Radical chemistry and ozone production at a UK coastal receptor site

Robert Woodward-Massey; Roberto Sommariva; Lisa K. Whalley; Danny R. Cryer; Trevor Ingham; William J. Bloss; Stephen M. Ball; Sam Cox; James D. Lee; Chris P. Reed; Leigh R. Crilley; Louisa J. Kramer; Brian J. Bandy; Grant L. Forster; Claire E. Reeves; Paul S. Monks; Dwayne E. Heard

doi:10.5194/acp-23-14393-2023

Radical chemistry and ozone production at a UK coastal receptor site

Robert Woodward-Massey, Roberto Sommariva, Lisa K. Whalley^*, Danny R. Cryer, Trevor Ingham, William J. Bloss, Stephen M. Ball, Sam Cox, James D. Lee, Chris P. Reed, Leigh R. Crilley, Louisa J. Kramer, Brian J. Bandy, Grant L. Forster, Claire E. Reeves, Paul S. Monks, Dwayne E. Heard^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

OH, HO₂, total and partially speciated RO₂, and OH reactivity (k'_OH) were measured during the July 2015 ICOZA (Integrated Chemistry of OZone in the Atmosphere) project that took place at a coastal site in north Norfolk, UK. Maximum measured daily OH, HO₂ and total RO₂ radical concentrations were in the range 2.6-17 × 10⁶, 0.75-4.2 × 10⁸ and 2.3-8.0 × 10⁸ molec. cm^-3, respectively. k'_OH ranged from 1.7 to 17.6 s^-1, with a median value of 4.7 s^-1. ICOZA data were split by wind direction to assess differences in the radical chemistry between air that had passed over the North Sea (NW-SE sectors) and that over major urban conurbations such as London (SW sector). A box model using the Master Chemical Mechanism (MCMv3.3.1) was in reasonable agreement with the OH measurements, but it overpredicted HO₂ observations in NW-SE air in the afternoon by a factor of 1/4 2-3, although slightly better agreement was found for HO₂ in SW air (factor of 1/4 1.4-2.0 underprediction). The box model severely underpredicted total RO₂ observations in both NW-SE and SW air by factors of 1/4 8-9 on average. Measured radical and k'_OH levels and measurement-model ratios displayed strong dependences on NO mixing ratios, with the results suggesting that peroxy radical chemistry is not well understood under high-NO_x conditions. The simultaneous measurement of OH, HO₂, total RO₂ and k'_OH was used to derive experimental (i.e. observationally determined) budgets for all radical species as well as total RO_x (i.e. OH + HO₂ + RO₂). In NW-SE air, the RO_x budget could be closed during the daytime within experimental uncertainty, but the rate of OH destruction exceeded the rate of OH production, and the rate of HO₂ production greatly exceeded the rate of HO₂ destruction, while the opposite was true for RO₂. In SW air, the RO_x budget analysis indicated missing daytime RO_x sources, but the OH budget was balanced, and the same imbalances were found with the HO₂ and RO₂ budgets as in NW-SE air. For HO₂ and RO₂, the budget imbalances were most severe at high-NO mixing ratios, and the best agreement between HO₂ and RO₂ rates of production and destruction rates was found when the RO₂ + NO rate coefficient was reduced by a factor of 5. A photostationary-steady-state (PSS) calculation underpredicted daytime OH in NW-SE air by 1/4 35 %, whereas agreement (1/4 15 %) was found within instrumental uncertainty (1/4 26 % at 2σ) in SW air. The rate of in situ ozone production (P(O_x)) was calculated from observations of RO_x, NO and NO₂ and compared to that calculated from MCM-modelled radical concentrations. The MCM-calculated P(O_x) significantly underpredicted the measurement-calculated P(Ox) in the morning, and the degree of underprediction was found to scale with NO.

Original language	English
Pages (from-to)	14393-14424
Number of pages	32
Journal	Atmospheric Chemistry and Physics
Volume	23
Issue number	22
DOIs	https://doi.org/10.5194/acp-23-14393-2023
Publication status	Published - 21 Nov 2023

Bibliographical note

Funding Information:
We thank the science team of the ICOZA project. Robert Woodward-Massey and Danny R. Cryer are grateful to the NERC for funding PhD studentships. Robert Woodward-Massey, Lisa K. Whalley, Danny R. Cryer, Trevor Ingham and Dwayne E. Heard would like to thank the University of Leeds' electronic and mechanical workshops. Robert Woodward-Massey is grateful to Hans Osthoff (University of Calgary) for the provision of Igor functions and to Chunxiang Ye (Peking University) and Samuel Seldon (University Of Leeds) for useful discussions. We thank Lloyd Hollis and Roland Leigh (University of Leicester) for assistance with the spectral radiometer and chemical ionisation mass spectrometer. We thank Sam Cox for his help with the AtChem modelling framework.

