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Alkyl nitrate photochemistry during the tropospheric organic chemistry experiment

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Author(s)

  • David R. Worton
  • Claire E. Reeves
  • Stuart A. Penkett
  • William T. Sturges
  • Jana Slemr
  • David E. Oram
  • Brian J. Bandy
  • William J. Bloss
  • James Davey
  • Kathryn M. Emmerson
  • Thomas J. Gravestock
  • Dwayne E. Heard
  • James R. Hopkins
  • Anne Hulse
  • Trevor Ingram
  • Mark J. Jacob
  • Roland J. Leigh
  • Paul S. Monks
  • Shona C. Smith

Department/unit(s)

Publication details

JournalAtmospheric Environment
DatePublished - Feb 2010
Issue number6
Volume44
Number of pages13
Pages (from-to)773-785
Original languageEnglish

Abstract

Alkyl nitrates (C-1-C-5) were measured at two sites (near urban and rural) in southeast England during the Tropospheric Organic Chemistry Experiment (TORCH). Methyl nitrate was the dominant species during both campaigns accounting for on average about one third of the total measured alkyl nitrates. High mixing ratios (>50 pptv) and variability of methyl nitrate were observed at the near urban site (TORCH1) that were not seen at the rural site (TORCH2) and which could not be explained by local photochemical production or direct emissions. The diurnal variation of methyl nitrate during TORCH1 showed a morning maximum that would be consistent with nighttime chemistry followed by transport to the surface by boundary layer dynamics. Similarly, elevated morning mixing ratios were also observed during TORCH2 although the magnitudes were much smaller. As a result, methyl nitrate could represent a tracer for nighttime chemistry seen at the ground the following day. At both campaigns, the dominant source of short chain alkyl nitrates and carbonyl precursor radicals (<= C-4) were from decomposition of larger compounds. The magnitude of the source increased with decreasing carbon number consistent with increasing total precursor abundance. Non-photochemical emissions of acetaldehyde and acetone could not be accounted for by automobile exhaust emissions alone and indicated that other direct sources are likely important in this environment. (C) 2009 Elsevier Ltd. All rights reserved.

    Research areas

  • Alkyl nitrates, Methyl nitrate, Acetone, Acetaldehyde, Photochemistry, Nighttime chemistry, IONIZATION MASS-SPECTROMETRY, ABSORPTION CROSS-SECTIONS, MASTER CHEMICAL MECHANISM, ATMOSPHERIC CHEMISTRY, THERMAL-DECOMPOSITION, PEROXYACETYL NITRATE, CARBONYL-COMPOUNDS, TORCH CAMPAIGN, METHYL NITRATE, EMISSIONS

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