A large source of atomic chlorine from ClNO2 photolysis at a UK landfill site

Thomas J. Bannan, M. Anwar H. Khan, Michael Le Breton, Michael Priestley, Stephen D Worrall, Asan Bacak, Nicholas Marsden, Douglas Lowe, Joseph Pitt, Grant Allen, David Topping, Hugh Coe, Gordon McFiggans, Dudley E. Shallcross, Carl J. Percival

Research output: Contribution to journalArticle

Abstract

Nitryl chloride (ClNO 2) acts as a source of highly reactive chlorine atoms as well as an important NO x reservoir. Measurements of ClNO 2 at an operational U.K. landfill site are reported here for the first time. A peak concentration of 4 ppb of ClNO 2 was found with a peak mean nighttime maximum of 0.9 ppb. Using models based upon the photolysis of observed ClNO 2 and atmospheric chlorine chemistry, chlorine atom concentrations reaching in excess of 1.20 × 10 5 molecules/cm 3 in the early morning following sunrise are calculated. These concentrations are approximately 10 times higher than previously reported in the United Kingdom, suggesting a significant impact on the oxidizing capacity around such sites. Given the ubiquity of landfill sites regionally and globally, and the large abundances of Cl atoms from the photolysis of ClNO 2, chlorine chemistry has a significant impact on ozone formation and volatile organic compounds oxidation as shown by WRF-Chem modeling.

Original languageEnglish
Pages (from-to)8508-8516
Number of pages9
JournalGeophysical Research Letters
Volume46
Issue number14
Early online date29 Jul 2019
DOIs
Publication statusPublished - 12 Aug 2019

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landfills
photolysis
chlorine
landfill
nitryl chlorides
chemistry
atom concentration
sunrise
United Kingdom
morning
volatile organic compounds
ozone
volatile organic compound
atoms
chloride
oxidation
modeling
molecules

Bibliographical note

©2019. The Authors.

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Keywords

  • CIMS
  • ClNO
  • landfill

Cite this

Bannan, T. J., Khan, M. A. H., Breton, M. L., Priestley, M., Worrall, S. D., Bacak, A., ... Percival, C. J. (2019). A large source of atomic chlorine from ClNO2 photolysis at a UK landfill site. Geophysical Research Letters, 46(14), 8508-8516. https://doi.org/10.1029/2019GL083764
Bannan, Thomas J. ; Khan, M. Anwar H. ; Breton, Michael Le ; Priestley, Michael ; Worrall, Stephen D ; Bacak, Asan ; Marsden, Nicholas ; Lowe, Douglas ; Pitt, Joseph ; Allen, Grant ; Topping, David ; Coe, Hugh ; McFiggans, Gordon ; Shallcross, Dudley E. ; Percival, Carl J. / A large source of atomic chlorine from ClNO2 photolysis at a UK landfill site. In: Geophysical Research Letters. 2019 ; Vol. 46, No. 14. pp. 8508-8516.
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Bannan, TJ, Khan, MAH, Breton, ML, Priestley, M, Worrall, SD, Bacak, A, Marsden, N, Lowe, D, Pitt, J, Allen, G, Topping, D, Coe, H, McFiggans, G, Shallcross, DE & Percival, CJ 2019, 'A large source of atomic chlorine from ClNO2 photolysis at a UK landfill site', Geophysical Research Letters, vol. 46, no. 14, pp. 8508-8516. https://doi.org/10.1029/2019GL083764

A large source of atomic chlorine from ClNO2 photolysis at a UK landfill site. / Bannan, Thomas J.; Khan, M. Anwar H.; Breton, Michael Le; Priestley, Michael; Worrall, Stephen D; Bacak, Asan; Marsden, Nicholas; Lowe, Douglas; Pitt, Joseph; Allen, Grant; Topping, David; Coe, Hugh; McFiggans, Gordon; Shallcross, Dudley E.; Percival, Carl J.

In: Geophysical Research Letters, Vol. 46, No. 14, 12.08.2019, p. 8508-8516.

Research output: Contribution to journalArticle

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T1 - A large source of atomic chlorine from ClNO2 photolysis at a UK landfill site

AU - Bannan, Thomas J.

AU - Khan, M. Anwar H.

AU - Breton, Michael Le

AU - Priestley, Michael

AU - Worrall, Stephen D

AU - Bacak, Asan

AU - Marsden, Nicholas

AU - Lowe, Douglas

AU - Pitt, Joseph

AU - Allen, Grant

AU - Topping, David

AU - Coe, Hugh

AU - McFiggans, Gordon

AU - Shallcross, Dudley E.

AU - Percival, Carl J.

N1 - ©2019. The Authors. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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N2 - Nitryl chloride (ClNO 2) acts as a source of highly reactive chlorine atoms as well as an important NO x reservoir. Measurements of ClNO 2 at an operational U.K. landfill site are reported here for the first time. A peak concentration of 4 ppb of ClNO 2 was found with a peak mean nighttime maximum of 0.9 ppb. Using models based upon the photolysis of observed ClNO 2 and atmospheric chlorine chemistry, chlorine atom concentrations reaching in excess of 1.20 × 10 5 molecules/cm 3 in the early morning following sunrise are calculated. These concentrations are approximately 10 times higher than previously reported in the United Kingdom, suggesting a significant impact on the oxidizing capacity around such sites. Given the ubiquity of landfill sites regionally and globally, and the large abundances of Cl atoms from the photolysis of ClNO 2, chlorine chemistry has a significant impact on ozone formation and volatile organic compounds oxidation as shown by WRF-Chem modeling.

AB - Nitryl chloride (ClNO 2) acts as a source of highly reactive chlorine atoms as well as an important NO x reservoir. Measurements of ClNO 2 at an operational U.K. landfill site are reported here for the first time. A peak concentration of 4 ppb of ClNO 2 was found with a peak mean nighttime maximum of 0.9 ppb. Using models based upon the photolysis of observed ClNO 2 and atmospheric chlorine chemistry, chlorine atom concentrations reaching in excess of 1.20 × 10 5 molecules/cm 3 in the early morning following sunrise are calculated. These concentrations are approximately 10 times higher than previously reported in the United Kingdom, suggesting a significant impact on the oxidizing capacity around such sites. Given the ubiquity of landfill sites regionally and globally, and the large abundances of Cl atoms from the photolysis of ClNO 2, chlorine chemistry has a significant impact on ozone formation and volatile organic compounds oxidation as shown by WRF-Chem modeling.

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