This research has been supported by the Natural Environment Research Council (grant nos. NE/K012029/1, NE/K012169/1 and NE/K004069/1).

Publisher Copyright:
© Copyright:

ASJC Scopus subject areas

Atmospheric Science

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10.5194/acp-23-14393-2023Licence: Creative Commons: Attribution (CC BY)

WoodwardMasseyR2023RadicalFinal published version, 6.09 MBLicence: Creative Commons: Attribution (CC BY)

ICOZA: Integrated Chemistry of Ozone in the Atmosphere
Bloss, W.
Natural Environment Research Council
31/12/13 → 30/06/17
Project: Research

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Woodward-Massey, R., Sommariva, R., Whalley, L. K., Cryer, D. R., Ingham, T., Bloss, W. J., Ball, S. M., Cox, S., Lee, J. D., Reed, C. P., Crilley, L. R., Kramer, L. J., Bandy, B. J., Forster, G. L., Reeves, C. E., Monks, P. S., & Heard, D. E. (2023). Radical chemistry and ozone production at a UK coastal receptor site. Atmospheric Chemistry and Physics, 23(22), 14393-14424. https://doi.org/10.5194/acp-23-14393-2023

@article{3335bf440e9349dca887c385c8d7f28f,

title = "Radical chemistry and ozone production at a UK coastal receptor site",

abstract = "OH, HO2, total and partially speciated RO2, and OH reactivity (k'OH) were measured during the July 2015 ICOZA (Integrated Chemistry of OZone in the Atmosphere) project that took place at a coastal site in north Norfolk, UK. Maximum measured daily OH, HO2 and total RO2 radical concentrations were in the range 2.6-17 × 106, 0.75-4.2 × 108 and 2.3-8.0 × 108 molec. cm-3, respectively. k'OH ranged from 1.7 to 17.6 s-1, with a median value of 4.7 s-1. ICOZA data were split by wind direction to assess differences in the radical chemistry between air that had passed over the North Sea (NW-SE sectors) and that over major urban conurbations such as London (SW sector). A box model using the Master Chemical Mechanism (MCMv3.3.1) was in reasonable agreement with the OH measurements, but it overpredicted HO2 observations in NW-SE air in the afternoon by a factor of 1/4 2-3, although slightly better agreement was found for HO2 in SW air (factor of 1/4 1.4-2.0 underprediction). The box model severely underpredicted total RO2 observations in both NW-SE and SW air by factors of 1/4 8-9 on average. Measured radical and k'OH levels and measurement-model ratios displayed strong dependences on NO mixing ratios, with the results suggesting that peroxy radical chemistry is not well understood under high-NOx conditions. The simultaneous measurement of OH, HO2, total RO2 and k'OH was used to derive experimental (i.e. observationally determined) budgets for all radical species as well as total ROx (i.e. OH + HO2 + RO2). In NW-SE air, the ROx budget could be closed during the daytime within experimental uncertainty, but the rate of OH destruction exceeded the rate of OH production, and the rate of HO2 production greatly exceeded the rate of HO2 destruction, while the opposite was true for RO2. In SW air, the ROx budget analysis indicated missing daytime ROx sources, but the OH budget was balanced, and the same imbalances were found with the HO2 and RO2 budgets as in NW-SE air. For HO2 and RO2, the budget imbalances were most severe at high-NO mixing ratios, and the best agreement between HO2 and RO2 rates of production and destruction rates was found when the RO2 + NO rate coefficient was reduced by a factor of 5. A photostationary-steady-state (PSS) calculation underpredicted daytime OH in NW-SE air by 1/4 35 %, whereas agreement (1/4 15 %) was found within instrumental uncertainty (1/4 26 % at 2σ) in SW air. The rate of in situ ozone production (P(Ox)) was calculated from observations of ROx, NO and NO2 and compared to that calculated from MCM-modelled radical concentrations. The MCM-calculated P(Ox) significantly underpredicted the measurement-calculated P(Ox) in the morning, and the degree of underprediction was found to scale with NO.",

author = "Robert Woodward-Massey and Roberto Sommariva and Whalley, {Lisa K.} and Cryer, {Danny R.} and Trevor Ingham and Bloss, {William J.} and Ball, {Stephen M.} and Sam Cox and Lee, {James D.} and Reed, {Chris P.} and Crilley, {Leigh R.} and Kramer, {Louisa J.} and Bandy, {Brian J.} and Forster, {Grant L.} and Reeves, {Claire E.} and Monks, {Paul S.} and Heard, {Dwayne E.}",

