has long been recognized. Despite its importance, there are still many unanswered questions regarding the formation and evolution of SOA in the atmosphere. This study uses a modeling approach to understand the preferred partitioning behavior of SOA species into aqueous or organic condensed phases. More specifically, this work uses statistical analyses of approximately 24,000 data values for each variable from a state of the art 3D airshed model. Spatial and temporal distributions of fractions of SOA residing in the aqueous phase (fAQ) in the South Coast Air Basin of California are presented. Typical values of fAQ within the basin near the surface range from 5 to 80%. Results show that the likelihood of large fAQ values is inversely proportional to the total SOA loading. Analysis of various meteorological parameters indicates that large fAQ values are predicted because modeled aqueous-phase SOA formation is less sensitive than that of organic-phase SOA to atmospheric conditions that are not conducive to SOA formation. There is a diurnal variation of fAQ near the surface: It tends to be larger during daytime hours than during nighttime hours. Results also indicate that the largest fAQ values are simulated in layers above ground level at night. In summary, one must consider SOA in both organic and aqueous phases for proper regional and global SOA budget estimation.

Formation of brown carbon via reactions of ammonia with secondary organic aerosols from biogenic and anthropogenic precursors

NASA Astrophysics Data System (ADS)

Updyke, Katelyn M.; Nguyen, Tran B.; Nizkorodov, Sergey A.

2012-12-01

Filter samples of secondary organic aerosols (SOA) generated from the ozone (O3)- and hydroxyl radical (OH)-initiated oxidation of various biogenic (isoprene, α-pinene, limonene, α-cedrene, α-humulene, farnesene, pine leaf essential oils, cedar leaf essential oils) and anthropogenic (tetradecane, 1,3,5-trimethylbenzene, naphthalene) precursors were exposed to humid air containing approximately 100 ppb of gaseous ammonia (NH3). Reactions of SOA compounds with NH3 resulted in production of light-absorbing "brown carbon" compounds, with the extent of browning ranging from no observable change (isoprene SOA) to visible change in color (limonene SOA). The aqueous phase reactions with dissolved ammonium (NH4+) salts, such as ammonium sulfate, were equally efficient in producing brown carbon. Wavelength-dependent mass absorption coefficients (MAC) of the aged SOA were quantified by extracting known amounts of SOA material in methanol and recording its UV/Vis absorption spectra. For a given precursor, the OH-generated SOA had systematically lower MAC compared to the O3-generated SOA. The highest MAC values, for brown carbon from SOA resulting from O3 oxidation of limonene and sesquiterpenes, were comparable to MAC values for biomass burning particles but considerably smaller than MAC values for black carbon aerosols. The NH3/NH4+ + SOA brown carbon aerosol may contribute to aerosol optical density in regions with elevated concentrations of NH3 or ammonium sulfate and high photochemical activity.

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

NASA Astrophysics Data System (ADS)

Hinks, Mallory L.; Montoya-Aguilera, Julia; Ellison, Lucas; Lin, Peng; Laskin, Alexander; Laskin, Julia; Shiraiwa, Manabu; Dabdub, Donald; Nizkorodov, Sergey A.

2018-02-01

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

The effect of gas-phase polycyclic aromatic hydrocarbons on the formation and properties of biogenic secondary organic aerosol particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zelenyuk, Alla; Imre, Dan G.; Wilson, Jacqueline

2017-01-01

When secondary organic aerosol (SOA) particles are formed by ozonolysis in the presence of gas-phase polycyclic aromatic hydrocarbons (PAHs), their formation and properties are significantly different from SOA particles formed without PAHs. For all SOA precursors and all PAHs, discussed in this study, the presence of the gas-phase PAHs during SOA formation significantly affects particle mass loadings, composition, growth, evaporation kinetics, and viscosity. SOA particles formed in the presence of PAHs have, as part of their compositions, trapped unreacted PAHs and products of heterogeneous reactions between PAHs and ozone. Compared to ‘pure’ SOA particles, these particles exhibit slower evaporation kinetics,more » have higher fractions of non-volatile components, like oligomers, and higher viscosities, assuring their longer atmospheric lifetimes. In turn, the increased viscosity and decreased volatility provide a shield that protects PAHs from chemical degradation and evaporation, allowing for the long-range transport of these toxic pollutants. The magnitude of the effect of PAHs on SOA formation is surprisingly large. The presence of PAHs during SOA formation increases mass loadings by factors of two to five, and particle number concentrations, in some cases, by more than a factor of 100. Increases in SOA mass, particle number concentrations, and lifetime have important implications to many atmospheric processes related to climate, weather, visibility, and human health, all of which relate to the interactions between biogenic SOA and anthropogenic PAHs. The synergistic relationship between SOA and PAHs presented here are clearly complex and call for future research to elucidate further the underlying processes and their exact atmospheric implications.« less

Global distribution of secondary organic aerosol particle phase state

NASA Astrophysics Data System (ADS)

Shiraiwa, M.; Li, Y., Sr.; Tsimpidi, A.; Karydis, V.; Berkemeier, T.; Pandis, S. N.; Lelieveld, J.; Koop, T.; Poeschl, U.

2016-12-01

Secondary organic aerosols (SOA) account for a large fraction of submicron particles in the atmosphere and play a key role in aerosol effects on climate, air quality and public health. The formation and aging of SOA proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of SOA evolution in atmospheric aerosol models. SOA particles can adopt liquid, semi-solid and amorphous solid (glassy) phase states depending on chemical composition, relative humidity and temperature. The particle phase state is crucial for various atmospheric gas-particle interactions, including SOA formation, heterogeneous and multiphase reactions and ice nucleation. We found that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. Based on the concept of molecular corridors, we develop a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, which is a key property for determination of particle phase state. We use the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the atmospheric SOA phase state. For the planetary boundary layer, global simulations indicate that SOA is mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes, and solid over dry lands. We find that in the middle and upper troposphere (>500 hPa) SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants, and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded within SOA.

Aqueous-Phase Mechanism for Secondary Organic Aerosol Formation from Isoprene: Application to the Southeast United States and Co-Benefit of SO2 Emission Controls

NASA Technical Reports Server (NTRS)

Marais, E. A.; Jacob, D. J.; Jimenez, J. L.; Campuzano-Jost, P.; Day, D. A.; Hu, W.; Krechmer, J.; Zhu, L.; Kim, P. S.; Miller, C. C.;

The Staff Observation Aggression Scale - Revised (SOAS-R) - adjustment and validation for emergency primary health care.

PubMed

Morken, Tone; Baste, Valborg; Johnsen, Grethe E; Rypdal, Knut; Palmstierna, Tom; Johansen, Ingrid Hjulstad

2018-05-08

Many emergency primary health care workers experience aggressive behaviour from patients or visitors. Simple incident-reporting procedures exist for inpatient, psychiatric care, but a similar and simple incident-report for other health care settings is lacking. The aim was to adjust a pre-existing form for reporting aggressive incidents in a psychiatric inpatient setting to the emergency primary health care settings. We also wanted to assess the validity of the severity scores in emergency primary health care. The Staff Observation Scale - Revised (SOAS-R) was adjusted to create a pilot version of the Staff Observation Scale - Revised Emergency (SOAS-RE). A Visual Analogue Scale (VAS) was added to the form to judge the severity of the incident. Data for validation of the pilot version of SOAS-RE were collected from ten casualty clinics in Norway during 12 months. Variance analysis was used to test gender and age differences. Linear regression analysis was performed to evaluate the relative impact that each of the five SOAS-RE columns had on the VAS score. The association between SOAS-RE severity score and VAS severity score was calculated by the Pearson correlation coefficient. The SOAS-R was adjusted to emergency primary health care, refined and called The Staff Observation Aggression Scale - Revised Emergency (SOAS-RE). A total of 350 SOAS-RE forms were collected from the casualty clinics, but due to missing data, 291 forms were included in the analysis. SOAS-RE scores ranged from 1 to 22. The mean total severity score of SOAS-RE was 10.0 (standard deviation (SD) =4.1) and the mean VAS score was 45.4 (SD = 26.7). We found a significant correlation of 0.45 between the SOAS-RE total severity scores and the VAS severity ratings. The linear regression analysis showed that individually each of the categories, which described the incident, had a low impact on the VAS score. The SOAS-RE seems to be a useful instrument for research, incident-recording and management of incidents in emergency primary care. The moderate correlation between SOAS-RE severity score and the VAS severity score shows that application of both the severity ratings is valuable to follow-up of workers affected by workplace violence.

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

NASA Astrophysics Data System (ADS)

Li, Y. P.; Elbern, H.; Lu, K. D.; Friese, E.; Kiendler-Scharr, A.; Mentel, Th. F.; Wang, X. S.; Wahner, A.; Zhang, Y. H.

2013-03-01

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, 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. 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 SOA concentrations by updated SORGAM were attributed to the mentioned three modifications. Embedding the temperature dependence functions of the SOA yields, including the new pathways from isoprene photo oxidations, and switching on the SOA formation from NO3 initiated biogenic VOCs oxidations contributed to this enhancement by 10%, 22% and 47%, respectively. However, the EURAD-IM model with updated SORGAM still clearly underestimated the afternoon SOA observations up to a factor of two. More work such as to improve the simulated OH concentrations under high VOCs and low NOx concentrations, further including the SOA formation from semi-volatile organic compounds, the correct aging process of aerosols, oligomerization process and the influence on the biogenic SOA by the anthropogenic SOA, are still required to fill the gap.

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

NASA Astrophysics Data System (ADS)

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

2013-09-01

Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices including diesel particulate filters (DPF), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOC). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle, Urban Dynamometer Driving Schedule, and creep+idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photo-oxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary and secondary fine particulate matter from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after three hours of oxidation at typical urban VOC : NOx ratios (3:1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the non-methane organic gas emissions that could not be speciated using traditional one-dimensional gas-chromatography. The unspeciated organics - likely comprising less volatile species, such as intermediate volatility organic compounds - appear to be important SOA precursors; we estimate that the effective SOA yield (defined as the ratio of SOA mass to reacted precursor mass) was 9 ± 6% if both speciated SOA precursors and unspeciated organics are included in the analysis. SOA production from creep+idle operation was 3-4 times larger than SOA production from the same vehicle operated over the Urban Dynamometer Driving Schedule (UDDS). Fuel properties had little or no effect on primary PM emissions or SOA formation.

