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Radical chemistry at night: Comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project

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Radical chemistry at night: Comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project. / Stone, D.; Evans, M. J.; Walker, H. et al.
In: Atmospheric Chemistry and Physics, Vol. 14, No. 3, 05.02.2014, p. 1299-1321.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Stone, D, Evans, MJ, Walker, H, Ingham, T, Vaughan, S, Ouyang, B, Kennedy, OJ, McLeod, MW, Jones, RL, Hopkins, J, Punjabi, S, Lidster, R, Hamilton, JF, Lee, JD, Lewis, AC, Carpenter, LJ, Forster, G, Oram, DE, Reeves, CE, Bauguitte, S, Morgan, W, Coe, H, Aruffo, E, Dari-Salisburgo, C, Giammaria, F, Di Carlo, P & Heard, DE 2014, 'Radical chemistry at night: Comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project', Atmospheric Chemistry and Physics, vol. 14, no. 3, pp. 1299-1321. https://doi.org/10.5194/acp-14-1299-2014

APA

Stone, D., Evans, M. J., Walker, H., Ingham, T., Vaughan, S., Ouyang, B., Kennedy, O. J., McLeod, M. W., Jones, R. L., Hopkins, J., Punjabi, S., Lidster, R., Hamilton, J. F., Lee, J. D., Lewis, A. C., Carpenter, L. J., Forster, G., Oram, D. E., Reeves, C. E., ... Heard, D. E. (2014). Radical chemistry at night: Comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project. Atmospheric Chemistry and Physics, 14(3), 1299-1321. https://doi.org/10.5194/acp-14-1299-2014

Vancouver

Stone D, Evans MJ, Walker H, Ingham T, Vaughan S, Ouyang B et al. Radical chemistry at night: Comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project. Atmospheric Chemistry and Physics. 2014 Feb 5;14(3):1299-1321. doi: 10.5194/acp-14-1299-2014

Author

Stone, D. ; Evans, M. J. ; Walker, H. et al. / Radical chemistry at night : Comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project. In: Atmospheric Chemistry and Physics. 2014 ; Vol. 14, No. 3. pp. 1299-1321.

Bibtex

@article{04a0aa9243984b7bb1f081656e092d23,
title = "Radical chemistry at night: Comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project",
abstract = "The RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the AtmOsphere) aircraft campaign during July 2010 and January 2011 made observations of OH, HO2, NO3, N2O5 and a number of supporting measurements at night over the UK, and reflects the first simultaneous airborne measurements of these species. We compare the observed concentrations of these short-lived species with those calculated by a box model constrained by the concentrations of the longer lived species using a detailed chemical scheme. OH concentrations were below the limit of detection, consistent with model predictions. The model systematically underpredicts HO2 by ∼200% and overpredicts NO3 and N2O5 by around 80 and 50%, respectively. Cycling between NO3 and N2O5 is fast and thus we define the NO3x (NO3xCombining double low lineNO3+N2O5) family. Production of NO3x is overwhelmingly dominated by the reaction of NO2 with O3, whereas its loss is dominated by aerosol uptake of N2O5, with NO3+VOCs (volatile organic compounds) and NO3+RO2 playing smaller roles. The production of HOx and ROx radicals is mainly due to the reaction of NO3 with VOCs. The loss of these radicals occurs through a combination of HO2+RO2 reactions, heterogeneous processes and production of HNO3 from OH+NO2, with radical propagation primarily achieved through reactions of NO3 with peroxy radicals. Thus NO3 at night plays a similar role to both OH and NO during the day in that it both initiates ROx radical production and acts to propagate the tropospheric oxidation chain. Model sensitivity to the N2O5 aerosol uptake coefficient (γN2O5) is discussed and we find that a value of γN2O5Combining double low line0.05 improves model simulations for NO3 and N2O5, but that these improvements are at the expense of model success for HO2. Improvements to model simulations for HO2, NO3 and N2O5 can be realised simultaneously on inclusion of additional unsaturated volatile organic compounds, however the nature of these compounds is extremely uncertain.",
author = "D. Stone and Evans, {M. J.} and H. Walker and T. Ingham and S. Vaughan and B. Ouyang and Kennedy, {O. J.} and McLeod, {M. W.} and Jones, {R. L.} and J. Hopkins and S. Punjabi and R. Lidster and Hamilton, {J. F.} and Lee, {J. D.} and Lewis, {A. C.} and Carpenter, {L. J.} and G. Forster and Oram, {D. E.} and Reeves, {C. E.} and S. Bauguitte and W. Morgan and H. Coe and E. Aruffo and C. Dari-Salisburgo and F. Giammaria and {Di Carlo}, P. and Heard, {D. E.}",
year = "2014",
month = feb,
day = "5",
doi = "10.5194/acp-14-1299-2014",
language = "English",
volume = "14",
pages = "1299--1321",
journal = "Atmospheric Chemistry and Physics",
issn = "1680-7316",
publisher = "Copernicus GmbH (Copernicus Publications) on behalf of the European Geosciences Union (EGU)",
number = "3",

}

RIS

TY - JOUR

T1 - Radical chemistry at night

T2 - Comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project

AU - Stone, D.

