Gas-phase kinetics modifies the CCN activity of a biogenic SOA

2018 ◽  
Vol 20 (9) ◽  
pp. 6591-6597
Author(s):  
A. E. Vizenor ◽  
A. A. Asa-Awuku
Keyword(s):  
Particle Size ◽  
Thermodynamic Properties ◽  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Aerosol Composition ◽  
Phase Partitioning ◽  
Gas Phase Kinetics ◽  
Ccn Activity

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. The gas-to-aerosol phase partitioning is critical for aerosol composition and thus gas-phase vapors and kinetics can play an important role in the CCN activity of SOA.

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

2010 ◽  
Vol 3 (6) ◽  
pp. 5211-5251 ◽  
Author(s):  
A. T. Lambe ◽  
A. T. Ahern ◽  
L. R. Williams ◽  
J. G. Slowik ◽  
J. P. S. Wong ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Transmission Efficiency ◽  
Smog Chamber ◽  
Flow Tube ◽  
Activity Measurements ◽  
Ccn Activity

Abstract. Motivated by the need to develop instrumental techniques for characterizing organic aerosol aging, we report on the performance of the Toronto Photo-Oxidation Tube (TPOT) and Potential Aerosol Mass (PAM) flow tube reactors under a variety of experimental conditions. The principal difference between the flow tubes was that the PAM system was designed to minimize wall effects, whereas the TPOT reactor was designed to study heterogeneous aerosol chemistry. The following studies were performed: (1) transmission efficiency measurements for CO2, SO2, and bis(2-ethylhexyl) sebacate (BES) particles, (2) H2SO4 yield measurements from the oxidation of SO2, (3) residence time distribution (RTD) measurements for CO2, SO2, and BES particles, (4) chemical composition and cloud condensation nuclei (CCN) activity measurements of BES particles exposed to OH radicals, and (5) chemical composition, CCN activity, and yield measurements of secondary organic aerosol (SOA) generated from gas-phase OH oxidation of m-xylene and α-pinene. OH exposures ranged from (2.0 ± 1.0) × 1010 to (1.8 ± 0.3) × 1012 molec cm−3 s. Where applicable, data from the flow tube reactors are compared with published results from the Caltech smog chamber. The TPOT yielded narrower RTDs. However, its transmission efficiency for SO2 was lower than that for the PAM. Transmission efficiency for BES and H2SO4 particles was size-dependent and was similar for the two flow tube designs. Oxidized BES particles had similar chemical composition and CCN activity at OH exposures greater than 1011 molec cm−3 s, but different CCN activity at lower OH exposures. The composition and yield of m-xylene and α-pinene SOA was strongly affected by reactor design and operating conditions, with wall interactions seemingly having the strongest influence on SOA yield. At comparable OH exposures, flow tube SOA was more oxidized than smog chamber SOA because of faster gas-phase oxidation relative to particle nucleation. SOA yields were lower in the TPOT than in the PAM, but CCN activity of flow-tube-generated SOA particles was similar. For comparable OH exposures, α-pinene SOA yields were similar in the PAM and Caltech chambers, but m-xylene SOA yields were much lower in the PAM compared to the Caltech chamber.

scholarly journals Development of aroCACM/MPMPO 1.0: a model to simulate secondary organic aerosol from aromatic precursors in regional models

2016 ◽  
Vol 9 (6) ◽  
pp. 2143-2151 ◽  
Author(s):  
Matthew L. Dawson ◽  
Jialu Xu ◽  
Robert J. Griffin ◽  
Donald Dabdub
Keyword(s):  
Gas Phase ◽  
Atmospheric Chemistry ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Three Dimensional ◽  
Organic Aerosol ◽  
Phase Partitioning ◽  
California Institute Of Technology ◽  
Institute Of Technology ◽  
Three Dimensional Models

Abstract. The atmospheric oxidation of aromatic compounds is an important source of secondary organic aerosol (SOA) in urban areas. The oxidation of aromatics depends strongly on the levels of nitrogen oxides (NOx). However, details of the mechanisms by which oxidation occurs have only recently been elucidated. Xu et al. (2015) developed an updated version of the gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) designed to simulate toluene and m-xylene oxidation in chamber experiments over a range of NOx conditions. The output from such a mechanism can be used in thermodynamic predictions of gas–particle partitioning leading to SOA. The current work reports the development of a model for SOA formation that combines the gas-phase mechanism of Xu et al. (2015) with an updated lumped SOA-partitioning scheme (Model to Predict the Multi-phase Partitioning of Organics, MPMPO) that allows partitioning to multiple aerosol phases and that is designed for use in larger-scale three-dimensional models. The resulting model is termed aroCACM/MPMPO 1.0. The model is integrated into the University of California, Irvine – California Institute of Technology (UCI-CIT) Airshed Model, which simulates the South Coast Air Basin (SoCAB) of California. Simulations using 2012 emissions indicate that “low-NOx” pathways to SOA formation from aromatic oxidation play an important role, even in regions that typically exhibit high-NOx concentrations.

