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

Atmospheric Chemistry and Physics ◽

10.5194/acp-14-5959-2014 ◽

2014 ◽

Vol 14 (12) ◽

pp. 5959-5967 ◽

Cited By ~ 6

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.

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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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Nitrate radical, ozone and hydroxyl radical initiated aging of limonene secondary organic aerosol

Atmospheric Environment X ◽

10.1016/j.aeaoa.2021.100102 ◽

2021 ◽

Vol 9 ◽

pp. 100102

Author(s):

Sathiyamurthi Ramasamy ◽

Tomoki Nakayama ◽

Yu Morino ◽

Takashi Imamura ◽

Yoshizumi Kajii ◽

...

Keyword(s):

Hydroxyl Radical ◽

Secondary Organic Aerosol ◽

Organic Aerosol ◽

Nitrate Radical

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TOTAL ORGANIC AEROSOL CONCENTRATIONS: RELATIVE CONTRIBUTIONS OF BIOGENIC AND ANTHROPOGENIC AND PRIMARY AND SECONDARY AEROSOL

Journal of Aerosol Science ◽

10.1016/s0021-8502(21)00430-4 ◽

2001 ◽

Vol 32 ◽

pp. 957-958

Author(s):

R.J. BARTHELMIE ◽

S.C. PRYOR

Keyword(s):

Organic Aerosol ◽

Secondary Aerosol

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In situ vertical profiles of aerosol extinction, mass, and composition over the southeast United States during SENEX and SEAC<sup>4</sup>RS: observations of a modest aerosol enhancement aloft

Atmospheric Chemistry and Physics ◽

10.5194/acp-15-7085-2015 ◽

2015 ◽

Vol 15 (12) ◽

pp. 7085-7102 ◽

Cited By ~ 40

Author(s):

N. L. Wagner ◽

C. A. Brock ◽

W. M. Angevine ◽

A. Beyersdorf ◽

P. Campuzano-Jost ◽

...

Keyword(s):

United States ◽

Mixed Layer ◽

Transition Layer ◽

Southeastern United States ◽

Vertical Mixing ◽

Organic Aerosol ◽

Vertical Profiles ◽

Free Troposphere ◽

Secondary Aerosol

Abstract. Vertical profiles of submicron aerosol from in situ aircraft-based measurements were used to construct aggregate profiles of chemical, microphysical, and optical properties. These vertical profiles were collected over the southeastern United States (SEUS) during the summer of 2013 as part of two separate field studies: the Southeast Nexus (SENEX) study and the Study of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS). Shallow cumulus convection was observed during many profiles. These conditions enhance vertical transport of trace gases and aerosol and create a cloudy transition layer on top of the sub-cloud mixed layer. The trace gas and aerosol concentrations in the transition layer were modeled as a mixture with contributions from the mixed layer below and the free troposphere above. The amount of vertical mixing, or entrainment of air from the free troposphere, was quantified using the observed mixing ratio of carbon monoxide (CO). Although the median aerosol mass, extinction, and volume decreased with altitude in the transition layer, they were ~10 % larger than expected from vertical mixing alone. This enhancement was likely due to secondary aerosol formation in the transition layer. Although the transition layer enhancements of the particulate sulfate and organic aerosol (OA) were both similar in magnitude, only the enhancement of sulfate was statistically significant. The column integrated extinction, or aerosol optical depth (AOD), was calculated for each individual profile, and the transition layer enhancement of extinction typically contributed less than 10 % to the total AOD. Our measurements and analysis were motivated by two recent studies that have hypothesized an enhanced layer of secondary aerosol aloft to explain the summertime enhancement of AOD (2–3 times greater than winter) over the southeastern United States. The first study attributes the layer aloft to secondary organic aerosol (SOA) while the second study speculates that the layer aloft could be SOA or secondary particulate sulfate. In contrast to these hypotheses, the modest enhancement we observed in the transition layer was not dominated by OA and was not a large fraction of the summertime AOD.

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Secondary organic aerosol formation from reaction of tertiary amines with nitrate radical

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-8-16585-2008 ◽

2008 ◽

Vol 8 (4) ◽

pp. 16585-16608 ◽

Cited By ~ 6

Author(s):

M. E. Erupe ◽

D. J. Price ◽

P. J. Silva ◽

Q. G. J. Malloy ◽

L. Qi ◽

...

