Preliminary examination of contaminant loadings in farmed salmon, wild salmon and commercial salmon feed

This pilot study examined five commercial salmon feeds, four farmed salmon (one Atlantic, three chinooks) and four wild salmon (one chinook, one chum, two sockeyes) from the Pacific Coast for PCBs (112 congeners), polybrominated diphenylethers (PBDEs - 41 congeners), 25 organochlorine pesticides (OPs), 20 polycyclic aromatic hydrocarbons (PAHs), and methyl and inorganic mercury. The farmed salmon showed consistently higher levels of PCBs, PBDEs, OPs (except toxaphene) than the wild salmon. The mean concentrations in pg/g were 51,216 vs 5302 for total PCBs; 2668 vs 178 for total PBDEs; 41,796 vs 12,164 for total OPs (except toxaphene). The farmed salmon levels are likely a consequence of the elevated level of contamination found in the commercial salmon feed (mean concentrations in pg/g were 65,535 for total PCBs; 1889 for total BPDEs; 48,124 for total OPs except toxaphene). Except for a single high wild chinook value, PAHs were highest in the feed samples followed by the farmed fish and the three other wild fish. The Bio-Oregon-1996 feed of hatchery origin showed a level of PAHs ten times higher than any other feed. The genotoxic implications of such a high PAH level are considered for juvenile chinook salmon. Toxaphene and methyl mercury concentrations were not notably different between the wild and farmed salmon. There was no clear low contaminant brand of salmon feed. The human health implications of eating farmed salmon are considered from the perspective of the current WHO and Health Canada (2000) tolerable daily intake (TDI) values for PCBs. Based on a TDI of 1 pg TEQ/kg bw/day, this analysis indicated a safety concern for individuals who on a regular weekly basis consume farmed salmon produced from contaminated feed.     

Levels of dioxins in fish and fishery products on the German market

In 1995-1998 the contents of polychlorinated dibenzodioxins and dibenzofurans of 184 pooled fish samples were analysed. Sampling focused on fish and fishery products with a market share of more than 1% and covered all fishing grounds important for the supply of the German market. Investigation included 15 different fish species, shrimp, mussel and squid samples and various fishery products, typically on the German market. Generally lean fish species like cod, saithe or Alaska pollock were less contaminated on fresh weight basis than fat fish species like herring, Greenland halibut and sardine. In herring the dioxin content is related to the fishing ground. Low concentrations were found in North Sea herring, high concentrations measured in samples from the Baltic Sea. Dioxin contents in fishery products did not differ significantly from the raw fish samples. Results allow an estimation of the daily intake of dioxins and furans via fish consumption in Germany. Based on a daily fish consumption of 20 g the average intake of dioxins via fish is 6.2 pg WHO-PCDD/F-TEQs per person and day.     

Organohalogen pollutants in herring from the northern Baltic Sea: concentrations, congener profiles and explanatory factors

Organohalogen contaminants were investigated in Baltic herring caught from three catchment areas in the Baltic Sea, off the coasts of Finland. Pools of both small and large herring were analysed for polychlorinated biphenyls (PCB), dibenzo-p-dioxins, dibenzofurans, naphthalenes, camphenes (toxaphene), polybrominated diphenyl ethers and the pesticide DDT and its metabolites. PCB concentrations per fresh weight in small herring were at the same level in all catchment areas, i.e. the Bothnian Bay, the Bothnian Sea and the Gulf of Finland, revealing no hot spots and reflecting most likely long term emissions and atmospheric deposition. Differences in the levels and/or congener profiles of other contaminants between catchment areas may be explained by point sources. Similar concentrations in small and large herring in the Gulf of Finland were possibly due to their common nutrition. In the other areas, differences between small and large herring most likely reflected their different food sources.     

Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and perfluorinated alkylated substances (PFASs) in traditional seafood items from western Greenland

In this study, contamination levels were determined for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and perfluorinated alkylated substances (PFASs) in traditional Greenland seafood items, such as raw and smoked fish fillet (salmon and halibut), whale and seal meat and narwhal mattak (skin and blubber). The daily intake of PCBs, PBDEs and PFASs through traditional seafood items in Greenland was assessed. Based on the presented levels of contaminants, in combination with earlier food intake studies, suggests that the daily exposure was below the tolerable daily intake threshold for all compounds. BDE-47 was the only PBDE-congener detected in all food items, except in smoked halibut. The levels of BDE-47 varied from < LOD in smoked halibut up to 18 ng/g lw in narwhal mattak and 21 ng/g lw in whale beef. ∑PCB were lowest in smoked halibut (37 ng/g lw) and highest in narwhal mattak with 1,146 ng/g lw. Perfluorooctane sulfonate (PFOS) was the most common of the PFASs. However, ΣPFASs were below detection limits in most fish fillet samples, and varied from 2.9 ng/g ww in whale beef to 13.5 ng/g ww in seal beef. The present study shows that the exclusion from the diet of local food items such as intestines and blubber have a strong positive effect for the reduction of POPs levels in food, without a reducing the health benefits of traditional food intake considerably.     

Toxaphene levels in salmon (Salmo salar) from the Baltic Sea

Three toxaphene congeners have been determined in salmon from the Swedish coastal environment using both supercritical fluid (SFE) and the traditional liquid/liquid extractions. The levels obtained using a modifier-free SFE technique, followed by group separation on a silica gel column, were by far much lower than concentrations obtained by SFE with a modifier or liquid/liquid extraction. The mean concentrations on fresh weight basis using a liquid/liquid extraction technique were 5.87, 8.70 and 1.59 microg/kg for CHBs 26, 50 and 62, respectively. There was a plausible relationship between the various fishing sites and the toxaphene levels.     

Marine and farmed fish on the Polish market: Comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins – A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.     

Marine and farmed fish on the Polish market: comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins - A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.     

Carry-over of dietary organochlorine pesticides, PCDD/Fs, PCBs, and brominated flame retardants to Atlantic salmon (Salmo salar L.) fillets

Information on carry-over of contaminants from feed to animal food products is essential for appropriate human risk assessment of feed contaminants. The carry-over of potentially hazardous persistent organic pollutants (POPs) from feed to fillet was assessed in consumption sized Atlantic salmon (Salmo salar). Relative carry-over (defined as the fraction of a certain dietary POP retained in the fillet) was assessed in a controlled feeding trial, which provided fillet retention of dietary organochlorine pesticides (OCPs), dioxins (PCDD/Fs), polychlorinated biphenyls (PCBs), and brominated flame retardants (BFRs). Highest retention was found for OCPs, BFRs and PCBs (31-58%), and the lowest retentions were observed for PCDD/Fs congeners (10-34%). National monitoring data on commercial fish feed and farmed Atlantic salmon on the Norwegian market were used to provide commercially relevant feed-to-fillet transfer factors (calculated as fillet POP level divided by feed POP level), which ranged from 0.4 to 0.5, which is a factor 5-10 times higher than reported for terrestrial meat products. For the OCP with one of the highest relative carry-over, toxaphene, uptake and elimination kinetics were established. Model simulations that are based on the uptake and elimination kinetics gave predicted levels that were in agreement with the measured values. Application of the model to the current EU upper limit for toxaphene in feed (50 μg kg⁻¹) gave maximum fillet levels of 22 μg kg⁻¹, which exceeds the estimated permissible level (21 μg kg⁻¹) for toxaphene in fish food samples in Norway.     

Toxaphene in minke whales (Balaenoptera acutorostrata) from the North Atlantic

Toxaphene contamination of minke whales (Balaenoptera acutorostrata) from North Atlantic waters was examined for the first time. Total toxaphene and SigmaCHB (sum of 11 chlorobornanes) concentrations in blubber samples ranged from 170+/-110 and 41+/-39 ng/g lipid weight (l.w.) for female minke whales from southeastern Greenland to 5800+/-4100 and 1100+/-780 ng/g l.w. for males from the North Sea, respectively. Very large variations in toxaphene concentrations among sampling areas were observed suggesting a spatial segregation of minke whales. However, much of the apparent geographical discrimination was explained by the seasonal fluctuation of animal fat mass. Patterns of CHBs in males revealed that recalcitrant CHBs were in higher proportions in animals from the more easterly areas than in animals from the more westerly areas. This trend may be influenced by the predominance of the US, over the European, input of toxaphene to North Atlantic waters.     

