Measurements of Ambient OH and HO2 by Laser-Induced Fluorescence Using FAGE

Measurements of OH (hydroxyl) and HO2 (hydroperoxyl) radicals provide a critical test of our understanding of the fast photochemistry of the atmosphere, but are challenging because of their short lifetimes and low concentrations. Several instruments developed during the last decade have successfully made measurements of these important radicals. However, these measurements have shown that there are still gaps in our understanding of OH and HO2 radical chemistry in the atmosphere. Additional measurements of OH and HO2 are needed to constrain and test current models of atmospheric chemistry. We will present a detailed description of our new Fluorescence Assay by Gas Expansion (FAGE) system and our ongoing work toward an automated field instrument, focusing on its characteristics in terms of sensitivity, limit of detection, selectivity, temporal resolution, stability and calibration. In this technique, ambient air is expanded through a pinhole into a low pressure cell. The OH radicals are then electronically excited using a transition in the (0, 0) band of the A-X system near 308 nm. The resulting fluorescence, which is proportional to the OH concentration, is collected and quantified. HO2 is converted into OH by adding a small flow of NO inside the fluorescence cell. Finally, we will present measurements of OH and HO2 concentrations on the Indiana University, Bloomington campus.