Observational Constraints on the Oxidation of NOx in the Upper Troposphere

Benjamin A. Nault, Charity Garland, Paul J. Wooldridge, William H. Brune, Pedro Campuzano-Jost, John D. Crounse, Douglas A. Day, Jack Dibb, Samuel R. Hall, L. Gregory Huey, José L. Jimenez, Xiaoxi Liu, Jingqiu Mao, Tomas Mikoviny, Jeff Peischl, Ilana B. Pollack, Xinrong Ren, Thomas B. Ryerson, Eric Scheuer, Kirk UllmannPaul O. Wennberg, Armin Wisthaler, Li Zhang, Ronald C. Cohen

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

NOx (NOx ≡ NO + NO2) regulates O3 and HOx (HOx ≡ OH + HO2) concentrations in the upper troposphere. In the laboratory, it is difficult to measure rates and branching ratios of the chemical reactions affecting NOx at the low temperatures and pressures characteristic of the upper troposphere, making direct measurements in the atmosphere especially useful. We report quasi-Lagrangian observations of the chemical evolution of an air parcel following a lightning event that results in high NOx concentrations. These quasi-Lagrangian measurements obtained during the Deep Convective Clouds and Chemistry experiment are used to characterize the daytime rates for conversion of NOx to different peroxy nitrates, the sum of alkyl and multifunctional nitrates, and HNO3. We infer the following production rate constants [in (cm3/molecule)/s] at 225 K and 230 hPa: 7.2(±5.7) × 10-12 (CH3O2NO2), 5.1(±3.1) × 10-13 (HO2NO2), 1.3(±0.8) × 10-11 (PAN), 7.3(±3.4) × 10-12 (PPN), and 6.2(±2.9) × 10-12 (HNO3). The HNO3 and HO2NO2 rates are ∼30-50% lower than currently recommended whereas the other rates are consistent with current recommendations to within ±30%. The analysis indicates that HNO3 production from the HO2 and NO reaction (if any) must be accompanied by a slower rate for the reaction of OH with NO2, keeping the total combined rate for the two processes at the rate reported for HNO3 production above.

Original languageEnglish (US)
Pages (from-to)1468-1478
Number of pages11
JournalJournal of Physical Chemistry A
Volume120
Issue number9
DOIs
StatePublished - Mar 10 2016

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Troposphere
troposphere
Nitrates
Oxidation
oxidation
Lightning
Chemical reactions
Rate constants
nitrates
Molecules
Air
polyacrylonitrile
chemical evolution
lightning
daytime
Experiments
recommendations
chemical reactions
Temperature
low pressure

