Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral
Within minutes after emission, complex photochemistry in biomass burning smoke plumes can cause large changes in the concentrations of ozone (O<sub>3</sub>) and organic aerosol (OA). Being able to understand and simulate this rapid chemical evolution under a wide variety of conditions is...
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doaj-35b83a87fb7a4899b0202db3f071704d2020-11-24T22:36:32ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242015-06-0115126667668810.5194/acp-15-6667-2015Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparralM. J. Alvarado0C. R. Lonsdale1R. J. Yokelson2S. K. Akagi3H. Coe4J. S. Craven5E. V. Fischer6G. R. McMeeking7J. H. Seinfeld8T. Soni9J. W. Taylor10D. R. Weise11C. E. Wold12Atmospheric and Environmental Research, Lexington, MA, USAAtmospheric and Environmental Research, Lexington, MA, USADepartment of Chemistry, University of Montana, Missoula, MT, USADepartment of Chemistry, University of Montana, Missoula, MT, USACentre for Atmospheric Science, University of Manchester, Manchester, United KingdomDivision of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USADepartment of Atmospheric Science, Colorado State University, Fort Collins, CO, USADepartment of Atmospheric Science, Colorado State University, Fort Collins, CO, USADivision of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USAAtmospheric and Environmental Research, Lexington, MA, USACentre for Atmospheric Science, University of Manchester, Manchester, United KingdomPSW Research Station, USDA Forest Service, Riverside, CA, USAFire Sciences Laboratory, United States Department of Agriculture (USDA) Forest Service, Missoula, MT, USAWithin minutes after emission, complex photochemistry in biomass burning smoke plumes can cause large changes in the concentrations of ozone (O<sub>3</sub>) and organic aerosol (OA). Being able to understand and simulate this rapid chemical evolution under a wide variety of conditions is a critical part of forecasting the impact of these fires on air quality, atmospheric composition, and climate. Here we use version 2.1 of the Aerosol Simulation Program (ASP) to simulate the evolution of O<sub>3</sub> and secondary organic aerosol (SOA) within a young biomass burning smoke plume from the Williams prescribed fire in chaparral, which was sampled over California in November 2009. We demonstrate the use of a method for simultaneously accounting for the impact of the unidentified intermediate volatility, semi-volatile, and extremely low volatility organic compounds (here collectively called "SVOCs") on the formation of OA (using the Volatility Basis Set – VBS) and O<sub>3</sub> (using the concept of mechanistic reactivity). We show that this method can successfully simulate the observations of O<sub>3</sub>, OA, NO<sub><i>x</i></sub>, ethylene (C<sub>2</sub>H<sub>4</sub>), and OH to within measurement uncertainty using reasonable assumptions about the average chemistry of the unidentified SVOCs. These assumptions were (1) a reaction rate constant with OH of ~ 10<sup>-11</sup> cm<sup>3</sup> s<sup>−1</sup>; (2) a significant fraction (up to ~ 50 %) of the RO<sub>2</sub> + NO reaction resulted in fragmentation, rather than functionalization, of the parent SVOC; (3) ~ 1.1 molecules of O<sub>3</sub> were formed for every molecule of SVOC that reacted; (4) ~ 60 % of the OH that reacted with the unidentified non-methane organic compounds (NMOC) was regenerated as HO<sub>2</sub>; and (5) that ~ 50 % of the NO that reacted with the SVOC peroxy radicals was lost, presumably to organic nitrate formation. Additional evidence for the fragmentation pathway is provided by the observed rate of formation of acetic acid (CH<sub>3</sub>COOH), which is consistent with our assumed fragmentation rate. However, the model overestimates peroxyacetyl nitrate (PAN) formation downwind by about 50 %, suggesting the need for further refinements to the chemistry. This method could provide a way for classifying different smoke plume observations in terms of the average chemistry of their SVOCs, and could be used to study how the chemistry of these compounds (and the O<sub>3</sub> and OA they form) varies between plumes.http://www.atmos-chem-phys.net/15/6667/2015/acp-15-6667-2015.pdf |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
