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Title: Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

Organic nitrates (ON = RONO2 + RO2NO2) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NOx=NO+NO2). ON formed from isoprene oxidation alone are responsible for the export of 8 to 30% of anthropogenic NOx out of the U.S. continental boundary layer [Horowitz et al., 1998; Liang et al., 1998]. Regional NOx budgets and tropospheric ozone (O3) production, are therefore particularly sensitive to uncertainties in the yields and fates of ON [Beaver et al., 2012; Browne et al., 2013]. The yields implemented in modeling studies are determined from laboratory experiments in which only a few of the first generation gaseous ON or the total gas and particle-phase ON have been quantified [Perring et al., 2013 and references therein], while production of highly functionalized ON capable of strongly partitioning to the particle-phase have been inferred [Farmer et al., 2010; Ng et al., 2007; Nguyen et al., 2011; Perraud et al., 2012; Rollins et al., 2012], or directly measured [Ehn et al., 2014]. Addition of a nitrate (–ONO2) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5 to 3 orders of magnitude [e.g. Capouet and Muller, 2006]. Thus, organic nitrate formation can potentiallymore » enhance particle-phase partitioning of hydrocarbons in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) formation [Ng et al., 2007]. There has, however, been no high time-resolved measurements of speciated ON in the particle-phase. We utilize a newly developed high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adduct ionization [B H Lee et al., 2014a] with a filter inlet for gases and aerosols (FIGAERO) [Lopez-Hilfiker et al., 2014] that allows alternating in situ measurement of the molecular composition of gas and particle phases. We present observations of speciated ON in the particle-phase obtained during the 2013 Southern Oxidant and Aerosol Study (SOAS). We compare these speciated measurements to total unspeciated particulate organic nitrate measured by three independent methods, and analyze using a zero-dimensional box model the diel cycles of individual components to elucidate differential source and sink terms. Biogenic volatile organic compounds (VOCs), including isoprene, monoterpenes, and sesquiterpenes appear to dominate the ON sources during SOAS. We show that the molecular compositions that dominate the particle-phase are significantly more oxygenated than the most abundant gas-phase counterparts, consistent with volatility and solubility driven partitioning requirements. However, the detailed mechanisms by which most of these ON arise are not yet clear. These speciated measurements put a strong constraint on the extent to which ON directly contribute to SOA in regions with high biogenic hydrocarbon emissions, and illustrate that the fate of particulate ON can have significant implications for SOA and the reactive nitrogen budget.« less
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Publication Date:
Report Number(s):
PNNL-SA-110400
Journal ID: ISSN 0027-8424; KP1701000
Grant/Contract Number:
AC05-76RL01830; SC0004577; SC0006867; SC0011791
Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 113; Journal Issue: 6; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; particulate organic nitrates; online measurement; lifetime calculation; high-resolution time-of-flight chemical ionization mass spectrometer; biogenic volatile organic compound oxidation
OSTI Identifier:
1235971
Alternate Identifier(s):
OSTI ID: 1255381; OSTI ID: 1390589

Lee, Ben H., Mohr, Claudia, Lopez-Hilfiker, Felipe D., Lutz, Anna, Hallquist, Mattias, Lee, Lance, Romer, Paul, Cohen, Ronald C., Iyer, Siddharth, Kurtén, Theo, Hu, Weiwei, Day, Douglas A., Campuzano-Jost, Pedro, Jimenez, Jose L., Xu, Lu, Ng, Nga Lee, Guo, Hongyu, Weber, Rodney J., Wild, Robert J., Brown, Steven S., Koss, Abigail, de Gouw, Joost, Olson, Kevin, Goldstein, Allen H., Seco, Roger, Kim, Saewung, McAvey, Kevin, Shepson, Paul B., Starn, Tim, Baumann, Karsten, Edgerton, Eric S., Liu, Jiumeng, Shilling, John E., Miller, David O., Brune, William, Schobesberger, Siegfried, D'Ambro, Emma L., and Thornton, Joel A.. Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets. United States: N. p., Web. doi:10.1073/pnas.1508108113.
Lee, Ben H., Mohr, Claudia, Lopez-Hilfiker, Felipe D., Lutz, Anna, Hallquist, Mattias, Lee, Lance, Romer, Paul, Cohen, Ronald C., Iyer, Siddharth, Kurtén, Theo, Hu, Weiwei, Day, Douglas A., Campuzano-Jost, Pedro, Jimenez, Jose L., Xu, Lu, Ng, Nga Lee, Guo, Hongyu, Weber, Rodney J., Wild, Robert J., Brown, Steven S., Koss, Abigail, de Gouw, Joost, Olson, Kevin, Goldstein, Allen H., Seco, Roger, Kim, Saewung, McAvey, Kevin, Shepson, Paul B., Starn, Tim, Baumann, Karsten, Edgerton, Eric S., Liu, Jiumeng, Shilling, John E., Miller, David O., Brune, William, Schobesberger, Siegfried, D'Ambro, Emma L., & Thornton, Joel A.. Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets. United States. doi:10.1073/pnas.1508108113.
