Controlled nitric oxide production via O(<sup>1</sup>D) + N<sub>2</sub>O reactions for use in oxidation flow reactor studies
Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O<sub>3</sub>) is photolyzed at 254 nm to produce O(<sup>1</sup>D) radicals, which rea...
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doaj-0f9b4a533b504e76812b159c6b13de8e2020-11-24T22:01:19ZengCopernicus PublicationsAtmospheric Measurement Techniques1867-13811867-85482017-06-01102283229810.5194/amt-10-2283-2017Controlled nitric oxide production via O(<sup>1</sup>D) + N<sub>2</sub>O reactions for use in oxidation flow reactor studiesA. Lambe0A. Lambe1P. Massoli2X. Zhang3X. Zhang4M. Canagaratna5J. Nowak6J. Nowak7C. Daube8C. Yan9W. Nie10W. Nie11T. Onasch12T. Onasch13J. Jayne14C. Kolb15P. Davidovits16D. Worsnop17D. Worsnop18W. Brune19Aerodyne Research, Inc., Billerica, Massachusetts, USAChemistry Department, Boston College, Chestnut Hill, Massachusetts, USAAerodyne Research, Inc., Billerica, Massachusetts, USAAerodyne Research, Inc., Billerica, Massachusetts, USACurrent address: Atmospheric Chemistry Observations & Modeling Laboratory, National Center for Atmospheric Research, Boulder, Colorado, USAAerodyne Research, Inc., Billerica, Massachusetts, USAAerodyne Research, Inc., Billerica, Massachusetts, USACurrent address: Chemistry and Dynamics Branch, NASA Langley Research Center, Hampton, Virginia, USAAerodyne Research, Inc., Billerica, Massachusetts, USAPhysics Department, University of Helsinki, Helsinki, FinlandJoint International Research Laboratory of Atmospheric and Earth System Sciences, School of Atmospheric Sciences, Nanjing University, Nanjing, ChinaPhysics Department, University of Helsinki, Helsinki, FinlandAerodyne Research, Inc., Billerica, Massachusetts, USAChemistry Department, Boston College, Chestnut Hill, Massachusetts, USAAerodyne Research, Inc., Billerica, Massachusetts, USAAerodyne Research, Inc., Billerica, Massachusetts, USAChemistry Department, Boston College, Chestnut Hill, Massachusetts, USAAerodyne Research, Inc., Billerica, Massachusetts, USAPhysics Department, University of Helsinki, Helsinki, FinlandDepartment of Meteorology and Atmospheric Sciences, The Pennsylvania State University, University Park, Pennsylvania, USAOxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O<sub>3</sub>) is photolyzed at 254 nm to produce O(<sup>1</sup>D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O<sub>3</sub> hinders the ability of oxidation flow reactors to simulate NO<sub><i>x</i></sub>-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NO<sub><i>x</i></sub> (NO + NO<sub>2</sub>) to nitric acid (HNO<sub>3</sub>), making it impossible to sustain NO<sub><i>x</i></sub> at levels that are sufficient to compete with hydroperoxy (HO<sub>2</sub>) radicals as a sink for organic peroxy (RO<sub>2</sub>) radicals. We developed a new method that is well suited to the characterization of NO<sub><i>x</i></sub>-dependent SOA formation pathways in oxidation flow reactors. NO and NO<sub>2</sub> are produced via the reaction O(<sup>1</sup>D) + N<sub>2</sub>O → 2NO, followed by the reaction NO + O<sub>3</sub> → NO<sub>2</sub> + O<sub>2</sub>. Laboratory measurements coupled with photochemical model simulations suggest that O(<sup>1</sup>D) + N<sub>2</sub>O reactions can be used to systematically vary the relative branching ratio of RO<sub>2</sub> + NO reactions relative to RO<sub>2</sub> + HO<sub>2</sub> and/or RO<sub>2</sub> + RO<sub>2</sub> reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO<sub>3</sub><sup>−</sup>) reagent ion to detect gas-phase oxidation products of isoprene and <i>α</i>-pinene previously observed in NO<sub><i>x</i></sub>-influenced environments and in laboratory chamber experiments.http://www.atmos-meas-tech.net/10/2283/2017/amt-10-2283-2017.pdf |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