Concentrations of polychlorinated dibenzo-p-dioxins and furans in fish downstream from a Ky-5 manufacturing

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in seven fish species, burbot (Lota lota), pike (Esox lucius), perch (Perca fluviatilis), pikeperch (Stizopedion lucioperca), bream (Abramis brama), salmon (Salmo salar) and Baltic herring (Clupea harengus membras) in River Kymijoki and its estuary polluted by Ky-5 manufacturing. The fish were caught at 14 localities along the river and its estuary. The selected species represent different trophic levels and/or inhabit different environments. The concentrations of PCDD/Fs were low, in most samples below 1 pg g(-1) ITEQ (NATO/CCMS 1988) fresh weight (fw) in muscle, except salmon and Baltic herring. These two species graze at the open sea and consequently accumulate contaminants at a large area in the Baltic Sea. The lipid content in salmon and Baltic herring was an order of magnitude higher than in other species. PCDD/Fs in fish muscle showed only slightly elevated levels in the Kymijoki area and its estuary as compared to the levels in the same species in Finnish freshwaters and sea areas. The concentration of the main impurities of the fungicide Ky-5 was higher in the Kymijoki River downstream the Ky-5 manufacturing place compared to the up-stream locations. The PCDD/F concentrations in fish liver and spawn were 10-100 times higher than the concentration in muscle, because of the much higher lipid concentrations of these organes. Consequently, the tolerable daily intake values could be as much as 100 times smaller (M. Korhonen, M. Verta, T. Vartiainen, Organohalog. Comp. 32 (1997) 305-310; P. Mikkelson, J. Paasivirta, H. Kiviranta, Organohalog. Comp. 39 (1998) 59-62).     

A gas chromatography/high-resolution mass spectrometry (GC/HRMS) method for determination of polybrominated diphenyl ethers in fish

A method for the determination of polybrominated diphenyl ethers (PBDEs) in biota for routine analysis is described. The mass spectroscopic (MS) evaluation of 23 brominated diphenyl ethers, under electron ionization and electron capture negative ion conditions using magnetic sector and quadrupole mass spectrometers, showed that high-resolution mass spectrometry (HRMS) under electron ionization conditions was the most reliable technique, with high selectivity and adequate sensitivity. The instrument detection limit for this method ranged for individual congeners between 4.8 and 0.1 pg for 3-bromodiphenyl ether (BDE-2) and 2,3',4,4'-tetrabromodiphenyl ether (BDE-66), respectively, and method detection limit for each homologue group ranged between 5 pg/g for salmon certified reference material (CRM) and 93 pg/g for lake trout CRM. The effectiveness of this method was evaluated by analyzing the occurrence of PBDEs in commercially available CRMs comprising Lake Ontario lake trout, Pacific herring, and sockeye salmon. The average coefficients of variation for the replicate analyses of PDBEs in several tissue samples were: 25% for lake trout, 36% for Pacific herring, and 34% for sockeye salmon. The average deviations in the inter-laboratory study were: 14% for lake trout, 15% for Pacific herring, and 37% for sockeye salmon. Results indicated that the described method, based on gas chromatography/high-resolution mass spectrometry, is reliable for determining PBDE concentrations in biological tissues.     

