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Insights Into NOx and HONO Chemistry in the Tropical Marine Boundary Layer at Cape Verde During the MarParCloud Campaign.

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Title: Insights Into NOx and HONO Chemistry in the Tropical Marine Boundary Layer at Cape Verde During the MarParCloud Campaign.
Authors: Jiang, Ying1,2 (AUTHOR), Hoffmann, Erik H.1 (AUTHOR), Tilgner, Andreas1 (AUTHOR), Aiyuk, Marvel B. E.1 (AUTHOR), Andersen, Simone T.3 (AUTHOR), Wen, Liang1,4 (AUTHOR), van Pinxteren, Manuela1 (AUTHOR), Shen, Hengqing2 (AUTHOR), Xue, Likun2 (AUTHOR) xuelikun@sdu.edu.cn, Wang, Wenxing2 (AUTHOR), Herrmann, Hartmut1,5 (AUTHOR) herrmann@tropos.de
Source: Journal of Geophysical Research. Atmospheres. 8/28/2023, Vol. 128 Issue 16, p1-19. 19p.
Subject Terms: *Nitrogen compounds, *Chemical processes, *Mineral dusts, Reactive nitrogen species, Chemical models, Nitrous acid, Radicals (Chemistry)
Geographic Terms: Cabo Verde
Abstract: Chemical processing of reactive nitrogen species, especially of NOx (= NO + NO2) and nitrous acid (HONO), determines the photochemical ozone production and oxidation capacity in the troposphere. However, sources of HONO and NOx in the remote marine atmosphere are still poorly understood. In this work, the multiphase chemistry mechanism CAPRAM in the model framework SPACCIM was used to study HONO formation at Cape Verde (CVAO) in October 2017, adopted with the input of current parameterizations for various HONO sources. Three simulations were performed that adequately reproduced ambient HONO levels and its diurnal pattern. The model performance for NOx and O3 improves significantly when considering dust‐surface‐photocatalytic conversions of reactive nitrogen compounds with high correlation coefficients up to 0.93, 0.56, and 0.89 for NO, NO2, and O3, respectively. Photocatalytic conversion of the adsorbed HNO3 on dust is modeled to be the predominant contributor for daytime HONO at CVAO, that is, accounting for about 62% of the chemical formation rate at noontime. In contrast, the ocean‐surface‐mediated conversion of NO2 to HONO and other discussed pathways are less important. The average OH levels at midday (9:00–16:00) modeled for cluster trajectory 1, 2, and 3 are 5.2, 5.1, and 5.2 × 106 molecules cm−3, respectively. Main OH formation is driven by O3 photolysis with a contribution of 74.6% to the total source rate, while HONO photolysis is negligible (∼1.8%). In summary, this study highlights the key role of dust aerosols for HONO formation and NOx cycling at CVAO and possibly in other dust‐affected regions, urgently calling for further investigations using field and model studies. Plain Language Summary: Chemical processing of NOx (= NO + NO2) and nitrous acid (HONO) is important for the tropospheric O3 budget and oxidation capacity. However, the sources of HONO and cycling of NOx in the remote marine atmosphere are still poorly explored. A detailed multiphase chemistry model simulation showed a better performance of HONO, NOx and O3 when considering dust‐surface‐photocatalytic conversions of reactive nitrogen compounds, especially the photocatalytic conversion of the adsorbed HNO3 on dust. The simulations demonstrated that OH formation is mainly driven by the O3 photolysis, while HONO photolysis is a negligible OH radical source due to its low concentration levels at Cape Verde. The study highlights the key role of dust aerosols for HONO and NOx chemistry in the remote marine boundary layer. Key Points: The sources of HONO and NOx at Cape Verde are well modeled with CAPRAMPhotocatalytic conversion of adsorbed HNO3 on dust is the predominant contributor for daytime HONOPhotolysis of O3 is the prevailing source of OH radical at Cape Verde, while HONO photolysis is a negligible OH radical source [ABSTRACT FROM AUTHOR]
Copyright of Journal of Geophysical Research. Atmospheres is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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Items – Name: Title
  Label: Title
  Group: Ti
  Data: Insights Into NO<subscript>x</subscript> and HONO Chemistry in the Tropical Marine Boundary Layer at Cape Verde During the MarParCloud Campaign.
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  Label: Authors
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  Data: <searchLink fieldCode="AR" term="%22Jiang%2C+Ying%22">Jiang, Ying</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Hoffmann%2C+Erik+H%2E%22">Hoffmann, Erik H.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Tilgner%2C+Andreas%22">Tilgner, Andreas</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Aiyuk%2C+Marvel+B%2E+E%2E%22">Aiyuk, Marvel B. E.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Andersen%2C+Simone+T%2E%22">Andersen, Simone T.</searchLink><relatesTo>3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wen%2C+Liang%22">Wen, Liang</searchLink><relatesTo>1,4</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22van+Pinxteren%2C+Manuela%22">van Pinxteren, Manuela</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Shen%2C+Hengqing%22">Shen, Hengqing</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Xue%2C+Likun%22">Xue, Likun</searchLink><relatesTo>2</relatesTo> (AUTHOR)<i> xuelikun@sdu.edu.cn</i><br /><searchLink fieldCode="AR" term="%22Wang%2C+Wenxing%22">Wang, Wenxing</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Herrmann%2C+Hartmut%22">Herrmann, Hartmut</searchLink><relatesTo>1,5</relatesTo> (AUTHOR)<i> herrmann@tropos.de</i>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Geophysical+Research%2E+Atmospheres%22">Journal of Geophysical Research. Atmospheres</searchLink>. 8/28/2023, Vol. 128 Issue 16, p1-19. 19p.
