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Criegee Intermediate Reactions with Carboxylic Acids: A Potential Source of Secondary Organic Aerosol in the Atmosphere

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Criegee Intermediate Reactions with Carboxylic Acids : A Potential Source of Secondary Organic Aerosol in the Atmosphere. / Chhantyal-Pun, Rabi; Rotavera, Brandon; McGillen, Max R.; Khan, M. Anwar H.; Eskola, Arkke J.; Caravan, Rebecca L.; Blacker, Lucy; Tew, David P.; Osborn, David L.; Percival, Carl J.; Taatjes, Craig A.; Shallcross, Dudley E.; Orr-Ewing, Andrew J.

In: ACS Earth and Space Chemistry, Vol. 2, No. 8, 16.08.2018, p. 833-842.

Research output: Contribution to journalArticle

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Chhantyal-Pun, R, Rotavera, B, McGillen, MR, Khan, MAH, Eskola, AJ, Caravan, RL, Blacker, L, Tew, DP, Osborn, DL, Percival, CJ, Taatjes, CA, Shallcross, DE & Orr-Ewing, AJ 2018, 'Criegee Intermediate Reactions with Carboxylic Acids: A Potential Source of Secondary Organic Aerosol in the Atmosphere', ACS Earth and Space Chemistry, vol. 2, no. 8, pp. 833-842. https://doi.org/10.1021/acsearthspacechem.8b00069

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Chhantyal-Pun, Rabi ; Rotavera, Brandon ; McGillen, Max R. ; Khan, M. Anwar H. ; Eskola, Arkke J. ; Caravan, Rebecca L. ; Blacker, Lucy ; Tew, David P. ; Osborn, David L. ; Percival, Carl J. ; Taatjes, Craig A. ; Shallcross, Dudley E. ; Orr-Ewing, Andrew J. / Criegee Intermediate Reactions with Carboxylic Acids : A Potential Source of Secondary Organic Aerosol in the Atmosphere. In: ACS Earth and Space Chemistry. 2018 ; Vol. 2, No. 8. pp. 833-842.

Bibtex

@article{844c61f52a864753b9b18dc489ece780,
title = "Criegee Intermediate Reactions with Carboxylic Acids: A Potential Source of Secondary Organic Aerosol in the Atmosphere",
abstract = "Trace atmospheric concentrations of carboxylic acids have a potent effect upon the environment, where they modulate aqueous chemistry and perturb Earth’s radiative balance. Halogenated carboxylic acids are produced by the tropospheric oxidation of halocarbons and are considered persistent pollutants because of their weak tropospheric and aqueous sinks. However, recent studies reported rapid reactions between selected carboxylic acids and Criegee intermediates, which may provide an efficient gas-phase removal process. Accordingly, absolute rate coefficients of two Criegee intermediates, CH2OO and (CH3)2COO, with a suite of carboxylic acids (HCOOH, CH3COOH, CClF2COOH, CF3CF2COOH, and pyruvic acid) were measured with a view to develop a structure-activity relationship (SAR). This SAR is based upon the dipole-capture model and predicts the reactivity of many further combinations of Criegee intermediates and carboxylic acids. Complementary synchrotron-based photoionization mass spectrometry measurements demonstrate that these reactions produce stable ester adducts, with a reaction coordinate involving transfer of the acidic hydrogen from the carboxylic acid to the terminal oxygen of the Criegee intermediate. The adduct products are predicted to have low vapour pressures, and coupling of this chemistry with a global atmospheric chemistry and transport model shows significant production of secondary organic aerosol at locations rich in biogenic alkene emissions.",
keywords = "Atmospheric Chemistry, Carboxylic Acids, Criegee Intermediate, Hydroperoxide Ester;, SOA",
author = "Rabi Chhantyal-Pun and Brandon Rotavera and McGillen, {Max R.} and Khan, {M. Anwar H.} and Eskola, {Arkke J.} and Caravan, {Rebecca L.} and Lucy Blacker and Tew, {David P.} and Osborn, {David L.} and Percival, {Carl J.} and Taatjes, {Craig A.} and Shallcross, {Dudley E.} and Orr-Ewing, {Andrew J.}",
year = "2018",
month = "8",
day = "16",
doi = "10.1021/acsearthspacechem.8b00069",
language = "English",
volume = "2",
pages = "833--842",
journal = "ACS Earth and Space Chemistry",
issn = "2472-3452",
publisher = "American Chemical Society",
number = "8",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Criegee Intermediate Reactions with Carboxylic Acids

T2 - A Potential Source of Secondary Organic Aerosol in the Atmosphere

AU - Chhantyal-Pun, Rabi

AU - Rotavera, Brandon

AU - McGillen, Max R.

