Organochlorine pesticides and polychlorinated biphenyl congeners in wild terrestrial mammals and birds from Chubu region, Japan: Interspecies comparison of the residue levels and compositions

In order to understand the residue levels of organochlorine compounds (OCs) and their accumulation patterns in wildlife inhabiting Chubu region, Japan, the concentrations of polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), DDT compounds (DDTs) and hexachlorobenzene (HCB) were measured in 8 species of terrestrial mammals and 10 species of birds. In view of feeding habits, the contamination levels of OCs were found to be higher in omnivorous mammals than in herbivorous ones, and in fish-eating ones and raptores than in omnivorous birds. In fox and dog, PCB-180 (2, 2′, 3, 4, 4′, 5, 5′-heptachlorobiphenyl) was the most dominant PCB congener, while in the other species PCB-153 (2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl) was the most persistent. The ratios of lower chlorinated PCB congeners (tri- to tetra-) to total PCBs were larger in fish-eating birds than in the other birds. The results indicate that the compositions of PCB congeners would reflect the differences of feeding habits and xenobiotic metabolizing systems among each species.     

Olive tree, Olea europaea L., leaves as a bioindicator of atmospheric PCB contamination

Olive tree leaf samples were collected to investigate their possible use for biomonitoring of lipophilic toxic substances. The samples were analyzed for 28 polychlorinated biphenyls (PCB) congeners. Twelve congeners were detected in the samples. PCB-60, 77, 81, 89, 105, 114, and 153 were the most frequently detected congeners ranging from 32 % for PCB-52 to 97 % for PCB-81. Σ₁₂PCBs concentration varied from below detection limit to 248 ng/g wet weight in the sampling area, while the mean congener concentrations ranged from 0.06 ng/g (PCB-128?+?167) to 64.2 ng/g wet weight (PCB-60). Constructed concentration maps showed that olive tree leaves can be employed for the estimation of spatial distrubution of these congeners.     

Concentration levels and congener profiles of polychlorinated biphenyls, pentachlorobenzene, and hexachlorobenzene in commercial pigments

The concentration levels and congener profiles of polychlorinated biphenyls (PCBs), pentachlorobenzene (PeCBz), and hexachlorobenzene (HxCBz) were assessed in commercially available organic pigments. Among the azo-type pigments tested, PCB-11, which is synthesized from 3,3′-dichlorobendizine, and PCB-52, which is synthesized from 2,2′,5,5′-tetrachlorobendizine, were the major congeners detected. It is speculated that these were byproducts of chlorobendizine, which has a very similar structure. The total PCB concentrations in this type of pigment ranged from 0.0070 to 740 mg/kg. Among the phthalocyanine-type pigments, highly chlorinated PCBs, mainly composed of PCB-209, PeCBz, and HxCBz were detected. Their concentration levels ranged from 0.011 to 2.5 mg/kg, 0.0035 to 8.4 mg/kg, and 0.027 to 75 mg/kg, respectively. It is suggested that PeCBz and HxCBz were formed as byproducts and converted into PCBs at the time of synthesizing the phthalocyanine green. For the polycyclic-type pigments that were assessed, a distinctive PCB congener profile was detected that suggested an impact of their raw materials and the organic solvent used in the pigment synthesis. PCB pollution from PCB-11, PCB-52, and PCB-209 pigments is of particular concern; therefore, the monthly variations in atmospheric concentrations of these pollutants were measured in an urban area (Sapporo city) and an industrial area (Muroran city). The study detected a certain level of PCB-11, which is not included in PCB technical mixtures, and revealed continuing PCB pollution originating from pigments in the ambient air.     

PCBs in the eggs of Eurasian kestrels indicate exposure to local pollution

Fail-to-hatch kestrel (Falco tinnunculus) eggs collected at the end of the 1999 and 2005 breeding seasons from nest boxes in and around the city of Rome, Italy, were analyzed by gas chromatography with electron capture detection for their PCB content and for the presence of DDT derivatives and other organochlorines. Among the various PCBs, congeners 153 and 180 were detected in all the eggs and showed the highest concentrations. Eggs collected from the same nest from a polluted location in Rome during 2 different years showed similar type and number of PCB congeners. These data and the fact that eggs from another nest near a sulphate mine had, atypically, low-chlorinated congeners support the conclusion that eggs of this species, whose adults in the Mediterranean and continental Europe perform only short or no migration movements, might be indicative of local pollution. When multiple eggs in the same clutch were analyzed, the PCBs were similar in type but their concentration decreased within clutch, likely in parallel to the laying order.     

