Short-lived alkyl iodides and bromides at Mace Head, Ireland: Links to biogenic sources and halogen oxide production

Automated in situ gas chromatograph/mass spectrometer (GC/MS) measurements of a range of predominantly biogenic alkyl halides in air, including CHBr3, CHBr2Cl, CH3Br, C2H5Br, CH3I, C2H5I, CH2ICl, CH2I2, and the hitherto unrep orted CH2IBr were made at Mace Head during a 3-week period in May 1997. C3H 7I and CH3CHICH3 were monitored but not detected. Positive correlations wer e observed between the polyhalomethane pairs CHBr3/CHBr2Cl and CHBr3/CH2IBr and between the monohalomethane pair CH3I/C2H5I, which are interpreted in terms of common or linked marine sources. During periods when air masses we re affected by emissions from local seaweed beds, the concentrations of CHB r3, CH2ICI, and CH2IBr not only showed remarkable correlation but also maxi mized at low water. These are the first field observations to provide evide nce for a link between the tidal cycle, polyhalomethanes in air, and potent ial marine production. The calculated total flux of iodine atoms into the b oundary layer at Mace Head from organic gaseous precursors was dominated by photolytic destruction of CH2I2 Photolysis of CH3I contributed less than 3 %. The calculated peak flux of iodine atoms during the campaign coincided w ith the highest measured levels of iodine oxide radicals, as determined usi ng Differential Optical Absorption Spectrometry (DOAS).