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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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https://doi.org/10.5194/amt-2020-164
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-2020-164
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 11 Jun 2020

Submitted as: research article | 11 Jun 2020

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This preprint is currently under review for the journal AMT.

Interference from alkenes in chemiluminescent NOx measurements

Mohammed S. Alam1, Leigh R. Crilley1,a, James D. Lee2, Louisa J. Kramer1, Christian Pfrang1, Mónica Vázquez-Moreno3,b, Amalia Muñoz3, Milagros Ródenas3, and William J. Bloss1 Mohammed S. Alam et al.
  • 1School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham, UK
  • 2National Centre for Atmospheric Science, Wolfson Atmospheric Chemistry Laboratories, University of York, York, UK
  • 3EUPHORE,Fundación CEAM, Valencia, Spain
  • anow at: Department of Chemistry, York University, Toronto, ON, Canada
  • bnow at: FISABIO, Valencia, Spain

Abstract. Nitrogen oxides (NOx = NO + NO2) are critical intermediates in atmospheric chemistry. NOx levels control the cycling and hence abundance of the primary atmospheric oxidants OH and NO3, and regulate the ozone production which results from the degradation of volatile organic compounds (VOCs) in the presence of sunlight. They are also atmospheric pollutants, and NO2 is commonly included in air quality objectives and regulations. NOx levels also affect the production of the nitrate component of secondary aerosol particles and other pollutants such as the lachrymator peroxyacetyl nitrate (PAN). The accurate measurement of NO and NO2 is therefore crucial to air quality monitoring and understanding atmospheric composition. The most commonly used approach for measurement of NO is chemiluminescent detection of electronically excited NO2 (NO2*) from the NO + O3 reaction. Alkenes, ubiquitous in the atmosphere from biogenic and anthropogenic sources, also react with ozone to produce chemiluminescence and thus may contribute to the measured NOx signal. Their ozonolysis reaction may also be sufficiently rapid that their abundance in the instrument background cycle, which also utilises reaction with ozone, differs from the measurement cycle – such that the background subtraction is incomplete, and an interference effect results. This interference has been noted previously, and indeed the effect has been used to measure both alkenes and ozone in the atmosphere. Here we report the results of a systematic investigation of the response of a selection of commercial NOx monitors, ranging from systems used for routine air quality monitoring to atmospheric research instrumentation, to a series of alkenes. Alkenes investigated range from short chain alkenes, such as ethene, to the biogenic monoterpenes. Experiments were performed in the European Photoreactor (EUPHORE) to ensure common calibration and samples for the monitors, and to unequivocally confirm the alkene levels present (via FTIR). The instrument interference responses ranged from negligible levels up to 11 % depending upon the alkene present and conditions used (e.g. presence of co-reactants and differing humidity). Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high-VOC, low-NOx environments such as forests, or indoor environments where alkene abundance from personal care and cleaning products may be significant.

Mohammed S. Alam et al.

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Short summary
We report a systematic study of the interference arising in measurements of the nitrogen oxides from the presence of a range of alkenes in sampled air, when using the most widespread air quality monitoring technique of chemiluminescence detection. Interferences of up to 11 % are reported depending upon the alkene present and conditions used. Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high-VOC and low-NOx environments.
We report a systematic study of the interference arising in measurements of the nitrogen oxides...
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