M. J. Alvarado C. R. Lonsdale R. J. Yokelson S. K. Akagi H. Coe J. S. Craven E. V. Fischer G. R. McMeeking J. H. Seinfeld T. Soni J. W. Taylor D. R. Weise C. E. Wold |
spellingShingle |
M. J. Alvarado C. R. Lonsdale R. J. Yokelson S. K. Akagi H. Coe J. S. Craven E. V. Fischer G. R. McMeeking J. H. Seinfeld T. Soni J. W. Taylor D. R. Weise C. E. Wold Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral Atmospheric Chemistry and Physics |
author_facet |
M. J. Alvarado C. R. Lonsdale R. J. Yokelson S. K. Akagi H. Coe J. S. Craven E. V. Fischer G. R. McMeeking J. H. Seinfeld T. Soni J. W. Taylor D. R. Weise C. E. Wold |
author_sort |
M. J. Alvarado |
title |
Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral |
title_short |
Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral |
title_full |
Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral |
title_fullStr |
Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral |
title_full_unstemmed |
Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral |
title_sort |
investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in california chaparral |
publisher |
Copernicus Publications |
series |
Atmospheric Chemistry and Physics |
issn |
1680-7316 1680-7324 |
publishDate |
2015-06-01 |
description |
Within minutes after emission, complex photochemistry in biomass burning
smoke plumes can cause large changes in the concentrations of ozone
(O<sub>3</sub>) and organic aerosol (OA). Being able to understand and simulate
this rapid chemical evolution under a wide variety of conditions is a
critical part of forecasting the impact of these fires on air quality,
atmospheric composition, and climate. Here we use version 2.1 of the Aerosol
Simulation Program (ASP) to simulate the evolution of O<sub>3</sub> and secondary
organic aerosol (SOA) within a young biomass burning smoke plume from the
Williams prescribed fire in chaparral, which was sampled over California in
November 2009. We demonstrate the use of a method for simultaneously
accounting for the impact of the unidentified intermediate volatility,
semi-volatile, and extremely low volatility organic compounds (here
collectively called "SVOCs") on the formation of OA (using the Volatility
Basis Set – VBS) and O<sub>3</sub> (using the concept of mechanistic reactivity). We
show that this method can successfully simulate the observations of O<sub>3</sub>,
OA, NO<sub><i>x</i></sub>, ethylene (C<sub>2</sub>H<sub>4</sub>), and OH to within measurement uncertainty using
reasonable assumptions about the average chemistry of the unidentified
SVOCs. These assumptions were (1) a reaction rate constant with OH of
~ 10<sup>-11</sup> cm<sup>3</sup> s<sup>−1</sup>; (2) a significant fraction (up to
~ 50 %) of the RO<sub>2</sub> + NO reaction resulted in
fragmentation, rather than functionalization, of the parent SVOC; (3)
~ 1.1 molecules of O<sub>3</sub> were formed for every molecule of
SVOC that reacted; (4) ~ 60 % of the OH that reacted with
the unidentified non-methane organic compounds (NMOC) was regenerated as HO<sub>2</sub>; and (5) that
~ 50 % of the NO that reacted with the SVOC peroxy radicals
was lost, presumably to organic nitrate formation. Additional evidence for
the fragmentation pathway is provided by the observed rate of formation of
acetic acid (CH<sub>3</sub>COOH), which is consistent with our assumed fragmentation rate.
However, the model overestimates peroxyacetyl nitrate (PAN) formation downwind by about 50 %,
suggesting the need for further refinements to the chemistry. This method
could provide a way for classifying different smoke plume observations in
terms of the average chemistry of their SVOCs, and could be used to study
how the chemistry of these compounds (and the O<sub>3</sub> and OA they form)
varies between plumes. |
url |
http://www.atmos-chem-phys.net/15/6667/2015/acp-15-6667-2015.pdf |
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