Human plasma samples from 50 wives of fishermen have been analyzed with respect to PCBs. The non-ortho-substituted PCB congeners CB-126 and CB-169 were determined by mass spectrometry in negative ion chemical ionization mode, which demonstrated a limit of detection of 30 fg. The recoveries of the internal standards used for determination of ortho-substituted CBs were approximately 95%. Two methods, one gravimetric and the other based on enzymatic determinations of triglycerides, cholesterol and phospholipids, were compared for the determination of total amount of lipids in the plasma samples; the correlation coefficient was 0.82 and the slope 0.98. For practical reasons, enzymatic determinations are recommended for further use. The total, lipid-adjusted concentrations of PCBs in plasma were influenced by age, total lactation time and consumption of fatty fish from the Baltic Sea.

Pine needles were used as passive samplers for monitoring polychlorinated biphenyls (PCBs) in the environment. A method for the determination of PCB in pine needle wax was developed. By applying an HPLC-based cleanup procedure to wax extracts of pine needles, a high selectivity toward PCB was obtained. High precision and accuracy was achieved, as well as high relative (91-108 f 4-8 % ) and absolute overall recoveries (81 i 14%). Pine needle wax from the central and northern parts of Europe were examined. High concentrations of PCBs with a profile shifted toward low molecular species were found in Western Germany (C 9 CBs = 47 ng/g of wax) when compared to the other investigated geographical sites (c 9 CBs = 4-7 ng/g of wax).

Abstract. Gas chromatography-atomic emission detection (GC-AED) has been evaluated in order to determine the optimal conditions for chlorine and sulfur response of chlorinated biphenyls (CBs) and methylsulfonyl metabolites of CBs (MeS02-CBs). The influence of the shape of the capillary column end facing the plasma, make-up gas flow, additional transfer line make-up gas flow and reagent gas flows on the detector response has been studied. Using an additional make-up gas flow applied through a transfer line capillary having a decreased outlet diameter yielded an increased detector response with minimum detectable levels for sulfur and chlorine of 1.7 and 20 pg, respectively.Further, a substantial decrease in peak tailing was achieved. The applicability of the method for analysis of biological materials is demonstrated by the determination of the main CB congeners present in human blood and of MeS0,-CBs in seal blubber.

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SummaryA method for the determination of non-, mono-and di-ortho substituted polychlorinated biphenyls in human blood plasma is presented. The non-ortho CBs are isolated from the bulk of PCBs by HPLC on a dinitroanilino-propyl silica column and collected as a heart-cut fraction that is transferred on-line to GC-MS utilizing concurrent solvent evaporation technique. The on-line coupling serves to lower the limit of determination and to partly automate the sample clean-up. The di-and mono-ortho CBs are analyzed by off-line GC-ECD using two different columns. Sample pre-treatment is performed by extraction with organic solvents and fractionation on silica gel. A high reproducibility and an absolute over-all recovery of approximately 70 % is demonstrated. The method is applied to samples of blood from 5 individuals. All the samples demonstrated a similar relative concentration profile. It was also shown that three CB congeners (CB 126, CB 156 and CB 170) contributed to the major part of the toxic equivalent quantity of the PCB content in the blood.