High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romonosky, Dian E.; Laskin, Alexander; Laskin, Julia

2015-03-19

A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate amore » remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NOx photooxidation of 1,3,5-trimethylbenzene and guaiacol were relatively resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of monoterpenes changed more significantly as a result of the photolysis. The results indicate that aqueous photolysis of dissolved SOA compounds in cloud/fog water can occur in a number of SOA, and on atmospherically relevant time scales. However, the extent of change depends on the specific type of SOA.« less

Monoterpene SOA - Contribution of first-generation oxidation products to formation and chemical composition

NASA Astrophysics Data System (ADS)

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

2016-04-01

Investigation of the consecutive reactions of first-generation terpene oxidation products provides insight into the formation of secondary organic aerosol (SOA). To this end, OH radical reactions with α-pinene, β-pinene, and limonene were examined along with the OH-oxidation of nopinone as a β-pinene oxidation product and pinonaldehyde and myrtenal as α-pinene oxidation products. The SOA yield of β-pinene (0.50) was much higher than that of α-pinene (0.35) and the limonene/OH system (0.30). This is opposite to the ozonolysis SOA yields described in the literature. The growth curve of SOA from β-pinene shows the contribution of secondary reactions, such as further reaction of nopinone. This contribution (17%) and the high SOA yield of nopinone (0.24) might lead to the high SOA formation potential observed for β-pinene. The majority of the C9 oxidation products observed from β-pinene can be attributed to the consecutive reaction of nopinone, whereas in the case of pinonaldehyde, only a few α-pinene oxidation products were identified. Nopinone contributes significantly to the formation of pinic acid (51%), homoterpenylic acid (74%), and 3-methyl-1,2,3-butane-tricarboxylic acid (MBTCA, 88%) during β-pinene oxidation. The oxidation of pinonaldehyde was expected to produce important SOA markers, but only negligible amounts were identified. This indicates that their formation by oxidation of α-pinene must proceed via different pathways from the further oxidation of pinonaldehyde. Only pinonic acid and MBTCA were found in considerable amounts and were formed in α-pinene oxidation with 57% yield, while that for the pinonaldehyde/OH reaction was 33%. The lack of important SOA marker compounds might cause the low SOA yield (0.07) observed for pinonaldehyde. Based on the low SOA yield, pinonaldehyde contributes only 4.5% to α-pinene SOA. Myrtenal was identified among the gas-phase products of α-pinene oxidation. A majority of α-pinene SOA marker compounds was indeed formed by myrtenal oxidation, especially terebic acid (84%), pinic acid (76%), and diaterpenylic acid acetate (DTAA; 40%). In general, the contribution of myrtenal to α-pinene SOA is estimated to be as high as 23%. Among the detected compounds, homoterpenylic acid was positively identified as a new SOA marker compound, which was formed from β-pinene/OH and nopinone/OH but not from α-pinene/OH. A new reaction pathway yielding MBTCA was also identified in the β-pinene/OH system formed by the oxidation of nopinone, while in the case of α-pinene, the oxidation of pinonaldehyde yielded MBTCA.

Quantum dot SOA input power dynamic range improvement for differential-phase encoded signals.

PubMed

Vallaitis, T; Bonk, R; Guetlein, J; Hillerkuss, D; Li, J; Brenot, R; Lelarge, F; Duan, G H; Freude, W; Leuthold, J

2010-03-15

Experimentally we find a 10 dB input power dynamic range advantage for amplification of phase encoded signals with quantum dot SOA as compared to low-confinement bulk SOA. An analysis of amplitude and phase effects shows that this improvement can be attributed to the lower alpha-factor found in QD SOA.

The Southeast Atmosphere Studies (SAS): coordinated investigation and discovery to answer critical questions about fundamental atmospheric processes

EPA Science Inventory

The Southeast Atmosphere Studies (SAS), encompassing the Southern Oxidant and Aerosol Study (SOAS), the Southeast Nexus of Air Quality and Climate (SENEX) study, the Nitrogen, Oxidants, Mercury and Aerosols: Distributions, Sources and Sinks (NOMADSS) study deployed in the field f...

Organic aerosol formation in citronella candle plumes.

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

NASA Astrophysics Data System (ADS)

Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

2012-08-01

The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

NASA Astrophysics Data System (ADS)

Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

2012-06-01

The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

Characterization of isoprene-derived secondary organic aerosols at a rural site in North China Plain with implications for anthropogenic pollution effects.

PubMed

Li, Jianjun; Wang, Gehui; Wu, Can; Cao, Cong; Ren, Yanqin; Wang, Jiayuan; Li, Jin; Cao, Junji; Zeng, Limin; Zhu, Tong

2018-01-11

Isoprene is the most abundant non-methane volatile organic compound (VOC) and the largest contributor to secondary organic aerosol (SOA) burden on a global scale. In order to examine the influence of high concentrations of anthropogenic pollutants on isoprene-derived SOA (SOA i ) formation, summertime PM 2.5 filter samples were collected with a three-hour sampling interval at a rural site in the North China Plain (NCP), and determined for SOA i tracers and other chemical species. RO 2 +NO pathway derived 2-methylglyceric acid presented a relatively higher contribution to the SOA i due to the high-NOx (~20 ppb) conditions in the NCP that suppressed the reactive uptake of RO 2 +HO 2 reaction derived isoprene epoxydiols. Compared to particle acidity and water content, sulfate plays a dominant role in the heterogeneous formation process of SOA i . Diurnal variation and correlation of 2-methyltetrols with ozone suggested an important effect of isoprene ozonolysis on SOA i formation. SOA i increased linearly with levoglucosan during June 10-18, which can be attributed to an increasing emission of isoprene caused by the field burning of wheat straw and a favorable aqueous SOA formation during the aging process of the biomass burning plume. Our results suggested that isoprene oxidation is highly influenced by intensive anthropogenic activities in the NCP.

Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-08-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-05-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Response Variability in Commercial MOSFET SEE Qualification

DOE PAGES

George, J. S.; Clymer, D. A.; Turflinger, T. L.; ...

2016-12-01

Single-event effects (SEE) evaluation of five different part types of next generation, commercial trench MOSFETs indicates large part-to-part variation in determining a safe operating area (SOA) for drain-source voltage (V DS) following a test campaign that exposed >50 samples per part type to heavy ions. These results suggest a determination of a SOA using small sample sizes may fail to capture the full extent of the part-to-part variability. An example method is discussed for establishing a Safe Operating Area using a one-sided statistical tolerance limit based on the number of test samples. Finally, burn-in is shown to be a criticalmore » factor in reducing part-to-part variation in part response. Implications for radiation qualification requirements are also explored.« less

Response Variability in Commercial MOSFET SEE Qualification

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, J. S.; Clymer, D. A.; Turflinger, T. L.

Single-event effects (SEE) evaluation of five different part types of next generation, commercial trench MOSFETs indicates large part-to-part variation in determining a safe operating area (SOA) for drain-source voltage (V DS) following a test campaign that exposed >50 samples per part type to heavy ions. These results suggest a determination of a SOA using small sample sizes may fail to capture the full extent of the part-to-part variability. An example method is discussed for establishing a Safe Operating Area using a one-sided statistical tolerance limit based on the number of test samples. Finally, burn-in is shown to be a criticalmore » factor in reducing part-to-part variation in part response. Implications for radiation qualification requirements are also explored.« less

When underadditivity of factor effects in the Psychological Refractory Period paradigm implies a bottleneck: evidence from psycholinguistics.

PubMed

Besner, Derek; Reynolds, Mike; O'Malley, Shannon

2009-11-01

The Psychological Refractory Period (PRP) paradigm is a dual-task procedure that can be used to examine the resource demands of specific cognitive processes. Inferences about the underlying processes are typically based on performance in the second of two speeded tasks. If the effect of a factor manipulated in Task 2 decreases as the stimulus onset asynchrony (SOA) between tasks decreases (underadditivity), the normative inference is that the effect of this factor occurs prior to a limited-capacity central processing mechanism. In contrast, if the effect of a factor is additive with SOA then the inference is that this indexes a process that either uses a limited-capacity central processing mechanism or occurs after some process that uses this mechanism. A heretofore unidentified exception to this logic arises when Task 2 involves two separate processes that operate in parallel, but compete. Interference with one process in Task 2 because of work on Task 1 will eliminate or reduce competition within Task 2 and is hence manifest as an underadditive interaction with decreasing SOA. This is illustrated here by reference to a PRP experiment in which the ubiquitous effect of spelling-to-sound regularity on reading aloud time is eliminated at a short SOA and by consideration of three converging lines of investigation in the PRP paradigm when Task 2 involves reading aloud.

All-optical 1st- and 2nd-order differential equation solvers with large tuning ranges using Fabry-Pérot semiconductor optical amplifiers.

PubMed

Chen, Kaisheng; Hou, Jie; Huang, Zhuyang; Cao, Tong; Zhang, Jihua; Yu, Yuan; Zhang, Xinliang

2015-02-09

We experimentally demonstrate an all-optical temporal computation scheme for solving 1st- and 2nd-order linear ordinary differential equations (ODEs) with tunable constant coefficients by using Fabry-Pérot semiconductor optical amplifiers (FP-SOAs). By changing the injection currents of FP-SOAs, the constant coefficients of the differential equations are practically tuned. A quite large constant coefficient tunable range from 0.0026/ps to 0.085/ps is achieved for the 1st-order differential equation. Moreover, the constant coefficient p of the 2nd-order ODE solver can be continuously tuned from 0.0216/ps to 0.158/ps, correspondingly with the constant coefficient q varying from 0.0000494/ps(2) to 0.006205/ps(2). Additionally, a theoretical model that combining the carrier density rate equation of the semiconductor optical amplifier (SOA) with the transfer function of the Fabry-Pérot (FP) cavity is exploited to analyze the solving processes. For both 1st- and 2nd-order solvers, excellent agreements between the numerical simulations and the experimental results are obtained. The FP-SOAs based all-optical differential-equation solvers can be easily integrated with other optical components based on InP/InGaAsP materials, such as laser, modulator, photodetector and waveguide, which can motivate the realization of the complicated optical computing on a single integrated chip.

Secondary organic aerosol formation in biomass-burning plumes: theoretical analysis of lab studies and ambient plumes

NASA Astrophysics Data System (ADS)

Bian, Qijing; Jathar, Shantanu H.; Kodros, John K.; Barsanti, Kelley C.; Hatch, Lindsay E.; May, Andrew A.; Kreidenweis, Sonia M.; Pierce, Jeffrey R.