Polybrominated diphenyl ethers (PBDEs) in farmed and wild salmon marketed in the Northeastern United States

Recently, we reported on the analysis of polychlorinated biphenyls (PCBs) and chlorinated pesticides in farmed Atlantic salmon (Salmo salar) from Maine, eastern Canada, and Norway, and wild Alaskan Chinook salmon (Oncorhynchus tshawytscha). In this paper, we extend the analysis to polybrominated diphenyl ethers (PBDEs) in these samples. Total PBDE concentrations in the farmed salmon (0.4-1.4ng/g, wet weight, ww) were not significantly different from those in the wild Alaskan Chinook samples (0.4-1.2ng/g, ww), nor were significant differences found among regions. However, significant intra-regional variations in concentrations of total PBDEs and tetra-BDE 47 were observed in the salmon from the Canadian farms (p<0.01). Congener profiles were dominated by BDE-47, followed by the penta-BDEs 99 and 100. PBDE concentrations in the Canadian samples were lower than those reported two years earlier. Removal of skin resulted in no overall reduction in PBDE concentrations in our farmed salmon, and in some cases, PBDE concentrations were higher in skin-off samples. PBDEs were correlated with lipids only in the skinned samples, suggesting that there is greater accumulation and retention of PBDEs in muscle lipids than in skin-associated fat. In skin-on samples, modest correlations were observed between concentrations of PBDEs and PCBs (R(2)=0.47) and mono-ortho PCBs (R(2)=0.50), whereas PBDEs were not correlated with non-ortho PCBs.     

Analysis of six relevant toxaphene congeners in biological samples using ion trap MS/MS

Farmed and wild Scottish Atlantic salmon were obtained from retail suppliers, producers, and Stirling University in Scotland during January, 1999, for determination of 17 2,3,7,8-C1-substituted PCDDs and PCDFs, and seven nonortho- and mono-ortho-PCBs. The study confirms previous reports of relatively high concentrations of PCDDs, PCDFs and, especially, PCBs in farmed Scottish salmon. The results indicate that high consumption of salmon, particularly by children under 5 years, could lead to intakes above the tolerable daily intake (TDI) and tolerable weekly intake (TWI) for these chemicals, especially the PCBs, when combined with mean or high level intakes from the typical UK diet. These results suggest further investigation of farmed salmon and salmon feed, including feed fortified with fish oil and feed fortified with selected vegetable oils, is warranted.     

Can seal eating explain elevated levels of PCBs and organochlorine pesticides in walrus blubber from eastern Hudson Bay (Canada)?

Walrus (Odobenus rosmarus) blubber samples from Inukjuak and Akulivik (East Hudson Bay), Foxe Basin (Igloolik and Hall Beach) and Loks Land (East Baffin Island) were analysed for PCB congeners (ortho and non-ortho substituted) and other persistent organochlorines (DDT, toxaphene, chlordanes, dieldrin, mirex), as well as chlorinated dioxins/furans, to document spatial trends in contaminants in Canadian Arctic marine biota. Samples from 19 of 53 individuals had concentrations of SigmaPCBs greater than 1000 ng g(-1) (wet wt); the remaining individuals had much lower concentrations (50-600 ng g(-1)). Highest concentrations were found in samples from Inukjuak where average concentrations in blubber of females (N = 9) were 1450 +/- 954 ng g(-1) toxaphene, 2750 +/- 1780 ng g(-1) SigmaCHLOR, 2160 +/- 925 ng g(-1) SigmaDDT and 4790 +/- 2380 ng g(-1) SigmaPCB. SigmaPCB and SigmaDDT concentrations greater than 1000 ng g(-1) were unexpected based on previous studies of walrus from Greenland and Alaska. Local contamination was ruled out because levels of all organochlorines were elevated in each animal from Inukjuak, and elevated levels were also found in animals from Akulivik and Loks Land. Walrus from Inukjuak had sigma13C and sigma15N values in muscle intermediate between those of ringed seals (Phoca hispida) and those of walrus from Akulivik with low organochlorine levels. There was a weak but significant correlation between and sigma15N and (log)SigmaPCB. The Inukjuak walrus also had higher proportions of highly chlorinated PCB congeners, and higher DDE/SigmaDDT ratios than walrus from Igloolik or Akulivik. The results suggest that the walrus with elevated organochlorines are feeding at a higher trophic level than those with low levels and are probably utilizing ringed seals for a portion of their diet.     

