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

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.

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CCN activity of aliphatic amine secondary aerosol

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-14-31-2014 ◽

2014 ◽

Vol 14 (1) ◽

pp. 31-56 ◽

Cited By ~ 2

Author(s):

X. Tang ◽

D. Price ◽

E. Praske ◽

D. Vu ◽

K. Purvis-Roberts ◽

...

Keyword(s):

Hydroxyl Radical ◽

Organic Material ◽

Thermal Gradient ◽

Aliphatic Amine ◽

Organic Aerosol ◽

Inorganic Salts ◽

Nitrate Radical ◽

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 composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction 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. TMA + N2O5 form semi-volatile organics in low RH conditions that have κ ~ 0.20, indicative of slightly soluble organic material. As RH increases, several 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. Higher CCN activity (κ > 0.3) was also observed for humid BA+N2O5 aerosols compared with dry aerosol (κ ~ 0.2), as a result of the formation of inorganic salts such as NH4NO3 and butylamine nitrate (C4H11N · HNO3). Compared with TMA, BA+N2O5 reactions produce more volatile aerosols. The BA+N2O5 aerosol products under humid experiments were found to be very sensitive to the temperature within the stream-wise continuous flow thermal gradient CCN counter. The CCN counter, when set above a 21 °C temperature difference, evaporates BA+N2O5 aerosol formed at RH ≥ 30%; κ ranges from 0.4 to 0.7 and is dependent on the instrument supersaturation (ss) settings. The aerosol behaves non-ideally, hence simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems κ ranges from 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. Thermal gradient CCN counters measurement will impact the observed CCN activity of volatile aerosol formed via a nitric acid pathway. The contributions of semi-volatile secondary organic and inorganic material from aliphatic amines must be considered for accurate hygroscopicity and CCN predictions from aliphatic amine systems.

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

Atmospheric Chemistry and Physics ◽

10.5194/acp-11-8913-2011 ◽

2011 ◽

Vol 11 (17) ◽

pp. 8913-8928 ◽

Cited By ~ 203

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.

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

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-11-13617-2011 ◽

2011 ◽

Vol 11 (5) ◽

pp. 13617-13653 ◽

Cited By ~ 4

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 0.003 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 that has been previously obtained. To first order, the κorg-to-O/C relationship is well represented by a linear function of the form κorg = (0.17 ± 0.04) × O/C + 0.04, suggesting that a simple, semi-empirical parameterization of OOA hygroscopicity and oxidation level can be defined for use in chemistry and climate models.

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

Physical Chemistry Chemical Physics ◽

10.1039/c8cp00075a ◽

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.

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A study of the ability of pure secondary organic aerosol to act as cloud condensation nuclei

Atmospheric Environment ◽

10.1016/s1352-2310(97)00054-x ◽

1997 ◽

Vol 31 (15) ◽

pp. 2205-2214 ◽

Cited By ~ 222

Author(s):

Celia N. Cruz ◽

Spyros N. Pandis

Keyword(s):

Secondary Organic Aerosol ◽

Cloud Condensation Nuclei ◽

Organic Aerosol ◽

Condensation Nuclei

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Cloud condensation nuclei activity and droplet formation of primary and secondary organic aerosol mixtures

Aerosol Science and Technology ◽

10.1080/02786826.2017.1392480 ◽

2017 ◽

Vol 52 (2) ◽

pp. 242-251 ◽

Cited By ~ 5

Author(s):

E. A. Fofie ◽

N. M. Donahue ◽

A. Asa-Awuku

Keyword(s):

Secondary Organic Aerosol ◽

Cloud Condensation Nuclei ◽

Organic Aerosol ◽

Droplet Formation ◽

Condensation Nuclei

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Aqueous Photochemistry of Secondary Organic Aerosol of α-Pinene and α-Humulene Oxidized with Ozone, Hydroxyl Radical, and Nitrate Radical

The Journal of Physical Chemistry A ◽

10.1021/acs.jpca.6b10900 ◽

2017 ◽

Vol 121 (6) ◽

pp. 1298-1309 ◽

Cited By ~ 26

Author(s):

Dian E. Romonosky ◽

Ying Li ◽

Manabu Shiraiwa ◽

Alexander Laskin ◽

Julia Laskin ◽

...

Keyword(s):

Hydroxyl Radical ◽

Secondary Organic Aerosol ◽

Organic Aerosol ◽

Nitrate Radical

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Cloud condensation nuclei activation of monoterpene and sesquiterpene secondary organic aerosol

Journal of Geophysical Research Atmospheres ◽

10.1029/2004jd005754 ◽

2005 ◽

Vol 110 (D14) ◽

pp. n/a-n/a ◽

Cited By ~ 91

Author(s):

Kara E. Huff Hartz ◽

Thomas Rosenørn ◽

Shaun R. Ferchak ◽

Timothy M. Raymond ◽

Merete Bilde ◽

...

Keyword(s):

Secondary Organic Aerosol ◽

Cloud Condensation Nuclei ◽

Organic Aerosol ◽

Condensation Nuclei

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CCN activity and volatility of β-caryophyllene secondary organic aerosol

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-12-20745-2012 ◽

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.

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