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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-2017-198
© Author(s) 2017. This work is distributed under
the Creative Commons Attribution 4.0 License.
Research article
09 Aug 2017
Review status
This discussion paper is a preprint. A revision of the manuscript is under review for the journal Atmospheric Measurement Techniques (AMT).
Measurement of interferences associated with the detection of the hydroperoxy radical in the atmosphere using laser-induced fluorescence
Michelle M. Lew1, Sebastien Dusanter2,3, and Philip S. Stevens1,3 1Department of Chemistry, Indiana University, Bloomington, IN, USA
2IMT Lille Douai, Univ. Lille, SAGE - Département Sciences de l'Atmosphère et Génie de l'Environnement, 59000 Lille, France
3School of Public and Environmental Affairs, Indiana University, Bloomington, IN , USA
Abstract. One technique used to measure concentrations of the hydroperoxy radical (HO2) in the atmosphere involves chemically converting it to OH by addition of NO and subsequent detection of OH. However, some organic peroxy radicals (RO2) can also be rapidly converted to HO2 (and subsequently OH) in the presence of NO, interfering with measurements of ambient HO2 radical concentrations. This interference must be characterized for each instrument to determine to what extent various RO2 radicals interfere with measurements of HO2 and to assess the impact of this interference on past measurements. The efficiency of RO2 to HO2 conversion for the Indiana University Laser-Induced Fluorescence – Fluorescence Assay by Gas Expansion (IU-FAGE) instrument was measured for a variety of RO2 radicals. Known quantities of OH and HO2 radicals were produced from the photolysis of water vapor at 184.9 nm, and RO2 radicals were produced by the reaction of several volatile organic compounds with OH. The conversion efficiency of RO2 radicals to HO2 was measured when NO was added to the sampling cell for conditions employed during several previous field campaigns. For these conditions, approximately 80 % of alkene derived RO2 radicals and 20 % of alkane derived RO2 radicals were converted to HO2. Based on these measurements, interferences from various RO2 radicals contributed to approximately 35 % of the measured HO2 signal during the Mexico City Metropolitan Area (MCMA) 2006 campaign, where the measured VOCs consisted of a mixture of saturated and unsaturated species. However, this interference can contribute more significantly to the measured HO2 signal in forested environments dominated by unsaturated biogenic emissions such as isoprene.

Citation: Lew, M. M., Dusanter, S., and Stevens, P. S.: Measurement of interferences associated with the detection of the hydroperoxy radical in the atmosphere using laser-induced fluorescence, Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2017-198, in review, 2017.
Michelle M. Lew et al.
Michelle M. Lew et al.
Michelle M. Lew et al.

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Short summary
This paper describes measurements of the conversion efficiency of several organic peroxy radicals upon reaction with nitric oxide to the hydroperoxy radical, which can interfere with measurements of the latter. This interference could explain some of discrepancies between measurements and model predictions of the hydroperoxy radical. Previous measurements of the hydroperoxy radical during the Mexico City Metropolitan Area campaign in 2006 are reanalyzed to account for the interference.
This paper describes measurements of the conversion efficiency of several organic peroxy...
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