Impact of Criegee Intermediate Reactions with Peroxy Radicals on Tropospheric Organic Aerosol

Rabi Chhantyal Pun; M. Anwar H.  Khan; Nicholas Zachhuber; Carl Percival; Dudley E Shallcross; Andrew J Orr-Ewing

doi:10.1021/acsearthspacechem.0c00147

Impact of Criegee Intermediate Reactions with Peroxy Radicals on Tropospheric Organic Aerosol

Rabi Chhantyal Pun^*, M. Anwar H. Khan, Nicholas Zachhuber, Carl Percival, Dudley E Shallcross, Andrew J Orr-Ewing

^*Corresponding author for this work

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Abstract

Peroxy radicals and carbonyl oxides (Criegee intermediates) are produced in the troposphere during OH and ozone-initiated oxidation of hydrocarbons. Reactions between these species have previously been shown to form highly oxidized molecules which can condense to form secondary organic aerosols. Here, cavity ring-down spectroscopy coupled with laser flash photolysis was used to measure directly rate coefficients for reactions of CH2OO with CH3O2 and CH3C(O)O2. The rate coefficients were found to be similar within the measurement uncertainties and only weakly dependent on temperature (in the range 243 – 310 K) and pressure (10 - 100 Torr, N2). A combined rate coefficient of k (CH2OO+RO2, RO2 = CH3O2/CH3C(O)O2) = (2.4 ± 1.2) × 10-11 cm3 molecule-1 s-1 was obtained under these conditions. Global modelling using STOCHEM-CRI, updated with monoterpene chemistry generating Criegee intermediates, and supplemented by regional box modelling, shows that this class of Criegee intermediate + peroxy radical reactions can contribute up to ~1.3% of secondary organic aerosol production in forested regions of the world.

Original language	English
Article number	10
Pages (from-to)	1743-1755
Number of pages	13
Journal	ACS Earth and Space Chemistry
Volume	4
Early online date	26 Aug 2020
DOIs	https://doi.org/10.1021/acsearthspacechem.0c00147
Publication status	Published - 15 Oct 2020

Keywords

atmospheric chemistry
Criegee intermediates
peroxy radicals
radical reactions
secondary organic aerosol
cavity ring-down spectroscopy chemical transport modeling

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10.1021/acsearthspacechem.0c00147

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Kinetic Studies of Reactive Intermediates from the Oxidation of Atmospheric Alkenes
Orr-Ewing, A. J.
1/04/17 → 30/09/20
Project: Research
Gas phase studies of the kinetics of Criegee Intermediates
Shallcross, D. E. & Orr-Ewing, A. J.
30/06/13 → 31/12/16
Project: Research

Cite this

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title = "Impact of Criegee Intermediate Reactions with Peroxy Radicals on Tropospheric Organic Aerosol",

abstract = "Peroxy radicals and carbonyl oxides (Criegee intermediates) are produced in the troposphere during OH and ozone-initiated oxidation of hydrocarbons. Reactions between these species have previously been shown to form highly oxidized molecules which can condense to form secondary organic aerosols. Here, cavity ring-down spectroscopy coupled with laser flash photolysis was used to measure directly rate coefficients for reactions of CH2OO with CH3O2 and CH3C(O)O2. The rate coefficients were found to be similar within the measurement uncertainties and only weakly dependent on temperature (in the range 243 – 310 K) and pressure (10 - 100 Torr, N2). A combined rate coefficient of k (CH2OO+RO2, RO2 = CH3O2/CH3C(O)O2) = (2.4 ± 1.2) × 10-11 cm3 molecule-1 s-1 was obtained under these conditions. Global modelling using STOCHEM-CRI, updated with monoterpene chemistry generating Criegee intermediates, and supplemented by regional box modelling, shows that this class of Criegee intermediate + peroxy radical reactions can contribute up to ~1.3% of secondary organic aerosol production in forested regions of the world.",

keywords = "atmospheric chemistry, Criegee intermediates, peroxy radicals, radical reactions, secondary organic aerosol, cavity ring-down spectroscopy chemical transport modeling",

author = "{Chhantyal Pun}, Rabi and Khan, {M. Anwar H.} and Nicholas Zachhuber and Carl Percival and Shallcross, {Dudley E} and Orr-Ewing, {Andrew J}",

year = "2020",

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doi = "10.1021/acsearthspacechem.0c00147",

language = "English",

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journal = "ACS Earth and Space Chemistry",