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

2011 ◽  
Vol 11 (17) ◽  
pp. 8913-8928 ◽  
Author(s):  
A. T. Lambe ◽  
T. B. Onasch ◽  
P. Massoli ◽  
D. R. Croasdale ◽  
J. P. Wright ◽  
...  
Keyword(s):  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Cloud Condensation Nuclei ◽  
Oxidation Mechanism ◽  
Organic Aerosol ◽  
Anthropogenic Sources ◽  
Oh Radicals ◽  
Condensation Nuclei ◽  
Aerosol Mass ◽  
Ccn Activity

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

scholarly journals Characterization of a large biogenic secondary organic aerosol event from eastern Canadian forests

2010 ◽  
Vol 10 (6) ◽  
pp. 2825-2845 ◽  
Author(s):  
J. G. Slowik ◽  
C. Stroud ◽  
J. W. Bottenheim ◽  
P. C. Brickell ◽  
R. Y.-W. Chang ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Cloud Condensation Nuclei ◽  
Coniferous Forest ◽  
Organic Aerosol ◽  
Chemical Mechanism ◽  
Rural Site ◽  
Chemical Transport Model ◽  
Aerosol Composition ◽  
Aerosol Mass

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

scholarly journals Cloud condensation nuclei (CCN) activity of aliphatic amine secondary aerosol

2014 ◽  
Vol 14 (12) ◽  
pp. 5959-5967 ◽  
Author(s):  
X. Tang ◽  
D. Price ◽  
E. Praske ◽  
D. N. Vu ◽  
K. Purvis-Roberts ◽  
...  
Keyword(s):  
Hydroxyl Radical ◽  
Aliphatic Amine ◽  
Secondary Organic Aerosol ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Nitrate Radical ◽  
Condensation Nuclei ◽  
Primary Aliphatic Amine ◽  
Secondary Aerosol ◽  
Ccn Activity

Abstract. Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g., hydroxyl radical and nitrate radical). The particle can contain both secondary organic aerosol (SOA) and inorganic salts. The ratio of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ, ≤ 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N2O5 (source of nitrate radical, NO3) contains less volatile compounds than the primary aliphatic amine (BA) aerosol. As relative humidity (RH) increases, inorganic amine salts are formed as a result of acid–base reactions. The CCN activity of the humid TMA–N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. The humid BA + N2O5 aerosol products were found to be very sensitive to the temperature at which the measurements were made within the streamwise continuous-flow thermal gradient CCN counter; κ ranges from 0.4 to 0.7 dependent on the instrument supersaturation (ss) settings. The variance of the measured aerosol κ values indicates that simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems' κ ranges within 0.2 < κ < 0.7. This work indicates that aerosols formed via nighttime reactions with amines are likely to produce hygroscopic and volatile aerosol, whereas photochemical reactions with OH produce secondary organic aerosol of lower CCN activity. The contributions of semivolatile secondary organic and inorganic material from aliphatic amines must be considered for accurate hygroscopicity and CCN predictions from aliphatic amine systems.

scholarly journals CCN activity and volatility of β-caryophyllene secondary organic aerosol

2012 ◽  
Vol 12 (8) ◽  
pp. 20745-20783
Author(s):  
M. Frosch ◽  
M. Bilde ◽  
A. Nenes ◽  
A. P. Praplan ◽  
Z. Jurányi ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Light Exposure ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Droplet Growth ◽  
Experimental Conditions ◽  
Initial Injection ◽  
Different Temperatures ◽  
Kinetics Of ◽  
Ccn Activity

Abstract. In a series of smog chamber experiments, the Cloud Condensation Nuclei (CCN) activity of Secondary Organic Aerosol (SOA) generated from ozonolysis of β-caryophyllene was characterized by determining the CCN derived hygroscopicity parameter, κCCN, from experimental data. Two types of CCN counters, operating at different temperatures, were used. The effect of semi-volatile organic compounds on the CCN activity of SOA was studied using a thermodenuder. Overall, SOA was only slightly CCN active (with κCCN in the range 0.001–0.16), and in dark experiments with no OH scavenger present, κCCN decreased when particles were sent through the thermodenuder (with a temperature up to 50 °C). SOA was generated under different experimental conditions: in some experiments, an OH scavenger (2-butanol) was added. SOA from these experiments was less CCN active than SOA produced in experiments without an OH scavenger (i.e. where OH was produced during ozonolysis). In other experiments, lights were turned on, either without or with the addition of HONO (OH source). This led to the formation of more CCN active SOA. SOA was aged up to 30 h through exposure to ozone and (in experiments with no OH scavenger present) to OH. In all experiments, the derived κCCN consistently increased with time after initial injection of β-caryophyllene, showing that chemical ageing increases the CCN activity of β-caryophyllene SOA. κCCN was also observed to depend on supersaturation, which was explained either as an evaporation artifact from semi-volatile SOA (only observed in experiments lacking light exposure) or, alternatively, by effects related to chemical composition depending on dry particle size. Using the method of Threshold Droplet Growth Analysis it was also concluded that the activation kinetics of the SOA do not differ significantly from calibration ammonium sulphate aerosol.

