Detection of iodine monoxide radicals in the marine boundary layer using laser induced fluorescence spectroscopy

A Laser Induced Fluorescence (LIF) instrument has been developed to detect iodine monoxide (IO) radicals in the atmosphere. An all solid-state Nd:YAG pumped Ti:Sapphire laser operating at approximately 445 nm was used to excite the (2,0) band of the IO A²Π_3/2 ← X²Π_3/2 electronic transition, with off-resonance fluorescence in the (2,5) band detected at 521 nm. The sensitivity of the instrument was determined by calibration. IO (between 10 and 150 pptV) was generated following the 184.9 nm photolysis of N₂O/CF₃I/N₂ mixtures with O₃ actinometry used to determine the photolysis flux. The detection limit was determined to be 0.3 pptV for a 300 s integration period, with an uncertainty of 23% (1σ). The instrument was deployed in August/September 2006 during the RHaMBLe (Reactive Halogens in the Marine Boundary Layer) campaign in Roscoff, France. Located on a small jetty, a few metres from the water’s edge at high tide, the instrument measured significant levels of IO on 11 days, with a maximum of 27.6 ± 3.2 pptV observed on one day (averaged over 10 s) representing the highest IO mixing ratio recorded in the marine boundary layer to date. IO displayed a clear diurnal profile with a maximum at low tide during the daytime. These results represent the first point measurements of IO in the atmosphere by LIF.