Articles | Volume 9, issue 9
Atmos. Meas. Tech., 9, 4533–4545, 2016
Atmos. Meas. Tech., 9, 4533–4545, 2016

Research article 14 Sep 2016

Research article | 14 Sep 2016

Measurement of isoprene nitrates by GCMS

Graham P. Mills1, Glyn D. Hiatt-Gipson2, Sean P. Bew2, and Claire E. Reeves1 Graham P. Mills et al.
  • 1Centre for Ocean and Atmospheric Sciences, School of Environmental Sciences, University of East Anglia, Norwich, NR4 7TJ, UK
  • 2School of Chemistry, University of East Anglia, Norwich, NR4 7TJ, UK

Abstract. According to atmospheric chemistry models, isoprene nitrates play an important role in determining the ozone production efficiency of isoprene; however this is very poorly constrained through observations as isoprene nitrates have not been widely measured. Measurements have been severely restricted largely due to a limited ability to measure individual isoprene nitrate isomers. An instrument based on gas chromatography/mass spectrometry (GCMS) and the associated calibration methods are described for the speciated measurements of individual isoprene nitrate isomers. Five of the primary isoprene nitrates which formed in the presence of NOx by reaction of isoprene with the hydroxyl radical (OH) in the Master Chemical Mechanism are identified using known isomers on two column phases and are fully separated on the Rtx-200 column. Three primary isoprene nitrates from the reaction of isoprene with the nitrate radical (NO3) are identified after synthesis from the already identified analogous hydroxy nitrate. A Tenax adsorbent-based trapping system allows the analysis of the majority of the known hydroxy and carbonyl primary isoprene nitrates, although not the (1,2)-IN isomer, under field-like levels of humidity and showed no impact from typical ambient concentrations of NOx and ozone.

Short summary
The paper describes the development of an instrument to measure isoprene-derived nitrates in the atmosphere, compounds that are crucial to understanding the impact of biogenic hydrocarbons on ozone production. The instrument is suitable for deployment in field studies.