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Determination of atropisomeric and planar polychlorinated biphenyls, their enantiomeric fractions and tissue distribution in grey seals using comprehensive 2D gas chromatography
Umeå University, Faculty of Science and Technology, Department of Chemistry.
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2003 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1019, no 1-2, 127-142 p.Article in journal (Refereed) Published
Abstract [en]

High prevalence of uterine occlusions and sterility is found among Baltic ringed and grey seal. Polychlorinated biphenyls (CBs) are suspected to be the main cause. The CB concentrations are higher in affected than in healthy animals, but the natural variation is considerable. Thus, it might be possible to assess the health status of seals by CB analysis. The ratios of chiral compounds (enantiomeric fractions (EFs)) such as atropisomeric CBs are of particular interest, since these may reflect differences in metabolic rates. An analytical procedure was developed and used to determine the levels of atropisomeric CBs, planar-CBs (WHO-PCBs) and total CBs in seals of different health status. Comprehensive 2D gas chromatography (GC×GC) was used to separate the target analytes from other CBs and interferences and a micro electron-capture detector (μECD) was used for detection. EFs of the atropisomeric CBs were difficult to determine as the levels were low and the interferences many. Two column combinations had to be used to avoid biased results—both had a chiral column as first-dimension column. The second-dimension column was coated with either a high-polarity cyanopropyl or a liquid crystal phase. EFs were determined for five atropisomeric CBs, i.e. CBs 91, 95, 132, 149 and 174. The results were verified by GC×GC–time-of-flight mass spectrometry (TOF-MS). Some atropisomeric CBs had EFs that deviated strongly from the racemic-mixture value. The deviations were larger in liver than blubber, which indicates enantioselective metabolism. However, there was no selective passage of the studied atropisomeric CBs across placenta and no selective blood–brain barrier. Similarly, no correlation between EFs and health status was observed, although there was a correlation between the total CB levels and health status.

Place, publisher, year, edition, pages
Amsterdam: Elsevier, 2003. Vol. 1019, no 1-2, 127-142 p.
Keyword [en]
gas chromatography, comprehensive two-dimensional, atropisomers, enantiomeric fractions, Baltic grey seal, polychlormated biphenyls
National Category
Biochemistry and Molecular Biology Analytical Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-4603DOI: 10.1016/j.chroma.2003.08.102ISI: 000186503600012OAI: oai:DiVA.org:umu-4603DiVA: diva2:143765
Note

Publicerad som manuskript i avhandling med titel:

Determination of levels, enantiomeric fractions and tissue distribution of atropisomeric PCBs in grey seals (Halichoreus Grypus) of varying health status using comprehensive twodimensional gas chromatography

Available from: 2003-06-06 Created: 2003-06-06 Last updated: 2017-05-26Bibliographically 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.
Keyword
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
Identifiers
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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