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One technique used to measure concentrations of the hydroperoxy radical(HO2) in the atmosphere involves chemically converting it to OH byaddition of NO and subsequent detection of OH. However, some organic peroxyradicals (RO2) can also be rapidly converted to HO2 (andsubsequently OH) in the presence of NO, interfering with measurements ofambient HO2 radical concentrations. This interference must becharacterized for each instrument to determine to what extent variousRO2 radicals interfere with measurements of HO2 and to assess theimpact of this interference on past measurements. The efficiency of RO2-to-HO2 conversion for the Indiana University laser-induced fluorescence–fluorescence assay by gasexpansion (IU-FAGE) instrument was measured fora variety of RO2 radicals. Known quantities of OH and HO2 radicalswere produced from the photolysis of water vapor at 184.9 nm, and RO2radicals were produced by the reaction of several volatile organic compounds(VOCs) with OH. The conversion efficiency of RO2 radicals to HO2 wasmeasured when NO was added to the sampling cell for conditions employedduring several previous field campaigns. For these conditions, approximately80 % of alkene-derived RO2 radicals and 20 % of alkane-derivedRO2 radicals were converted to HO2. Based on these measurements,interferences from various RO2 radicals contributed to approximately35 % of the measured HO2 signal during the Mexico City MetropolitanArea (MCMA) 2006 campaign (MCMA-2006), where the measured VOCs consisted of a mixture ofsaturated and unsaturated species. However, this interference can contributemore significantly to the measured HO2 signal in forested environmentsdominated by unsaturated biogenic emissions such as isoprene

Measurement of interferences associated with the detection of the hydroperoxy radical in the atmosphere using laser-induced fluorescence