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Title: Mixing times of organic molecules within secondary organic aerosol particles: a global planetary boundary layer perspective

Abstract

When simulating the formation and life cycle of secondary organic aerosol (SOA) with chemical transport models, it is often assumed that organic molecules are well mixed within SOA particles on the timescale of 1h. While this assumption has been debated vigorously in the literature, the issue remains unresolved in part due to a lack of information on the mixing times within SOA particles as a function of both temperature and relative humidity. Using laboratory data, meteorological fields, and a chemical transport model, we estimated how often mixing times are < 1h within SOA in the planetary boundary layer (PBL), the region of the atmosphere where SOA concentrations are on average the highest. First, a parameterization for viscosity as a function of temperature and RH was developed for α-pinene SOA using room-temperature and low-temperature viscosity data for α-pinene SOA generated in the laboratory using mass concentrations of ~1000µg m -3. Based on this parameterization, the mixing times within α-pinene SOA are < 1h for 98.5% and 99.9% of the occurrences in the PBL during January and July, respectively, when concentrations are significant (total organic aerosol concentrations are > 0.5µg m -3 at the surface). Next, as a starting point to quantifymore » how often mixing times of organic molecules are < 1h within α-pinene SOA generated using low, atmospherically relevant mass concentrations, we developed a temperature-independent parameterization for viscosity using the room-temperature viscosity data for α-pinene SOA generated in the laboratory using a mass concentration of ~70µg m -3. Based on this temperature-independent parameterization, mixing times within α-pinene SOA are < 1h for 27 and 19.5% of the occurrences in the PBL during January and July, respectively, when concentrations are significant. However, associated with these conclusions are several caveats, and due to these caveats we are unable to make strong conclusions about how often mixing times of organic molecules are < 1h within α-pinene SOA generated using low, atmospherically relevant mass concentrations. Finally, a parameterization for viscosity of anthropogenic SOA as a function of temperature and RH was developed using sucrose–water data. Based on this parameterization, and assuming sucrose is a good proxy for anthropogenic SOA, 70 and 83% of the mixing times within anthropogenic SOA in the PBL are < 1h for January and July, respectively, when concentrations are significant. These percentages are likely lower limits due to the assumptions used to calculate mixing times.« less

Authors:
 [1];  [2];  [1];  [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of British Columbia, Vancouver, BC (Canada). Dept. of Chemistry
  2. Portland State Univ., OR (United States). Dept. of Physics
  3. Univ. of California, Riverside, CA (United States). Dept. of Chemical and Environmental Engineering. Center for Environmental Research and Technology
  4. Univ. of Colorado, Boulder, CO (United States). Cooperative Inst. for Research in the Environmental Sciences. Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States); Portland State Univ., OR (United States); Univ. of British Columbia, Vancouver, BC (Canada)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); USEPA; MJ Murdock Charitable Trust (United States); Natural Sciences and Engineering Research Council of Canada (NSERC)
OSTI Identifier:
1501918
Grant/Contract Number:  
SC0016559; 83587701-0; 2012183
Resource Type:
Accepted Manuscript
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Name: Atmospheric Chemistry and Physics (Online); Journal Volume: 17; Journal Issue: 21; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES

Citation Formats

Maclean, Adrian M., Butenhoff, Christopher L., Grayson, James W., Barsanti, Kelley, Jimenez, Jose L., and Bertram, Allan K. Mixing times of organic molecules within secondary organic aerosol particles: a global planetary boundary layer perspective. United States: N. p., 2017. Web. doi:10.5194/acp-17-13037-2017.
Maclean, Adrian M., Butenhoff, Christopher L., Grayson, James W., Barsanti, Kelley, Jimenez, Jose L., & Bertram, Allan K. Mixing times of organic molecules within secondary organic aerosol particles: a global planetary boundary layer perspective. United States. doi:10.5194/acp-17-13037-2017.
Maclean, Adrian M., Butenhoff, Christopher L., Grayson, James W., Barsanti, Kelley, Jimenez, Jose L., and Bertram, Allan K. Mon . "Mixing times of organic molecules within secondary organic aerosol particles: a global planetary boundary layer perspective". United States. doi:10.5194/acp-17-13037-2017. https://www.osti.gov/servlets/purl/1501918.
@article{osti_1501918,
title = {Mixing times of organic molecules within secondary organic aerosol particles: a global planetary boundary layer perspective},
author = {Maclean, Adrian M. and Butenhoff, Christopher L. and Grayson, James W. and Barsanti, Kelley and Jimenez, Jose L. and Bertram, Allan K.},
abstractNote = {When simulating the formation and life cycle of secondary organic aerosol (SOA) with chemical transport models, it is often assumed that organic molecules are well mixed within SOA particles on the timescale of 1h. While this assumption has been debated vigorously in the literature, the issue remains unresolved in part due to a lack of information on the mixing times within SOA particles as a function of both temperature and relative humidity. Using laboratory data, meteorological fields, and a chemical transport model, we estimated how often mixing times are < 1h within SOA in the planetary boundary layer (PBL), the region of the atmosphere where SOA concentrations are on average the highest. First, a parameterization for viscosity as a function of temperature and RH was developed for α-pinene SOA using room-temperature and low-temperature viscosity data for α-pinene SOA generated in the laboratory using mass concentrations of ~1000µg m-3. Based on this parameterization, the mixing times within α-pinene SOA are < 1h for 98.5% and 99.9% of the occurrences in the PBL during January and July, respectively, when concentrations are significant (total organic aerosol concentrations are > 0.5µg m-3 at the surface). Next, as a starting point to quantify how often mixing times of organic molecules are < 1h within α-pinene SOA generated using low, atmospherically relevant mass concentrations, we developed a temperature-independent parameterization for viscosity using the room-temperature viscosity data for α-pinene SOA generated in the laboratory using a mass concentration of ~70µg m-3. Based on this temperature-independent parameterization, mixing times within α-pinene SOA are < 1h for 27 and 19.5% of the occurrences in the PBL during January and July, respectively, when concentrations are significant. However, associated with these conclusions are several caveats, and due to these caveats we are unable to make strong conclusions about how often mixing times of organic molecules are < 1h within α-pinene SOA generated using low, atmospherically relevant mass concentrations. Finally, a parameterization for viscosity of anthropogenic SOA as a function of temperature and RH was developed using sucrose–water data. Based on this parameterization, and assuming sucrose is a good proxy for anthropogenic SOA, 70 and 83% of the mixing times within anthropogenic SOA in the PBL are < 1h for January and July, respectively, when concentrations are significant. These percentages are likely lower limits due to the assumptions used to calculate mixing times.},
doi = {10.5194/acp-17-13037-2017},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 21,
volume = 17,
place = {United States},
year = {2017},
month = {11}
}

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Cited by: 14 works
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Figures / Tables:

Figure 1 Figure 1: Monthly averaged total organic aerosol concentrations (colour scale) at the Earth’s surface in (a) January and (b) July, as calculated using GEOS-Chem.

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