note = "Funding Information: We thank the science team of the ICOZA project. Robert Woodward-Massey and Danny R. Cryer are grateful to the NERC for funding PhD studentships. Robert Woodward-Massey, Lisa K. Whalley, Danny R. Cryer, Trevor Ingham and Dwayne E. Heard would like to thank the University of Leeds' electronic and mechanical workshops. Robert Woodward-Massey is grateful to Hans Osthoff (University of Calgary) for the provision of Igor functions and to Chunxiang Ye (Peking University) and Samuel Seldon (University Of Leeds) for useful discussions. We thank Lloyd Hollis and Roland Leigh (University of Leicester) for assistance with the spectral radiometer and chemical ionisation mass spectrometer. We thank Sam Cox for his help with the AtChem modelling framework. This research has been supported by the Natural Environment Research Council (grant nos. NE/K012029/1, NE/K012169/1 and NE/K004069/1). Publisher Copyright: {\textcopyright} Copyright: ",

year = "2023",

month = nov,

day = "21",

doi = "10.5194/acp-23-14393-2023",

language = "English",

volume = "23",

pages = "14393--14424",

journal = "Atmospheric Chemistry and Physics",

issn = "1680-7316",

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Woodward-Massey, R, Sommariva, R, Whalley, LK, Cryer, DR, Ingham, T, Bloss, WJ, Ball, SM, Cox, S, Lee, JD, Reed, CP, Crilley, LR, Kramer, LJ, Bandy, BJ, Forster, GL, Reeves, CE, Monks, PS & Heard, DE 2023, 'Radical chemistry and ozone production at a UK coastal receptor site', Atmospheric Chemistry and Physics, vol. 23, no. 22, pp. 14393-14424. https://doi.org/10.5194/acp-23-14393-2023

TY - JOUR

T1 - Radical chemistry and ozone production at a UK coastal receptor site

AU - Woodward-Massey, Robert

AU - Sommariva, Roberto

AU - Whalley, Lisa K.

AU - Cryer, Danny R.

AU - Ingham, Trevor

AU - Bloss, William J.

AU - Ball, Stephen M.

AU - Cox, Sam

AU - Lee, James D.

AU - Reed, Chris P.

AU - Crilley, Leigh R.

AU - Kramer, Louisa J.

AU - Bandy, Brian J.

AU - Forster, Grant L.

AU - Reeves, Claire E.

AU - Monks, Paul S.

AU - Heard, Dwayne E.

N1 - Funding Information: We thank the science team of the ICOZA project. Robert Woodward-Massey and Danny R. Cryer are grateful to the NERC for funding PhD studentships. Robert Woodward-Massey, Lisa K. Whalley, Danny R. Cryer, Trevor Ingham and Dwayne E. Heard would like to thank the University of Leeds' electronic and mechanical workshops. Robert Woodward-Massey is grateful to Hans Osthoff (University of Calgary) for the provision of Igor functions and to Chunxiang Ye (Peking University) and Samuel Seldon (University Of Leeds) for useful discussions. We thank Lloyd Hollis and Roland Leigh (University of Leicester) for assistance with the spectral radiometer and chemical ionisation mass spectrometer. We thank Sam Cox for his help with the AtChem modelling framework. This research has been supported by the Natural Environment Research Council (grant nos. NE/K012029/1, NE/K012169/1 and NE/K004069/1). Publisher Copyright: © Copyright:

