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Title: Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds–water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % inmore » the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May–June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m -3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m -3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.« less
Authors:
 [1] ; ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [3] ;  [4] ;  [5] ;  [6] ; ORCiD logo [7] ;  [8] ; ORCiD logo [9] ;  [1] ; ORCiD logo [10] ; ORCiD logo [11] ; ORCiD logo [1]
  1. National Exposure Research Laboratory, US Environmental Protection Agency, Research Triangle Park, NC (United States)
  2. Univ. of Colorado, Boulder, CO (United States). Cooperative Institute for Research in Environmental Sciences and Department of Chemistry and Biochemistry
  3. Univ. of California, Irvine, CA (United States). Department of Chemistry
  4. Université de Montréal, QC (Canada). Department of Chemistry
  5. University of Science and Technology of China, Hefei (China). School of Earth and Space Sciences
  6. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering and School of Earth and Atmospheric Sciences
  7. University of California, San Diego, La Jolla, CA (United States). Scripps Institution of Oceanography
  8. EMPA, Swiss Federal Laboratories for Materials Science and Technology (Switzerland)
  9. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
  10. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC)
  11. Univ. of California, Davis, CA (United States). Department of Environmental Toxicology
Publication Date:
Report Number(s):
PNNL-SA-124491
Journal ID: ISSN 1680-7324; KP1701000
Grant/Contract Number:
AC05-76RL01830; FG02-11ER65293
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: 18; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES
OSTI Identifier:
1406733

Murphy, Benjamin N., Woody, Matthew C., Jimenez, Jose L., Carlton, Ann Marie G., Hayes, Patrick L., Liu, Shang, Ng, Nga L., Russell, Lynn M., Setyan, Ari, Xu, Lu, Young, Jeff, Zaveri, Rahul A., Zhang, Qi, and Pye, Havala O. T.. Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning. United States: N. p., Web. doi:10.5194/acp-17-11107-2017.
Murphy, Benjamin N., Woody, Matthew C., Jimenez, Jose L., Carlton, Ann Marie G., Hayes, Patrick L., Liu, Shang, Ng, Nga L., Russell, Lynn M., Setyan, Ari, Xu, Lu, Young, Jeff, Zaveri, Rahul A., Zhang, Qi, & Pye, Havala O. T.. Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning. United States. doi:10.5194/acp-17-11107-2017.
Murphy, Benjamin N., Woody, Matthew C., Jimenez, Jose L., Carlton, Ann Marie G., Hayes, Patrick L., Liu, Shang, Ng, Nga L., Russell, Lynn M., Setyan, Ari, Xu, Lu, Young, Jeff, Zaveri, Rahul A., Zhang, Qi, and Pye, Havala O. T.. 2017. "Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning". United States. doi:10.5194/acp-17-11107-2017. https://www.osti.gov/servlets/purl/1406733.
@article{osti_1406733,
title = {Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning},
author = {Murphy, Benjamin N. and Woody, Matthew C. and Jimenez, Jose L. and Carlton, Ann Marie G. and Hayes, Patrick L. and Liu, Shang and Ng, Nga L. and Russell, Lynn M. and Setyan, Ari and Xu, Lu and Young, Jeff and Zaveri, Rahul A. and Zhang, Qi and Pye, Havala O. T.},
abstractNote = {Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds–water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May–June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m-3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m-3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.},
doi = {10.5194/acp-17-11107-2017},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 18,
volume = 17,
place = {United States},
year = {2017},
month = {9}
}