Enantioselective gas chromatography/mass spectrometry of methylsulfonyl PCBs with application to arctic marine mammals
1998 (English)In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 70, no 18, 3845-3852 p.Article in journal (Refereed) Published
Four different commercially available cyclodextrin (CD) capillary gas chromatography (GC) columns were tested for the enantioselective separation of nine environmentally persistent atropisomeric 3- and 4-methylsulfonyl PCBs (MeSO2-CBs). The selected columns contained cyclodextrins with various cavity diameters (β- or γ-CD), which were methylated and/or tert-butyldimethylsilylated (TBDMS) in the 2,3,6-O-positions. The β-CD column with TBDMS substituents in all of the 2,3,6-O-positions was by far the most selective column for the MeSO2-CBs tested. Enantiomers of congeners with 3-MeSO2 substitution were more easily separated than those with 4-MeSO2 substitution. The separation also seemed to be enhanced for congeners with the chlorine atoms on the non-MeSO2-containing ring and clustered on one side of the same ring. The 2,3-di-O-methyl-6-O-TBDMS-β-CD was found to give somewhat better selectivity than the corresponding γ-CD, in comparison between the two columns, which were identical in all other respects. Enantioselective analysis of arctic ringed seal (Phoca hispida) and polar bear (Ursus maritimus) adipose tissue revealed a strong dominance of certain enantiomers. For example, the enantiomer ratio (ER) of 3-MeSO2-CB149 was 0.32 and <0.1 in ringed seal blubber and polar bear fat, respectively. These low ER values are indicative of highly enantioselective formation, enantioselective metabolism, enantioselective transport across cell membranes, or a combination of the three in both species. Comparable results for the enantiomeric analysis of MeSO2-CBs in biotic tissue extracts were obtained using two highly selective mass spectrometric techniques, ion trap mass spectrometry/mass spectrometry and electron capture negative ion low-resolution mass spectrometry.
Place, publisher, year, edition, pages
Washington: American Chemical Society (ACS), 1998. Vol. 70, no 18, 3845-3852 p.
polychlorinated biphenyls, modified cyclodextrins, separation, enantiomers, atropisomers, contaminants, metabolites, pollutants, samples, ratios
IdentifiersURN: urn:nbn:se:umu:diva-5444DOI: 10.1021/ac980064gISI: 000075911500019OAI: oai:DiVA.org:umu-5444DiVA: diva2:144959