2017-04-01

Secondary organic aerosol (SOA) has been shown to form in biomass-burning emissions in laboratory and field studies. However, there is significant variability among studies in mass enhancement, which could be due to differences in fuels, fire conditions, dilution, and/or limitations of laboratory experiments and observations. This study focuses on understanding processes affecting biomass-burning SOA formation in laboratory smog-chamber experiments and in ambient plumes. Vapor wall losses have been demonstrated to be an important factor that can suppress SOA formation in laboratory studies of traditional SOA precursors; however, impacts of vapor wall losses on biomass-burning SOA have not yet been investigated. We use an aerosol-microphysical model that includes representations of volatility and oxidation chemistry to estimate the influence of vapor wall loss on SOA formation observed in the FLAME III smog-chamber studies. Our simulations with base-case assumptions for chemistry and wall loss predict a mean OA mass enhancement (the ratio of final to initial OA mass, corrected for particle-phase wall losses) of 1.8 across all experiments when vapor wall losses are modeled, roughly matching the mean observed enhancement during FLAME III. The mean OA enhancement increases to over 3 when vapor wall losses are turned off, implying that vapor wall losses reduce the apparent SOA formation. We find that this decrease in the apparent SOA formation due to vapor wall losses is robust across the ranges of uncertainties in the key model assumptions for wall-loss and mass-transfer coefficients and chemical mechanisms.We then apply similar assumptions regarding SOA formation chemistry and physics to smoke emitted into the atmosphere. In ambient plumes, the plume dilution rate impacts the organic partitioning between the gas and particle phases, which may impact the potential for SOA to form as well as the rate of SOA formation. We add Gaussian dispersion to our aerosol-microphysical model to estimate how SOA formation may vary under different ambient-plume conditions (e.g., fire size, emission mass flux, atmospheric stability). Smoke from small fires, such as typical prescribed burns, dilutes rapidly, which drives evaporation of organic vapor from the particle phase, leading to more effective SOA formation. Emissions from large fires, such as intense wildfires, dilute slowly, suppressing OA evaporation and subsequent SOA formation in the near field. We also demonstrate that different approaches to the calculation of OA enhancement in ambient plumes can lead to different conclusions regarding SOA formation. OA mass enhancement ratios of around 1 calculated using an inert tracer, such as black carbon or CO, have traditionally been interpreted as exhibiting little or no SOA formation; however, we show that SOA formation may have greatly contributed to the mass in these plumes.In comparison of laboratory and plume results, the possible inconsistency of OA enhancement between them could be in part attributed to the effect of chamber walls and plume dilution. Our results highlight that laboratory and field experiments that focus on the fuel and fire conditions also need to consider the effects of plume dilution or vapor losses to walls.

Secondary organic aerosol formation in biomass-burning plumes: theoretical analysis of lab studies and ambient plumes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bian, Qijing; Jathar, Shantanu H.; Kodros, John K.

Secondary organic aerosol (SOA) has been shown to form in biomass-burning emissions in laboratory and field studies. However, there is significant variability among studies in mass enhancement, which could be due to differences in fuels, fire conditions, dilution, and/or limitations of laboratory experiments and observations. This study focuses on understanding processes affecting biomass-burning SOA formation in laboratory smog-chamber experiments and in ambient plumes. Vapor wall losses have been demonstrated to be an important factor that can suppress SOA formation in laboratory studies of traditional SOA precursors; however, impacts of vapor wall losses on biomass-burning SOA have not yet been investigated.more » We use an aerosol-microphysical model that includes representations of volatility and oxidation chemistry to estimate the influence of vapor wall loss on SOA formation observed in the FLAME III smog-chamber studies. Our simulations with base-case assumptions for chemistry and wall loss predict a mean OA mass enhancement (the ratio of final to initial OA mass, corrected for particle-phase wall losses) of 1.8 across all experiments when vapor wall losses are modeled, roughly matching the mean observed enhancement during FLAME III. The mean OA enhancement increases to over 3 when vapor wall losses are turned off, implying that vapor wall losses reduce the apparent SOA formation. We find that this decrease in the apparent SOA formation due to vapor wall losses is robust across the ranges of uncertainties in the key model assumptions for wall-loss and mass-transfer coefficients and chemical mechanisms. We then apply similar assumptions regarding SOA formation chemistry and physics to smoke emitted into the atmosphere. In ambient plumes, the plume dilution rate impacts the organic partitioning between the gas and particle phases, which may impact the potential for SOA to form as well as the rate of SOA formation. We add Gaussian dispersion to our aerosol-microphysical model to estimate how SOA formation may vary under different ambient-plume conditions (e.g., fire size, emission mass flux, atmospheric stability). Smoke from small fires, such as typical prescribed burns, dilutes rapidly, which drives evaporation of organic vapor from the particle phase, leading to more effective SOA formation. Emissions from large fires, such as intense wildfires, dilute slowly, suppressing OA evaporation and subsequent SOA formation in the near field. We also demonstrate that different approaches to the calculation of OA enhancement in ambient plumes can lead to different conclusions regarding SOA formation. OA mass enhancement ratios of around 1 calculated using an inert tracer, such as black carbon or CO, have traditionally been interpreted as exhibiting little or no SOA formation; however, we show that SOA formation may have greatly contributed to the mass in these plumes.In comparison of laboratory and plume results, the possible inconsistency of OA enhancement between them could be in part attributed to the effect of chamber walls and plume dilution. Lastly, our results highlight that laboratory and field experiments that focus on the fuel and fire conditions also need to consider the effects of plume dilution or vapor losses to walls.« less

Secondary organic aerosol formation in biomass-burning plumes: theoretical analysis of lab studies and ambient plumes

DOE PAGES

Bian, Qijing; Jathar, Shantanu H.; Kodros, John K.; ...

2017-04-28

Secondary organic aerosol (SOA) has been shown to form in biomass-burning emissions in laboratory and field studies. However, there is significant variability among studies in mass enhancement, which could be due to differences in fuels, fire conditions, dilution, and/or limitations of laboratory experiments and observations. This study focuses on understanding processes affecting biomass-burning SOA formation in laboratory smog-chamber experiments and in ambient plumes. Vapor wall losses have been demonstrated to be an important factor that can suppress SOA formation in laboratory studies of traditional SOA precursors; however, impacts of vapor wall losses on biomass-burning SOA have not yet been investigated.more » We use an aerosol-microphysical model that includes representations of volatility and oxidation chemistry to estimate the influence of vapor wall loss on SOA formation observed in the FLAME III smog-chamber studies. Our simulations with base-case assumptions for chemistry and wall loss predict a mean OA mass enhancement (the ratio of final to initial OA mass, corrected for particle-phase wall losses) of 1.8 across all experiments when vapor wall losses are modeled, roughly matching the mean observed enhancement during FLAME III. The mean OA enhancement increases to over 3 when vapor wall losses are turned off, implying that vapor wall losses reduce the apparent SOA formation. We find that this decrease in the apparent SOA formation due to vapor wall losses is robust across the ranges of uncertainties in the key model assumptions for wall-loss and mass-transfer coefficients and chemical mechanisms. We then apply similar assumptions regarding SOA formation chemistry and physics to smoke emitted into the atmosphere. In ambient plumes, the plume dilution rate impacts the organic partitioning between the gas and particle phases, which may impact the potential for SOA to form as well as the rate of SOA formation. We add Gaussian dispersion to our aerosol-microphysical model to estimate how SOA formation may vary under different ambient-plume conditions (e.g., fire size, emission mass flux, atmospheric stability). Smoke from small fires, such as typical prescribed burns, dilutes rapidly, which drives evaporation of organic vapor from the particle phase, leading to more effective SOA formation. Emissions from large fires, such as intense wildfires, dilute slowly, suppressing OA evaporation and subsequent SOA formation in the near field. We also demonstrate that different approaches to the calculation of OA enhancement in ambient plumes can lead to different conclusions regarding SOA formation. OA mass enhancement ratios of around 1 calculated using an inert tracer, such as black carbon or CO, have traditionally been interpreted as exhibiting little or no SOA formation; however, we show that SOA formation may have greatly contributed to the mass in these plumes.In comparison of laboratory and plume results, the possible inconsistency of OA enhancement between them could be in part attributed to the effect of chamber walls and plume dilution. Lastly, our results highlight that laboratory and field experiments that focus on the fuel and fire conditions also need to consider the effects of plume dilution or vapor losses to walls.« less

Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study

NASA Astrophysics Data System (ADS)

Rattanavaraha, Weruka; Chu, Kevin; Hapsari Budisulistiorini, Sri; Riva, Matthieu; Lin, Ying-Hsuan; Edgerton, Eric S.; Baumann, Karsten; Shaw, Stephanie L.; Guo, Hongyu; King, Laura; Weber, Rodney J.; Neff, Miranda E.; Stone, Elizabeth A.; Offenberg, John H.; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.

2016-04-01

In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA) that contributes to fine particulate matter (PM2.5). Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2), oxides of nitrogen (NOx), and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH)-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter samples were collected at the Birmingham, Alabama (BHM), ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS). Sample extracts were analyzed by gas chromatography-electron ionization-mass spectrometry (GC/EI-MS) with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH) network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM) ( ˜ 7 to ˜ 20 %). Isoprene-derived SOA tracers correlated with sulfate (SO42-) (r2 = 0.34, n = 117) but not with NOx. Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML)-derived SOA tracers with nitrate radical production (P[NO3]) (r2 = 0.57, n = 40) were observed during nighttime, suggesting a potential role of the NO3 radical in forming this SOA type. However, the nighttime correlation of these tracers with nitrogen dioxide (NO2) (r2 = 0.26, n = 40) was weaker. Ozone (O3) correlated strongly with MAE/HMML-derived tracers (r2 = 0.72, n = 30) and moderately with 2-methyltetrols (r2 = 0.34, n = 15) during daytime only, suggesting that a fraction of SOA formation could occur from isoprene ozonolysis in urban areas. No correlation was observed between aerosol pH and isoprene-derived SOA. Lack of correlation between aerosol acidity and isoprene-derived SOA is consistent with the observation that acidity is not a limiting factor for isoprene SOA formation at the BHM site as aerosols were acidic enough to promote multiphase chemistry of isoprene-derived epoxides throughout the duration of the study. All in all, these results confirm previous studies suggesting that anthropogenic pollutants enhance isoprene-derived SOA formation.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter (PM) after 3 h of oxidation inside the chamber at typical atmospheric oxidant levels (and 5 times the amount of SOA as primary PM after 5 × 106 molecules cm-3 h of OH exposure). Therefore, the contribution of light-duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photooxidizing exhaust from newer (LEV2) vehicles was a factor of 3 lower than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions (a factor of 11-15) in nonmethane organic gas emissions. These data suggest that a complex and nonlinear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the timescale of these experiments, the mixture of organic vapors emitted by newer vehicles appears to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the nonmethane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. By comparing this study with a companion study of diesel trucks, we conclude that both primary PM emissions and SOA production for light-duty gasoline vehicles are much greater than for late-model (2007 and later) on-road heavy-duty diesel trucks.

