Air–water gas exchange of chiral and achiral organochlorine pesticides in the Great Lakes

Parallel air and water samples were taken on lakes Superior, Huron, Erie and Ontario between 1996 and 2000 to determine the occurrence and levels of hexachlorocyclohexanes (HCHs), trans-chlordane (TC), cis-chlordane (CC), dieldrin (DIEL) and the metabolite heptachlor exo-epoxide (HEPX). Concentrations in the water varied greatly among the lakes, but air concentrations were similar, thus resulting fugacity ratios varied by lake and compound. The enantiomer fraction, EF = (+)/[(+) + (−)], was determined for α-HCH, TC, CC and HEPX. Enantioselective degradation of (+)α-HCH was found in water of all the lakes where the depletion was greatest for Lake Superior, which has the longest water residence time. Preferential loss of (+)TC and enrichment of (+)HEPX were found in lakes Superior and Ontario, with similar EFs in both lakes. CC was racemic in Lake Superior and showed depletion of the (+) enantiomer in Lake Ontario. Depletion of (+)α-HCH, (+)TC and enrichment of (+)HEPX was seen in all air samples. CC varied from depletion of the (+) or (−) enantiomer and was racemic in some cases. Higher concentrations of α-HCH in the air over Lake Superior were correlated with less racemic composition, providing evidence of water-to-air exchange. Fugacity ratios for the HCHs approached equilibrium conditions within a factor of 2, with slight excursions toward net volatilization or deposition, where generally higher excursions were seen for the cyclodienes.