Detection of tropospheric OH and HO2 by laser-induced fluorescence at low pressure using the 308nm excitation of OH

Abstract

Laser-induced fluorescence (LIF) spectroscopy is a highly sensitive method for the direct in situ measurement of hydroxyl concentrations in the atmosphere. Its sensitivity and selectivity relies on the intense discrete UV-absorption lines of OH which are strongest around 282nm and 308nm. We have developed a LIF-instrument based on the low-pressure experiment (FAGE). However, we use 308nm instead of 282nm as excitation wavelength for OH, a concept that is also pursued by other groups. One advantage of the longer excitation wavelength is the higher detection sensitivity due to the about 6 times larger effective OH-fluorescence cross-section. Moreover, the O3/H2O-interference (OH self-generation by the laser) is about a factor of 200 smaller at 308nm than at 282nm. This keeps the interference level well below the projected detection limit of 10(exp 5) OH/cm(exp 3). Atmospheric HO2-radicals are detected by chemical conversion of HO2 into OH with NO.