Formation of nitrogen- and sulfur-containing light-absorbing compounds accelerated by evaporation of water from secondary organic aerosols

NASA Astrophysics Data System (ADS)

Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey A.

2012-01-01

Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of d-limonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (<2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>105 L mol-1 cm-1 at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 103 cm2 g-1 - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH ˜ 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

TRIAD: The Translational Research Informatics and Data Management Grid

PubMed Central

Payne, P.; Ervin, D.; Dhaval, R.; Borlawsky, T.; Lai, A.

2011-01-01

Objective Multi-disciplinary and multi-site biomedical research programs frequently require infrastructures capable of enabling the collection, management, analysis, and dissemination of heterogeneous, multi-dimensional, and distributed data and knowledge collections spanning organizational boundaries. We report on the design and initial deployment of an extensible biomedical informatics platform that is intended to address such requirements. Methods A common approach to distributed data, information, and knowledge management needs in the healthcare and life science settings is the deployment and use of a service-oriented architecture (SOA). Such SOA technologies provide for strongly-typed, semantically annotated, and stateful data and analytical services that can be combined into data and knowledge integration and analysis “pipelines.” Using this overall design pattern, we have implemented and evaluated an extensible SOA platform for clinical and translational science applications known as the Translational Research Informatics and Data-management grid (TRIAD). TRIAD is a derivative and extension of the caGrid middleware and has an emphasis on supporting agile “working interoperability” between data, information, and knowledge resources. Results Based upon initial verification and validation studies conducted in the context of a collection of driving clinical and translational research problems, we have been able to demonstrate that TRIAD achieves agile “working interoperability” between distributed data and knowledge sources. Conclusion Informed by our initial verification and validation studies, we believe TRIAD provides an example instance of a lightweight and readily adoptable approach to the use of SOA technologies in the clinical and translational research setting. Furthermore, our initial use cases illustrate the importance and efficacy of enabling “working interoperability” in heterogeneous biomedical environments. PMID:23616879

TRIAD: The Translational Research Informatics and Data Management Grid.

PubMed

Payne, P; Ervin, D; Dhaval, R; Borlawsky, T; Lai, A

2011-01-01

Multi-disciplinary and multi-site biomedical research programs frequently require infrastructures capable of enabling the collection, management, analysis, and dissemination of heterogeneous, multi-dimensional, and distributed data and knowledge collections spanning organizational boundaries. We report on the design and initial deployment of an extensible biomedical informatics platform that is intended to address such requirements. A common approach to distributed data, information, and knowledge management needs in the healthcare and life science settings is the deployment and use of a service-oriented architecture (SOA). Such SOA technologies provide for strongly-typed, semantically annotated, and stateful data and analytical services that can be combined into data and knowledge integration and analysis "pipelines." Using this overall design pattern, we have implemented and evaluated an extensible SOA platform for clinical and translational science applications known as the Translational Research Informatics and Data-management grid (TRIAD). TRIAD is a derivative and extension of the caGrid middleware and has an emphasis on supporting agile "working interoperability" between data, information, and knowledge resources. Based upon initial verification and validation studies conducted in the context of a collection of driving clinical and translational research problems, we have been able to demonstrate that TRIAD achieves agile "working interoperability" between distributed data and knowledge sources. Informed by our initial verification and validation studies, we believe TRIAD provides an example instance of a lightweight and readily adoptable approach to the use of SOA technologies in the clinical and translational research setting. Furthermore, our initial use cases illustrate the importance and efficacy of enabling "working interoperability" in heterogeneous biomedical environments.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thornton, Joel A

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 secondarymore » 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.« less

­­Secondary organic aerosol formation from photo-oxidation of wood combustion emissions: Characterization of gas phase precursors and their link to SOA budget

NASA Astrophysics Data System (ADS)

Bhattu, D.; Stefenelli, G.; Zotter, P.; Zhou, J.; Nussbaumer, T.; Bertrand, A.; Marchand, N.; Termine-Roussel, B.; Baltensperger, U.; Slowik, J.; Prevot, A. S.; El-Haddad, I.; Dommen, J.

2016-12-01

Current legislation limits the emission of particulate matter, but does not regulate the precursors potentially forming secondary organic aerosol (SOA). Recent literature has shown that only 22 non-traditional SOA precursors from residential wood combustion explains 84-116% of the observed SOA mass whereas traditional precursors in the models account for only 3-27% of the SOA mass (Bruns et al., 2016). Investigation of gas phase emissions from wood combustion and their SOA formation potential have largely focused on single combustion devices with limited operating conditions. As, both primary emissions and SOA formation is a strong function of device type, load, fuel and operating conditions, we have performed a detailed chamber study investigating the gas-phase precursors from beech wood using three combustion devices namely a pellet boiler (combustion conditions: optimum, lack and excess of oxygen), an industrial wood chip grate boiler (30% and 100% power), and a log wood stove (varying fuel load and moisture content) using a potential aerosol mass reactor (PAM) with varying OH exposure. The short residence time in the reactor allowed a time resolved picture of SOA production potential and reduced wall losses. The main aim of this study is to characterize the primary and aged gaseous emissions and investigate their SOA formation potential depending on their mass yield, molecular structures, functional groups and OH reactivity in order to ascertain the contribution of residential wood burning in total carbonaceous OA budget. The physical and chemical effects of different OA aging conditions were monitored using an SMPS, an Aethalometer, an HR-ToF-AMS, as well as a PTR-ToF-MS and other gas monitors. In pellet boiler, significant SOA mass enhancement is observed in excess oxygen conditions compared to optimum and oxygen deprived conditions. Highest gas phase emissions from wood stove are observed at cold start (start of each burn cycle) and lowest in burn out phase (end of each burn cycle). Despite of the comparable total gas phase emissions, the compositional space of wood stove emissions is largely occupied by SOA precursors compared to pellet boiler. Finally we will determine effective SOA mass yield of the speciated and unspeciated precursors and assess the extent to which SOA mass closure can be achieved.

Dithiothreitol activity by particulate oxidizers of SOA produced from photooxidation of hydrocarbons under varied NOx levels

NASA Astrophysics Data System (ADS)

Jiang, Huanhuan; Jang, Myoseon; Yu, Zechen

2017-08-01

When hydrocarbons (HCs) are atmospherically oxidized, they form particulate oxidizers, including quinones, organic hydroperoxides, and peroxyacyl nitrates (PANs). These particulate oxidizers can modify cellular materials (e.g., proteins and enzymes) and adversely modulate cell functions. In this study, the contribution of particulate oxidizers in secondary organic aerosols (SOAs) to the oxidative potential was investigated. SOAs were generated from the photooxidation of toluene, 1,3,5-trimethylbenzene, isoprene, and α-pinene under varied NOx levels. Oxidative potential was determined from the typical mass-normalized consumption rate (reaction time t = 30 min) of dithiothreitol (DTTt), a surrogate for biological reducing agents. Under high-NOx conditions, the DTTt of toluene SOA was 2-5 times higher than that of the other types of SOA. Isoprene DTTt significantly decreased with increasing NOx (up to 69 % reduction by changing the HC / NOx ratio from 30 to 5). The DTTt of 1,3,5-trimethylbenzene and α-pinene SOA was insensitive to NOx under the experimental conditions of this study. The significance of quinones to the oxidative potential of SOA was tested through the enhancement of DTT consumption in the presence of 2,4-dimethylimidazole, a co-catalyst for the redox cycling of quinones; however, no significant effect of 2,4-dimethylimidazole on modulation of DTT consumption was observed for all SOA, suggesting that a negligible amount of quinones was present in the SOA of this study. For toluene and isoprene, mass-normalized DTT consumption (DTTm) was determined over an extended period of reaction time (t = 2 h) to quantify their maximum capacity to consume DTT. The total quantities of PANs and organic hydroperoxides in toluene SOA and isoprene SOA were also measured using the Griess assay and the 4-nitrophenylboronic acid assay, respectively. Under the NOx conditions (HC / NOx ratio: 5-36 ppbC ppb-1) applied in this study, the amount of organic hydroperoxides was substantial, while PANs were found to be insignificant for both SOAs. Isoprene DTTm was almost exclusively attributable to organic hydroperoxides, while toluene DTTm was partially attributable to organic hydroperoxides. The DTT assay results of the model compound study suggested that electron-deficient alkenes, which are abundant in toluene SOA, could also modulate DTTm.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigatedmore » with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ~100 µg m -3 of pure H 2SO 4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical ( k OH) was estimated as 4.0 ± 2.0 ×10 -13 cm 3 molec -1 s -1, which is equivalent to more than a 2-week lifetime. A similar k OH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 10 12 molec cm -3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients ( γ OH = 0.59±0.33 in SE US and γ OH = 0.68±0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of k OH and γ OH was observed, consistent with surface-area-limited OH uptake. No decrease of k OH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.« less

Limited Effect of Anthropogenic Nitrogen Oxides on Secondary Organic Aerosol Formation

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Secondary organic aerosol from atmospheric photooxidation of indole

NASA Astrophysics Data System (ADS)

Montoya-Aguilera, Julia; Horne, Jeremy R.; Hinks, Mallory L.; Fleming, Lauren T.; Perraud, Véronique; Lin, Peng; Laskin, Alexander; Laskin, Julia; Dabdub, Donald; Nizkorodov, Sergey A.

