The effect of distribution processes on the isomeric composition of hexachlorocyclohexane in a contaminated riverine system

Various factors influence the isomeric composition of hexachlorocyclohexanes which are released to the environment. Original compositions in technical mixtures may vary slightly, but higher shifts are observable for transfer processes, bioaccumulation and microbial transformation. Consequently, the isomeric composition in environmental samples is a superposition of these processes. In this study, isomeric distributions and concentrations of hexachlorocyclohexanes were analyzed in water, sediment, and soil samples of a riverine system known to be highly contaminated by hexachlorocyclohexanes. To assess desorption of hexachlorocyclohexanes from particulate matter to water, batch shaking and percolation experiments were conducted complementary. Analyzed samples exhibited total hexachlorocyclohexane concentrations of up to 2.8 µg/g in sediments and up to 21 µg/L in river water predominated by the α-isomer. Downstream hexachlorocyclohexane pattern changed toward δ-isomer domination, while overall hexachlorocyclohexane concentrations decreased. Desorption experiments supported the assumption of discrimination by preferred association of the α- and β-isomers with particulate matter, showing elevated mobilization of γ-, δ- and ε-hexachlorocyclohexanes and lower mobilization of the α- and β-isomers. Soil samples of a riparian wetland exhibited elevated concentrations of hexachlorocyclohexanes exceeding 200 µg/g and predominance of α-hexachlorocyclohexanes in the top soil layer. Subjacent soil layers showed rapidly decreasing hexachlorocyclohexane concentrations and an isomeric shift toward the β-isomer. The assumed preferential mobilization of β-hexachlorocyclohexane was supported by desorption experiments. This study demonstrated firstly that transfer processes influence substantially hexachlorocyclohexane isomer distribution in the aquatic environment. Secondly, conditions of aging determine strength of association and remobilization potential of hexachlorocyclohexane residue down to an isomer-specific level.