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Title: Observations and implications of liquid–liquid phase separation at high relative humidities in secondary organic material produced by α-pinene ozonolysis without inorganic salts

Particles consisting of secondary organic material (SOM) are abundant in the atmosphere. In order to predict the role of these particles in climate, visibility and atmospheric chemistry, information on particle phase state (i.e., single liquid, two liquids and solid) is needed. Our paper focuses on the phase state of SOM particles free of inorganic salts produced by the ozonolysis of α-pinene. Phase transitions were investigated in the laboratory using optical microscopy and theoretically using a thermodynamic model at 290 K and for relative humidities ranging from < 0.5 to 100%. In the laboratory studies, a single phase was observed from 0 to 95% relative humidity (RH) while two liquid phases were observed above 95% RH. For increasing RH, the mechanism of liquid–liquid phase separation (LLPS) was spinodal decomposition. The RH range over which two liquid phases were observed did not depend on the direction of RH change. In the modeling studies, the SOM took up very little water and was a single organic-rich phase at low RH values. At high RH, the SOM underwent LLPS to form an organic-rich phase and a water-rich phase, consistent with the laboratory studies. The presence of LLPS at high RH values can have consequencesmore » for the cloud condensation nuclei (CCN) activity of SOM particles. In the simulated Köhler curves for SOM particles, two local maxima were observed. Depending on the composition of the SOM, the first or second maximum can determine the critical supersaturation for activation. Recently researchers have observed inconsistencies between measured CCN properties of SOM particles and hygroscopic growth measured below water saturation (i.e., hygroscopic parameters measured below water saturation were inconsistent with hygroscopic parameters measured above water saturation). Furthermore, the work presented here illustrates that such inconsistencies are expected for systems with LLPS when the water uptake at subsaturated conditions represents the hygroscopicity of an organic-rich phase while the barrier for CCN activation can be determined by the second maximum in the Köhler curve when the particles are water rich.« less
Authors:
 [1] ;  [1] ;  [2] ;  [3] ;  [3] ;  [1] ;  [4] ;  [5] ;  [1]
  1. Univ. of British Columbia, Vancouver, BC (Canada). Dept. of Chemistry
  2. Marcolli Chemistry and Physics Consulting GmbH, Zurich (Switzerland); ETH Zurich (Switzerland). Inst. for Atmospheric and Climate Science
  3. Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  5. Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences and Dept. of Earth and Planetary Sciences
Publication Date:
Type:
Accepted Manuscript
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Name: Atmospheric Chemistry and Physics (Online); Journal Volume: 16; Journal Issue: 12; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Research Org:
Univ. of British Columbia, Vancouver, BC (Canada)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES
OSTI Identifier:
1375410

Renbaum-Wolff, Lindsay, Song, Mijung, Marcolli, Claudia, Zhang, Yue, Liu, Pengfei F., Grayson, James W., Geiger, Franz M., Martin, Scot T., and Bertram, Allan K.. Observations and implications of liquid–liquid phase separation at high relative humidities in secondary organic material produced by α-pinene ozonolysis without inorganic salts. United States: N. p., Web. doi:10.5194/acp-16-7969-2016.
Renbaum-Wolff, Lindsay, Song, Mijung, Marcolli, Claudia, Zhang, Yue, Liu, Pengfei F., Grayson, James W., Geiger, Franz M., Martin, Scot T., & Bertram, Allan K.. Observations and implications of liquid–liquid phase separation at high relative humidities in secondary organic material produced by α-pinene ozonolysis without inorganic salts. United States. doi:10.5194/acp-16-7969-2016.
Renbaum-Wolff, Lindsay, Song, Mijung, Marcolli, Claudia, Zhang, Yue, Liu, Pengfei F., Grayson, James W., Geiger, Franz M., Martin, Scot T., and Bertram, Allan K.. 2016. "Observations and implications of liquid–liquid phase separation at high relative humidities in secondary organic material produced by α-pinene ozonolysis without inorganic salts". United States. doi:10.5194/acp-16-7969-2016. https://www.osti.gov/servlets/purl/1375410.
@article{osti_1375410,
title = {Observations and implications of liquid–liquid phase separation at high relative humidities in secondary organic material produced by α-pinene ozonolysis without inorganic salts},
author = {Renbaum-Wolff, Lindsay and Song, Mijung and Marcolli, Claudia and Zhang, Yue and Liu, Pengfei F. and Grayson, James W. and Geiger, Franz M. and Martin, Scot T. and Bertram, Allan K.},
abstractNote = {Particles consisting of secondary organic material (SOM) are abundant in the atmosphere. In order to predict the role of these particles in climate, visibility and atmospheric chemistry, information on particle phase state (i.e., single liquid, two liquids and solid) is needed. Our paper focuses on the phase state of SOM particles free of inorganic salts produced by the ozonolysis of α-pinene. Phase transitions were investigated in the laboratory using optical microscopy and theoretically using a thermodynamic model at 290 K and for relative humidities ranging from < 0.5 to 100%. In the laboratory studies, a single phase was observed from 0 to 95% relative humidity (RH) while two liquid phases were observed above 95% RH. For increasing RH, the mechanism of liquid–liquid phase separation (LLPS) was spinodal decomposition. The RH range over which two liquid phases were observed did not depend on the direction of RH change. In the modeling studies, the SOM took up very little water and was a single organic-rich phase at low RH values. At high RH, the SOM underwent LLPS to form an organic-rich phase and a water-rich phase, consistent with the laboratory studies. The presence of LLPS at high RH values can have consequences for the cloud condensation nuclei (CCN) activity of SOM particles. In the simulated Köhler curves for SOM particles, two local maxima were observed. Depending on the composition of the SOM, the first or second maximum can determine the critical supersaturation for activation. Recently researchers have observed inconsistencies between measured CCN properties of SOM particles and hygroscopic growth measured below water saturation (i.e., hygroscopic parameters measured below water saturation were inconsistent with hygroscopic parameters measured above water saturation). Furthermore, the work presented here illustrates that such inconsistencies are expected for systems with LLPS when the water uptake at subsaturated conditions represents the hygroscopicity of an organic-rich phase while the barrier for CCN activation can be determined by the second maximum in the Köhler curve when the particles are water rich.},
doi = {10.5194/acp-16-7969-2016},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 12,
volume = 16,
place = {United States},
year = {2016},
month = {7}
}