2017-09-01

Indole is a heterocyclic compound emitted by various plant species under stressed conditions or during flowering events. The formation, optical properties, and chemical composition of secondary organic aerosol (SOA) formed by low-NOx photooxidation of indole were investigated. The SOA yield (1. 3 ± 0. 3) was estimated from measuring the particle mass concentration with a scanning mobility particle sizer (SMPS) and correcting it for wall loss effects. The high value of the SOA mass yield suggests that most oxidized indole products eventually end up in the particle phase. The SOA particles were collected on filters and analysed offline with UV-vis spectrophotometry to measure the mass absorption coefficient (MAC) of the bulk sample. The samples were visibly brown and had MAC values of ˜ 2 m2 g-1 at λ = 300 nm and ˜ 0. 5 m2 g-1 at λ = 400 nm, comparable to strongly absorbing brown carbon emitted from biomass burning. The chemical composition of SOA was examined with several mass spectrometry methods. Direct analysis in real-time mass spectrometry (DART-MS) and nanospray desorption electrospray high-resolution mass spectrometry (nano-DESI-HRMS) were both used to provide information about the overall distribution of SOA compounds. High-performance liquid chromatography, coupled to photodiode array spectrophotometry and high-resolution mass spectrometry (HPLC-PDA-HRMS), was used to identify chromophoric compounds that are responsible for the brown colour of SOA. Indole derivatives, such as tryptanthrin, indirubin, indigo dye, and indoxyl red, were found to contribute significantly to the visible absorption spectrum of indole SOA. The potential effect of indole SOA on air quality was explored with an airshed model, which found elevated concentrations of indole SOA during the afternoon hours contributing considerably to the total organic aerosol under selected scenarios. Because of its high MAC values, indole SOA can contribute to decreased visibility and poor air quality.

Synthesis and coherent vibrational laser spectroscopy of putative molecular constituents in isoprene-derived secondary organic aerosol particles

NASA Astrophysics Data System (ADS)

Ebben, C. J.; Strick, B. F.; Upshur, M. A.; Chase, H. M.; Achtyl, J. L.; Thomson, R. J.; Geiger, F. M.

2013-11-01

SOA particle formation ranks among the least understood processes in the atmosphere, rooted in part in (a) the limited knowledge about SOA chemical composition; (b) the availability of only little concrete evidence for chemical structures; and (c) little availability of reference compounds needed for benchmarking and chemical identification in pure and homogenous form. Here, we address these challenges by synthesizing and subjecting to physical and chemical analysis putative isoprene-derived SOA particle constituents. Our surface-selective spectroscopic analysis of these compounds is followed by comparison to synthetic SOA particles prepared at the Harvard Environmental Chamber (HEC) and to authentic SOA particles collected in a tropical forest environment, namely the Amazon Basin, where isoprene oxidation by OH radicals has been reported to dominate SOA particle formation (Martin et al., 2010b; Sun et al., 2003; Hudson et al., 2008; Yasmeen et al., 2010). We focus on the epoxides and tetraols that have been proposed to be present in the SOA particles. We characterize the compounds prepared here by a variety of physical measurements and polarization-resolved vibrational sum frequency generation (SFG), paying particular attention to the phase state (condensed vs. vapor) of four epoxides and two tetraols in contact with a fused silica window. We compare the spectral responses from the tetraol and epoxide model compounds with those obtained from the natural and synthetic SOA particle samples that were collected on filter substrates and pressed against a fused silica window and discuss a possible match for the SFG response of one of the epoxides with that of the synthetic SOA particle material. We conclude our work by discussing how the approach described here will allow for the study of the SOA particle formation pathways from first- and second-generation oxidation products by effectively "fast-forwarding" through the initial reaction steps of particle nucleation via a chemically resolved approach aimed at testing the underlying chemical mechanisms of SOA particle formation.

A review of stereochemical implications in the generation of secondary organic aerosol from isoprene oxidation.

PubMed

Cash, James M; Heal, Mathew R; Langford, Ben; Drewer, Julia

2016-11-09

The atmospheric reactions leading to the generation of secondary organic aerosol (SOA) from the oxidation of isoprene are generally assumed to produce only racemic mixtures, but aspects of the chemical reactions suggest this may not be the case. In this review, the stereochemical outcomes of published isoprene-degradation mechanisms contributing to high amounts of SOA are evaluated. Despite evidence suggesting isoprene first-generation oxidation products do not contribute to SOA directly, this review suggests the stereochemistry of first-generation products may be important because their stereochemical configurations may be retained through to the second-generation products which form SOA. Specifically, due to the stereochemistry of epoxide ring-opening mechanisms, the outcome of the reactions involving epoxydiols of isoprene (IEPOX), methacrylic acid epoxide (MAE) and hydroxymethylmethyl-α-lactone (HMML) are, in principle, stereospecific which indicates the stereochemistry is predefined from first-generation precursors. The products from these three epoxide intermediates oligomerise to form macromolecules which are proposed to form chiral structures within the aerosol and are considered to be the largest contributors to SOA. If conditions in the atmosphere such as pH, aerosol water content, relative humidity, pre-existing aerosol, aerosol coatings and aerosol cation/anion content (and other) variables acting on the reactions leading to SOA affect the tacticity (arrangement of chiral centres) in the SOA then they may influence its physical properties, for example its hygroscopicity. Chamber studies of SOA formation from isoprene encompass particular sets of controlled conditions of these variables. It may therefore be important to consider stereochemistry when upscaling from chamber study data to predictions of SOA yields across the range of ambient atmospheric conditions. Experiments analysing the stereochemistry of the reactions under varying conditions of the above variables would help elucidate whether there is stereoselectivity in SOA formation from isoprene and if the rates of SOA formation are affected.

A Combined Kinetic and Volatility Basis Set Approach to Model Secondary Organic Aerosol from Toluene and Diesel Exhaust/Meat Cooking Mixtures

NASA Astrophysics Data System (ADS)

Parikh, H. M.; Carlton, A. G.; Zhang, H.; Kamens, R.; Vizuete, W.

2011-12-01

Secondary organic aerosol (SOA) is simulated for 6 outdoor smog chamber experiments using a SOA model based on a kinetic chemical mechanism in conjunction with a volatility basis set (VBS) approach. The experiments include toluene, a non-SOA-forming hydrocarbon mixture, diesel exhaust or meat cooking emissions and NOx, and are performed under varying conditions of relative humidity. SOA formation from toluene is modeled using a condensed kinetic aromatic mechanism that includes partitioning of lumped semi-volatile products in particle organic-phase and incorporates particle aqueous-phase chemistry to describe uptake of glyoxal and methylglyoxal. Modeling using the kinetic mechanism alone, along with primary organic aerosol (POA) from diesel exhaust (DE) /meat cooking (MC) fails to simulate the rapid SOA formation at the beginning hours of the experiments. Inclusion of a VBS approach with the kinetic mechanism to characterize the emissions and chemistry of complex mixture of intermediate volatility organic compounds (IVOCs) from DE/MC, substantially improves SOA predictions when compared with observed data. The VBS model includes photochemical aging of IVOCs and evaporation of POA after dilution. The relative contribution of SOA mass from DE/MC is as high as 95% in the morning, but substantially decreases after mid-afternoon. For high humidity experiments, aqueous-phase SOA fraction dominates the total SOA mass at the end of the day (approximately 50%). In summary, the combined kinetic and VBS approach provides a new and improved framework to semi-explicitly model SOA from VOC precursors in conjunction with a VBS approach that can be used on complex emission mixtures comprised with hundreds of individual chemical species.

Sense of agency, associative learning, and schizotypy

PubMed Central

Moore, James W.; Dickinson, Anthony; Fletcher, Paul C.

2011-01-01

Despite the fact that the role of learning is recognised in empirical and theoretical work on sense of agency (SoA), the nature of this learning has, rather surprisingly, received little attention. In the present study we consider the contribution of associative mechanisms to SoA. SoA can be measured quantitatively as a temporal linkage between voluntary actions and their external effects. Using an outcome blocking procedure, it was shown that training action–outcome associations under conditions of increased surprise augmented this temporal linkage. Moreover, these effects of surprise were correlated with schizotypy scores, suggesting that individual differences in higher level experiences are related to associative learning and to its impact on SoA. These results are discussed in terms of models of SoA, and our understanding of disrupted SoA in certain disorders. PMID:21295497

Neural correlates of cross-domain affective priming.

PubMed

Zhang, Qin; Li, Xiaohua; Gold, Brian T; Jiang, Yang

2010-05-06

The affective priming effect has mostly been studied using reaction time (RT) measures; however, the neural bases of affective priming are not well established. To understand the neural correlates of cross-domain emotional stimuli presented rapidly, we obtained event-related potential (ERP) measures during an affective priming task using short SOA (stimulus onset asynchrony) conditions. Two sets of 480 picture-word pairs were presented at SOAs of either 150ms or 250ms between prime and target stimuli. Participants decided whether the valence of each target word was pleasant or unpleasant. Behavioral results from both SOA conditions were consistent with previous reports of affective priming, with longer RTs for incongruent than congruent pairs at SOAs of 150ms (771 vs. 738ms) and 250ms (765 vs. 720ms). ERP results revealed that the N400 effect (associated with incongruent pairs in affective processing) occurred at anterior scalp regions at an SOA of 150ms, and this effect was only observed for negative target words across the scalp at an SOA of 250ms. In contrast, late positive potentials (LPPs) (associated with attentional resource allocation) occurred across the scalp at an SOA of 250ms. LPPs were only observed for positive target words at posterior parts of the brain at an SOA of 150ms. Our finding of ERP signatures at very short SOAs provides the first neural evidence that affective pictures can exert an automatic influence on the evaluation of affective target words. Copyright 2010 Elsevier B.V. All rights reserved.

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

PubMed

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

2005-01-01

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

Detailed Chemical Characterization of Unresolved Complex Mixtures (UCM) inAtmospheric Organics: Insights into Emission Sources, Atmospheric Processing andSecondary Organic Aerosol Formation

EPA Science Inventory

Recent studies suggest that semivolatile organic compounds (SVOCs) are important precursors to secondary organic aerosol (SOA) in urban atmospheres. However, knowledge of the chemical composition of SVOCs is limited by current analytical techniques, which are typically unable to...