Keyword(s):

Mass Spectrometer ◽

Secondary Organic Aerosol ◽

Organic Aerosol ◽

Nitrate Radical ◽

Tertiary Amines ◽

Aerosol Formation ◽

Night Time ◽

Aerosol Mass Spectrometer ◽

Aerosol Mass ◽

Secondary Organic Aerosol Formation

Abstract. Secondary organic aerosol formation from the reaction of tertiary amines with nitrate radical was investigated in an indoor environmental chamber. Particle chemistry was monitored using a high resolution aerosol mass spectrometer while gas-phase species were detected using a proton transfer reaction mass spectrometer. Trimethylamine, triethylamine and tributylamine were studied. Results indicate that tributylamine forms the most aerosol mass followed by trimethylamine and triethylamine respectively. Spectra from the aerosol mass spectrometer indicate the formation of complex non-salt aerosol products. We propose a reaction mechanism that proceeds via abstraction of a proton by nitrate radical followed by RO2 chemistry. Rearrangement of the aminyl alkoxy radical through hydrogen shift leads to the formation of hydroxylated amides, which explain most of the higher mass ions in the mass spectra. These experiments show that oxidation of tertiary amines by nitrate radical may be an important night-time source of secondary organic aerosol.

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Evaluation of the SOA Formation in the Reaction of Furfural with Atmospheric Oxidants

Atmosphere ◽

10.3390/atmos11090927 ◽

2020 ◽

Vol 11 (9) ◽

pp. 927

Author(s):

Inmaculada Colmenar ◽

Pilar Martín ◽

Beatriz Cabañas ◽

Sagrario Salgado ◽

Florentina Villanueva ◽

...

Keyword(s):

Gas Phase ◽

Ultrafine Particles ◽

Analytical Techniques ◽

Organic Aerosol ◽

Nitrate Radical ◽

Atmospheric Conditions ◽

Severe Damage ◽

Infrared Spectrophotometer ◽

Cl Atoms ◽

Product Study

An experimental product study of the reactions of furfural with the main tropospheric oxidants (Cl, OH and NO3) has been carried out using a Fourier Transform Infrared spectrophotometer (FTIR) and a gas chromatograph–mass spectrometer with a time of flight detector (GC–TOFMS). The main gas-phase products detected were 5-chloro-2(5H)-furanone, maleic anhydride, 2-nitrofuran and CO. Molar yields were quantified for the detected products in these reactions, thus suggesting the existence of nongaseous products that could not be observed with the analytical techniques employed. The formation of Secondary Organic Aerosol (SOA) from the oxidation of furfural with Cl atoms, OH, NO3 and ozone was investigated in a smog chamber in the absence of inorganic seed aerosols. The experimental results show the formation of ultrafine particles (less than 1 µm in diameter) for all of the studied reactions except for the nitrate radical. Given their small size, these ultrafine particles (<1 µm) can easily penetrate into the respiratory tract and reach the alveolar region. These particles, therefore, have the potential to cause severe damage to the respiratory system. The aerosol yield obtained, Y, was low (<0.04) in all cases, which means that the aerosols generated from furfural, under atmospheric conditions, could have little impact.

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Liquid-liquid phase separation in particles containing secondary organic material free of inorganic salts

10.5194/acp-2017-408 ◽

2017 ◽

Cited By ~ 1

Author(s):

Mijung Song ◽

Pengfei Liu ◽

Scot T. Martin ◽

Allan K. Bertram

Keyword(s):

Phase Separation ◽

Liquid Phase ◽

Organic Material ◽

Water Saturation ◽

Liquid Phase Separation ◽

Inorganic Salts ◽

Photo Oxidation ◽

Condensation Nucleation ◽

The Difference ◽

Liquid Liquid Phase Separation

Abstract. Particles containing secondary organic material (SOM) are ubiquitous in the atmosphere and play a role in climate and air quality. Recently, research has shown that liquid-liquid phase separation (LLPS) occurs at high relative humidities (RH) (greater than ~ 95 %) in α-pinene-derived SOM particles free of inorganic salts while LLPS does not occur in isoprene-derived SOM particles free of inorganic salts. We expand on these findings by investigating LLPS in SOM particles free of inorganic salts produced from ozonolysis of β-caryophyllene, ozonolysis of limonene, and photo-oxidation of toluene. LLPS was observed at greater than ~ 95 % RH in the biogenic SOM particles derived from β-caryophyllene and limonene while LLPS was not observed in the anthropogenic SOM particles derived from toluene at 290 ± 1 K. This work combined with the earlier work on LLPS in SOM particles free of inorganic salts suggests that the occurrence of LLPS in SOM particles free of inorganic salts is related to the average oxygen-to-carbon elemental ratio (O : C) of the organic material. When the average O : C is between 0.25 and 0.60, LLPS was observed, but when the average O : C was between 0.52 and 1.3, LLPS was not observed. These results help explain the difference between the hygroscopic parameter k of SOM particles measured above and below water saturation in the laboratory and field, and have implications for predicting the cloud condensation nucleation properties of SOM particles.

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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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