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Nault, B. A., Garland, C., Wooldridge, P. J., Brune, W. H., Campuzano-Jost, P., Crounse, J. D., ... Cohen, R. C. (2016). Observational Constraints on the Oxidation of NOx in the Upper Troposphere. Journal of Physical Chemistry A, 120(9), 1468-1478. https://doi.org/10.1021/acs.jpca.5b07824
Nault, Benjamin A. ; Garland, Charity ; Wooldridge, Paul J. ; Brune, William H. ; Campuzano-Jost, Pedro ; Crounse, John D. ; Day, Douglas A. ; Dibb, Jack ; Hall, Samuel R. ; Huey, L. Gregory ; Jimenez, José L. ; Liu, Xiaoxi ; Mao, Jingqiu ; Mikoviny, Tomas ; Peischl, Jeff ; Pollack, Ilana B. ; Ren, Xinrong ; Ryerson, Thomas B. ; Scheuer, Eric ; Ullmann, Kirk ; Wennberg, Paul O. ; Wisthaler, Armin ; Zhang, Li ; Cohen, Ronald C. / Observational Constraints on the Oxidation of NOx in the Upper Troposphere. In: Journal of Physical Chemistry A. 2016 ; Vol. 120, No. 9. pp. 1468-1478.
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title = "Observational Constraints on the Oxidation of NOx in the Upper Troposphere",
abstract = "NOx (NOx ≡ NO + NO2) regulates O3 and HOx (HOx ≡ OH + HO2) concentrations in the upper troposphere. In the laboratory, it is difficult to measure rates and branching ratios of the chemical reactions affecting NOx at the low temperatures and pressures characteristic of the upper troposphere, making direct measurements in the atmosphere especially useful. We report quasi-Lagrangian observations of the chemical evolution of an air parcel following a lightning event that results in high NOx concentrations. These quasi-Lagrangian measurements obtained during the Deep Convective Clouds and Chemistry experiment are used to characterize the daytime rates for conversion of NOx to different peroxy nitrates, the sum of alkyl and multifunctional nitrates, and HNO3. We infer the following production rate constants [in (cm3/molecule)/s] at 225 K and 230 hPa: 7.2(±5.7) × 10-12 (CH3O2NO2), 5.1(±3.1) × 10-13 (HO2NO2), 1.3(±0.8) × 10-11 (PAN), 7.3(±3.4) × 10-12 (PPN), and 6.2(±2.9) × 10-12 (HNO3). The HNO3 and HO2NO2 rates are ∼30-50{\%} lower than currently recommended whereas the other rates are consistent with current recommendations to within ±30{\%}. The analysis indicates that HNO3 production from the HO2 and NO reaction (if any) must be accompanied by a slower rate for the reaction of OH with NO2, keeping the total combined rate for the two processes at the rate reported for HNO3 production above.",
author = "Nault, {Benjamin A.} and Charity Garland and Wooldridge, {Paul J.} and Brune, {William H.} and Pedro Campuzano-Jost and Crounse, {John D.} and Day, {Douglas A.} and Jack Dibb and Hall, {Samuel R.} and Huey, {L. Gregory} and Jimenez, {Jos{\'e} L.} and Xiaoxi Liu and Jingqiu Mao and Tomas Mikoviny and Jeff Peischl and Pollack, {Ilana B.} and Xinrong Ren and Ryerson, {Thomas B.} and Eric Scheuer and Kirk Ullmann and Wennberg, {Paul O.} and Armin Wisthaler and Li Zhang and Cohen, {Ronald C.}",
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Nault, BA, Garland, C, Wooldridge, PJ, Brune, WH, Campuzano-Jost, P, Crounse, JD, Day, DA, Dibb, J, Hall, SR, Huey, LG, Jimenez, JL, Liu, X, Mao, J, Mikoviny, T, Peischl, J, Pollack, IB, Ren, X, Ryerson, TB, Scheuer, E, Ullmann, K, Wennberg, PO, Wisthaler, A, Zhang, L & Cohen, RC 2016, 'Observational Constraints on the Oxidation of NOx in the Upper Troposphere', Journal of Physical Chemistry A, vol. 120, no. 9, pp. 1468-1478. https://doi.org/10.1021/acs.jpca.5b07824

Observational Constraints on the Oxidation of NOx in the Upper Troposphere. / Nault, Benjamin A.; Garland, Charity; Wooldridge, Paul J.; Brune, William H.; Campuzano-Jost, Pedro; Crounse, John D.; Day, Douglas A.; Dibb, Jack; Hall, Samuel R.; Huey, L. Gregory; Jimenez, José L.; Liu, Xiaoxi; Mao, Jingqiu; Mikoviny, Tomas; Peischl, Jeff; Pollack, Ilana B.; Ren, Xinrong; Ryerson, Thomas B.; Scheuer, Eric; Ullmann, Kirk; Wennberg, Paul O.; Wisthaler, Armin; Zhang, Li; Cohen, Ronald C.

In: Journal of Physical Chemistry A, Vol. 120, No. 9, 10.03.2016, p. 1468-1478.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Observational Constraints on the Oxidation of NOx in the Upper Troposphere

AU - Nault, Benjamin A.

AU - Garland, Charity

AU - Wooldridge, Paul J.

AU - Brune, William H.

