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The first UK measurements of nitryl chloride using a chemical ionisation mass spectrometer in central London in the summer of 2012, and an investigation of the role of Cl atom oxidation.

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Published copy (DOI)

Author(s)

  • Thomas J. Bannan
  • A. Murray Booth
  • Asan Bacak
  • Jennifer B A Muller
  • Kimberley E. Leather
  • Michael Le Breton
  • Benjamin Jones
  • Dominique Young
  • Hugh Coe
  • James Allan
  • Suzanne Visser
  • Jay G. Slowik
  • Markus Furger
  • André S H Prévôt
  • James R. Hopkins
  • Lisa K. Whalley
  • Thomas Sharp
  • Daniel Stone
  • Dwayne E. Heard
  • Zoë L. Fleming
  • Roland Leigh
  • Dudley E. Shallcross
  • Carl J. Percival

Department/unit(s)

Publication details

JournalJournal of Geophysical Research: Atmospheres
DateE-pub ahead of print - 13 Apr 2015
DatePublished (current) - 1 Jun 2015
Issue number11
Volume120
Number of pages20
Pages (from-to)5638-5657
Early online date13/04/15
Original languageEnglish

Abstract

The first nitryl chloride (ClNO<inf>2</inf>) measurements in the UK were made during the summer 2012 ClearfLo campaign with a chemical ionization mass spectrometer, utilizing an I<sup>-</sup> ionization scheme. Concentrations of ClNO<inf>2</inf> exceeded detectable limits (11 ppt) every night with a maximum concentration of 724 ppt. A diurnal profile of ClNO<inf>2</inf> peaking between 4 and 5 A.M., decreasing directly after sunrise, was observed. Concentrations of ClNO<inf>2</inf> above the detection limit are generally observed between 8 P.M. and 11 A.M. Different ratios of the production of ClNO<inf>2</inf>:N<inf>2</inf>O<inf>5</inf> were observed throughout with both positive and negative correlations between the two species being reported. The photolysis of ClNO<inf>2</inf> and a box model utilizing the Master Chemical Mechanism modified to include chlorine chemistry was used to calculate Cl atom concentrations. Simultaneous measurements of hydroxyl radicals (OH) using low pressure laser-induced fluorescence and ozone enabled the relative importance of the oxidation of three groups of measured VOCs (alkanes, alkenes, and alkynes) by OH radicals, Cl atoms, and O<inf>3</inf> to be compared. For the day with the maximum calculated Cl atom concentration, Cl atoms in the early morning were the dominant oxidant for alkanes and, over the entire day, contributed 15%, 3%, and 26% toward the oxidation of alkanes, alkenes, and alkynes, respectively. Key Points The first UK measurements of ClNO<inf>2</inf> using CIMS Relationships between N<inf>2</inf>O<inf>5</inf> and ClNO<inf>2</inf> were dependent on air mass origins Cl oxidizes 14.5%, 2.6%, and 25% of alkanes, alkenes, and alkynes.

Bibliographical note

2014JD022629

    Research areas

  • Troposphere, composition and chemistry, nitryl chloride, CIMS

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