Modeling SOA production from the oxidation of intermediate volatility alkanes

NASA Astrophysics Data System (ADS)

Aumont, B.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

2012-12-01

Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapour pressure. This process was investigated using the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). Results for the C8-C24 n-alkane series show the expected trends, i.e. (i) SOA yield grows with the carbon backbone of the parent hydrocarbon, (ii) SOA yields decreases with the decreasing pre-existing organic aerosol concentration, (iii) the number of generations required to describe SOA production increases when the pre-existing organic aerosol concentration decreases. Most SOA contributors were found to be not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA). Branched alkanes are more prone to fragment in the early stage of the oxidation than their corresponding linear analogues. Fragmentation is expected to alter both the yield and the mean oxidation state of the SOA. Here, GECKO-A is applied to generate highly detailed oxidation schemes for various series of branched and cyclised alkanes. Branching and cyclisation effects on SOA yields and oxidation states will be examined.

Visual Feedback Dominates the Sense of Agency for Brain-Machine Actions

PubMed Central

Evans, Nathan; Gale, Steven; Schurger, Aaron; Blanke, Olaf

2015-01-01

Recent advances in neuroscience and engineering have led to the development of technologies that permit the control of external devices through real-time decoding of brain activity (brain-machine interfaces; BMI). Though the feeling of controlling bodily movements (sense of agency; SOA) has been well studied and a number of well-defined sensorimotor and cognitive mechanisms have been put forth, very little is known about the SOA for BMI-actions. Using an on-line BMI, and verifying that our subjects achieved a reasonable level of control, we sought to describe the SOA for BMI-mediated actions. Our results demonstrate that discrepancies between decoded neural activity and its resultant real-time sensory feedback are associated with a decrease in the SOA, similar to SOA mechanisms proposed for bodily actions. However, if the feedback discrepancy serves to correct a poorly controlled BMI-action, then the SOA can be high and can increase with increasing discrepancy, demonstrating the dominance of visual feedback on the SOA. Taken together, our results suggest that bodily and BMI-actions rely on common mechanisms of sensorimotor integration for agency judgments, but that visual feedback dominates the SOA in the absence of overt bodily movements or proprioceptive feedback, however erroneous the visual feedback may be. PMID:26066840

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

PubMed

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

2006-05-01

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

Reactive Uptake of Ammonia to Secondary Organic Aerosols: Kinetics of Organonitrogen Formation

NASA Astrophysics Data System (ADS)

Liu, Yongchun; Liggio, John; Staebler, Ralf; Li, Shao-Meng

2015-04-01

Organonitrogen compounds originating from the heterogeneous uptake of NH3 or amines by secondary organic aerosol (SOA) has received significant attention recently. This is primarily due to its potential contribution to brown carbon (BrC), which can absorb solar radiation and affect climate. In addition, particle phase Organonitrogen species may represent a means of altering regional nitrogen cycles and/or nitrogen deposition patterns though the sequestering of ambient ammonia which is ultimately deposited downwind. Several reduced nitrogen forming heterogeneous reactions have previously been proposed, including Schiff base and/or Mannich reactions between NH3, ammonium salts or amines and organic carbonyl functional groups in particles. In order to assess and model the possible impact of Schiff base, Mannich or other N-forming reactions (via NH3) on the radiative forcing ability of ambient SOA and/or its impact on N-deposition, the kinetics of such heterogeneous reactions are required, and yet remain largely unknown. In the current study, the uptake kinetics of NH3 to form organonitrogen compounds in SOA derived from the ozonolysis of α-pinene and the OH oxidation of m-xylene is reported for the first time from experiments performed in a 9 m3 smog chamber equipped with a High Resolution Time-of-Flight Aerosol Mass Spectrometer. The results demonstrate that particle bound organonitrogen compounds are mainly formed by NH3 uptake onto newly formed SOA (~1 hr), but relatively little onto more aged SOA. The uptake coefficients of NH3 to form organonitrogen compounds (between 0-150 min) are on the order of 10-4-10-3 and are prominently dependent upon particle acidity. Following 6 hours of reaction, the total organonitrogen mass contributed up to 10.0±1.5 wt% and 31.5±4.4 wt% to the total SOA mass from the ozonolysis of α-pinene and OH oxidation of m-xylene. The influence of VOC precursors, seed particle acidity and gaseous NH3 concentration on the obtained uptake coefficients is described. The implications of the kinetics on atmospheric BrC and N-deposition are also discussed.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsui, H.; Koike, Makoto; Kondo, Yutaka

2014-09-30

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

Assessing the influence of NOx concentrations and relative humidity on secondary organic aerosol yields from α-pinene photo-oxidation through smog chamber experiments and modelling calculations

NASA Astrophysics Data System (ADS)

Stirnweis, Lisa; Marcolli, Claudia; Dommen, Josef; Barmet, Peter; Frege, Carla; Platt, Stephen M.; Bruns, Emily A.; Krapf, Manuel; Slowik, Jay G.; Wolf, Robert; Prévôt, Andre S. H.; Baltensperger, Urs; El-Haddad, Imad

2017-04-01

Secondary organic aerosol (SOA) yields from the photo-oxidation of α-pinene were investigated in smog chamber (SC) experiments at low (23-29 %) and high (60-69 %) relative humidity (RH), various NOx / VOC ratios (0.04-3.8) and with different aerosol seed chemical compositions (acidic to neutralized sulfate-containing or hydrophobic organic). A combination of a scanning mobility particle sizer and an Aerodyne high-resolution time-of-flight aerosol mass spectrometer was used to determine SOA mass concentration and chemical composition. We used a Monte Carlo approach to parameterize smog chamber SOA yields as a function of the condensed phase absorptive mass, which includes the sum of OA and the corresponding bound liquid water content. High RH increased SOA yields by up to 6 times (1.5-6.4) compared to low RH. The yields at low NOx / VOC ratios were in general higher compared to yields at high NOx / VOC ratios. This NOx dependence follows the same trend as seen in previous studies for α-pinene SOA. A novel approach of data evaluation using volatility distributions derived from experimental data served as the basis for thermodynamic phase partitioning calculations of model mixtures in this study. These calculations predict liquid-liquid phase separation into organic-rich and electrolyte phases. At low NOx conditions, equilibrium partitioning between the gas and liquid phases can explain most of the increase in SOA yields observed at high RH, when in addition to the α-pinene photo-oxidation products described in the literature, fragmentation products are added to the model mixtures. This increase is driven by both the increase in the absorptive mass and the solution non-ideality described by the compounds' activity coefficients. In contrast, at high NOx, equilibrium partitioning alone could not explain the strong increase in the yields with RH. This suggests that other processes, e.g. reactive uptake of semi-volatile species into the liquid phase, may occur and be enhanced at higher RH, especially for compounds formed under high NOx conditions, e.g. carbonyls.

Analytical Characterization on Pulse Propagation in a Semiconductor Optical Amplifier Based on Homotopy Analysis Method

NASA Astrophysics Data System (ADS)

Jia, Xiaofei

2018-06-01

Starting from the basic equations describing the evolution of the carriers and photons inside a semiconductor optical amplifier (SOA), the equation governing pulse propagation in the SOA is derived. By employing homotopy analysis method (HAM), a series solution for the output pulse by the SOA is obtained, which can effectively characterize the temporal features of the nonlinear process during the pulse propagation inside the SOA. Moreover, the analytical solution is compared with numerical simulations with a good agreement. The theoretical results will benefit the future analysis of other problems related to the pulse propagation in the SOA.

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

PubMed

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

2015-02-15

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

Gain-clamped semiconductor optical amplifiers based on compensating light: Theoretical model and performance analysis

NASA Astrophysics Data System (ADS)

Jia, Xin-Hong; Wu, Zheng-Mao; Xia, Guang-Qiong

2006-12-01

It is well known that the gain-clamped semiconductor optical amplifier (GC-SOA) based on lasing effect is subject to transmission rate restriction because of relaxation oscillation. The GC-SOA based on compensating effect between signal light and amplified spontaneous emission by combined SOA and fiber Bragg grating (FBG) can be used to overcome this problem. In this paper, the theoretical model on GC-SOA based on compensating light has been constructed. The numerical simulations demonstrate that good gain and noise figure characteristics can be realized by selecting reasonably the FBG insertion position, the peak reflectivity of FBG and the biasing current of GC-SOA.

Monoterpene oxidation in an oxidative flow reactor: SOA yields and the relationship between bulk gas-phase properties and organic aerosol growth

NASA Astrophysics Data System (ADS)

Friedman, B.; Link, M.; Farmer, D.

2016-12-01

We use an oxidative flow reactor (OFR) to determine the secondary organic aerosol (SOA) yields of five monoterpenes (alpha-pinene, beta-pinene, limonene, sabinene, and terpinolene) at a range of OH exposures. These OH exposures correspond to aging timescales of a few hours to seven days. We further determine how SOA yields of beta-pinene and alpha-pinene vary as a function of seed particle type (organic vs. inorganic) and seed particle mass concentration. We hypothesize that the monoterpene structure largely accounts for the observed variance in SOA yields for the different monoterpenes. We also use high-resolution time-of-flight chemical ionization mass spectrometry to calculate the bulk gas-phase properties (O:C and H:C) of the monoterpene oxidation systems as a function of oxidant concentrations. Bulk gas-phase properties can be compared to the SOA yields to assess the capability of the precursor gas-phase species to inform the SOA yields of each monoterpene oxidation system. We find that the extent of oxygenated precursor gas-phase species corresponds to SOA yield.

Laboratory studies of monoterpene secondary organic aerosol formation and evolution

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

How color, regularity, and good Gestalt determine backward masking.

PubMed

Sayim, Bilge; Manassi, Mauro; Herzog, Michael

2014-06-18

The strength of visual backward masking depends on the stimulus onset asynchrony (SOA) between target and mask. Recently, it was shown that the conjoint spatial layout of target and mask is as crucial as SOA. Particularly, masking strength depends on whether target and mask group with each other. The same is true in crowding where the global spatial layout of the flankers and target-flanker grouping determine crowding strength. Here, we presented a vernier target followed by different flanker configurations at varying SOAs. Similar to crowding, masking of a red vernier target was strongly reduced for arrays of 10 green compared with 10 red flanking lines. Unlike crowding, single green lines flanking the red vernier showed strong masking. Irregularly arranged flanking lines yielded stronger masking than did regularly arranged lines, again similar to crowding. While cuboid flankers reduced crowding compared with single lines, this was not the case in masking. We propose that, first, masking is reduced when the flankers are part of a larger spatial structure. Second, spatial factors counteract color differences between the target and the flankers. Third, complex Gestalts, such as cuboids, seem to need longer processing times to show ungrouping effects as observed in crowding. Strong parallels between masking and crowding suggest similar underlying mechanism; however, temporal factors in masking additionally modulate performance, acting as an additional grouping cue. © 2014 ARVO.

