Description: Kanechlor-300, -400, -500 and -600, Phenoclor DP-3, -4, -5 and -6 and Sovol mixtures were analyzed for their chlorobiphenyl (CB) composition using high-resolution one-dimensional and multidimensional gas chromatography-electron capture detection (MDGC-ECD) techniques. The congener patterns of tested Kanechlor and Phenoclor mixtures resembled Aroclor 1016, 1242, 1254 and 1260. However, differences in the percentage contribution of minor constituents were noticed among these mixtures, which could be due to variations in the boiling-point fractionation of these commercial products. CB pattern of Sovol was different from the rest of the mixtures tested. It showed a composition in between ca. 30%, 40%, 50% and 60% overall chlorine levels. MDGC-ECD study showed the presence of hitherto unnoticed non-CB compounds coeluting with CBs in some commercial PCBs. The use of these mixtures as quantitation standards should be considered with caution. CB patterns of Sovol and a water extract of the Gulf of Finland matched closely, indicating a point source contamination to these waters.

Description: Individual polychlorinated biphenyl (CB) congeners in adipose and whole blood tissues of a capacitor manufacture worker (occupational/accidental exposure) and of the general population were determined. Nondestructive sample cleanup and multidimensional gas chromatography-electron capture detection (MDGC-ECD) techniques were applied. Special attention was given to the toxicologically relevant congeners CB-77, CB-126, CB-169, CB-105, CB-114, CB-118, CB-156, CB-167, and CB-189 (IUPAC). Lipid-based tissue contents of sigma CBs were higher in the occupationally/accidentally exposed worker (adipose = 7,000 ng/g; whole blood = 11 ng/g) than in the general population (adipose = 300 ng/g; whole blood = 1.9 ng/g). Among the non-ortho Cl CBs, CB-77 was below detection limit (〈 1.0 pg/g). The contents of CB-126 for the capacitor manufacture worker were 2,000 and 3 pg/g, and in the general population were 100 and 2 pg/g for adipose and whole blood, respectively. The corresponding data for CB-169 were 3,500 and 4 for adipose and whole blood, respectively, in the exposed worker, and 40 and 2 for adipose and whole blood, respectively, in the general population. Congeners with highest contents were CB-153, CB-138, CB-180, CB-170, and CB-187. These congeners possess chlorine substitution patterns, making them resistant to metabolism. X/153 ratios suggest that both PB and 3-MC type cytochrome P-450 enzymes were induced in the exposed worker, as well as in the general population.

Description: Metabolism of chlorobiphenyls (CBs) was studied in harbour porpoise by comparing patterns of CB-X/CB-153 ratios in blood, brain, liver and blubber with the patterns in herring, the main food source. The CBs were classified in five groups, based on the presence/absence of vicinal H-atoms (vic. Hs) in meta,para (m,p) and/or ortho,meta (o,m) positions and the number of ortho-Cl-atoms (ortho-Cls). Plots of CB-X/CB-153 ratios in porpoise tissue vs the ratios in herring appeared to be linear for each CB group in all tissues. Slopes of these plots (metabolic slopes) were used as quantitative indicators of metabolic activity. In this way, activity of PB-type isozymes of the P450 monooxygenase system was apparent: in contrast to existing literature data, harbour porpoise appears to be able to metabolize congeners with m,p vic. Hs, even in the presence of more than 2 ortho-Cls. The presence of 3-MC-type (MC-type) isozymes was also detected. The metabolic slopes were also used as basis for risk assessment. Due to their metabolism the most toxic non-ortho CBs were not present in the tissues at detectable levels. We suggest a risk assessment approach which takes this into account. It is considered to be an alternative and more reliable basis for risk assessment than the use of toxic equivalent factors. The results support the model of equilibrium distribution of CBs in harbour porpoise and the role of blood as central transport medium. The model has been developed for persistent compounds; it appears to hold for metabolizable CB congeners as well.

Description: Individual chlorinated biphenyls (CBs) and chlorinated pesticides (p,p′-DDT and metabolites, HCHs and HCB) were determined in blubber samples of 40 harbour porpoises (Phocoena phocoena) of different age and sex from the North Sea, the Baltic Sea and Greenland coastal waters. Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were analysed in a selected group of animals. ΣCB concentrations (medians) in North Sea immature specimens were similar (14.9 μg/g lipid) to those from the Baltic Sea (17.0 μg/g lipid) and exceeding those in Greenland specimens by an order of magnitude (1.3 μg/g lipid). The median concentrations (μg/g lipid) of HCB, p,p′-DDE, p,p′-DDD and γ-HCH were in the order Greenland〈North Sea〈Baltic Sea. The highest concentrations of α-HCH (0.14 μg/g lipid) were found in the Greenland population, and p,p′-DDT was detected only in this group. The North Sea and Baltic Sea populations were identified as distinctly separate on the basis of levels and compositions of these contaminants. The ecological risk associated with dioxin-like toxicity was dominated by the CB congeners 118 and 170; the PCDD/Fs were playing only a minor role.

