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Role of Criegee Intermediates in Secondary Sulfate Aerosol Formation in Nocturnal Power Plant Plumes in the Southeast US

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Role of Criegee Intermediates in Secondary Sulfate Aerosol Formation in Nocturnal Power Plant Plumes in the Southeast US. / Meidan, Daphne; Holloway, John S.; Edwards, Peter; Dube, William P.; Middlebrook, Ann M.; Liao, Jin; Welti, Andre; Graus, Martin; Warneke, Carsten; Ryerson, Thomas B.; Pollack, Ilana B.; Brown, Steven S.; Rudcih, Yinon.

In: ACS Earth and Space Chemistry, 06.03.2019.

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Harvard

Meidan, D, Holloway, JS, Edwards, P, Dube, WP, Middlebrook, AM, Liao, J, Welti, A, Graus, M, Warneke, C, Ryerson, TB, Pollack, IB, Brown, SS & Rudcih, Y 2019, 'Role of Criegee Intermediates in Secondary Sulfate Aerosol Formation in Nocturnal Power Plant Plumes in the Southeast US', ACS Earth and Space Chemistry. https://doi.org/10.1021/acsearthspacechem.8b00215

APA

Meidan, D., Holloway, J. S., Edwards, P., Dube, W. P., Middlebrook, A. M., Liao, J., ... Rudcih, Y. (2019). Role of Criegee Intermediates in Secondary Sulfate Aerosol Formation in Nocturnal Power Plant Plumes in the Southeast US. ACS Earth and Space Chemistry. https://doi.org/10.1021/acsearthspacechem.8b00215

Vancouver

Meidan D, Holloway JS, Edwards P, Dube WP, Middlebrook AM, Liao J et al. Role of Criegee Intermediates in Secondary Sulfate Aerosol Formation in Nocturnal Power Plant Plumes in the Southeast US. ACS Earth and Space Chemistry. 2019 Mar 6. https://doi.org/10.1021/acsearthspacechem.8b00215

Author

Meidan, Daphne ; Holloway, John S. ; Edwards, Peter ; Dube, William P. ; Middlebrook, Ann M. ; Liao, Jin ; Welti, Andre ; Graus, Martin ; Warneke, Carsten ; Ryerson, Thomas B. ; Pollack, Ilana B. ; Brown, Steven S. ; Rudcih, Yinon. / Role of Criegee Intermediates in Secondary Sulfate Aerosol Formation in Nocturnal Power Plant Plumes in the Southeast US. In: ACS Earth and Space Chemistry. 2019.

