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Volume 15, issue 14
Atmos. Chem. Phys., 15, 8101-8114, 2015
https://doi.org/10.5194/acp-15-8101-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.

Special issue: Uintah Basin Winter Ozone Studies (ACP/AMT inter-journal SI)

Atmos. Chem. Phys., 15, 8101-8114, 2015
https://doi.org/10.5194/acp-15-8101-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 23 Jul 2015

Research article | 23 Jul 2015

Peroxynitric acid (HO2NO2) measurements during the UBWOS 2013 and 2014 studies using iodide ion chemical ionization mass spectrometry

P. R. Veres1,2, J. M. Roberts2, R. J. Wild1,2, P. M. Edwards1,2,a, S. S. Brown2, T. S. Bates3,4, P. K. Quinn4, J. E. Johnson3, R. J. Zamora5, and J. de Gouw1,2 P. R. Veres et al.
  • 1Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
  • 2Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, USA
  • 3Joint Institute for the Study of the Oceans and Atmosphere, University of Washington, Seattle, WA, USA
  • 4Pacific Marine Environmental Laboratory, National Oceanic and Atmospheric Administration, Seattle, Washington 98115, USA
  • 5Physical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, USA
  • anow at: Department of Chemistry, University of York, York, YO10 5DD, UK

Abstract. In this paper laboratory work is documented establishing iodide ion chemical ionization mass spectrometry (I- CIMS) as a sensitive method for the unambiguous detection of peroxynitric acid (HO2NO2; PNA). A dynamic calibration source for HO2NO2, HO2, and HONO was developed and calibrated using a novel total NOy cavity ring-down spectroscopy (CaRDS) detector. Photochemical sources of these species were used for the calibration and validation of the I- CIMS instrument for detection of HO2NO2. Ambient observations of HO2NO2 using I- CIMS during the 2013 and 2014 Uintah Basin Wintertime Ozone Study (UBWOS) are presented. Strong inversions leading to a build-up of many primary and secondary pollutants as well as low temperatures drove daytime HO2NO2 as high as 1.5 ppbv during the 2013 study. A comparison of HO2NO2 observations to mixing ratios predicted using a chemical box model describing an ozone formation event observed during the 2013 wintertime shows agreement in the daily maxima HO2NO2 mixing ratio, but a differences of several hours in the timing of the observed maxima. Observations of vertical gradients suggest that the ground snow surface potentially serves as both a net sink and source of HO2NO2 depending on the time of day. Sensitivity tests using a chemical box model indicate that the lifetime of HO2NO2 with respect to deposition has a non-negligible impact on ozone production rates on the order of 10 %.

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In this paper laboratory work is documented establishing iodide ion chemical ionization mass spectrometry (I- CIMS) as a sensitive method for the unambiguous detection of peroxynitric acid (HO2NO2; PNA). A dynamic calibration source for HO2NO2, HO2, and HONO was developed and calibrated using a novel total NOy detector (NOy CaRDS). The ambient observations of HO2NO2 using I- CIMS made during the 2013 and 2014 Uintah Basin Wintertime Ozone Study (UBWOS) are presented.
In this paper laboratory work is documented establishing iodide ion chemical ionization mass...
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