PY - 2023/11/21

Y1 - 2023/11/21

N2 - OH, HO2, total and partially speciated RO2, and OH reactivity (k'OH) were measured during the July 2015 ICOZA (Integrated Chemistry of OZone in the Atmosphere) project that took place at a coastal site in north Norfolk, UK. Maximum measured daily OH, HO2 and total RO2 radical concentrations were in the range 2.6-17 × 106, 0.75-4.2 × 108 and 2.3-8.0 × 108 molec. cm-3, respectively. k'OH ranged from 1.7 to 17.6 s-1, with a median value of 4.7 s-1. ICOZA data were split by wind direction to assess differences in the radical chemistry between air that had passed over the North Sea (NW-SE sectors) and that over major urban conurbations such as London (SW sector). A box model using the Master Chemical Mechanism (MCMv3.3.1) was in reasonable agreement with the OH measurements, but it overpredicted HO2 observations in NW-SE air in the afternoon by a factor of 1/4 2-3, although slightly better agreement was found for HO2 in SW air (factor of 1/4 1.4-2.0 underprediction). The box model severely underpredicted total RO2 observations in both NW-SE and SW air by factors of 1/4 8-9 on average. Measured radical and k'OH levels and measurement-model ratios displayed strong dependences on NO mixing ratios, with the results suggesting that peroxy radical chemistry is not well understood under high-NOx conditions. The simultaneous measurement of OH, HO2, total RO2 and k'OH was used to derive experimental (i.e. observationally determined) budgets for all radical species as well as total ROx (i.e. OH + HO2 + RO2). In NW-SE air, the ROx budget could be closed during the daytime within experimental uncertainty, but the rate of OH destruction exceeded the rate of OH production, and the rate of HO2 production greatly exceeded the rate of HO2 destruction, while the opposite was true for RO2. In SW air, the ROx budget analysis indicated missing daytime ROx sources, but the OH budget was balanced, and the same imbalances were found with the HO2 and RO2 budgets as in NW-SE air. For HO2 and RO2, the budget imbalances were most severe at high-NO mixing ratios, and the best agreement between HO2 and RO2 rates of production and destruction rates was found when the RO2 + NO rate coefficient was reduced by a factor of 5. A photostationary-steady-state (PSS) calculation underpredicted daytime OH in NW-SE air by 1/4 35 %, whereas agreement (1/4 15 %) was found within instrumental uncertainty (1/4 26 % at 2σ) in SW air. The rate of in situ ozone production (P(Ox)) was calculated from observations of ROx, NO and NO2 and compared to that calculated from MCM-modelled radical concentrations. The MCM-calculated P(Ox) significantly underpredicted the measurement-calculated P(Ox) in the morning, and the degree of underprediction was found to scale with NO.

AB - OH, HO2, total and partially speciated RO2, and OH reactivity (k'OH) were measured during the July 2015 ICOZA (Integrated Chemistry of OZone in the Atmosphere) project that took place at a coastal site in north Norfolk, UK. Maximum measured daily OH, HO2 and total RO2 radical concentrations were in the range 2.6-17 × 106, 0.75-4.2 × 108 and 2.3-8.0 × 108 molec. cm-3, respectively. k'OH ranged from 1.7 to 17.6 s-1, with a median value of 4.7 s-1. ICOZA data were split by wind direction to assess differences in the radical chemistry between air that had passed over the North Sea (NW-SE sectors) and that over major urban conurbations such as London (SW sector). A box model using the Master Chemical Mechanism (MCMv3.3.1) was in reasonable agreement with the OH measurements, but it overpredicted HO2 observations in NW-SE air in the afternoon by a factor of 1/4 2-3, although slightly better agreement was found for HO2 in SW air (factor of 1/4 1.4-2.0 underprediction). The box model severely underpredicted total RO2 observations in both NW-SE and SW air by factors of 1/4 8-9 on average. Measured radical and k'OH levels and measurement-model ratios displayed strong dependences on NO mixing ratios, with the results suggesting that peroxy radical chemistry is not well understood under high-NOx conditions. The simultaneous measurement of OH, HO2, total RO2 and k'OH was used to derive experimental (i.e. observationally determined) budgets for all radical species as well as total ROx (i.e. OH + HO2 + RO2). In NW-SE air, the ROx budget could be closed during the daytime within experimental uncertainty, but the rate of OH destruction exceeded the rate of OH production, and the rate of HO2 production greatly exceeded the rate of HO2 destruction, while the opposite was true for RO2. In SW air, the ROx budget analysis indicated missing daytime ROx sources, but the OH budget was balanced, and the same imbalances were found with the HO2 and RO2 budgets as in NW-SE air. For HO2 and RO2, the budget imbalances were most severe at high-NO mixing ratios, and the best agreement between HO2 and RO2 rates of production and destruction rates was found when the RO2 + NO rate coefficient was reduced by a factor of 5. A photostationary-steady-state (PSS) calculation underpredicted daytime OH in NW-SE air by 1/4 35 %, whereas agreement (1/4 15 %) was found within instrumental uncertainty (1/4 26 % at 2σ) in SW air. The rate of in situ ozone production (P(Ox)) was calculated from observations of ROx, NO and NO2 and compared to that calculated from MCM-modelled radical concentrations. The MCM-calculated P(Ox) significantly underpredicted the measurement-calculated P(Ox) in the morning, and the degree of underprediction was found to scale with NO.

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U2 - 10.5194/acp-23-14393-2023

DO - 10.5194/acp-23-14393-2023

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AN - SCOPUS:85179453316

SN - 1680-7316

VL - 23

SP - 14393

EP - 14424

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

IS - 22

ER -

Radical chemistry and ozone production at a UK coastal receptor site

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Bibliographical note

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Projects

ICOZA: Integrated Chemistry of Ozone in the Atmosphere

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