Articles | Volume 16, issue 7
Atmos. Chem. Phys., 16, 4707–4724, 2016
Atmos. Chem. Phys., 16, 4707–4724, 2016

Research article 15 Apr 2016

Research article | 15 Apr 2016

Interferences in photolytic NO2 measurements: explanation for an apparent missing oxidant?

Chris Reed1, Mathew J. Evans1,2, Piero Di Carlo3,4, James D. Lee1,2, and Lucy J. Carpenter1 Chris Reed et al.
  • 1Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York YO10 5DD, UK
  • 2National Centre for Atmospheric Science (NCAS), University of York, Heslington, York YO10 5DD, UK
  • 3Centre of Excellence CEMTEPs, Universita' degli studi di L'Aquila, Via Vetoio, 67010 Coppito, L'Aquila, Italy
  • 4Dipartmento di Scienze Fisiche e Chimiche, Universita' degli studi di L'Aquila, Via Vetoio, 67010 Coppito, L'Aquila, Italy

Abstract. Measurement of NO2 at low concentrations (tens of ppts) is non-trivial. A variety of techniques exist, with the conversion of NO2 into NO followed by chemiluminescent detection of NO being prevalent. Historically this conversion has used a catalytic approach (molybdenum); however, this has been plagued with interferences. More recently, photolytic conversion based on UV-LED irradiation of a reaction cell has been used. Although this appears to be robust there have been a range of observations in low-NOx environments which have measured higher NO2 concentrations than might be expected from steady-state analysis of simultaneously measured NO, O3, jNO2, etc. A range of explanations exist in the literature, most of which focus on an unknown and unmeasured “compound X” that is able to convert NO to NO2 selectively. Here we explore in the laboratory the interference on the photolytic NO2 measurements from the thermal decomposition of peroxyacetyl nitrate (PAN) within the photolysis cell. We find that approximately 5 % of the PAN decomposes within the instrument, providing a potentially significant interference. We parameterize the decomposition in terms of the temperature of the light source, the ambient temperature, and a mixing timescale ( ∼ 0.4 s for our instrument) and expand the parametric analysis to other atmospheric compounds that decompose readily to NO2 (HO2NO2, N2O5, CH3O2NO2, IONO2, BrONO2, higher PANs). We apply these parameters to the output of a global atmospheric model (GEOS-Chem) to investigate the global impact of this interference on (1) the NO2 measurements and (2) the NO2 : NO ratio, i.e. the Leighton relationship. We find that there are significant interferences in cold regions with low NOx concentrations such as the Antarctic, the remote Southern Hemisphere, and the upper troposphere. Although this interference is likely instrument-specific, the thermal decomposition to NO2 within the instrument's photolysis cell could give an at least partial explanation for the anomalously high NO2 that has been reported in remote regions. The interference can be minimized by better instrument characterization, coupled to instrumental designs which reduce the heating within the cell, thus simplifying interpretation of data from remote locations.

Short summary
The self-cleaning capacity of the atmosphere in places like Antarctica can be measured by quantifying very low amounts of combustion products that exist in a well-known ratio. When this ratio deviates from 1 it points to the existence of unknown compounds. Several unknown compounds have been theorized to exist but never measured. We have found the method for measuring the ratio of combustion products suffers a bias in remote places, which when taken into account disproves any unknown compounds.
Final-revised paper