Polychlorinated biphenyls (PCBs) in indoor air and in serum among older residents of upper Hudson River communities

A study was conducted to evaluate the association between PCBs in residential indoor air and in the serum of older, long time residents of three upper Hudson River communities. Samples of indoor air and of serum were collected from 170 persons 55 to 74 years of age, and analyzed for PCBs using glass capillary gas chromatography. After adjusting for age, BMI, cigarette smoking, and Hudson River fish consumption with multiple linear regression analysis, the results indicated statistically significant associations between concentrations in indoor air and serum for PCB-28, a lightly chlorinated congener common in air that accumulates in serum, and PCB-105. Duration of exposure was an important factor, since among persons who had lived in their home for 39 years or more, 11 of the 12 most commonly detected congeners were significantly correlated, as was their sum (∑ PCB). Significant associations between indoor air and serum PCB concentrations also were more likely when collected in cooler months and if the two samples were collected within 20 d of each other. The study is among the first to indicate that PCB concentrations characteristic of residential indoor air are associated with a detectable increase in body burden.     

Congener-specific egg contribution of polychlorinated biphenyls to nestlings in two passerine species

Quantifying polychlorinated biphenyl (PCB) residues in nestlings of avian species is a common method for assessing trophic transfer and risk at PCB-contaminated sites. The proportion of nestling PCB mass due to maternal transfer is often accounted for by subtracting total PCB mass in eggs from nestlings. However, variation in physicochemical properties and metabolism among congeners may lead to differences between egg contribution based on total PCBs and dioxin-like congeners. We examined congener-specific variation in contribution of PCBs from eggs to nestlings in tree swallows and European starlings. Egg contribution of total PCB mass was 14.3 and 16.2%, respectively, whereas contribution based on dioxin-like congeners was 14.8 and 13.6%, respectively. These data suggest that using total PCB mass in eggs to adjust estimates of PCB accumulation in nestlings may not reflect patterns for dioxin-like congeners, potentially over or under-estimating the risk of toxicity of PCBs.     

Trends of PCDD/F and PCB concentrations and depositions in ambient air in Northwestern Germany

Time series of polychlorinated dioxins and furans (PCDD/F) and polychlorinated biphenyls (PCB) in ambient air of a large conurbation in North-Western Germany are presented and analyzed. The trend of PCDD/F concentrations, starting from as early as 1988, shows a pronounced decrease by at least one order of magnitude, demonstrating that the emission reductions were effective. The PCDD/F depositions also have decreased by a factor of 5 since 1992. However, both trends have leveled out since 2005. Time series of PCB concentrations and depositions starting in 1994 show only slight decreases for the concentrations and almost no decrease for the depositions. From the decay rates following first order kinetics, half-lives in the order of 5-15 years for the PCDD/F and 15-31 years for the sum of the six indicator PCB could be calculated, which are much longer than the half-lives estimated from their reactivity towards the OH radical. Apparently, small fresh emissions (PCDD/F), considerable secondary emissions and evaporation from contaminated soils slow down their decay in the atmosphere of big conurbations. Analyzing the decay rates of individual PCB congeners shows that the lower chlorinated and more volatile ones are removed faster than the higher chlorinated congeners, probably via gas phase reactions with the OH radical. It can be concluded from the present study that the input of PCDD/F and PCB into the food chain via the air path will continue for another one or two decades in big conurbations.     