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

DOE PAGES

Ortega, Amber M.; Hayes, Patrick L.; Peng, Zhe; ...

2016-06-15

Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient andmore » reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and O x, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive ( τ OH ~ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ~ –0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OS C ~ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to higher ages where OA loss dominates. The mass added at low-to-intermediate ages is due primarily to condensation of oxidized species, not heterogeneous oxidation. The OA decrease at high photochemical ages is dominated by heterogeneous oxidation followed by fragmentation/evaporation. A comparison of urban SOA formation in this study with a similar study of vehicle SOA in a tunnel suggests the importance of vehicle emissions for urban SOA. Pre-2007 SOA models underpredict SOA formation by an order of magnitude, while a more recent model performs better but overpredicts at higher ages. Furthermore, these results demonstrate the value of the reactor as a tool for in situ evaluation of the SOA formation potential and OA evolution from ambient air.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ortega, Amber M.; Hayes, Patrick L.; Peng, Zhe

Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient andmore » reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and O x, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive ( τ OH ~ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ~ –0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OS C ~ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to higher ages where OA loss dominates. The mass added at low-to-intermediate ages is due primarily to condensation of oxidized species, not heterogeneous oxidation. The OA decrease at high photochemical ages is dominated by heterogeneous oxidation followed by fragmentation/evaporation. A comparison of urban SOA formation in this study with a similar study of vehicle SOA in a tunnel suggests the importance of vehicle emissions for urban SOA. Pre-2007 SOA models underpredict SOA formation by an order of magnitude, while a more recent model performs better but overpredicts at higher ages. Furthermore, these results demonstrate the value of the reactor as a tool for in situ evaluation of the SOA formation potential and OA evolution from ambient air.« less

What do PANs Tell us about VOC-NOx Photochemistry in the Urban/Rural Interface?

NASA Astrophysics Data System (ADS)

Roberts, J. M.; Flocke, F. M.; Zheng, W.; Bertman, S.; Marchewka, M.; Williams, E.; Lerner, B.; Kuster, W.; Goldan, P.; Gilman, J.; Sommariva, R.; Trainer, M.; Fehsenfeld, F.

2006-12-01

Peroxycarboxylic Nitric Anhydrides (PANs) are co-products of the VOC-NOx photochemistry that is responsible for O3 and secondary organic aerosol (SOA) formation in the troposphere. The relative abundance of the various PAN type compounds can provide important diagnostic information as to the contribution of different VOC sources to these processes. Anthropogenic, biogenic and petrochemical VOC sources have shown distinct profiles of PAN, PPN, MPAN, PiBN, and APAN, which can be analyzed using simple numerical models and compared to the results of detailed chemical mechanisms. One result of these studies is that the PAN compounds can be used to better define the contribution of isoprene to O3 production in the urban/rural interface. Another result is that high relative concentrations of APAN are characteristic of high petrochemical source impact. In addition, changes in the relative abundance of PPN and PAN can indicate the aging of a continental photochemical plume. This paper will present selected results from five field experiments and modeling studies from the Nashville 1999 Southern Oxidant Study up through the TexAQS 2006 study, in and around Houston, TX.

A novel co-occurrence-based approach to predict pure associative and semantic priming.

PubMed

Roelke, Andre; Franke, Nicole; Biemann, Chris; Radach, Ralph; Jacobs, Arthur M; Hofmann, Markus J

2018-03-15

The theoretical "difficulty in separating association strength from [semantic] feature overlap" has resulted in inconsistent findings of either the presence or absence of "pure" associative priming in recent literature (Hutchison, 2003, Psychonomic Bulletin & Review, 10(4), p. 787). The present study used co-occurrence statistics of words in sentences to provide a full factorial manipulation of direct association (strong/no) and the number of common associates (many/no) of the prime and target words. These common associates were proposed to serve as semantic features for a recent interactive activation model of semantic processing (i.e., the associative read-out model; Hofmann & Jacobs, 2014). With stimulus onset asynchrony (SOA) as an additional factor, our findings indicate that associative and semantic priming are indeed dissociable. Moreover, the effect of direct association was strongest at a long SOA (1,000 ms), while many common associates facilitated lexical decisions primarily at a short SOA (200 ms). This response pattern is consistent with previous performance-based accounts and suggests that associative and semantic priming can be evoked by computationally determined direct and common associations.

Development and evaluation of SOA-based AAL services in real-life environments: a case study and lessons learned.

PubMed

Stav, Erlend; Walderhaug, Ståle; Mikalsen, Marius; Hanke, Sten; Benc, Ivan

2013-11-01

The proper use of ICT services can support seniors in living independently longer. While such services are starting to emerge, current proprietary solutions are often expensive, covering only isolated parts of seniors' needs, and lack support for sharing information between services and between users. For developers, the challenge is that it is complex and time consuming to develop high quality, interoperable services, and new techniques are needed to simplify the development and reduce the development costs. This paper provides the complete view of the experiences gained in the MPOWER project with respect to using model-driven development (MDD) techniques for Service Oriented Architecture (SOA) system development in the Ambient Assisted Living (AAL) domain. To address this challenge, the approach of the European research project MPOWER (2006-2009) was to investigate and record the user needs, define a set of reusable software services based on these needs, and then implement pilot systems using these services. Further, a model-driven toolchain covering key development phases was developed to support software developers through this process. Evaluations were conducted both on the technical artefacts (methodology and tools), and on end user experience from using the pilot systems in trial sites. The outcome of the work on the user needs is a knowledge base recorded as a Unified Modeling Language (UML) model. This comprehensive model describes actors, use cases, and features derived from these. The model further includes the design of a set of software services, including full trace information back to the features and use cases motivating their design. Based on the model, the services were implemented for use in Service Oriented Architecture (SOA) systems, and are publicly available as open source software. The services were successfully used in the realization of two pilot applications. There is therefore a direct and traceable link from the user needs of the elderly, through the service design knowledge base, to the service and pilot implementations. The evaluation of the SOA approach on the developers in the project revealed that SOA is useful with respect to job performance and quality. Furthermore, they think SOA is easy to use and support development of AAL applications. An important finding is that the developers clearly report that they intend to use SOA in the future, but not for all type of projects. With respect to using model-driven development in web services design and implementation, the developers reported that it was useful. However, it is important that the code generated from the models is correct if the full potential of MDD should be achieved. The pilots and their evaluation in the trial sites showed that the services of the platform are sufficient to create suitable systems for end users in the domain. A SOA platform with a set of reusable domain services is a suitable foundation for more rapid development and tailoring of assisted living systems covering reoccurring needs among elderly users. It is feasible to realize a tool-chain for model-driven development of SOA applications in the AAL domain, and such a tool-chain can be accepted and found useful by software developers. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Crosstalk: The Journal of Defense Software Engineering. Volume 22, Number 2, February 2009

DTIC Science & Technology

2009-02-01

IT Investment With Service-Oriented Architecture ( SOA ), Geoffrey Raines examines how an SOA offers federal senior leadership teams an incremental and...values, and is used by 30 million people. [1] Given budget constraints, an incre- mental approach seems to be required. A Path Forward SOA , as implemented...point of view, SOA offers several positive benefits. Language Neutral Integration Web-enabling applications with a com- mon browser interface became a

Research and design of logistical information system based on SOA

NASA Astrophysics Data System (ADS)

Zhang, Bo

2013-03-01

Through the study on the existing logistics information systems and SOA technology, based on the current situation of enterprise logistics management and business features, this paper puts forward a SOA-based logistics system design program. This program is made in the WCF framework, with the combination of SOA and the actual characteristics of logistics enterprises, is simple to realize, easy to operate, and has strong expansion characteristic, therefore has high practical value.

Influence of vapor wall loss in laboratory chambers on yields of secondary organic aerosol

PubMed Central

Zhang, Xuan; Cappa, Christopher D.; Jathar, Shantanu H.; McVay, Renee C.; Ensberg, Joseph J.; Kleeman, Michael J.; Seinfeld, John H.

2014-01-01

Secondary organic aerosol (SOA) constitutes a major fraction of submicrometer atmospheric particulate matter. Quantitative simulation of SOA within air-quality and climate models—and its resulting impacts—depends on the translation of SOA formation observed in laboratory chambers into robust parameterizations. Worldwide data have been accumulating indicating that model predictions of SOA are substantially lower than ambient observations. Although possible explanations for this mismatch have been advanced, none has addressed the laboratory chamber data themselves. Losses of particles to the walls of chambers are routinely accounted for, but there has been little evaluation of the effects on SOA formation of losses of semivolatile vapors to chamber walls. Here, we experimentally demonstrate that such vapor losses can lead to substantially underestimated SOA formation, by factors as much as 4. Accounting for such losses has the clear potential to bring model predictions and observations of organic aerosol levels into much closer agreement. PMID:24711404

Factors controlling the evaporation of secondary organic aerosol from α‐pinene ozonolysis

PubMed Central

Pajunoja, Aki; Tikkanen, Olli‐Pekka; Buchholz, Angela; Faiola, Celia; Väisänen, Olli; Hao, Liqing; Kari, Eetu; Peräkylä, Otso; Garmash, Olga; Shiraiwa, Manabu; Ehn, Mikael; Lehtinen, Kari; Virtanen, Annele

2017-01-01

Abstract Secondary organic aerosols (SOA) forms a major fraction of organic aerosols in the atmosphere. Knowledge of SOA properties that affect their dynamics in the atmosphere is needed for improving climate models. By combining experimental and modeling techniques, we investigated the factors controlling SOA evaporation under different humidity conditions. Our experiments support the conclusion of particle phase diffusivity limiting the evaporation under dry conditions. Viscosity of particles at dry conditions was estimated to increase several orders of magnitude during evaporation, up to 109 Pa s. However, at atmospherically relevant relative humidity and time scales, our results show that diffusion limitations may have a minor effect on evaporation of the studied α‐pinene SOA particles. Based on previous studies and our model simulations, we suggest that, in warm environments dominated by biogenic emissions, the major uncertainty in models describing the SOA particle evaporation is related to the volatility of SOA constituents. PMID:28503004

Modeling of Semiconductor Optical Amplifier Gain Characteristics for Amplification and Switching

NASA Astrophysics Data System (ADS)

Mahad, Farah Diana; Sahmah, Abu; Supa'at, M.; Idrus, Sevia Mahdaliza; Forsyth, David

2011-05-01

The Semiconductor Optical Amplifier (SOA) is presently commonly used as a booster or pre-amplifier in some communication networks. However, SOAs are also a strong candidate for utilization as multi-functional elements in future all-optical switching, regeneration and also wavelength conversion schemes. With this in mind, the purpose of this paper is to simulate the performance of the SOA for improved amplification and switching functions. The SOA is modeled and simulated using OptSim software. In order to verify the simulated results, a MATLAB mathematical model is also used to aid the design of the SOA. Using the model, the gain difference between simulated and mathematical results in the unsaturated region is <1dB. The mathematical analysis is in good agreement with the simulation result, with only a small offset due to inherent software limitations in matching the gain dynamics of the SOA.

