The enantiomer ratios of some chlordane congeners were found to be gender-specific in cod from the Barents Sea. Concentrations of U81, U82, trans-chlordane, MC5, cis-chlordane, MC7, trans-nonachlor, MC6, and cis-nonachlor as well as the metabolites cis-heptachlorepoxide and oxychlordane were determined. Female cod preferentially accumulated (−)-cis-chlordane and (−)-trans-chlordane, while male cod had an excess of (+)-cis-chlordane and (+)-trans-chlordane. A significant difference was also observed for MC6. Only chlordane congeners without a chlorine atom at the C3 position showed gender-specific enantiomer ratios. No exception was found within the sample set of 16 individuals. Furthermore, the isomer and enantiomer patterns were very similar in muscle tissue, gonads, and liver.

A method for the quantification of selected toxaphene congeners as well as "total toxaphene" was developed based on electron ionization (EI) tandem (MS/MS) ion trap mass spectrometry (MS) and a combination of fragment ion dissociations. Congeners were separated by highresolution gas chromatography. Compared to conventional EI low-resolution MS, a 5-20-fold gain in sensitivity could be obtained for octa-or nonachlorinated compounds such as toxaphene #26 and #62 (according to Parlar nomenclature), allowing for their detection in the low picogram range in biota. In addition, response factors for important congeners such as #26, #32, #40/41, #42, #44, #50, and #62 deviated not more than a factor of 2, which is much less as compared to negative ion chemical ionization. This reduces the risk for systematic errors when determining total toxaphene on the basis of a limited number of reference compounds or the technical mixture. Furthermore, chlordanes and polychlorinated biphenyls did not interfere when applying the proposed MS/MS technique. The applicability of the method was tested by determining both total toxaphene and levels of selected congeners in six Arctic wildlife samples collected from Nunavut, Canada, as well as by repetitive analyses of the SRM 1588 certified reference material.

High resolution gas chromatography (HRGC) coupled to quadrupole negative ion chemical ionization (NICI) mass spectrometry (MS) was used to investigate congener patterns, levels and enantiomer distribution of selected toxaphene congeners (#26, #41, #44, #50, #63, B7-1453) in human milk from Germany. #50 and #26 were the most abundant congeners. Furthermore, the identification of B7-1453, B8-1412, #41, #42, #44 and #63 was possible. Levels for the sum of #26, #41, #44 and #50 ranged from 7 to 24 microg kg(-1) milk fat and contributed between 2 and 9% to the total burden of investigated organochlorines such as selected compounds of the chlordane group, HCH, DDT and polychlorinated biphenyls (PCB). Capillaries coated with heptakis-(2,3,6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-gamma-cyclodextrin (TEG-CD) were used for the enantioselective separations. Enantiomer ratios (ER) and enantiomer fractions (EF) of the abundant toxaphene congeners #26 and #50 as well as of B7-1453, #41 and #63 were determined. Greatest deviations from a racemic composition in individual human milk samples were found for #41 (1.54-2.37), #50 (1.37-1.72) and #63 (0.53-0.71) whereas ERs for #26 were close to 1. Compared to wildlife biota such as fish and raptors ER changes were more pronounced in human milk but comparable to human adipose tissue.

The detection of some chlordane compounds (heptachlor, cis-/trans-chlordane and cis-/trans-nonachlor) by positive ion chemical ionization (PICI) in an ion trap was studied using acetonitrile, acrylonitrile and dichloromethane as non-conventional reagent gases. These reagent gases initiated specific fragmentation reactions and resulted in different response factors. All reagent gases enabled detection limits in the low-pg range for heptachlor, whereas the detection limits of cis-/trans-chlordane and cis-/trans-nonachlor were in the mid-pg range. Additionally, the acetonitrile and dichloromethane PICI mass spectra of the cis- and trans-stereoisomers of chlordane and nonachlor were different.