Long-term trends of continental-scale PCB patterns studied using a global atmosphere–ocean general circulation model

Continental-scale distribution and inter-continental transport of four polychlorinated biphenyl (PCB) congeners (28, 101, 153, 180) from 1950 to 2010 were studied using the global multicompartment chemistry transport model MPI-MCTM. Following identical primary emissions for all PCB congeners into air, most of the burden is stored in terrestrial (soil and vegetation) compartments. Thereby, PCB-28, PCB-101 and PCB-153 show a shift of the soil burden maxima from source to remote regions. This shift is downwind with regard to the westerlies for Eurasia and upwind for North America and more prominent for the lighter PCBs than for PCB-153 or PCB-180. In meridional direction, all congeners' distributions underwent a northward migration in Eurasia and North America since the 1950s. Inter-continental transport from Eurasian sources accounts largely for contamination of Alaska and British Columbia and determines the migration of the PCB distribution in soil in North America. Trans-Pacific transport occurs mainly in the gas phase in boreal winter (December-January-February) at 3-4 km altitude and is on a multi-year time scale strongly linked to the atmospheric pressure systems over the Pacific. Inter-continental transport of the lighter, more volatile PCBs is more efficient than for the heavier PCBs.     

Chlorinated persistent organic pollutants in black-tailed gulls (Larus crassirostris) from Hokkaido, Japan

Concentrations and patterns of several chlorinated persistent organic pollutants (POPs) including polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) and DDTs, HCHs, CHLs and HCB were determined in black-tailed gulls (Larus crassirostris) from breeding grounds in Hokkaido, Japan. Subcutaneous fat of five adult gulls was analyzed, which had different concentrations of target compounds, whereas gull eggs contained similar concentrations of target compounds. Similar congener profiles were found between adult gulls and eggs. The concentrations of non-ortho PCBs varied from 3.4 to 13.5 ng/g lipid weight (lw) in the fat of black-tailed gulls and from 2.4 to 7.4 ng/g lw in their eggs. 2,3,7,8-PCDD/Fs occurred at relatively lower concentrations than non-ortho PCB congeners in both adult gulls and eggs. The total TEQs (toxic equivalents, PCDD/Fs+ non-ortho PCB) ranged from 0.26 to 1.0 ng/g lw in adult gulls and ranged from 0.19 to 0.58 ng/g lw in eggs.     

Bioaccumulation of PCBs in Arctic seabirds: influence of dietary exposure and congener biotransformation

Four seabird species and their prey (zooplankton or fish) were collected in the Barents Sea to determine how dietary exposure, cytochrome P450 (CYP) enzyme activities and sex influenced their hepatic PCB concentrations and accumulation patterns. Five males and five females from each seabird species (little auk (Alle alle), Brunnich's guillemot (Uria lomvia), black guillemot (Cepphus grylle) and black-legged kittiwake (Rissa tridactyla)) were analysed. PCB concentrations could not be explained directly by carbon source (delta13C) or trophic position (delta15N), but by a combination of dietary parameters (delta13C, delta15N, migratory pattern, age) and contaminant metabolism. Contrary to previous studies, the PCB pattern differed among seabirds, with a higher proportion of persistent congeners (% of PCB-153, RPCB-153) in black-legged kittiwake than in auks. The PCB pattern also differed among auks, with little auk as the most efficient biotransformer (highest RPCB-153 values of persistent congeners). Based on high RPCB-153 values, Brunnich's guillemot poorly metabolised ortho-meta-unsubstituted congeners, whereas black guillemot poorly metabolised meta-para unsubstituted congeners. Species-specific differences in PCB biotransformation were confirmed by metabolic indices, where PCB patterns in seabirds were adjusted for PCB pattern in prey. The relative contribution of ortho-meta-unsubstituted congeners to SigmaPCBs decreased with increasing EROD activity. There were no differences in PCB concentrations, PCB patterns or cytochrome P450 enzyme activities between males and females. CYP P450 activities (CYP1A- and CYP2B/3A-like: EROD and testosterone 6beta-hydroxylation, respectively) were low and did not correlate with concentrations of non- or mono-ortho Cl-substituted PCBs (NO- and MO-PCBs), or with total toxic equivalent concentrations (TEQs) for dioxin-like effects of NO- and MO-PCBs.     