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

2011 ◽  
Vol 4 (3) ◽  
pp. 445-461 ◽  
Author(s):  
A. T. Lambe ◽  
A. T. Ahern ◽  
L. R. Williams ◽  
J. G. Slowik ◽  
J. P. S. Wong ◽  
...  
Keyword(s):  
Gas Phase ◽  
Mass Spectra ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Transmission Efficiency ◽  
Smog Chamber ◽  
Flow Tube ◽  
Aerosol Mass ◽  
Activity Measurements ◽  
Ccn Activity

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

scholarly journals Prediction of cloud condensation nuclei activity for organic compounds using functional group contribution methods

2016 ◽  
Vol 9 (1) ◽  
pp. 111-124 ◽  
Author(s):  
M. D. Petters ◽  
S. M. Kreidenweis ◽  
P. J. Ziemann
Keyword(s):  
Organic Compounds ◽  
Field Experiments ◽  
Functional Group ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Group Contribution ◽  
Condensation Nuclei ◽  
Aerosol Composition ◽  
Group Contribution Methods ◽  
Ccn Activity

Abstract. A wealth of recent laboratory and field experiments demonstrate that organic aerosol composition evolves with time in the atmosphere, leading to changes in the influence of the organic fraction to cloud condensation nuclei (CCN) spectra. There is a need for tools that can realistically represent the evolution of CCN activity to better predict indirect effects of organic aerosol on clouds and climate. This work describes a model to predict the CCN activity of organic compounds from functional group composition. Following previous methods in the literature, we test the ability of semi-empirical group contribution methods in Köhler theory to predict the effective hygroscopicity parameter, kappa. However, in our approach we also account for liquid–liquid phase boundaries to simulate phase-limited activation behavior. Model evaluation against a selected database of published laboratory measurements demonstrates that kappa can be predicted within a factor of 2. Simulation of homologous series is used to identify the relative effectiveness of different functional groups in increasing the CCN activity of weakly functionalized organic compounds. Hydroxyl, carboxyl, aldehyde, hydroperoxide, carbonyl, and ether moieties promote CCN activity while methylene and nitrate moieties inhibit CCN activity. The model can be incorporated into scale-bridging test beds such as the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to evaluate the evolution of kappa for a complex mix of organic compounds and to develop suitable parameterizations of CCN evolution for larger-scale models.

scholarly journals Prediction of cloud condensation nuclei activity for organic compounds using functional group contribution methods

2015 ◽  
Vol 8 (9) ◽  
pp. 7445-7475 ◽  
Author(s):  
M. D. Petters ◽  
S. M. Kreidenweis ◽  
P. J. Ziemann
Keyword(s):  
Organic Compounds ◽  
Field Experiments ◽  
Functional Group ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Group Contribution ◽  
Condensation Nuclei ◽  
Aerosol Composition ◽  
Group Contribution Methods ◽  
Ccn Activity

Abstract. A wealth of recent laboratory and field experiments demonstrate that organic aerosol composition evolves with time in the atmosphere, leading to changes in the influence of the organic fraction to cloud condensation nuclei (CCN) spectra. There is a need for tools that can realistically represent the evolution of CCN activity to better predict indirect effects of organic aerosol on clouds and climate. This work describes a model to predict the CCN activity of organic compounds from functional group composition. The model combines Köhler theory with semi-empirical group contribution methods to estimate molar volumes, activity coefficients and liquid-liquid phase boundaries to predict the effective hygroscopicity parameter, kappa. Model evaluation against a selected database of published laboratory measurements demonstrates that kappa can be predicted within a factor of two. Simulation of homologous series is used to identify the relative effectiveness of different functional groups in increasing the CCN activity of weakly functionalized organic compounds. Hydroxyl, carboxyl, aldehyde, hydroperoxide, carbonyl, and ether moieties promote CCN activity while methylene and nitrate moieties inhibit CCN activity. The model can be incorporated into scale-bridging testbeds such as the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere to evaluate the evolution of kappa for a complex mix of organic compounds and to develop suitable parameterizations of CCN evolution for larger scale models.

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