AU - Campuzano-Jost, Pedro

AU - Crounse, John D.

AU - Day, Douglas A.

AU - Dibb, Jack

AU - Hall, Samuel R.

AU - Huey, L. Gregory

AU - Jimenez, José L.

AU - Liu, Xiaoxi

AU - Mao, Jingqiu

AU - Mikoviny, Tomas

AU - Peischl, Jeff

AU - Pollack, Ilana B.

AU - Ren, Xinrong

AU - Ryerson, Thomas B.

AU - Scheuer, Eric

AU - Ullmann, Kirk

AU - Wennberg, Paul O.

AU - Wisthaler, Armin

AU - Zhang, Li

AU - Cohen, Ronald C.

PY - 2016/3/10

Y1 - 2016/3/10

N2 - NOx (NOx ≡ NO + NO2) regulates O3 and HOx (HOx ≡ OH + HO2) concentrations in the upper troposphere. In the laboratory, it is difficult to measure rates and branching ratios of the chemical reactions affecting NOx at the low temperatures and pressures characteristic of the upper troposphere, making direct measurements in the atmosphere especially useful. We report quasi-Lagrangian observations of the chemical evolution of an air parcel following a lightning event that results in high NOx concentrations. These quasi-Lagrangian measurements obtained during the Deep Convective Clouds and Chemistry experiment are used to characterize the daytime rates for conversion of NOx to different peroxy nitrates, the sum of alkyl and multifunctional nitrates, and HNO3. We infer the following production rate constants [in (cm3/molecule)/s] at 225 K and 230 hPa: 7.2(±5.7) × 10-12 (CH3O2NO2), 5.1(±3.1) × 10-13 (HO2NO2), 1.3(±0.8) × 10-11 (PAN), 7.3(±3.4) × 10-12 (PPN), and 6.2(±2.9) × 10-12 (HNO3). The HNO3 and HO2NO2 rates are ∼30-50% lower than currently recommended whereas the other rates are consistent with current recommendations to within ±30%. The analysis indicates that HNO3 production from the HO2 and NO reaction (if any) must be accompanied by a slower rate for the reaction of OH with NO2, keeping the total combined rate for the two processes at the rate reported for HNO3 production above.

AB - NOx (NOx ≡ NO + NO2) regulates O3 and HOx (HOx ≡ OH + HO2) concentrations in the upper troposphere. In the laboratory, it is difficult to measure rates and branching ratios of the chemical reactions affecting NOx at the low temperatures and pressures characteristic of the upper troposphere, making direct measurements in the atmosphere especially useful. We report quasi-Lagrangian observations of the chemical evolution of an air parcel following a lightning event that results in high NOx concentrations. These quasi-Lagrangian measurements obtained during the Deep Convective Clouds and Chemistry experiment are used to characterize the daytime rates for conversion of NOx to different peroxy nitrates, the sum of alkyl and multifunctional nitrates, and HNO3. We infer the following production rate constants [in (cm3/molecule)/s] at 225 K and 230 hPa: 7.2(±5.7) × 10-12 (CH3O2NO2), 5.1(±3.1) × 10-13 (HO2NO2), 1.3(±0.8) × 10-11 (PAN), 7.3(±3.4) × 10-12 (PPN), and 6.2(±2.9) × 10-12 (HNO3). The HNO3 and HO2NO2 rates are ∼30-50% lower than currently recommended whereas the other rates are consistent with current recommendations to within ±30%. The analysis indicates that HNO3 production from the HO2 and NO reaction (if any) must be accompanied by a slower rate for the reaction of OH with NO2, keeping the total combined rate for the two processes at the rate reported for HNO3 production above.

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Nault BA, Garland C, Wooldridge PJ, Brune WH, Campuzano-Jost P, Crounse JD et al. Observational Constraints on the Oxidation of NOx in the Upper Troposphere. Journal of Physical Chemistry A. 2016 Mar 10;120(9):1468-1478. https://doi.org/10.1021/acs.jpca.5b07824