Abstract

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 µg 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)-β-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-γ-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.