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@article{328e80c7b054415496a8cd8ae192bb73,
title = "Role of Criegee Intermediates in Secondary Sulfate Aerosol Formation in Nocturnal Power Plant Plumes in the Southeast US",
abstract = "Criegee intermediates (CI) from ozonolysis of biogenic volatile organic compounds (BVOC) have been suggested to be important atmospheric oxidants. However, due to their low atmospheric concentrations, possible high reactivity with water vapor, and unconstrained thermal unimolecular decay rates, their impact on atmospheric oxidation of trace species such as SO2 and NO2 remains uncertain. In this study, we investigate the formation of secondary sulfate aerosols (SSA) in nocturnal power plant plumes in the Southeastern US. These plumes have large mixing ratios of SO2 and NOx that make reaction with CI competitive with other pathways, such as thermal unimolecular decay and water vapor reaction. The background into which these plumes are emitted has high levels of BVOC and O3, whose reaction produces a large source of CI. Observed nighttime power plant plume intercepts had measurable sulfate aerosol, ranging from 0.7–1.2{\%} of the total plume sulfur (SO2 + sulfate) on a molar basis. In the absence of photochemical OH oxidation, these observed sulfate levels can be compared to calculated CI + SO2 production. We present a plume dispersion model that simulates the chemical evolution of these nighttime plumes and compare the results to observed sulfate aerosol. Thermal unimolecular decay of CI is the largest uncertainty. In the absence of thermal unimolecular CI decay, CI reactions with SO2 in the dark account for up to 41{\%} of the total observed sulfate aerosol, with the remainder attributable to reaction of SO2 with secondary OH and direct emission. Conversely, with a thermal unimolecular decay rate for all CI of 200 s–1, equivalent to the highest measured rate, CI reactions with SO2 accounted for only 5.7{\%} of the total SSA. A second uncertainty is the rate coefficients for larger, and as yet unmeasured, CI species. The most important CI in the modeled scenario is the C1 compound, CH2OO, which accounts for up to 50{\%} of the CIs produced from isoprene. C4 CIs may contribute up to 40{\%} of the CIs produced and are expected to have substantially slower thermal unimolecular decay rates and water vapor reaction rate coefficients. Therefore, the model results may be a lower limit to the CI contribution to SSA. Calculated nighttime (10 h) total SO2 oxidation was 1.8{\%}, of which 1.1{\%} was due to CI + SO2, and the remainder to secondary OH + SO2. This compares to daytime (14 h) SO2 oxidation rates of 4{\%} due to photochemical OH + SO2 reaction.",
keywords = "Criegee intermediate, Power plant plumes, SO oxidation, dispersion-kinetic model, nocturnal atmospheric chemistry, secondary sulfate aerosols",
author = "Daphne Meidan and Holloway, {John S.} and Peter Edwards and Dube, {William P.} and Middlebrook, {Ann M.} and Jin Liao and Andre Welti and Martin Graus and Carsten Warneke and Ryerson, {Thomas B.} and Pollack, {Ilana B.} and Brown, {Steven S.} and Yinon Rudcih",
note = "{\circledC} 2019 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.",
year = "2019",
month = "3",
day = "6",
doi = "10.1021/acsearthspacechem.8b00215",
language = "English",
journal = "ACS Earth and Space Chemistry",
issn = "2472-3452",
publisher = "American Chemical Society",

}

RIS (suitable for import to EndNote) - Download

TY - JOUR

T1 - Role of Criegee Intermediates in Secondary Sulfate Aerosol Formation in Nocturnal Power Plant Plumes in the Southeast US

AU - Meidan, Daphne

AU - Holloway, John S.

AU - Edwards, Peter

AU - Dube, William P.

AU - Middlebrook, Ann M.

AU - Liao, Jin

AU - Welti, Andre

AU - Graus, Martin

AU - Warneke, Carsten

AU - Ryerson, Thomas B.

AU - Pollack, Ilana B.

AU - Brown, Steven S.

AU - Rudcih, Yinon

N1 - © 2019 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2019/3/6

Y1 - 2019/3/6

N2 - Criegee intermediates (CI) from ozonolysis of biogenic volatile organic compounds (BVOC) have been suggested to be important atmospheric oxidants. However, due to their low atmospheric concentrations, possible high reactivity with water vapor, and unconstrained thermal unimolecular decay rates, their impact on atmospheric oxidation of trace species such as SO2 and NO2 remains uncertain. In this study, we investigate the formation of secondary sulfate aerosols (SSA) in nocturnal power plant plumes in the Southeastern US. These plumes have large mixing ratios of SO2 and NOx that make reaction with CI competitive with other pathways, such as thermal unimolecular decay and water vapor reaction. The background into which these plumes are emitted has high levels of BVOC and O3, whose reaction produces a large source of CI. Observed nighttime power plant plume intercepts had measurable sulfate aerosol, ranging from 0.7–1.2% of the total plume sulfur (SO2 + sulfate) on a molar basis. In the absence of photochemical OH oxidation, these observed sulfate levels can be compared to calculated CI + SO2 production. We present a plume dispersion model that simulates the chemical evolution of these nighttime plumes and compare the results to observed sulfate aerosol. Thermal unimolecular decay of CI is the largest uncertainty. In the absence of thermal unimolecular CI decay, CI reactions with SO2 in the dark account for up to 41% of the total observed sulfate aerosol, with the remainder attributable to reaction of SO2 with secondary OH and direct emission. Conversely, with a thermal unimolecular decay rate for all CI of 200 s–1, equivalent to the highest measured rate, CI reactions with SO2 accounted for only 5.7% of the total SSA. A second uncertainty is the rate coefficients for larger, and as yet unmeasured, CI species. The most important CI in the modeled scenario is the C1 compound, CH2OO, which accounts for up to 50% of the CIs produced from isoprene. C4 CIs may contribute up to 40% of the CIs produced and are expected to have substantially slower thermal unimolecular decay rates and water vapor reaction rate coefficients. Therefore, the model results may be a lower limit to the CI contribution to SSA. Calculated nighttime (10 h) total SO2 oxidation was 1.8%, of which 1.1% was due to CI + SO2, and the remainder to secondary OH + SO2. This compares to daytime (14 h) SO2 oxidation rates of 4% due to photochemical OH + SO2 reaction.

