Atmospheric hexachlorocyclohexanes in the North Pacific Ocean and the adjacent Arctic region: Spatial patterns, chiral signatures, and sea-air exchanges

During the 2003 Chinese Arctic Research Expedition (CHINARE2003) from the Bohai Sea to the high Arctic (37 degrees N to 80 degrees N) aboard the icebreaker Xuelong (Snow Dragon), air samples were collected for the analysis of hexachlorocyclohexanes (HCHs) in the North Pacific Ocean and adjacent Arctic region. The Sigma HCHs (alpha-HCH + gamma-HCH) ranged from 2.3 to 95.1 pg/m(3) with the highest levels observed in Far East Asia (32.5 pg/m(3)), followed by the North Pacific Ocean (17.0 pg/m(3)) and the Arctic (7.3 pg/m(3)). Compared to previous studies in the same areas in 1990s, our measurements were approximately 1 order of magnitude lower. Because of disproportionate chemical reduction and physical fractioning during long-range transport, the ratios of alpha-HCH to gamma-HCH (alpha/gamma-HCH) showed a significant increasing trend from low to high latitudes, suggesting that the alpha/gamma-HCH range of 4-7 could not be used to identify sources of technical HCHs especially in remote areas. The ratios of (+)-alpha-HCH to the sum of (+)-alpha-HCH and (-)-alpha-HCH were on average much more biased from 0.5 compared to previous observations in mid-1990s, indicating the exchange of atmospheric alpha-HCH with those in the oceans, where (+)-alpha-HCH was selectively depleted in biological degradation processes. Estimated fugacity ratios based on available data for both alpha-HCH and gamma-HCH further implied their net volatilization from seawater to air in the Arctic Ocean.