Controlled nitric oxide production via O(<sup>1</sup>D)  + N<sub>2</sub>O reactions for use in oxidation flow reactor studies

Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John; Kolb, Charles; Davidovits, Paul; Worsnop, Douglas; Brune, William

doi:https://doi.org/10.5194/amt-10-2283-2017

Articles | Volume 10, issue 6

https://doi.org/10.5194/amt-10-2283-2017

© Author(s) 2017. This work is distributed under
the Creative Commons Attribution 3.0 License.

https://doi.org/10.5194/amt-10-2283-2017

© Author(s) 2017. This work is distributed under
the Creative Commons Attribution 3.0 License.

Articles | Volume 10, issue 6

Research article

|

22 Jun 2017

Research article |

| 22 Jun 2017

Controlled nitric oxide production via O(¹D)  + N₂O reactions for use in oxidation flow reactor studies

Andrew Lambe, Paola Massoli, Xuan Zhang, Manjula Canagaratna, John Nowak, Conner Daube, Chao Yan, Wei Nie, Timothy Onasch, John Jayne, Charles Kolb, Paul Davidovits, Douglas Worsnop, and William Brune

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Final revised paper (published on 22 Jun 2017)
Supplement to the final revised paper
Preprint (discussion started on 06 Jan 2017)
Supplement to the preprint

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Status: closed

AC: Author comment | RC: Referee comment | SC: Short comment | EC: Editor comment

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RC1: 'review of manuscript by Lambe et al', Anonymous Referee #1, 06 Feb 2017
RC2: 'Review of Lambe et al.', Anonymous Referee #2, 04 Mar 2017
AC1: 'final response', Andrew Lambe, 14 Apr 2017

Peer-review completion

AR: Author's response | RR: Referee report | ED: Editor decision

AR by Andrew Lambe on behalf of the Authors (20 Apr 2017) Author's response Manuscript

ED: Referee Nomination & Report Request started (01 May 2017) by Thomas F. Hanisco

RR by Anonymous Referee #2 (08 May 2017)

Suggestions for revision or reasons for rejection

The revised manuscript is significantly improved with respect to its initial AMTD version. The authors have made good efforts in NOx measurements, product identification at mechanistic level, and comparison of CIMS spectra obtained in their lab experiments and SOAS, which help clarify the atmospheric relevance of their study and the origin of observed N-containing compounds. This paper can be accepted for publication in AMT after the following issues are addressed.

- In Point (4) of the response to Reviewer 1’s 7th comment, C4 and C5 are assumed to be products from RO2 + NO and from other pathways, respectively. However, RO2 + HO2 also leads to C4 formation (Liu et al., 2013), although to a smaller extent. If this is taken into account for the experiments in this work, where HO2 concentration should be very high, how would this impact the analysis of product formation pathways (RO2 + NO vs. others)?

- Reviewers had asked to measure NO and HO2, whose ratio determines whether the chemistry is high- or low-NOx and is directly comparable to the modeled one in the AMTD paper, while only NO measurements were added in the revised manuscript. I understand that HO2 measurements may be much more difficult and/or less accurate than those of NOx. But the authors need to say why they do not measure HO2 to provide a direct measurement-modeling comparison on NO:HO2.

- Can all conditions where the experiments were conducted in this study avoid the unwanted chemistry discussed in the AMTD paper and raised by the reviewers? If so, they need to say it; otherwise, they should clarify under what conditions they used the chemistry is undesired. In addition, based on the results of this study, can the authors suggest any preferred conditions to obtain high-NOx chemistry by the new method?

Reference:
Liu, Y. J., Herdlinger-Blatt, I., McKinney, K. A. and Martin, S. T.: Production of methyl vinyl ketone and methacrolein via the hydroperoxyl pathway of isoprene oxidation, Atmos. Chem. Phys., 13(11), 5715–5730, doi:10.5194/acp-13-5715-2013, 2013.

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ED: Publish subject to minor revisions (Editor review) (09 May 2017) by Thomas F. Hanisco

AR by Andrew Lambe on behalf of the Authors (11 May 2017) Author's response Manuscript

ED: Publish as is (23 May 2017) by Thomas F. Hanisco

AR by Andrew Lambe on behalf of the Authors (23 May 2017)

Short summary

This work enables the study of NO_x-influenced secondary organic aerosol formation chemistry in oxidation flow reactors to an extent that was not previously possible. The method uses reactions of exited oxygen O(¹D) radicals (formed from ozone photolysis at 254 nm or nitrous oxide photolysis at 185 nm) with nitrous oxide (N₂O) to produce NO. We demonstrate proof of concept using chemical ionization mass spectrometer measurements to detect gas-phase oxidation products of isoprene and α-pinene.

Controlled nitric oxide production via O(1D) + N2O reactions for use in oxidation flow reactor studies

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Controlled nitric oxide production via O(¹D)  + N₂O reactions for use in oxidation flow reactor studies