AB - Criegee intermediates (CI) from ozonolysis of biogenic volatile organic compounds (BVOC) have been suggested to be important atmospheric oxidants. However, due to their low atmospheric concentrations, possible high reactivity with water vapor, and unconstrained thermal unimolecular decay rates, their impact on atmospheric oxidation of trace species such as SO2 and NO2 remains uncertain. In this study, we investigate the formation of secondary sulfate aerosols (SSA) in nocturnal power plant plumes in the Southeastern US. These plumes have large mixing ratios of SO2 and NOx that make reaction with CI competitive with other pathways, such as thermal unimolecular decay and water vapor reaction. The background into which these plumes are emitted has high levels of BVOC and O3, whose reaction produces a large source of CI. Observed nighttime power plant plume intercepts had measurable sulfate aerosol, ranging from 0.7–1.2% of the total plume sulfur (SO2 + sulfate) on a molar basis. In the absence of photochemical OH oxidation, these observed sulfate levels can be compared to calculated CI + SO2 production. We present a plume dispersion model that simulates the chemical evolution of these nighttime plumes and compare the results to observed sulfate aerosol. Thermal unimolecular decay of CI is the largest uncertainty. In the absence of thermal unimolecular CI decay, CI reactions with SO2 in the dark account for up to 41% of the total observed sulfate aerosol, with the remainder attributable to reaction of SO2 with secondary OH and direct emission. Conversely, with a thermal unimolecular decay rate for all CI of 200 s–1, equivalent to the highest measured rate, CI reactions with SO2 accounted for only 5.7% of the total SSA. A second uncertainty is the rate coefficients for larger, and as yet unmeasured, CI species. The most important CI in the modeled scenario is the C1 compound, CH2OO, which accounts for up to 50% of the CIs produced from isoprene. C4 CIs may contribute up to 40% of the CIs produced and are expected to have substantially slower thermal unimolecular decay rates and water vapor reaction rate coefficients. Therefore, the model results may be a lower limit to the CI contribution to SSA. Calculated nighttime (10 h) total SO2 oxidation was 1.8%, of which 1.1% was due to CI + SO2, and the remainder to secondary OH + SO2. This compares to daytime (14 h) SO2 oxidation rates of 4% due to photochemical OH + SO2 reaction.

KW - Criegee intermediate

KW - Power plant plumes

KW - SO oxidation

KW - dispersion-kinetic model

KW - nocturnal atmospheric chemistry

KW - secondary sulfate aerosols

UR - http://www.scopus.com/inward/record.url?scp=85063470844&partnerID=8YFLogxK

U2 - 10.1021/acsearthspacechem.8b00215

DO - 10.1021/acsearthspacechem.8b00215

M3 - Article

JO - ACS Earth and Space Chemistry

T2 - ACS Earth and Space Chemistry

JF - ACS Earth and Space Chemistry

SN - 2472-3452

ER -