The air-sea equilibrium and time trend of hexachlorocyclohexanes in the Atlantic Ocean between the Arctic and Antarctica.

Hexachlorocyclohexanes (HCHs) were determined simultaneously in air and seawater during two cruises across the Atlantic Ocean between the Arctic Ocean (Ny-Alesund/ Svalbard, 79 degrees N; 12 degrees E) and the Antarctic Continent (Neumayer Station/ Ekstroem Ice Shelf, 70 degrees S; 8.2 degrees W) in 1999/ 2000. The concentrations of alpha-HCH and gamma-HCH in air and surface waters of the Arctic exceeded those in Antarctica by 1-2 orders of magnitude. The gaseous concentrations of gamma-HCH were highest above the North Sea and between 20 degrees N and 30 degrees S. Fugacity fractions were used to estimate the direction of the air-sea gas exchange. These showed for alpha-HCH thatthe measured concentrations in both phases were close to equilibrium in the North Atlantic (78 degrees N-40 degrees N), slightly undersaturated between 30 degrees N and 10 degrees S and again close to equilibrium between 20 degrees S and 50 degrees S. Y-HCH has reached phase equilibrium in the North Atlantic as alpha-HCH, but the surface waters of the tropical and southern Atlantic were strongly undersaturated with y-HCH, especially between 30 degrees N and 20 degrees S. These findings are significantly different from two earlier estimates around 1990 as a result of global emission changes within the past decade. Therefore, we investigated the time trend of the HCHs in the surface waters of the Atlantic between 50 degrees N and 60 degrees S on the basis of archived samples taken in 1987-1997 and those from 1999. A decrease of alpha-HCH by a factor of approximately 4 is observed at all sampling locations. No decrease of gamma-HCH occurred between 30 degrees N and 30 degrees S, but there was a decrease in the North Atlantic, North Sea, and in the South Atlantic south of 40 degrees S. The constant level of gamma-HCH in the tropical Atlantic confirms the conclusion that the tropical Atlantic acts as a sink for y-HCH at present time. The measured alpha-HCH seawater concentrations were compared with results from a global multimedia fate and transport model. Whereas the time trend over 13 years and the latitudinal gradient were well reproduced by the model, the absolute levels were too high by a factor of 4.5. This may be explained by the zonal averaging employed in the model as well as uncertain emissions and degradation rates.