AU - Evans, M. J.

AU - Walker, H.

AU - Ingham, T.

AU - Vaughan, S.

AU - Ouyang, B.

AU - Kennedy, O. J.

AU - McLeod, M. W.

AU - Jones, R. L.

AU - Hopkins, J.

AU - Punjabi, S.

AU - Lidster, R.

AU - Hamilton, J. F.

AU - Lee, J. D.

AU - Lewis, A. C.

AU - Carpenter, L. J.

AU - Forster, G.

AU - Oram, D. E.

AU - Reeves, C. E.

AU - Bauguitte, S.

AU - Morgan, W.

AU - Coe, H.

AU - Aruffo, E.

AU - Dari-Salisburgo, C.

AU - Giammaria, F.

AU - Di Carlo, P.

AU - Heard, D. E.

PY - 2014/2/5

Y1 - 2014/2/5

N2 - The RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the AtmOsphere) aircraft campaign during July 2010 and January 2011 made observations of OH, HO2, NO3, N2O5 and a number of supporting measurements at night over the UK, and reflects the first simultaneous airborne measurements of these species. We compare the observed concentrations of these short-lived species with those calculated by a box model constrained by the concentrations of the longer lived species using a detailed chemical scheme. OH concentrations were below the limit of detection, consistent with model predictions. The model systematically underpredicts HO2 by ∼200% and overpredicts NO3 and N2O5 by around 80 and 50%, respectively. Cycling between NO3 and N2O5 is fast and thus we define the NO3x (NO3xCombining double low lineNO3+N2O5) family. Production of NO3x is overwhelmingly dominated by the reaction of NO2 with O3, whereas its loss is dominated by aerosol uptake of N2O5, with NO3+VOCs (volatile organic compounds) and NO3+RO2 playing smaller roles. The production of HOx and ROx radicals is mainly due to the reaction of NO3 with VOCs. The loss of these radicals occurs through a combination of HO2+RO2 reactions, heterogeneous processes and production of HNO3 from OH+NO2, with radical propagation primarily achieved through reactions of NO3 with peroxy radicals. Thus NO3 at night plays a similar role to both OH and NO during the day in that it both initiates ROx radical production and acts to propagate the tropospheric oxidation chain. Model sensitivity to the N2O5 aerosol uptake coefficient (γN2O5) is discussed and we find that a value of γN2O5Combining double low line0.05 improves model simulations for NO3 and N2O5, but that these improvements are at the expense of model success for HO2. Improvements to model simulations for HO2, NO3 and N2O5 can be realised simultaneously on inclusion of additional unsaturated volatile organic compounds, however the nature of these compounds is extremely uncertain.

AB - The RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the AtmOsphere) aircraft campaign during July 2010 and January 2011 made observations of OH, HO2, NO3, N2O5 and a number of supporting measurements at night over the UK, and reflects the first simultaneous airborne measurements of these species. We compare the observed concentrations of these short-lived species with those calculated by a box model constrained by the concentrations of the longer lived species using a detailed chemical scheme. OH concentrations were below the limit of detection, consistent with model predictions. The model systematically underpredicts HO2 by ∼200% and overpredicts NO3 and N2O5 by around 80 and 50%, respectively. Cycling between NO3 and N2O5 is fast and thus we define the NO3x (NO3xCombining double low lineNO3+N2O5) family. Production of NO3x is overwhelmingly dominated by the reaction of NO2 with O3, whereas its loss is dominated by aerosol uptake of N2O5, with NO3+VOCs (volatile organic compounds) and NO3+RO2 playing smaller roles. The production of HOx and ROx radicals is mainly due to the reaction of NO3 with VOCs. The loss of these radicals occurs through a combination of HO2+RO2 reactions, heterogeneous processes and production of HNO3 from OH+NO2, with radical propagation primarily achieved through reactions of NO3 with peroxy radicals. Thus NO3 at night plays a similar role to both OH and NO during the day in that it both initiates ROx radical production and acts to propagate the tropospheric oxidation chain. Model sensitivity to the N2O5 aerosol uptake coefficient (γN2O5) is discussed and we find that a value of γN2O5Combining double low line0.05 improves model simulations for NO3 and N2O5, but that these improvements are at the expense of model success for HO2. Improvements to model simulations for HO2, NO3 and N2O5 can be realised simultaneously on inclusion of additional unsaturated volatile organic compounds, however the nature of these compounds is extremely uncertain.

U2 - 10.5194/acp-14-1299-2014

DO - 10.5194/acp-14-1299-2014

M3 - Journal article

AN - SCOPUS:84893459318

VL - 14

SP - 1299

EP - 1321

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

SN - 1680-7316

IS - 3

ER -