Black and Brown Carbon in Biogenic Settings with Different Levels of Anthropogenic Influence, and The Effect of Semivolatile Compounds on Aerosol Optical Properties

NASA Astrophysics Data System (ADS)

Tasoglou, A.; Ramachandran, S.; Khlystov, A.; Saha, P.; Grieshop, A. P.; Pandis, S. N.

2015-12-01

Secondary organic aerosol (SOA) is a major contributor to the global aerosol burden. Black carbon (BC) is a significant climate warming agent, while light-absorbing organic carbon (brown carbon, BrC), also impacts the atmospheric radiative balance. The optical properties of ambient aerosols can be affected by biogenic SOA through the lensing effect (coating of BC cores by semivolatile SOA), and by the potential formation of BrC from biogenic sources influenced by anthropogenic sources. To evaluate these effects, measurements of ambient aerosol optical properties and BC concentrations were made in rural Centreville, AL (a remote site with little anthropogenic influence) in summer 2013 and at Duke Forest in Chapel Hill, NC (a site close to high density vehicular traffic and industrial sources), during summer 2015. Photoacoustic extinctiometers (PAX, 405 nm and 532 nm) measured particulate light absorption and a single particle soot photometer (SP2) measured BC mass at both locations. A seven-wavelength Aethalometer and a three-wavelength nephelometer were also deployed at Duke Forest. A third PAX (870 nm) was deployed at Centreville. For absorption and BC measurements, the sample was cycled between a dry line and a dry/thermally-denuded line. Hourly samples were collected with a steam jet aerosol collector (SJAC) for online (2013) and offline (2015) chemical composition analysis. BC concentrations were generally higher at Duke Forest compared to the rural Centreville site. The Aethalometer readings at Duke Forest show greater absorption at the shorter wavelengths (370 nm and 470 nm) than expected from the absorption at 880 nm coupled with an inverse wavelength dependence, suggesting the presence of brown carbon. This presentation will examine the evidence for brown carbon at the two sites, as well as the effect of non-BC coatings on BC light absorption (the lensing effect.)

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

NASA Astrophysics Data System (ADS)

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

2016-07-01

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

Determining contributions of biomass burning and other sources to fine particle contemporary carbon in the western United States

NASA Astrophysics Data System (ADS)

Holden, Amanda S.; Sullivan, Amy P.; Munchak, Leigh A.; Kreidenweis, Sonia M.; Schichtel, Bret A.; Malm, William C.; Collett, Jeffrey L., Jr.

2011-02-01

Six-day integrated fine particle samples were collected at urban and rural sampling sites using Hi-Volume samplers during winter and summer 2004-2005 as part of the IMPROVE (Interagency Monitoring of PROtected Visual Environments) Radiocarbon Study. Filter samples from six sites (Grand Canyon, Mount Rainier, Phoenix, Puget Sound, Rocky Mountain National Park, and Tonto National Monument) were analyzed for levoglucosan, a tracer for biomass combustion, and other species by High-Performance Anion-Exchange Chromatography with Pulsed Amperometric Detection (HPAEC-PAD). Contemporary carbon concentrations were available from previous carbon isotope measurements at Lawrence Livermore National Laboratory. Primary contributions of biomass burning to measured fine particle contemporary carbon were estimated for residential wood burning (winter) and wild/prescribed fires (summer). Calculated contributions ranged from below detection limit to more than 100% and were typically higher at rural sites and during winter. Mannitol, a sugar alcohol emitted by fungal spores, was analyzed and used to determine contributions of fungal spores to fine particle contemporary carbon. Contributions reached up to 13% in summer samples, with higher contributions at rural sites. Concentrations of methyltetrols, oxidation products of isoprene, were also measured by HPAEC-PAD. Secondary organic aerosol (SOA) from isoprene oxidation was estimated to contribute up to 22% of measured contemporary carbon. For each sampling site, a substantial portion of the contemporary carbon was unexplained by primary biomass combustion, fungal spores, or SOA from isoprene oxidation. This unexplained fraction likely contains contributions from other SOA sources, including oxidation products of primary smoke emissions and plant emissions other than isoprene, as well as other primary particle emissions from meat cooking, plant debris, other biological aerosol particles, bio-diesel combustion, and other sources. Loss of levoglucosan during atmospheric aging of biomass burning emissions likely also results in an underestimate of apportioned primary smoke contributions.

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

NASA Astrophysics Data System (ADS)

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

2013-09-01

The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter after three hours of oxidation inside the chamber at typical atmospheric oxidant levels. Therefore, the contribution of light duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photo-oxidizing exhaust from newer (LEV1 and LEV2) vehicles was only modestly lower (38%) than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions in non-methane organic gas emissions. These data suggest that a complex and non-linear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the time scale of these experiments, the mixture of organic vapors emitted by newer vehicles appear to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the non-methane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. These results for light-duty gasoline vehicles contrast with the results from a companion study of on-road heavy-duty diesel trucks; in that study late model (2007 and later) diesel trucks equipped with catalyzed diesel particulate filters emitted very little primary PM, and the photo-oxidized emissions produced negligible amounts of SOA.

Long-term chemical analysis and organic aerosol source apportionment at nine sites in central Europe: source identification and uncertainty assessment

NASA Astrophysics Data System (ADS)

Daellenbach, Kaspar R.; Stefenelli, Giulia; Bozzetti, Carlo; Vlachou, Athanasia; Fermo, Paola; Gonzalez, Raquel; Piazzalunga, Andrea; Colombi, Cristina; Canonaco, Francesco; Hueglin, Christoph; Kasper-Giebl, Anne; Jaffrezo, Jean-Luc; Bianchi, Federico; Slowik, Jay G.; Baltensperger, Urs; El-Haddad, Imad; Prévôt, André S. H.

2017-11-01

Long-term monitoring of organic aerosol is important for epidemiological studies, validation of atmospheric models, and air quality management. In this study, we apply a recently developed filter-based offline methodology using an aerosol mass spectrometer (AMS) to investigate the regional and seasonal differences of contributing organic aerosol sources. We present offline AMS measurements for particulate matter smaller than 10 µm at nine stations in central Europe with different exposure characteristics for the entire year of 2013 (819 samples). The focus of this study is a detailed source apportionment analysis (using positive matrix factorization, PMF) including in-depth assessment of the related uncertainties. Primary organic aerosol (POA) is separated in three components: hydrocarbon-like OA related to traffic emissions (HOA), cooking OA (COA), and biomass burning OA (BBOA). We observe enhanced production of secondary organic aerosol (SOA) in summer, following the increase in biogenic emissions with temperature (summer oxygenated OA, SOOA). In addition, a SOA component was extracted that correlated with an anthropogenic secondary inorganic species that is dominant in winter (winter oxygenated OA, WOOA). A factor (sulfur-containing organic, SC-OA) explaining sulfur-containing fragments (CH3SO2+), which has an event-driven temporal behaviour, was also identified. The relative yearly average factor contributions range from 4 to 14 % for HOA, from 3 to 11 % for COA, from 11 to 59 % for BBOA, from 5 to 23 % for SC-OA, from 14 to 27 % for WOOA, and from 15 to 38 % for SOOA. The uncertainty of the relative average factor contribution lies between 2 and 12 % of OA. At the sites north of the alpine crest, the sum of HOA, COA, and BBOA (POA) contributes less to OA (POA / OA = 0.3) than at the southern alpine valley sites (0.6). BBOA is the main contributor to POA with 87 % in alpine valleys and 42 % north of the alpine crest. Furthermore, the influence of primary biological particles (PBOAs), not resolved by PMF, is estimated and could contribute significantly to OA in PM10.

The Joint Space Operations Center (JSpOC) Mission System (JMS) and the Advanced Research, Collaboration, and Application Development Environment (ARCADE)

NASA Astrophysics Data System (ADS)

Runco, A.; Echeverry, J.; Kim, R.; Sabol, C.; Zetocha, P.; Murray-Krezan, J.

2014-09-01

The JSpOC Mission System is a modern service-oriented architecture (SOA) infrastructure with increased process automation and improved tools to enhance Space Situational Awareness (SSA). The JMS program has already delivered Increment 1 in April 2013 as initial capability to operations. The programs current focus, Increment 2, will be completed by 2016 and replace the legacy Space Defense Operations Center (SPADOC) and Astrodynamics Support Workstation (ASW) capabilities. Post 2016, JMS Increment 3 will continue to provide additional SSA and C2 capabilities that will require development of new applications and procedures as well as the exploitation of new data sources with more agility. In 2012, the JMS Program Office entered into a partnership with AFRL/RD (Directed Energy) and AFRL/RV (Space Vehicles) to create the Advanced Research, Collaboration, and Application Development Environment (ARCADE). The purpose of the ARCADE is to: (1) serve as a centralized testbed for all research and development (R&D) activities related to JMS applications, including algorithm development, data source exposure, service orchestration, and software services, and provide developers reciprocal access to relevant tools and data to accelerate technology development, (2) allow the JMS program to communicate user capability priorities and requirements to developers, (3) provide the JMS program with access to state-of-the-art research, development, and computing capabilities, and (4) support market research efforts by identifying outstanding performers that are available to shepherd into the formal transition process. AFRL/RV and AFRL/RD have created development environments at both unclassified and classified levels that together allow developers to develop applications and work with data sources. The unclassified ARCADE utilizes the Maui high performance computing (HPC) Portal, and can be accessed using a CAC or Kerberos using Yubikey. This environment gives developers a sandbox environment to test and benchmark algorithms and services. The classified environments allow these new applications to be integrated with the JMS SOA and other data sources to help mature the capability to TRL 6.