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TY - JOUR

T1 - Impact of Criegee Intermediate Reactions with Peroxy Radicals on Tropospheric Organic Aerosol

AU - Chhantyal Pun, Rabi

AU - Khan, M. Anwar H.

AU - Zachhuber, Nicholas

AU - Percival, Carl

AU - Shallcross, Dudley E

AU - Orr-Ewing, Andrew J

PY - 2020/10/15

Y1 - 2020/10/15

N2 - Peroxy radicals and carbonyl oxides (Criegee intermediates) are produced in the troposphere during OH and ozone-initiated oxidation of hydrocarbons. Reactions between these species have previously been shown to form highly oxidized molecules which can condense to form secondary organic aerosols. Here, cavity ring-down spectroscopy coupled with laser flash photolysis was used to measure directly rate coefficients for reactions of CH2OO with CH3O2 and CH3C(O)O2. The rate coefficients were found to be similar within the measurement uncertainties and only weakly dependent on temperature (in the range 243 – 310 K) and pressure (10 - 100 Torr, N2). A combined rate coefficient of k (CH2OO+RO2, RO2 = CH3O2/CH3C(O)O2) = (2.4 ± 1.2) × 10-11 cm3 molecule-1 s-1 was obtained under these conditions. Global modelling using STOCHEM-CRI, updated with monoterpene chemistry generating Criegee intermediates, and supplemented by regional box modelling, shows that this class of Criegee intermediate + peroxy radical reactions can contribute up to ~1.3% of secondary organic aerosol production in forested regions of the world.

AB - Peroxy radicals and carbonyl oxides (Criegee intermediates) are produced in the troposphere during OH and ozone-initiated oxidation of hydrocarbons. Reactions between these species have previously been shown to form highly oxidized molecules which can condense to form secondary organic aerosols. Here, cavity ring-down spectroscopy coupled with laser flash photolysis was used to measure directly rate coefficients for reactions of CH2OO with CH3O2 and CH3C(O)O2. The rate coefficients were found to be similar within the measurement uncertainties and only weakly dependent on temperature (in the range 243 – 310 K) and pressure (10 - 100 Torr, N2). A combined rate coefficient of k (CH2OO+RO2, RO2 = CH3O2/CH3C(O)O2) = (2.4 ± 1.2) × 10-11 cm3 molecule-1 s-1 was obtained under these conditions. Global modelling using STOCHEM-CRI, updated with monoterpene chemistry generating Criegee intermediates, and supplemented by regional box modelling, shows that this class of Criegee intermediate + peroxy radical reactions can contribute up to ~1.3% of secondary organic aerosol production in forested regions of the world.

KW - atmospheric chemistry

KW - Criegee intermediates

KW - peroxy radicals

KW - radical reactions

KW - secondary organic aerosol

KW - cavity ring-down spectroscopy chemical transport modeling

U2 - 10.1021/acsearthspacechem.0c00147

DO - 10.1021/acsearthspacechem.0c00147

M3 - Article (Academic Journal)

SN - 2472-3452

VL - 4

SP - 1743

EP - 1755

JO - ACS Earth and Space Chemistry

JF - ACS Earth and Space Chemistry

M1 - 10

ER -

Impact of Criegee Intermediate Reactions with Peroxy Radicals on Tropospheric Organic Aerosol

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Keywords

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Projects

Kinetic Studies of Reactive Intermediates from the Oxidation of Atmospheric Alkenes

Gas phase studies of the kinetics of Criegee Intermediates

Cite this