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Title: Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US

Abstract

Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (ratio of ammonium to 2×sulfate, R N/2S≈0.8 to 0.9) with approximately 70% of total ammonia and ammonium (NH x) in the particle. Southeastern Aerosol Research and Characterization Network (SEARCH) gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for AeRosols and Gases in Ambient air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to a factor of 3 overestimate of the nonvolatile cations. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and aerosol mass spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent inmore » the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H +] air (H + in µgm -3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid-liquid phase separation. In addition, accounting for nonideal mixing modified the pH such that a fully interactive inorganic-organic system had a pH roughly 0.7 units higher than predicted using traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O:C ≥ 0.6) compounds including several isoprene-derived tracers as well as levoglucosan but decrease particle-phase partitioning for low O:C, monoterpene-derived species.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [5];  [1]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [8];  [9]
  1. US Environmental Protection Agency, Research Triangle Park, NC (United States). National Exposure Research Lab.
  2. McGill Univ., Montreal, QC (Canada). Dept of Atmospheric and Oceanic Sciences
  3. Reed College, Portland, OR (United States). Dept. of Chemistry
  4. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Civil and Environmental Engineering; Univ. of California, Berkeley, CA (United States). Dept. of Environmental Science, Policy, and Management
  5. Drexel Univ., Philadelphia, PA (United States). Civil, Architectural, and Environmental Engineering
  6. US Environmental Protection Agency, Research Triangle Park, NC (United States). National Exposure Research Lab.; Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Biomedical Engineering and Mechanics
  7. California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Environmental Science and Engineering
  8. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering, and School of Earth and Atmospheric Sciences
  9. Univ. of California, Berkeley, CA (United States). Dept. of Environmental Science, Policy, and Management, and Dept. of Civil and Environmental Engineering
Publication Date:
Research Org.:
Aerosol Dynamics, Inc., Berkeley, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1502399
Grant/Contract Number:  
SC0004698
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Volume: 18; Journal Issue: 1; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pye, Havala O. T., Zuend, Andreas, Fry, Juliane L., Isaacman-VanWertz, Gabriel, Capps, Shannon L., Appel, K. Wyat, Foroutan, Hosein, Xu, Lu, Ng, Nga L., and Goldstein, Allen H. Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US. United States: N. p., 2018. Web. doi:10.5194/acp-18-357-2018.
Pye, Havala O. T., Zuend, Andreas, Fry, Juliane L., Isaacman-VanWertz, Gabriel, Capps, Shannon L., Appel, K. Wyat, Foroutan, Hosein, Xu, Lu, Ng, Nga L., & Goldstein, Allen H. Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US. United States. doi:10.5194/acp-18-357-2018.
Pye, Havala O. T., Zuend, Andreas, Fry, Juliane L., Isaacman-VanWertz, Gabriel, Capps, Shannon L., Appel, K. Wyat, Foroutan, Hosein, Xu, Lu, Ng, Nga L., and Goldstein, Allen H. Fri . "Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US". United States. doi:10.5194/acp-18-357-2018. https://www.osti.gov/servlets/purl/1502399.
@article{osti_1502399,
title = {Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US},
author = {Pye, Havala O. T. and Zuend, Andreas and Fry, Juliane L. and Isaacman-VanWertz, Gabriel and Capps, Shannon L. and Appel, K. Wyat and Foroutan, Hosein and Xu, Lu and Ng, Nga L. and Goldstein, Allen H.},
abstractNote = {Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (ratio of ammonium to 2×sulfate, RN/2S≈0.8 to 0.9) with approximately 70% of total ammonia and ammonium (NHx) in the particle. Southeastern Aerosol Research and Characterization Network (SEARCH) gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for AeRosols and Gases in Ambient air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to a factor of 3 overestimate of the nonvolatile cations. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and aerosol mass spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H+]air (H+ in µgm-3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid-liquid phase separation. In addition, accounting for nonideal mixing modified the pH such that a fully interactive inorganic-organic system had a pH roughly 0.7 units higher than predicted using traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O:C ≥ 0.6) compounds including several isoprene-derived tracers as well as levoglucosan but decrease particle-phase partitioning for low O:C, monoterpene-derived species.},
doi = {10.5194/acp-18-357-2018},
journal = {Atmospheric Chemistry and Physics (Online)},
issn = {1680-7324},
number = 1,
volume = 18,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
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Cited by: 19 works
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Figures / Tables:

Figure 1 Figure 1: Molar ratios of aerosol ammonium to 2× sulfate ($R$N/2S) (a, b) and cations to anions ($R$+/−) (c, d) over the eastern US for 1 June–15 July 2013 based on observations and predicted by the CMAQ model.

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