Seasonal variation in the levels of organohalogen compounds in herring (Clupea harengus) from the Norwegian Sea

The Norwegian spring spawning (NSS) herring is an ecologically important fish stock in the Norwegian Sea, and with a catch volume exceeding one million tons a year it is also economically important and a valuable food source. In order to provide a baseline of the levels of contaminants in this fish stock, the levels of organohalogen compounds were determined in 800 individual herring sampled at 29 positions in the Norwegian Sea and off the coast of Norway. Due to seasonal migration, the herring were sampled where they were located during the different seasons. Concentrations of dioxins and dioxin-like PCBs, non-dioxin-like PCBs (PCB₇) and PBDEs were determined in fillet samples of individual herring, and found to be relatively low, with means (min-max) of 0.77 (0.24-3.5) ng TEQ kg⁻¹ wet weight (ww), 5.0 (1.4-24) μg kg⁻¹ ww and 0.47 (0.091-3.1) μg kg⁻¹ ww, respectively. The concentrations varied throughout the year due to the feeding- and spawning cycle: Starved, pre-spawning herring caught off the Norwegian coast in January-February had the highest levels and those caught in the Norwegian Sea in April-June, after further starvation and spawning, had the lowest levels. These results show that the concentrations of organohalogen compounds in NSS herring are relatively low and closely tied to their physiological condition, and that in the future regular monitoring of NSS herring should be made in the spawning areas off the Norwegian coast in late winter.     

Investigation of PCDD/Fs and dl-PCBs in fish from the southern Baltic Sea during the 2002–2006 period

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in the southern Baltic herring (Clupea harengus), sprat (Sprattus sprattus), and salmon (Salmo salar) are reported.The significant interspecies and season-specific differences in PCDD/Fs and dl-PCBs concentrations were observed. The contribution of dl-PCBs to the total toxicity equivalents (TEQs) ranged between 50% and 70%, dependently on fish species. In all samples, concentrations of PCDF were higher in comparison with that of PCDD.The permissible limits of the content of PCDD/Fs and dl-PCBs (8 pg g⁻¹ fresh weight for the sum of PCDD/Fs and dl-PCBs, and 4 pg g⁻¹ fresh weight for the PCDD/Fs) were exceeded mainly in salmon samples (in 80% of salmon samples studied). The elevated levels of PCDD/F and dl-PCB were observed only in two of seventy two herring samples, and in ten of 62 sprat samples.The multiple regression analysis revealed that fish lipid content, and concentration of PCB 153, used simultaneously, might be useful in the prediction of TEQ values of fish samples. These two variables explained more than 80% of total variance. For all fish species studied, the correlation coefficients obtained with the multiple regression analysis were higher than that obtained with the regression analysis involving total TEQ values, and only one independent variable: fish lipid content.     

Toxaphene congeners in the Canadian Great Lakes basin: temporal and spatial food web dynamics

Samples of a top predator fish species, lake trout (Salvelinus namaycush) and predominant forage species including smelt (Osmerus mordax), alewife (Alosa pseudoharengus), slimy sculpin (Cottus cognatus), deepwater sculpin (Myoxocephalus quadricornis) and lake herring (Coregonus artedii) were, collected from throughout 4 of the 5 Great Lakes (Superior, Huron, Erie and Ontario) (Fig. 1). Lake trout were also collected from three isolated lake systems (Lakes Nipigon, Simcoe and Opeongo), all located within the basin. All the samples were analysed for body burdens of total toxaphene and 22 toxaphene congeners. In addition, from each of the Great Lakes sites samples of major invertebrate dietary items, which included Mysis relicta, Diporeia hoyi and plankton, were similarly analysed. Whole lake trout samples, archived at -80 degrees C, were reanalysed to determine historical trends of toxaphene congeners plus carbon and nitrogen stable isotope signatures. The Lake Superior food web consistently had the highest levels of total toxaphene of all the Great Lakes monitored. The primary source of toxaphene to Lake Superior has been identified as atmospheric transport and deposition from sites in the southern US, Mexico and Central America (Hoff, R.M., Strachan, W.M.J., Sweet, C.W., Chan, C.H., Shackelton, M., Bidleman, T.F., Brice, K.A., Burnison, D.A., Cussion, S., Gatz, D.F., Harlin, K., Schroeder, W.H., 1996. Atmospheric deposition of toxic chemicals to the Great Lakes: A review of data through 1994. Atmospheric Environ. 30, 3505-3527). Of the offsystem lakes surveyed. Lake Nipigon, situated due north of Lake Superior and with a Lake Basin area of about 6% of Lake Superior (Hendendorf, C.E., 1982. J. Great Lakes Res. 8(3), 379-412) had total toxaphene levels in lake trout equivalent to about 50% of those found in lake trout from Lake Superior. Temporal trend toxaphene congener analysis was conducted on archived whole fish samples collected over the period 1980 through to the 1990's. Initially a nonachlorobornane congener (Parlar #50) was predominant, with congeners #40, #62 and #21 being the next most prominent in the 1980 samples. Samples from the 1990's showed a significant decline in the presence of lower chlorinated congeners #40 and #21. Analysis of total toxaphene in food webs, indicated elevated levels in lower trophic level species such as Diporeia and Cottus sp. which have a benthic association. The stable isotope temporal trend 13C signature identified a significant shift in the lake trout diet over the period 1993 to 1996.     

