Enantioselective determination of chiral toxaphene congeners in laying hens and eggs using multidimensional high-resolution gas chromatography

A total of 22 chiral toxaphene congeners were analyzed in organ tissues and eggs of laying hens after they had been fed with food spiked with technical toxaphene. For the analysis, multidimensional high-resolution gas chromatography using a chiral column coated with randomly silylated heptakis(O-tert-butyldimethylsilyl)-beta-cyclodextrin, electron capture detection, and valveless "live column switching" technique was applied. The analytical results were additionally confirmed with mass spectral data, recorded in electron-capture negative ionization mode with selected-ion monitoring mass spectrometry. During both the feeding period of the laying hens with toxaphene-contaminated food (38 weeks, accumulation phase) and the following subsiding period without toxaphenes (another 14 weeks, decontamination phase), organs (liver, kidney, skin/fat), blood, meat, and eggs of the hens served as model matrices for toxaphene uptake. The enantiomeric ratios (ERs) of congeners 26, 31, 32, 40, 41, 42(a+b), 44, 50, and 62--known as the most important components of technical toxaphene occurring in the environment--could be analytically determined. Significant differences were observed with respect to their initial racemic ratios. On the basis of their chemical structures, the metabolic pathways of some congeners could be explained. Astonishingly, some of the toxaphenes applied as racemates could merely be found as single enantiomers at the end of the feeding program, for example, congener 32 in blood and meat samples or congener 44, especially in organ tissues, which showed ERs of zero or infinity. The findings of this study impressively emphasize that it is essential to isolate and analyze individual toxaphene enantiomers in food and biota tissues to be capable of evaluating their toxicity and metabolization more specifically.