Annegret Buthe

Qualitative and quantitative determination of PCB congeners by using a HT-5 GC column and an efficient quadrupole MS

The determination of CB congeners by means of a new HT-5 column (SGE Australia) was carried out with a quadrupole GC-MS. A method is presented that permits the qualitative and quantitative determination of environmental and technical PCB mixtures with the help of only 14 single CBs, 2–4 reference CBs per degree of chlorination in SIM mode. More than 70 individual CBs, including some coplanar congeners such as CB-77, CB-126 and CB-169, were measured as pure standards. Additionally Clophen A30/A40/A60 and Aroclor 12541260 were measured. With our method a total of 131 single CBs could be identified. For the quantitative determination several PCB congener groups were formed for each level of chlorination according to their fragmentation pattern. One CB with group-typical fragmentation was used as reference for the calibration within the group. The fragmentation pattern is strongly correlated with the molecular structure of the single CB, so that CBs not available as pure standards can be identified. Some remarkable correlations between structure of CBs of all degrees of chlorination and their fragmentation in MS EI-mode were discovered. A similar retention time does not mean a similar fragmentation pattern of these CBs and vice versa. The measurements were carried out in scan mode measuring masses 100–650 and in SIM-mode, considering the [M]+, [MCL]+ and [M2Cl]+ ions.

Correlation between concentration and composition of PCB mixtures in seals (Phoca vitulina)

Abstract Two methods for characterizing the composition of PCB mixtures, degree of metabolisation and ring stability values, allow recognition of variations between and within species easily. Blubber of harbour seals from Iceland and the North Sea were analyzed. The degree of metabolisation is presented as a function of the concentration.

Weitere Untersuchungen zur Belastung niedersächsischer Saatkrähen (Corvus frugilegus) mit chlorierten Kohlenwasserstoffen

In addition to the investigations on environmental pollutants in rookeries in 1982 and 1983, further examinations were made in 1986. Decreasing residues of σ DDT in livers of nestlings and eggs, and increasing residues of Lindan in livers of nestlings were determined. In contrast, the concentrations of Lindan in eggs diminished. As reported for 1982 and 1983, the PCBs were mainly found in industrialized areas and pesticides in rural environments.

Vergleich der Schadstoffbelastung in Eiern des Sperbers (Accipiter nisus) aus Brandenburg und Nordrhein-Westfalen, Deutschland

Eggs from Sparrowhawks from Brandenburg (former GDR) and North-Rhine-Westphalia (former FRG) were examined for their burden of PCB, DDT, HCH, HCB and the heavy metals lead and cadmium. Significant differences emerged in the cases of PCB and DDT and its metabolites between the populations of the two regions. The other examined xenobiotics were detectable only in low concentrations. The DDT concentrations were distinctly higher in the samples from the former GDR, while PCB concentrations were higher in the eggs from North-Rhine-Westphalia. The results reflect clearly the different use and prohibition of the examined xenobiotics in the two former german states. In spite of the differences in the PCB burden, the PCB pattern in the eggs of the different regions is nearly identical. Eggshell indices correlate negatively with DDT burden in both sample areas. Eier von Sperbern aus Brandenburg und aus Nordhrein-Westfalen wurden auf ihren Gehalt an PCB, DDT, HCH, HCB und die Schwermetalle Blei und Cadmium untersucht. Bei den PCB und beim DDT und seinen Abbauprodukten traten signifikante Unterschiede in der Belastung der beiden Populationen auf, während die anderen untersuchten Stoffe in den Eiern beider Untersuchungsgebiete nur in geringen Mengen nachzuweisen waren. Dabei waren in den Proben aus der ehemaligen DDR die DDT-Konzentrationen deutlich höher als in den Eiern aus dem westfälischen Münsterland. Bei den PCB-Konzentrationen ergab sich ein genau umgekehrtes Ergebnis, im Münsterland waren diese erheblich höher. Die Ergebnisse stehen im klaren Zusammenhang mit der unterschiedlichen Anwendung und dem zeitlich unterschiedlich erfolgtem Verbot der untersuchten Schadstoffe in den beiden ehemaligen deutschen Staaten. Trotz der Belastungsunterschiede bezüglich der PCB ist das PCB-Muster in den Eiern aus den Untersuchungsgebieten aufgrund des artspezifischen Metabolismus nahezu identisch.

Veränderungen in der Zusammensetzung der PCB- und DDT-Gemische in verschiedenen Lebensstadien der Wiesenweihe (Circus pygargus) und der Rohrweihe (Circus aeruginosus) in Nordrhein-Westfalen, Deutschland.@@@Changes in the DDT and PCB burden in life stages of Montagu's (Circus pygargus) and Marsh Harriers (Circus aeruginosus) from North-Rhine Westfalia, Germany

Egg and liver samples of Montagus and Marsh Harriers from the 1990s were examined for their burden of DDT and PCB. The DDT burden in both species was distinctly higher in the eggs than in juveniles and adults, whereby the values for the adults were clearly higher than those for the juveniles. The composition of the DDT isomers of both species varies between the life stages. In the egg samples nearly only p,p′-DDE was found, while in the livers of the adults and more especially of the juveniles higher parts of p,p′-DDT were detected. In both species the PCB burden of the eggs and of the adults was clearly higher than that of the juveniles. The composition of the PCB mixtures of both species differed distinctly between each of the life stages. While the PCB mixtures in eggs and in the livers of adults are nearly identical, in the livers of juveniles a distinct shift to lower chlorinated congeners reaching higher parts of the PCB mixtures becomes evident. The changes in the composition of DDT and PCB mixtures in the different life stages reflect a new uptake of these xenobiotics with the food animals. Ei- und Leberproben von Wiesen- und Rohrweihen aus den 1990er Jahren wurden auf ihre Belastung mit DDT und PCB untersucht. Die DDT Belastung der Eier überragt bei beiden Arten deutlich die Belastung der Jungvogel und der Adulten, wobei die Belastung der Adulten deutlich höher als die der Jungvögel ist. Wesentliche Unterschiede sind in der Zusammensetzung der DDT-Isomere in den Proben beider Arten ersichtlich. In den Eiproben findet sich fast nur p,p′-DDE, wdhrend in den Lebern der Adulten und besonders der Jungvögel auch ein erhöhter Anteil von p,p′-DDT zu finden ist. Bei beiden Arten lag die PCB-Belastung der Eier und der Adulten deutlich höher als die der Jungvögel. In der Zusammensetzung der PCB-Gemische beider Arten zeigen sich bezüglich der einzelnen Lebensstadien klare Unterschiede. Während die PCB-Gemische in den Eiern und in den Lebern der Adulten relativ identisch sind, tritt in den Lebern der Jungvögel eine deutliche Verschiebung zu niedrig chlorierten Kongeneren auf, die höhere prozentuale Anteile des Gemisches bilden. Aus den genannten Veränderungen der DDT- und PCB-Gemische lässt sich eine Aufnahme dieser Stoffe über die Nahrungstiere klar belegen.