Diurnal and seasonal variations of iodocarbons (CH2ClI, CH2I2, CH3I, and C2H5I) in the marine atmosphere

Four iodocarbons, chloroiodomethane (CH2ClI), diiodomethane (CH2I2), methyl iodide (CH3I), and ethyl iodide (C2H5I), were measured with an automated preconcentration gas chromatography-mass spectrometry system at two remote marine sites, Hateruma Island (24.05 degrees N, 123.8 degrees E) in the East China Sea and Cape Ochiishi (43.15 degrees N, 145.5 degrees E) on the eastern coast of Hokkaido, for 17 months, giving the first full-year high-frequency data sets for all these compounds. CH2ClI and CH2I2, which are highly photolyzed, showed remarkable diurnal variation in all seasons, with lower concentrations in the daytime, whereas CH3I and C2H5I showed no significant diurnal changes. At Cape Ochiishi, all of the iodocarbons showed clear seasonal variations and were highest in summer and autumn, which are characterized by algal blooms in the adjacent ocean. At Hateruma Island, which is surrounded by subtropical oligotrophic waters, the seasonal variations were not significant, but C2H5I and CH2I2 showed lower mixing ratios in summer. The nighttime mixing ratio of CH2ClI was strongly and positively correlated with wind speed throughout the observation period at Hateruma Island, suggesting the ubiquitous presence of CH2ClI sources, probably nonbiogenic, in the subtropical ocean. CH3I and C2H5I mixing ratios occasionally increased at Hateruma Island concurrently with winter and spring pollution events from the Asian continent, indicating possible continental anthropogenic sources or emissions from seawater off the continental coast. A rise in the CH3I baseline mixing ratio was also observed at Hateruma Island, when the air mass origin became more southerly, compared with the earlier, easterly source area, suggesting higher concentrations in equatorial regions.