– Name: Subject
  Label: Subject Terms
  Group: Su
  Data: *<searchLink fieldCode="DE" term="%22Nitrogen+compounds%22">Nitrogen compounds</searchLink><br />*<searchLink fieldCode="DE" term="%22Chemical+processes%22">Chemical processes</searchLink><br />*<searchLink fieldCode="DE" term="%22Mineral+dusts%22">Mineral dusts</searchLink><br /><searchLink fieldCode="DE" term="%22Reactive+nitrogen+species%22">Reactive nitrogen species</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+models%22">Chemical models</searchLink><br /><searchLink fieldCode="DE" term="%22Nitrous+acid%22">Nitrous acid</searchLink><br /><searchLink fieldCode="DE" term="%22Radicals+%28Chemistry%29%22">Radicals (Chemistry)</searchLink>
– Name: SubjectGeographic
  Label: Geographic Terms
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Cabo+Verde%22">Cabo Verde</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Chemical processing of reactive nitrogen species, especially of NOx (= NO + NO2) and nitrous acid (HONO), determines the photochemical ozone production and oxidation capacity in the troposphere. However, sources of HONO and NOx in the remote marine atmosphere are still poorly understood. In this work, the multiphase chemistry mechanism CAPRAM in the model framework SPACCIM was used to study HONO formation at Cape Verde (CVAO) in October 2017, adopted with the input of current parameterizations for various HONO sources. Three simulations were performed that adequately reproduced ambient HONO levels and its diurnal pattern. The model performance for NOx and O3 improves significantly when considering dust‐surface‐photocatalytic conversions of reactive nitrogen compounds with high correlation coefficients up to 0.93, 0.56, and 0.89 for NO, NO2, and O3, respectively. Photocatalytic conversion of the adsorbed HNO3 on dust is modeled to be the predominant contributor for daytime HONO at CVAO, that is, accounting for about 62% of the chemical formation rate at noontime. In contrast, the ocean‐surface‐mediated conversion of NO2 to HONO and other discussed pathways are less important. The average OH levels at midday (9:00–16:00) modeled for cluster trajectory 1, 2, and 3 are 5.2, 5.1, and 5.2 × 106 molecules cm−3, respectively. Main OH formation is driven by O3 photolysis with a contribution of 74.6% to the total source rate, while HONO photolysis is negligible (∼1.8%). In summary, this study highlights the key role of dust aerosols for HONO formation and NOx cycling at CVAO and possibly in other dust‐affected regions, urgently calling for further investigations using field and model studies. Plain Language Summary: Chemical processing of NOx (= NO + NO2) and nitrous acid (HONO) is important for the tropospheric O3 budget and oxidation capacity. However, the sources of HONO and cycling of NOx in the remote marine atmosphere are still poorly explored. A detailed multiphase chemistry model simulation showed a better performance of HONO, NOx and O3 when considering dust‐surface‐photocatalytic conversions of reactive nitrogen compounds, especially the photocatalytic conversion of the adsorbed HNO3 on dust. The simulations demonstrated that OH formation is mainly driven by the O3 photolysis, while HONO photolysis is a negligible OH radical source due to its low concentration levels at Cape Verde. The study highlights the key role of dust aerosols for HONO and NOx chemistry in the remote marine boundary layer. Key Points: The sources of HONO and NOx at Cape Verde are well modeled with CAPRAMPhotocatalytic conversion of adsorbed HNO3 on dust is the predominant contributor for daytime HONOPhotolysis of O3 is the prevailing source of OH radical at Cape Verde, while HONO photolysis is a negligible OH radical source [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Geophysical Research. Atmospheres is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=8gh&AN=170749455
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      – Type: doi
        Value: 10.1029/2023JD038865
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 19
        StartPage: 1
    Subjects:
      – SubjectFull: Nitrogen compounds
        Type: general
      – SubjectFull: Chemical processes
        Type: general
      – SubjectFull: Mineral dusts
        Type: general
      – SubjectFull: Reactive nitrogen species
        Type: general
      – SubjectFull: Chemical models
        Type: general
      – SubjectFull: Nitrous acid
        Type: general
      – SubjectFull: Radicals (Chemistry)
        Type: general
      – SubjectFull: Cabo Verde
        Type: general
    Titles:
      – TitleFull: Insights Into NOx and HONO Chemistry in the Tropical Marine Boundary Layer at Cape Verde During the MarParCloud Campaign.
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              M: 08
              Text: 8/28/2023
              Type: published
              Y: 2023
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