A novel instrument for measuring OH reactivity in the troposphere has been developed by using a laser-induced pump and probe technique. Air was introduced into a flow tube and OH was produced artificially using O3 photolysis by 266 nm laser. The OH decay rate in the flow tube was monitored by the time-resolved laser-induced fluorescence technique. In this article, the instrument, that is, the measurement principle, the flow tube and the fluorescence detection cell, is presented in detail. Interference by absorption of the 266 nm laser light by O3, and photolysis of NO2 and HCHO was found to be negligible. The influence of recycled OH from the HO2+NO reaction on the measured OH reactivity was estimated by a box model calculation. The systematic error of the measured decay rate was found to be less than 5% even in high NO condition ([NO]=20 ppbv). The dependence of the measured decay rate on the flow rate in the reaction tube was investigated. A slight change in the total flow rate does not influence the measured decay rate in our experimental condition. The second-order rate coefficients of the OH+CO reactions were measured in order to confirm the accuracy of the measured OH decay rate. The measured rate coefficients were agreed excellently with the recent recommended values. The results of observations in our institute are briefly presented.

Abstract. The daytime variation of hydroperoxy (HO:) radical concentration was observed by an instrument based on laser-induced fluorescence with NO addition at Oki Island, Japan, in July/August 1998. Although OH was not detected due to the high detection limit of the instrument, HO: was determined with the detection limit of 0.

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An instrument for measuring atmospheric peroxy radicals has been developed by chemical amplification/laser-induced fluorescence (PERCA/LIF) technique. The small concentration of peroxy radicals is converted to the large amount of NO2, which is measured by laser-induced fluorescence instead of luminol chemiluminescence. Several advantages, that is, high sensitivity, high selectively, and fast time response, are expected by use of LIF for the NO2 measurement, in comparison with luminol chemiluminescence. When using this system, simultaneous measurements of NO2 and peroxy radicals are available. The present optimum condition for the reaction tube (1/4 in. Teflon) was determined to be the reaction tube length of 3 m, the NO and CO concentrations of 3 ppmv and 10%, respectively. The calibration, including humidity dependence of the detection sensitivity of peroxy radicals, was conducted and the present detection limit of peroxy radicals was determined to be 2.7 and 3.6 pptv at the ambient relative humidity of 50 and 80%, respectively, for the integration time of 1 min (S/N=2). This detection limit was calculated assuming the ambient O3 and NO2 mixing ratios of 30 and 20 ppbv, respectively. The influence of the NO2 detection sensitivity by adding high concentrations of CO was investigated and the quenching of excited NO2 by CO can affect the ambient measurement significantly under the high NO2 and low peroxy radical concentrations. Exploratory ambient air measurements were made in suburban area of Osaka, Japan. These results demonstrated the performance of PERCA/LIF for ambient measurements.