Airborne concentrations of toxaphene congeners at Point Petre (Ontario) using gas-chromatography-electron capture negative ion mass spectrometry (GC-ECNIMS).

A reliable analytical method has been developed using GC-ECNIMS for the determination of individual toxaphene congeners in ambient air. To allow a reasonable comparison with previous data for toxaphene reported by Muir and co-workers using GC-ECD, this method has adopted their approach of focussing upon the identification and quantification of specific peaks or clusters ("T" species) typically observed in environmental samples, with the sum of these "T" species then being reported as "total toxaphene". Technical toxaphene has been used as the analytical standard, but independent response factors have been assigned to the target peaks and clusters. Because of the appreciable variability in ECNIMS response shown by individual toxaphene congeners, this is considered to be a reasonable and potentially more accurate procedure than the application of a "single response factor" used by many other workers. The methodology has been used for the determination of toxaphene in air samples collected over the annual cycle in 1992 and then from October 1995 to September 1997 at Point Petre, Ontario. Of the forty-four calibrated components, only 10 were detected in all of the air samples collected over the latter 2-year period. Airborne concentrations of toxaphene (defined as the sum of the calibrated components) range from 0.9 pg/m3 to 10.1 pg/m3. A clear seasonality has been observed, with a summer-to-winter concentration ratio of about 6.     

Levels of toxaphene congeners in fish from Danish waters

The levels of toxaphene congeners, in addition to PCB congeners and organochlorine pesticides, were determined in various fish samples from different Danish waters. While PCB-153 and p,p'-DDE show different levels depending on the fishing area, with highest levels in fish from the Western Baltic Sea, toxaphene was detected in all the samples investigated at a more constant level. The distribution of the three toxaphene congeners Parlar #26, #50 and #62 depends on the fishing area, with the Western Baltic Sea being different from the other waters by having almost equal levels of toxaphene congeners #26 and #50.     

PCDD/Fs and PCBs in Baltic herring during the 1990s

Baltic herring samples caught from the Baltic Sea during the spring periods of 1993-1994 and 1999 were analysed for polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and polychlorinated biphenyls (PCB). For analyses, 1570 individual herring were combined to 120 pools. Correlations between concentrations of congeners 1,2,3,7,8-PeCDD, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, and 2,3,4,6,7,8-HxCDF, and age of herring were the strongest (r>0.8) followed by correlations between PCB congeners PCB 105, 118, 126, 156, 169 and 180 (r>0.7), and age of herring. Due to higher fat percentage in herring in the Gulf of Bothnia the concentrations of PCDD/Fs and PCBs on fresh weight (fw) basis were higher than in herring in the Gulf of Finland. The concentrations of WHO(PCDD/F)-TEQs ranged from 1 to 27 pg/g fw, depending on the age and catchment area of herring, and concentrations of WHO(PCB)-TEQs reached 32 pg/g fw. Between the two studied time points no clear downward trend in concentrations was observed.