[1] Bromoform (CHBr 3 ), dibromochloromethane (CHBr 2 Cl), and dibromomethane (CH 2 Br 2 ) in the atmosphere were measured at various sites, including tropical islands, the Arctic, and the open Pacific Ocean. Up to 40 ppt of bromoform was observed along the coasts of tropical islands under a sea breeze. Polybromomethane concentrations were highly correlated among the coastal samples, and the ratios CH 2 Br 2 /CHBr 3 and CHBr 2 Cl/ CHBr 3 showed a clear tendency to decrease with increasing CHBr 3 concentration. These findings are consistent with the observations that polybromomethanes are emitted mostly from macroalgae whose growth is highly localized to coastal areas and that CHBr 3 has the shortest lifetime among these three compounds. The relationship between the concentration ratios CHBr 3 /CH 2 Br 2 and CHBr 2 Cl/CH 2 Br 2 suggested a large mixing/ dilution effect on bromomethane ratios in coastal regions and yielded a rough estimate of 9 for the molar emission ratio of CHBr 3 /CH 2 Br 2 and of 0.7 for that of CHBr 2 Cl/CH 2 Br 2 . Using these ratios and an global emission estimate for CH 2 Br 2 (61 Gg/yr (Br)) calculated from its background concentration, the global emission rates of CHBr 3 and CHBr 2 Cl were calculated to be approximately 820(±310) Gg/yr (Br) and 43(±16) Gg/yr (Br), respectively, assuming that the bromomethanes ratios measured in this study are global representative. The estimated CHBr 3 emission is consistent with that estimated in a very recent study by integrating the sea-to-air flux database. Thus the contribution of CHBr 3 and CHBr 2 Cl to inorganic Br in the atmosphere is likely to be more important than previously thought. Citation: Yokouchi, Y., et al. (2005), Correlations and emission ratios among bromoform, dibromochloromethane, and dibromomethane in the atmosphere,

[1] Here we present extensive observations of stratospheric and upper tropospheric water vapor using the balloon-borne Cryogenic Frost point Hygrometer (CFH) in support of the Aura Microwave Limb Sounder (MLS) satellite instrument. Coincident measurements were used for the validation of MLS version 1.5 and for a limited validation of MLS version 2.2 water vapor. The sensitivity of MLS is on average 30% lower than that of CFH, which is fully compensated by a constant offset at stratospheric levels but only partially compensated at tropospheric levels, leading to an upper tropospheric dry bias. The sensitivity of MLS observations may be adjusted using the correlation parameters provided here. For version 1.5 stratospheric observations at pressures of 68 hPa and smaller MLS retrievals and CFH in situ observations agree on average to within 2.3% ± 11.8%. At 100 hPa the agreement is to within 6.4% ± 22% and at upper tropospheric pressures to within 23% ± 37%. In the tropical stratosphere during the boreal winter the agreement is not as good. The ''tape recorder'' amplitude in MLS observations depends on the vertical profile of water vapor mixing ratio and shows a significant interannual variation. The agreement between stratospheric observations by MLS version 2.2 and CFH is comparable to the agreement using MLS version 1.5. The variability in the difference between observations by MLS version 2.2 and CFH at tropospheric levels is significantly reduced, but a tropospheric dry bias and a reduced sensitivity remain in this version. In the validation data set a dry bias at 177.8 hPa of À24.1% ± 16.0% is statistically significant.

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Balloon‐borne observations of frost‐point temperature and ozone in the equatorial western, central and eastern Pacific as well as over equatorial eastern Brazil provide a highly accurate data set of water vapor across the tropical tropopause. Data were obtained at San Cristóbal, Galapagos, Ecuador (0.9°S, 89.6°W), during the late northern winter and the late northern summer in 1998 and 1999 and at Juazeiro do Norte, Brazil (7.2°S, 39.3°W), in February and November 1997. Earlier data in the western Pacific region in March 1993 were reanalyzed to extend the scope of the observations. The data show three different circumstances in which saturation or supersaturation occurs and imply different mechanisms for dehydration at the tropical tropopause: (1) convective dehydration, (2) slow‐ascent dehydration, and (3) large‐scale wave‐driven dehydration. Furthermore, air that crosses the tropical tropopause in the late northern summer may be dehydrated further during late northern fall, as the average tropical tropopause rises and cools. Not all soundings show dehydration, and there are clear differences in the frequency and depth of saturation in different regions and seasons. The tropopause transition region can be identified in accurate measurements of relative humidity, even under conditions where ozone observations are ambiguous. Deep convection plays an important role in setting up this transition region, which is then subject to large‐scale wave activity and wave breaking at the tropopause or midlatitude intrusions. High relative humidities over regions of strong subsidence show that descending motion in the troposphere is limited to levels below the transition region.