An instrument for measurements of BrO with LED-based Cavity-Enhanced Differential Optical Absorption Spectroscopy

Abstract. The chemistry of the troposphere and specifically the global tropospheric ozone budget is affected by reactive halogen species such as bromine monoxide (BrO) or chlorine monoxide (ClO). Especially BrO plays an important role in the processes of ozone destruction, disturbance of NO_x and HO_x chemistry, oxidation of dimethyl sulfide (DMS), and the deposition of elementary mercury. In the troposphere BrO has been detected in polar regions, at salt lakes, in volcanic plumes, and in the marine boundary layer. For a better understanding of these processes, field measurements as well as reaction chamber studies are performed. In both cases instruments with high spatial resolution and high sensitivity are necessary. A Cavity-Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) instrument with an open path measurement cell was designed and applied. For the first time, a CE-DOAS instrument is presented using an UV LED in the 325–365 nm wavelength range. In laboratory studies, BrO as well as HONO, HCHO, O₃, and O₄ could be reliably determined at detection limits of 20 ppt for BrO, 9.1 ppb for HCHO, 970 ppt for HONO, and 91 ppb for O₃, for five minutes integration time. The best detection limits were achieved for BrO (11 ppt), HCHO (5.1 ppb), HONO (490 ppt), and O₃ (59 ppb) for integration times of 81 minutes or less. Comparison with established White system (WS) DOAS and O₃ monitor measurements demonstrate the reliability of the instrument.