AU - Khan, M. Anwar H.

AU - Eskola, Arkke J.

AU - Caravan, Rebecca L.

AU - Blacker, Lucy

AU - Tew, David P.

AU - Osborn, David L.

AU - Percival, Carl J.

AU - Taatjes, Craig A.

AU - Shallcross, Dudley E.

AU - Orr-Ewing, Andrew J.

PY - 2018/8/16

Y1 - 2018/8/16

N2 - Trace atmospheric concentrations of carboxylic acids have a potent effect upon the environment, where they modulate aqueous chemistry and perturb Earth’s radiative balance. Halogenated carboxylic acids are produced by the tropospheric oxidation of halocarbons and are considered persistent pollutants because of their weak tropospheric and aqueous sinks. However, recent studies reported rapid reactions between selected carboxylic acids and Criegee intermediates, which may provide an efficient gas-phase removal process. Accordingly, absolute rate coefficients of two Criegee intermediates, CH2OO and (CH3)2COO, with a suite of carboxylic acids (HCOOH, CH3COOH, CClF2COOH, CF3CF2COOH, and pyruvic acid) were measured with a view to develop a structure-activity relationship (SAR). This SAR is based upon the dipole-capture model and predicts the reactivity of many further combinations of Criegee intermediates and carboxylic acids. Complementary synchrotron-based photoionization mass spectrometry measurements demonstrate that these reactions produce stable ester adducts, with a reaction coordinate involving transfer of the acidic hydrogen from the carboxylic acid to the terminal oxygen of the Criegee intermediate. The adduct products are predicted to have low vapour pressures, and coupling of this chemistry with a global atmospheric chemistry and transport model shows significant production of secondary organic aerosol at locations rich in biogenic alkene emissions.

AB - Trace atmospheric concentrations of carboxylic acids have a potent effect upon the environment, where they modulate aqueous chemistry and perturb Earth’s radiative balance. Halogenated carboxylic acids are produced by the tropospheric oxidation of halocarbons and are considered persistent pollutants because of their weak tropospheric and aqueous sinks. However, recent studies reported rapid reactions between selected carboxylic acids and Criegee intermediates, which may provide an efficient gas-phase removal process. Accordingly, absolute rate coefficients of two Criegee intermediates, CH2OO and (CH3)2COO, with a suite of carboxylic acids (HCOOH, CH3COOH, CClF2COOH, CF3CF2COOH, and pyruvic acid) were measured with a view to develop a structure-activity relationship (SAR). This SAR is based upon the dipole-capture model and predicts the reactivity of many further combinations of Criegee intermediates and carboxylic acids. Complementary synchrotron-based photoionization mass spectrometry measurements demonstrate that these reactions produce stable ester adducts, with a reaction coordinate involving transfer of the acidic hydrogen from the carboxylic acid to the terminal oxygen of the Criegee intermediate. The adduct products are predicted to have low vapour pressures, and coupling of this chemistry with a global atmospheric chemistry and transport model shows significant production of secondary organic aerosol at locations rich in biogenic alkene emissions.

KW - Atmospheric Chemistry

KW - Carboxylic Acids

KW - Criegee Intermediate

KW - Hydroperoxide Ester;

KW - SOA

UR - http://www.scopus.com/inward/record.url?scp=85049259255&partnerID=8YFLogxK

U2 - 10.1021/acsearthspacechem.8b00069

DO - 10.1021/acsearthspacechem.8b00069

M3 - Article

AN - SCOPUS:85049259255

VL - 2

SP - 833

EP - 842

JO - ACS Earth and Space Chemistry

JF - ACS Earth and Space Chemistry

SN - 2472-3452

IS - 8

ER -