Enantiomer separation of chiral toxaphene components in biological samples was studied by application of different chiral stationary phases based on modified cyclodextrins. Several pairs of enantiomers were resolved on permethylated beta-cyclodextrin (beta-PMCD), among them 2-endo,3-exo,5-endo,6-exo,8,8,9,10-octachlorobornane (B8-1412), which was not enantiomerically resolved on tert-butyldimethylsilylated beta-cyclodextrin (beta-BSCD). The latter column was applied to determine the enantiomer ratios (ERs) of 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P-26) in brain tissue of three seal species. The ER of B8-1413 (P-26) in brain was virtually racemic as well as those of the two persistent and chiral components of technical chlordane, 1-exo,2,2,4,5,6,7,8,8-octachloro-3a,4,7,7a-tetrahydro-4,7-metha noindane (trans-nonachlor III or MC 6) and 1-exo,2-endo,3-exo,4,5,6,8,8-octachloro-3a,7,7a-tetrahydro-4,7- methanoindane (U82). In contrast, B8-1412 and 2-exo,5,5,8,9,9,10,10-octachlorobornane (B8-2229 or P-44) were significantly enantiomerically enriched in several samples of high trophic level biota. 2,2,5,5,8,9,9,10,10-Nonachlorobornane (B9-1025 or P-62), a chlorobornane metabolisable by seals and the presumable precursor of B8-2229 (P-44), was also enantiomerically enriched in seal blubber. These results confirm the assumption that some less persistent toxaphene components may be significantly degraded in biological samples. Enantioselective gas chromatography provides the information that such a degradation is happening by the characteristic change of the ratio of the two enantiomers in the respective tissues.