Description: Determination of polychlorinated biphenyls (PCBs) and nonylphenols (NoPhs) in the Sea of Japan not only points out the extent of marine pollution but also helps to understand the deep sea structure of that semi-enclosed “small ocean”. Using an in-situ filtration/extraction technique, two vertical profiles (deep water and shallow coastal water) and two space-integrated surface profiles were taken. Concentrations of ∑CBs (sum of 30 individual congeners) in solution were between 0.1 and 1.2 pg dm-3 and in suspension were between 0.2 and 1.5 pg dm-3; those of ∑NoPhs in solution were 2−150 pg dm-3 and below detection limits in suspension. The concentrations of ∑CBs and nonylphenols in solution as well as the compositions of the CB mixtures in solution in the vertical profile indicates a vertical structure similar to the situation in the open ocean as suggested by Kim (Biogeochemical processes in the North Pacific; Tsunogai, S., Ed.; Japan Marine Science Foundation:  Tokyo 1996; pp 41−51). The concentrations of CBs in solution were determined primarily by characteristics of the water bodies involved, solution−suspension interactions playing only a minor role. Principal component analyses of the data revealed a relation between deep and bottom waters and surface waters of the nearby region.

Description: A PYE 2-(1-pyrenyl)ethyldimethylsilylated silica gel] column HPLC in combination with MDGC-ECD has been developed for a sensitive and selective determination of toxic mono- and non-ortho PCBs in environmental samples. This technique was applied to environmental samples such as coastal water, suspended particulate material (SPM), coastal sediment, mussels, fish, bird and marine mammal. Determination of PCB 156 along with non-ortho congeners acted as matrix-integrated quality control parameter. This hyphenated technique offers one of the most sensitive way of determining non-ortho PCBs but also reveals the immense complexity of the coelution problem which unnoticed results in over estimation of toxic PCBs in the environmental samples.

Description: Single and multidimensional GC-ECD techniques were applied to determine individual chlorobiphenyls (CBs) in solution and in suspended particles in the Baltic Sea (some data were also obtained for the adjacent German Bight in the North Sea). Large volumes (up to 1100 dm3) were analysed in transects in November 1988 and 1989 and in spring 1991. Salinity and temperature were measured continuously along the sampling tracks in all three cruises; nutrients and pH only in the latter two cruises. Concentrations of individual CBs in solution were in the sub- and low pg dm−3 range (detection limit being 0.05 pg dm−3), and of their sum between 2 and 237 pg dm−3. These concentrations are considerably lower than previously reported data. This is mainly the result of the elimination of contamination and interference problems in the sampling, clean-up and GC-ECD procedures. It may also partly reflect the reduction in the production and use of PCBs in the last decade. The highest concentrations in solution originated from local sources in the Belt Sea and the Gulf of Finland. Regional differences were found for the compositions of the CB mixtures in solution. The lowest concentrations of CBs in solution were found in areas and periods of plankton production (spring 1991), with ΣCB concentrations between 2 and 14 pg dm−3. The compositions of the CB mixtures showed regional differences in each cruise. These could be interpreted in terms of mixing between different water bodies. The classification of transects on the basis of these CB patterns agreed well with the distinction of water bodies on the basis of T-S diagrams and hydrochemical data. Concentrations of individual CBs in suspension were generally 0.1–0.5 pg dm−3, those of their sum (ΣCB) between 4 and 6 pg dm−3 during the autumn cruises. Extremely high values were found in the Belt Sea-Kattegat area in spring 1991 (up to 589 pg dm−3 for individual CBs and up to 2859 pg dm−3 for ΣCB). This probably reflects the uptake of CBs into particulates during a plankton bloom. Primary production may effectively remove CBs from the water column into the sediments. The amounts of chlorobiphenyls presently stored in the sediments of the Baltic Sea exceed the amounts in the water column by several orders of magnitude. The compositions of the CB mixtures differed considerably between solution and suspension. The relations between log K′d (apparent particle/water partition coefficient) and log Kow (octanol-water distribution coefficient) suggest the existence of (quasi-)equilibrium conditions in autumn. Deviations from this behaviour arise from biological activity in spring. The contribution of toxic congeners to the CB mixtures was dominated by the mono- and di-ortho-Cl substituted derivatives of the most toxic non-ortho-Cl CBs. The toxicity of the CB mixtures in solution was between 0.01 and 12fg dm−3 TEQs (TCDD toxic equivalents). CBs-77, -118, -105 and -156 had the largest contributions to TEQs.