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Title: Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter

Abstract

Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet–visible spectrophotometry, was kinetically inhibited for RH < 20% for exposure times of 6 min to 24 h. By comparison, from 20% to 60% RH organonitrogen production took place, implying ammonia uptake and reaction. Correspondingly, the absorption index k across 280 to 320 nm increased from 0.012 to 0.02, indicative of PM browning. The k value across 380 to 420 nm increased from 0.001 to 0.004. The observed RH-dependent behavior of ammonia uptake and browning was well captured by a model that considered the diffusivities of both the large organic molecules that made up the PM and the small reactant molecules taken up from the gas phasemore » into the PM. Within the model, large-molecule diffusivity was calculated based on observed SOM viscosity and evaporation. Small-molecule diffusivity was represented by the water diffusivity measured by a quartz-crystal microbalance. The model showed that the browning reaction rates at RH < 60% could be controlled by the low diffusivity of the large organic molecules from the interior region of the particle to the reactive surface region. The results of this study have implications for accurate modeling of atmospheric brown carbon production and associated influences on energy balance.« less

Authors:
ORCiD logo;  [1];  [2]; ;  [3]; ;  [4];
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  1. Department of Civil and Environmental Engineering, Faculty of Science and Technology, University of Macau, Macau, China
  2. T. H. Chan School of Public Health, Harvard University, Boston, Massachusetts 02115, United States
  3. Aerodyne Research Inc., Billerica, Massachusetts 01821, United States
  4. Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada
Publication Date:
Research Org.:
Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1417220
Alternate Identifier(s):
OSTI ID: 1498677; OSTI ID: 1508596
Grant/Contract Number:  
SC0012792
Resource Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Name: ACS Central Science Journal Volume: 4 Journal Issue: 2; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES

Citation Formats

Liu, Pengfei, Li, Yong Jie, Wang, Yan, Bateman, Adam P., Zhang, Yue, Gong, Zhaoheng, Bertram, Allan K., and Martin, Scot T. Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter. United States: N. p., 2018. Web. doi:10.1021/acscentsci.7b00452.
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Liu, Pengfei, Li, Yong Jie, Wang, Yan, Bateman, Adam P., Zhang, Yue, Gong, Zhaoheng, Bertram, Allan K., & Martin, Scot T. Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter. United States. https://doi.org/10.1021/acscentsci.7b00452
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Liu, Pengfei, Li, Yong Jie, Wang, Yan, Bateman, Adam P., Zhang, Yue, Gong, Zhaoheng, Bertram, Allan K., and Martin, Scot T. Wed . "Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter". United States. https://doi.org/10.1021/acscentsci.7b00452.
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@article{osti_1417220,
title = {Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter},
author = {Liu, Pengfei and Li, Yong Jie and Wang, Yan and Bateman, Adam P. and Zhang, Yue and Gong, Zhaoheng and Bertram, Allan K. and Martin, Scot T.},
abstractNote = {Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet–visible spectrophotometry, was kinetically inhibited for RH < 20% for exposure times of 6 min to 24 h. By comparison, from 20% to 60% RH organonitrogen production took place, implying ammonia uptake and reaction. Correspondingly, the absorption index k across 280 to 320 nm increased from 0.012 to 0.02, indicative of PM browning. The k value across 380 to 420 nm increased from 0.001 to 0.004. The observed RH-dependent behavior of ammonia uptake and browning was well captured by a model that considered the diffusivities of both the large organic molecules that made up the PM and the small reactant molecules taken up from the gas phase into the PM. Within the model, large-molecule diffusivity was calculated based on observed SOM viscosity and evaporation. Small-molecule diffusivity was represented by the water diffusivity measured by a quartz-crystal microbalance. The model showed that the browning reaction rates at RH < 60% could be controlled by the low diffusivity of the large organic molecules from the interior region of the particle to the reactive surface region. The results of this study have implications for accurate modeling of atmospheric brown carbon production and associated influences on energy balance.},
doi = {10.1021/acscentsci.7b00452},
journal = {ACS Central Science},
number = 2,
volume = 4,
place = {United States},
year = {Wed Jan 17 00:00:00 EST 2018},
month = {Wed Jan 17 00:00:00 EST 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acscentsci.7b00452
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Citation Metrics:
Cited by: 45 works
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Figures / Tables:

Figure 1 Figure 1: (a) Schematic of ammonia reactive uptake for a highly viscous droplet in the left panel and a well-mixed liquid droplet in the right panel. The accessible reactive volume is highlighted in both panels. (b) A simplified mechanism of ammonia uptake and brown carbon production for SOM derived frommore » aromatic precursors. For instance, SOM carbonyls can react with ammonia to produce imines, which in turn oligomerize to yield conjugated light-absorbing organonitrogen compounds. This browning pathway competes with other reactions that may not produce chromophores, such as the NH3-neutralization of SOM carboxylic acids to form ammonium salts.« less
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Works referencing / citing this record:

Water diffusion measurements of single charged aerosols using H 2 O/D 2 O isotope exchange and Raman spectroscopy in an electrodynamic balance
journal, January 2019

  • Nadler, Katherine A.; Kim, Pyeongeun; Huang, Dao-Ling
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 27
  • DOI: 10.1039/c8cp07052k

Water diffusion measurements of single charged aerosols using H 2 O/D 2 O isotope exchange and Raman spectroscopy in an electrodynamic balance
journal, January 2019

  • Nadler, Katherine A.; Kim, Pyeongeun; Huang, Dao-Ling
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 27
  • DOI: 10.1039/c8cp07052k

Electrospray surface-enhanced Raman spectroscopy (ES-SERS) for studying organic coatings of atmospheric aerosol particles
journal, April 2019

Effect of Bulk Composition on the Heterogeneous Oxidation of Semi-Solid Atmospheric Aerosols
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Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition
journal, January 2018

  • DeRieux, Wing-Sy Wong; Li, Ying; Lin, Peng
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 9
  • DOI: 10.5194/acp-18-6331-2018

Predictions of diffusion rates of large organic molecules in secondary organic aerosols using the Stokes–Einstein and fractional Stokes–Einstein relations
journal, January 2019

  • Evoy, Erin; Maclean, Adrian M.; Rovelli, Grazia
  • Atmospheric Chemistry and Physics, Vol. 19, Issue 15
  • DOI: 10.5194/acp-19-10073-2019
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