Observations of Cl2, Br2, and I2 in coastal marine air

Cl2, Br2, and I2 were measured in coastal Pacific air from 2 to 29 January 2006. Air was sampled at 10 m over the sea surface near the end of Scripps Pier (La Jolla, California). The measurements were made using atmospheric pressure chemical ionization with tandem mass spectrometry (APCI/MS/MS). Over the course of this study, Cl2, Br2, and I2 levels ranged from below detection limits of 1.0, 0.5, and 0.2 ppt, respectively, to maxima of 26, 19, and 8 ppt, respectively. Mean dihalogen levels for the study period were 2.3 ± 1 ppt for Cl2, 2.3 ± 0.4 ppt for Br2, and 0.7 ± 0.1 ppt for I2 (expressed as geometric mean ±1 geometric standard error). The mixed dihalogens BrCl, ICl, and IBr had geometric mean levels below 0.3 ± 1 ppt and never exceeded their detection limits of 0.5 ppt. Consistent patterns of diurnal variability were observed for Cl2 and I2, with Cl2 maxima during daytime and I2 appearing almost exclusively at night. The detection of I2 appeared to be related to the passage of air over nearby kelp beds. The observed dihalogen levels suggest that (1) chlorine atom oxidation of hydrocarbons makes a significant contribution to the formation of ozone and (2) halogen atom oxidation of airborne mercury contributes to mercury deposition in polluted coastal air