Comparison of seven indicator PCBs and three coplanar PCBs in beef, pork, and chicken fat

The risk assessment of polychlorinated biphenyls (PCBs) is difficult since complex congeners were used in many industrial applications for a long period of time and the residue monitoring in foods of animal origin and the environment were not established in comparable systems. The relationships of determined concentrations in indicator PCB congeners (mono- and di-ortho PCBs) and coplanar PCB congeners (non-ortho PCBs) in livestock products are presented in this study. The concentrations of seven indicator PCBs were compared with three coplanar PCBs in beef, pork, and chicken fat. Distributions of concentration for the indicator PCBs in three different animal species were similar except for that of PCB-118 (2,3',4,4',5-pentachlorobiphenyl) in pork fat. The congeners with the highest concentration were PCB-138 (2,2',3,4,4',5'-hexachlorobiphenyl) in beef and pork fat and PCB-28 (2,4,4'-trichlorobiphenyl) in chicken fat. The bioaccumulation and metabolism of PCBs in animal species represent different congener profiles in livestock products. The percentage of the total concentration of three coplanar PCBs was about 2% of the total concentration of the seven indicator PCBs. Relatively high concentration of mono-ortho and di-ortho PCBs in fat samples of livestock products may be calculated with the concentration of coplanar PCBs that can be usually determined on a sequential procedure with dioxin analysis. Therefore, the relationship of the amounts between seven indicator PCBs and three coplanar PCBs may be useful to derive the composition and level of contaminants in beef, pork, and chicken.     

Concentrations of organochlorine pesticides and polychlorinated biphenyls in human serum and their relation with age,gender, and BMI for the general population of Bizerte,Tunisia

Human serum samples (n?=?113) from Bizerte, northern Tunisia, collected between 2011 and 2012 were analyzed for 8 organochlorine pesticides (OCPs) including p,p′-dichlorodiphenyltrichloroethane (DDT) and its metabolites, hexachlorobenzene (HCB), hexachlorocyclohexane isomers, dieldrin, and heptachlor and 12 polychlorinated biphenyls (PCBs) congeners. Concentrations of these residues in serum were determined by gas chromatography with electron capture detector and total cholesterol (CHOL) and triglycerides (TG) levels were evaluated by enzymatic colorimetric method. HCB, p,p′-DDE, PCB-138, PCB-153, and PCB-180, were the most abundant organochlorine compounds (OCs) detected in >95 % of the study subjects. The mean levels of p,p′-DDE and HCB in serum were 168.8 and 49.1 ng?g^?1 lipid, respectively. The sum PCBs concentrations ranged from 37.5 to 284.6 ng?g^?1 lipid in the samples, with mean and median value of 136.1 and 123.2 ng?g^?1 lipid, respectively. The PCB profile consisted of persistent congeners, such as PCB-138, PCB-153, and PCB-180 which contributed for approximately 82.7 % to the ∑PCBs. Statistical analysis showed that most OCs correlated significantly with age, considering all samples together or with gender differentiation. The present study shows that the levels of p,p′-DDE and ∑DDTs were significantly higher in females than in males (p?<?0.05), while PCBs levels were significantly higher in male (p?<?0.05) than in females. No statistically significant association was found between body mass index and concentration of any organochlorine pesticide or PCB congeners 153, 138, 180, or ∑PCBs.     

Some heavy metals, essential elements, and chlorinated hydrocarbons in polar bear (Ursus maritimus) at Svalbard

During the period 1978-1989, samples of liver, kidney and subcutaneous fat from 24 polar bears, Ursus maritimus, from Svalbard were analysed for mercury, cadmium, lead, copper, zinc, selenium, arsenic, HCB, DDE, PCBs (as Aroclor 1260 or Phenoclor DP6). In a selected number of liver (seven) and fat (three) samples, the composition of individual PCB congeners was studied by comparison with 23 individual PCB congeners (IUPAC nos 28, 52, 74, 101, 99, 110, 149, 118, 114, 105, 153, 141, 138, 187, 128, 183, 156, 157, 180, 170, 194, 206 and 209). In the seven liver samples, the concentrations of o,p'- and p,p'-isomers of DDT, TDE, DDE, alpha-, beta- and gamma-HCH, oxychlordane, heptachlor, heptachlorepoxide, aldrin and dieldrin were also determined. The hepatic concentrations of mercury, cadmium and lead in animals of all ages were 0.4-6.0, <0.1-1.2, and <0.5-1.6 microg g(-1), respectively. This indicates a moderate exposure. Concentrations of mercury and selenium were correlated (r=0.80). The levels of copper and zinc represented normal physiological concentrations. The concentrations of HCB, DDE and PCBs in fat were <0.05-1.5, <0.1-3.4 and 2.9-90 microg g(-1), respectively. The corresponding results for liver were <0.01-0.11, <0.1-0.5 and 0.1-78 microg g(-1), respectively. Six PCB congeners, PCB-99, -153, -138, -180, -170, and, -194 accounted for about 99 and 87% of the total PCB content (sum of the 12 congeners, nos. 28, 99, 153, 138, 128 + 187, 156, 157, 180, 170, 194, 206 and 209) in liver and fat, respectively. PCB-153 represented 37+/-3 30+/-16% of the sum PCB (sum of 12 congeners) in liver and fat, respectively. The range of the hepatic concentration of oxychlordane was 5-19 microg g(-1). Quantifiable concentrations of heptachlor, heptachlorepoxide, beta-HCH and dieldrin were also found in all the liver samples analysed. Low concentrations of p,p'- and o,p'-DDT were found in two of seven liver and two of two fat samples. Comparisons are made with investigations from Canada and Greenland. Possible effects of PCBs, especially on reproduction, cannot be excluded. Ringed seal, Foca hispida, and to some extent bearded seal, Erignathus barbatus, are the main food of the polar bear. It is therefore likely that the exposure to environmental pollutants occurs via the consumption of these two species.     

