Abstract
FAGE (fluorescence assay with gas expansion) was developed as a sensitive technique for the detection of low-concentration free radicals in the atmosphere. The application of FAGE to tropospheric hydroxyl (H0) and hydroperoxyl (H02) radicals has yielded calibrated measurements of both species in both clean air and highly polluted urban air. For HO calibration, a continuously stirred tank reactor provides a uniform external HO concentration, which can be measured by gas chromatography of an HO-reactive hydrocarbon. The aerodynamics of the air-sampling process has been modeled computationally, with results that agree with empirical observations of the effects of nozzle diameter on HO loss during sampling. The authors have also modeled airborne fluid dynamics of a FAGE probe. They have recently obtained FAGE sensitivity as high as ± 1 × 106 cm−3 for a 6-minute averaging period, during field studies in highly polluted Los Angeles air, yielding a 7:1 signal-to-noise ratio near midday. Multipass excitation can further improve this sensitivity. The authors summarize their recent field studies of HO and HO2, current work on improved calibration methods, other improvements, and future plans.