Lee, Ben H., Mohr, Claudia, Lopez-Hilfiker, Felipe D., Lutz, Anna, Hallquist, Mattias, Lee, Lance, Romer, Paul, Cohen, Ronald C., Iyer, Siddharth, Kurtén, Theo, Hu, Weiwei, Day, Douglas A., Campuzano-Jost, Pedro, Jimenez, Jose L., Xu, Lu, Ng, Nga Lee, Guo, Hongyu, Weber, Rodney J., Wild, Robert J., Brown, Steven S., Koss, Abigail, de Gouw, Joost, Olson, Kevin, Goldstein, Allen H., Seco, Roger, Kim, Saewung, McAvey, Kevin, Shepson, Paul B., Starn, Tim, Baumann, Karsten, Edgerton, Eric S., Liu, Jiumeng, Shilling, John E., Miller, David O., Brune, William, Schobesberger, Siegfried, D'Ambro, Emma L., and Thornton, Joel A.. 2016. "Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets". United States. doi:10.1073/pnas.1508108113.
@article{osti_1235971,
title = {Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets},
author = {Lee, Ben H. and Mohr, Claudia and Lopez-Hilfiker, Felipe D. and Lutz, Anna and Hallquist, Mattias and Lee, Lance and Romer, Paul and Cohen, Ronald C. and Iyer, Siddharth and Kurtén, Theo and Hu, Weiwei and Day, Douglas A. and Campuzano-Jost, Pedro and Jimenez, Jose L. and Xu, Lu and Ng, Nga Lee and Guo, Hongyu and Weber, Rodney J. and Wild, Robert J. and Brown, Steven S. and Koss, Abigail and de Gouw, Joost and Olson, Kevin and Goldstein, Allen H. and Seco, Roger and Kim, Saewung and McAvey, Kevin and Shepson, Paul B. and Starn, Tim and Baumann, Karsten and Edgerton, Eric S. and Liu, Jiumeng and Shilling, John E. and Miller, David O. and Brune, William and Schobesberger, Siegfried and D'Ambro, Emma L. and Thornton, Joel A.},
abstractNote = {Organic nitrates (ON = RONO2 + RO2NO2) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NOx=NO+NO2). ON formed from isoprene oxidation alone are responsible for the export of 8 to 30% of anthropogenic NOx out of the U.S. continental boundary layer [Horowitz et al., 1998; Liang et al., 1998]. Regional NOx budgets and tropospheric ozone (O3) production, are therefore particularly sensitive to uncertainties in the yields and fates of ON [Beaver et al., 2012; Browne et al., 2013]. The yields implemented in modeling studies are determined from laboratory experiments in which only a few of the first generation gaseous ON or the total gas and particle-phase ON have been quantified [Perring et al., 2013 and references therein], while production of highly functionalized ON capable of strongly partitioning to the particle-phase have been inferred [Farmer et al., 2010; Ng et al., 2007; Nguyen et al., 2011; Perraud et al., 2012; Rollins et al., 2012], or directly measured [Ehn et al., 2014]. Addition of a nitrate (–ONO2) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5 to 3 orders of magnitude [e.g. Capouet and Muller, 2006]. Thus, organic nitrate formation can potentially enhance particle-phase partitioning of hydrocarbons in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) formation [Ng et al., 2007]. There has, however, been no high time-resolved measurements of speciated ON in the particle-phase. We utilize a newly developed high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adduct ionization [B H Lee et al., 2014a] with a filter inlet for gases and aerosols (FIGAERO) [Lopez-Hilfiker et al., 2014] that allows alternating in situ measurement of the molecular composition of gas and particle phases. We present observations of speciated ON in the particle-phase obtained during the 2013 Southern Oxidant and Aerosol Study (SOAS). We compare these speciated measurements to total unspeciated particulate organic nitrate measured by three independent methods, and analyze using a zero-dimensional box model the diel cycles of individual components to elucidate differential source and sink terms. Biogenic volatile organic compounds (VOCs), including isoprene, monoterpenes, and sesquiterpenes appear to dominate the ON sources during SOAS. We show that the molecular compositions that dominate the particle-phase are significantly more oxygenated than the most abundant gas-phase counterparts, consistent with volatility and solubility driven partitioning requirements. However, the detailed mechanisms by which most of these ON arise are not yet clear. These speciated measurements put a strong constraint on the extent to which ON directly contribute to SOA in regions with high biogenic hydrocarbon emissions, and illustrate that the fate of particulate ON can have significant implications for SOA and the reactive nitrogen budget.},
doi = {10.1073/pnas.1508108113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 6,
volume = 113,
place = {United States},
year = {2016},
month = {1}
}