Application of a compact all solid-state laser system to the in situ detection of atmospheric OH, HO2, NO and IO by laser-induced fluorescence.

A tuneable, high pulse-repetition-frequency, solid state Nd:YAG pumped titanium sapphire laser capable of generating radiation for the detection of OH, HO2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF) has been developed. The integration of the laser system operating at 308 nm into a field measurement apparatus for the simultaneous detection of hydroxyl and hydroperoxy radicals is described, with detection limits of 3.1 x 10(5) molecule cm(-3) (0.012 pptv in the boundary layer) and 2.6 x 10(6) molecule cm(-3) (0.09 pptv) achieved for OH and HO2 respectively (30 s signal integration, 30 s background integration, signal-to-noise ratio = 1). The system has been field tested and offers several advantages over copper vapour laser pumped dye laser systems for the detection of atmospheric OH and HO2 radicals by LIF, with benefits of greater tuning range and ease of use coupled with reduced power consumption, instrument footprint and warm-up time. NO has been detected in the atmosphere at approximately 1 ppbv by single photon LIF using the Alpha 2Sigma+ <-- Chi 2Pi1/2 (0,0) transition at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a chemiluminescence analyser. With some improvements in performance, particularly with regard to laser power, the theoretical detection limit for NO is projected to be approximately 2 x 10(6) molecule cm(-3) (0.08 pptv). Whilst operating at 445 nm, the laser system has been used to readily detect the IO radical in the laboratory, and although it is difficult to project the sensitivity in the field, an estimate of the detection limit is < 1 x 10(5) molecule cm(-3) (< 0.004 pptv), well below previously measured atmospheric concentrations of IO.