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Comprehensive two-dimensional gas chromatography (GC x GC) of atropisomeric PCBs, combining a narrow bore beta-cyclodextrin column and a liquid crystal column
Umeå University, Faculty of Science and Technology, Chemistry.
Umeå University, Faculty of Science and Technology, Chemistry.
2001 (English)In: Journal of Microcolumn Separations, ISSN 1040-7685, Vol. 13, no 7, 300-305 p.Article in journal (Refereed) Published
Abstract [en]

Peak assignment and quantification of PCBs in environmental samples is a time-consuming and costly process, and the analysis of atropisomeric PCBs is even more laborious and costly due to the elaborate analytical work involved. GC X GC can solve some of the problems entailed by increasing congener resolution and instrument sensitivity. In this study. a comprehensive two-dimensional gas chromatography (GC X GC) system was utilized with a combination of a permethylated beta -cyclodextrin column in the first dimension and a liquid crystal column in the second dimension. Using this system, in a single GC X GC run six out of nine studied atropisomeric PCBs (PCBs 91, 132, 135. 136, 149, and 176) can be resolved, and two (PCBs 84 and 174) can be partially separated from coeluting congeners in a mixture of 144 congeners (the most abundant congeners in technical PCBs). The chiral resolution (Rs) of the enantiomeric pairs ranged between 0.6 and 2.0, with PCB 132 having the highest resolution. Furthermore, the congers that (partially) coelute with enantiomers of PCBs 84, 95, and 174 have low abundance in technical PCB as well as in environmental samples. Thus, all of the nine target PCBs could be separated from significant interfering compounds in a single GC X GC run.

Place, publisher, year, edition, pages
2001. Vol. 13, no 7, 300-305 p.
Keyword [en]
polychlorinated biphenyls, PCB, atropisomers, chiral analysis, comprehensive two-dimensional gas chromatography, beta-cyclodextrin, liquid crystal
URN: urn:nbn:se:umu:diva-8878DOI: 10.1002/mcs.10010OAI: diva2:148549
Available from: 2008-02-19 Created: 2008-02-19 Last updated: 2009-12-07Bibliographically approved
In thesis
1. Analysis of PCBs with special emphasis on comprehensive two-dimensional gas chromatography of atropisomers
Open this publication in new window or tab >>Analysis of PCBs with special emphasis on comprehensive two-dimensional gas chromatography of atropisomers
2003 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

There are 209 PCB congeners, 136 of which have been found in technical PCB mixtures and hence may be found in the environment as a result of either intentional or unintentional release. The identification and quantification of the congeners are difficult due to analytical bias from coeluting PCBs and other persistent organic pollutants.

Among the 209 possible PCB congeners, 19 tri- and tetra-ortho chlorinated congeners exist in stable atropisomeric conformations. The racemization barrier were determined for twelve of the nineteen atropisomers and was found to be between 176-185 kJ × mol-1 and ca. 250 kJ × mol-1 for tri- and tetra-ortho PCB, respectively. Further, a buttressing effect of 6.4 kJ × mol-1 was observed for congeners with vicinal ortho-meta chlorines.

Comprehensive two-dimensional gas chromatography (GC×GC) was used to analyze the atropisomers and other PCBs. A Longitudinally Modulated Cryogenic System (LMCS) was used with liquid CO2 as cryogen. The LMCS was optimized for semi-volatile organic substances, primarily PCBs. The trap temperature was shown to be an important factor for the trapping and desorption efficiency, as was the thermal mass of the column used in the modulator region. A number of column sets were tested and the separation efficiency, congener resolution and analysis time was evaluated. Good separation of non- and mono-ortho PCBs and “bulk” PCBs (in a technical PCB) was obtained within 8 min using a smectic liquid crystal column (LC50) as the first and a nonpolar column as the second dimension column. Using a second column, an efficient nonpolar (DB-XLB) column, which separates many PCB congeners, were combined with a polar (cyanopropyl) or shape selective (LC50) second dimension column. As a maximum, 181 of the 209 congeners and 126 of the 136 Aroclor PCBs were resolved. The seven frequently measured PCBs (PCBs 28, 52, 101, 118, 138, 153 and 180) and all WHO-PCBs were separated from all other Aroclor PCBs.

Chiral PCBs are released into the environment as racemic mixtures. However, organisms have been shown to enantiomerically enrich many of the atropisomers, suggesting that enantioselective biotransformations occur. Non-racemic PCB enrichment has also been seen in mammalians including humans, which is of particular concern because of the potential health risk. An analytical procedure were therefore developed and used to determine the levels of atropisomeric PCBs, planar-PCBs (WHO-PCBs) and total PCBs in seals with different health status. GC×GC was used to separate the target PCBs from other PCBs and potential interferences. A chiral column (permethylated â-cyclodextrin) was used in combination with a polar or shape selective column and enantiomeric fractions (EFs) were determined for five atropisomeric PCBs, i.e. CBs 91, 95, 132, 149 and 174. Some atropisomers had EF that deviated largely from racemic. The deviation was larger in liver than blubber, indicating enantioselective metabolism. However, there was no selective passage of the studied atropisomeric PCBs across placenta and no selective blood-brain barrier. Similarly, no correlation between EFs and health status was observed, although there was a correlation between total PCBs and health status.

Place, publisher, year, edition, pages
Umeå: Kemi, 2003. 61 p.
Environmental chemistry, PCB, Atropisomers, Chiral, GC×GC, Enantiomeric barriers, Seal, polar, shape selective, Cyclodextrin, 2D, ECD, FID, TOF-MS, Comprehensive two-dimensional GC, Miljökemi
National Category
Environmental Sciences
Research subject
Analytical Chemistry
urn:nbn:se:umu:diva-54 (URN)91-7305-475-5 (ISBN)
Public defence
2003-06-06, Umeå, 13:00 (English)
Available from: 2003-06-06 Created: 2003-06-06 Last updated: 2009-12-07Bibliographically approved

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