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The HO 2  radical is one of the most important intermediate species in atmospheric chemistry. We report on the development of a new photoreactor with first  in-situ  measurement of HO 2  radical photostationary concentrations using continuous wave cavity ring-down spectrometry (cw-CRDS). Characterization of the actinic photon flux was carried out by NO 2  actinometry. Photolysis of Cl 2 /methanol mixtures in air under UV light allowed the measurement of HO 2  photostationary concentrations of a few 10 10  molecules cm -3  with an HO 2  detection limit of 1.5 × 10 10  molecules cm -3  at 6638.207 cm -1 . The feasibility of HO 2  direct measurement in a reaction chamber is demonstrated through the measurement of the HO 2  overall loss at different pressures showing the importance of HO 2  diffusion and wall loss in such low pressure quartz reactor. The rate coefficient for the HO 2 +HO 2  reaction has been measured at 6.6, 24 and 118 mbar and found to be in good agreement with the recommended value.

First Cavity Ring-Down Spectroscopy HO 2 Measurements in a Large Photoreactor