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Title: Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol

Abstract

Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversibly reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.

Authors:
ORCiD logo [1];  [1];  [2];  [1];  [3]; ORCiD logo [4];  [5]; ORCiD logo [4]; ORCiD logo [6];  [6];  [2];  [1];  [7];  [8];  [9];  [10];  [11]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Div.
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Div.; Paul Scherrer Inst. (PSI), Villigen (Switzerland). Lab. of Atmospheric Chemistry
  4. Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences and Dept. of Chemistry
  5. Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences; Univ. of Miami, Miami, FL (United States). Rosenstiel School of Marine and Atmospheric Science
  6. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
  7. Brookhaven National Lab. (BNL), Upton, NY (United States). Environmental & Climate Sciences Dept.
  8. Univ. of British Columbia, Vancouver, BC (Canada). Dept. of Chemistry
  9. Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences (SEAS) and Dept. of Earth and Planetary Sciences
  10. California Inst. of Technology (CalTech), Pasadena, CA (United States). Div. of Chemistry and Chemical Engineering and Div. of Engineering and Applied Science
  11. Aerodyne Research, Billerica, MA (United States). Center for Aerosol and Cloud Chemistry
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1424984
Alternate Identifier(s):
OSTI ID: 1426444
Report Number(s):
BNL-203207-2018-JAAM; PNNL-SA-128966; BNL-203357-2018-JAAM
Journal ID: ISSN 0013-936X
Grant/Contract Number:  
SC0012704; AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 52; Journal Issue: 3; Journal ID: ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES

Citation Formats

Zaveri, Rahul A., Shilling, John E., Zelenyuk, Alla, Liu, Jiumeng, Bell, David M., D’Ambro, Emma L., Gaston, Cassandra J., Thornton, Joel A., Laskin, Alexander, Lin, Peng, Wilson, Jacqueline, Easter, Richard C., Wang, Jian, Bertram, Allan K., Martin, Scot T., Seinfeld, John H., and Worsnop, Douglas R. Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol. United States: N. p., 2017. Web. doi:10.1021/acs.est.7b04623.
Zaveri, Rahul A., Shilling, John E., Zelenyuk, Alla, Liu, Jiumeng, Bell, David M., D’Ambro, Emma L., Gaston, Cassandra J., Thornton, Joel A., Laskin, Alexander, Lin, Peng, Wilson, Jacqueline, Easter, Richard C., Wang, Jian, Bertram, Allan K., Martin, Scot T., Seinfeld, John H., & Worsnop, Douglas R. Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol. United States. doi:10.1021/acs.est.7b04623.
Zaveri, Rahul A., Shilling, John E., Zelenyuk, Alla, Liu, Jiumeng, Bell, David M., D’Ambro, Emma L., Gaston, Cassandra J., Thornton, Joel A., Laskin, Alexander, Lin, Peng, Wilson, Jacqueline, Easter, Richard C., Wang, Jian, Bertram, Allan K., Martin, Scot T., Seinfeld, John H., and Worsnop, Douglas R. Fri . "Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol". United States. doi:10.1021/acs.est.7b04623. https://www.osti.gov/servlets/purl/1424984.
@article{osti_1424984,
title = {Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol},
author = {Zaveri, Rahul A. and Shilling, John E. and Zelenyuk, Alla and Liu, Jiumeng and Bell, David M. and D’Ambro, Emma L. and Gaston, Cassandra J. and Thornton, Joel A. and Laskin, Alexander and Lin, Peng and Wilson, Jacqueline and Easter, Richard C. and Wang, Jian and Bertram, Allan K. and Martin, Scot T. and Seinfeld, John H. and Worsnop, Douglas R.},
abstractNote = {Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversibly reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.},
doi = {10.1021/acs.est.7b04623},
journal = {Environmental Science and Technology},
number = 3,
volume = 52,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

Figure 1 Figure 1: Observed time evolutions of (a, b) aerosol number size distributions and (c, d) aerosol volume size distributions in Experiments 1 and 2. The initial (Stage 1) bimodal aerosol in Experiment 1 consists of an Aitken mode composed of ammonium sulfate (AS) and an accumulation mode composed of isoprenemore » SOA. The initial (Stage 1) bimodal aerosol in Experiment 2 consists of an Aitken mode composed of AS and an accumulation mode composed of α-­pinene SOA. Growth of the bimodal aerosol in Stage 2 occurred due to isoprene SOA formation in both experiments.« less

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Works referencing / citing this record:

Thermal desorption behavior of hemiacetal, acetal, ether, and ester oligomers
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Thermal desorption behavior of hemiacetal, acetal, ether, and ester oligomers
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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.