A. Lambe A. Lambe P. Massoli X. Zhang X. Zhang M. Canagaratna J. Nowak J. Nowak C. Daube C. Yan W. Nie W. Nie T. Onasch T. Onasch J. Jayne C. Kolb P. Davidovits D. Worsnop D. Worsnop W. Brune |
spellingShingle |
A. Lambe A. Lambe P. Massoli X. Zhang X. Zhang M. Canagaratna J. Nowak J. Nowak C. Daube C. Yan W. Nie W. Nie T. Onasch T. Onasch J. Jayne C. Kolb P. Davidovits D. Worsnop D. Worsnop W. Brune Controlled nitric oxide production via O(<sup>1</sup>D) + N<sub>2</sub>O reactions for use in oxidation flow reactor studies Atmospheric Measurement Techniques |
author_facet |
A. Lambe A. Lambe P. Massoli X. Zhang X. Zhang M. Canagaratna J. Nowak J. Nowak C. Daube C. Yan W. Nie W. Nie T. Onasch T. Onasch J. Jayne C. Kolb P. Davidovits D. Worsnop D. Worsnop W. Brune |
author_sort |
A. Lambe |
title |
Controlled nitric oxide production via O(<sup>1</sup>D) + N<sub>2</sub>O reactions for use in oxidation flow reactor studies |
title_short |
Controlled nitric oxide production via O(<sup>1</sup>D) + N<sub>2</sub>O reactions for use in oxidation flow reactor studies |
title_full |
Controlled nitric oxide production via O(<sup>1</sup>D) + N<sub>2</sub>O reactions for use in oxidation flow reactor studies |
title_fullStr |
Controlled nitric oxide production via O(<sup>1</sup>D) + N<sub>2</sub>O reactions for use in oxidation flow reactor studies |
title_full_unstemmed |
Controlled nitric oxide production via O(<sup>1</sup>D) + N<sub>2</sub>O reactions for use in oxidation flow reactor studies |
title_sort |
controlled nitric oxide production via o(<sup>1</sup>d) + n<sub>2</sub>o reactions for use in oxidation flow reactor studies |
publisher |
Copernicus Publications |
series |
Atmospheric Measurement Techniques |
issn |
1867-1381 1867-8548 |
publishDate |
2017-06-01 |
description |
Oxidation flow reactors that use low-pressure mercury lamps to produce
hydroxyl (OH) radicals are an emerging technique for studying the oxidative
aging of organic aerosols. Here, ozone (O<sub>3</sub>) is photolyzed at 254 nm
to produce O(<sup>1</sup>D) radicals, which react with water vapor to produce
OH. However, the need to use parts-per-million levels of O<sub>3</sub> hinders
the ability of oxidation flow reactors to simulate NO<sub><i>x</i></sub>-dependent
secondary organic aerosol (SOA) formation pathways. Simple addition of nitric
oxide (NO) results in fast conversion of NO<sub><i>x</i></sub>
(NO + NO<sub>2</sub>) to nitric acid (HNO<sub>3</sub>), making it impossible to
sustain NO<sub><i>x</i></sub> at levels that are sufficient to compete with
hydroperoxy (HO<sub>2</sub>) radicals as a sink for organic peroxy (RO<sub>2</sub>)
radicals. We developed a new method that is well suited to the
characterization of NO<sub><i>x</i></sub>-dependent SOA formation pathways in
oxidation flow reactors. NO and NO<sub>2</sub> are produced via the reaction
O(<sup>1</sup>D) + N<sub>2</sub>O → 2NO, followed by the reaction
NO + O<sub>3</sub> → NO<sub>2</sub> + O<sub>2</sub>. Laboratory
measurements coupled with photochemical model simulations suggest that
O(<sup>1</sup>D) + N<sub>2</sub>O reactions can be used to systematically vary
the relative branching ratio of RO<sub>2</sub> + NO reactions relative to
RO<sub>2</sub> + HO<sub>2</sub> and/or RO<sub>2</sub> + RO<sub>2</sub> reactions
over a range of conditions relevant to atmospheric SOA formation. We
demonstrate proof of concept using high-resolution time-of-flight chemical
ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate
(NO<sub>3</sub><sup>−</sup>) reagent ion to detect gas-phase oxidation products of
isoprene and <i>α</i>-pinene previously observed in
NO<sub><i>x</i></sub>-influenced environments and in laboratory chamber
experiments. |
url |
http://www.atmos-meas-tech.net/10/2283/2017/amt-10-2283-2017.pdf |
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