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Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: Application to the Southeast United States and co-benefit of SO2 emission controls

Journal Article


Abstract


  • Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake probabilities (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the Southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the Southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of OA and formaldehyde (a product of isoprene oxidation). The yield is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the indirect effect of sulfate on aerosol acidity and volume, rather than a direct mechanistic role for sulfate. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US EPA projects 2013-2025 decreases in anthropogenic emissions of 34 % for NOx (leading to 7 % increase in isoprene SOA) and 48 % for SO2 (35 % decrease in isoprene SOA). The combined projected decreases in NOx and SO2 emissions reduce isoprene SOA yields from 3.3 to 2.3 %. Reducing SO2 emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM2.5 from SO2 emission controls.

Publication Date


  • 2015

Citation


  • Marais, E. A., Jacob, D. J., Jimenez, J. L., Campuzano-Jost, P., Day, D. A., Hu, W., . . . McNeill, V. F. (2015). Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: Application to the Southeast United States and co-benefit of SO2 emission controls. Atmospheric Chemistry and Physics Discussions, 15(21), 32005-32047. doi:10.5194/acpd-15-32005-2015

Scopus Eid


  • 2-s2.0-85029845390

Web Of Science Accession Number


Start Page


  • 32005

End Page


  • 32047

Volume


  • 15

Issue


  • 21

Abstract


  • Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake probabilities (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the Southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the Southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of OA and formaldehyde (a product of isoprene oxidation). The yield is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the indirect effect of sulfate on aerosol acidity and volume, rather than a direct mechanistic role for sulfate. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US EPA projects 2013-2025 decreases in anthropogenic emissions of 34 % for NOx (leading to 7 % increase in isoprene SOA) and 48 % for SO2 (35 % decrease in isoprene SOA). The combined projected decreases in NOx and SO2 emissions reduce isoprene SOA yields from 3.3 to 2.3 %. Reducing SO2 emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM2.5 from SO2 emission controls.

Publication Date


  • 2015

Citation


  • Marais, E. A., Jacob, D. J., Jimenez, J. L., Campuzano-Jost, P., Day, D. A., Hu, W., . . . McNeill, V. F. (2015). Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: Application to the Southeast United States and co-benefit of SO2 emission controls. Atmospheric Chemistry and Physics Discussions, 15(21), 32005-32047. doi:10.5194/acpd-15-32005-2015

Scopus Eid


  • 2-s2.0-85029845390

Web Of Science Accession Number


Start Page


  • 32005

End Page


  • 32047

Volume


  • 15

Issue


  • 21