Levels,distribution profile,and risk assessment of polychlorinated biphenyls (PCBs) in water and sediment from two tributaries of the River Chenab,Pakistan

The first study aimed to investigate the polychlorinated biphenyl (PCB) concentration level, spatial distribution pattern, and ecological risk assessment of water and sediment samples from two tributaries (Nullah Aik and Palkhu) of the River Chenab, Punjab Province, Pakistan. A total of 32 PCB congeners were analyzed, and PCB concentration in sediment and water samples ranged between 0.80 and 60 ng/g and 0.20 and 28 ng/L, respectively, where tetra-CBs and tri-CBs dominated over other studied PCB homologs. Dioxin toxicity equivalency (TEQ) was calculated and PCB-126 and PCB-169 showed the higher TEQ values compared with the WHO guidelines, and sediment samples were more toxic than the water samples. The results of the present study should be considered seriously by government authorities to take a proper action against unchecked discharge of contaminants in ecological integrities; otherwise, there may be drastic results in the near future.     

Airborne PCB as a contamination risk on freeze-drying of sediment

In a study of polychlorinated biphenyls (PCB) in freeze-dried sediments from Swedish lakes, the samples were found to contain unexpectedly high concentrations of PCBs. In one of the lakes (Bj?rken), e.g. the concentration of PCB-28 was found to be 189 ng/g dw after freeze-drying compared to 7 ng/g dw after air-drying of the sediment and therefore our hypothesis was that the contamination had occurred during the freeze-drying procedure. Hence, a dry reference sediment (RS) was used in order to identify potential sources of PCB contamination. The investigation included freeze-drying of the dry RS in five different laboratories, exposure to the air in the freeze-drying room, storage at room temperature and air-drying in a certain fume hood and in a laminar flow clean bench. The pattern and concentrations of PCBs detected in the exposed RS were strongly influenced by low chlorinated PCB congeners under all of these conditions with exception for air-drying in the fume hood. Storage in the laboratory air resulted in a slight elevation in the concentrations of low chlorinated PCB congeners, whereas higher concentrations of all PCB congeners were observed after freeze-drying. In all experiments the contamination appeared to be due to adsorption of PCB from the laboratory air. On the basis of these findings we recommend that reference material be subjected to the entire procedure, including sample preparation, in order to monitor contamination and that a procedure involving solvent extraction of wet sediment samples is used, whenever possible, instead of procedures involving dry samples.     

Effects of point-source PCB contamination on breeding performance and post-fledging survival in the dipper Cinclus cinclus

Despite widespread information on the incidence and biochemical effects of polychlorinated biphenyls (PCBs) in birds, field studies of effects on population processes are still scarce. This is particularly so in passerines. We therefore assessed breeding performance and post-fledging survival in dippers, Cinclus cinclus, breeding along the Afon Mule, a Welsh river where previous work indicated locally elevated PCB concentrations. We hypothesised that marked toxicological effects, including endocrine disruption, would be detectable as altered clutch-size, hatching success, nest success, brood-size, post-fledging survival or recruitment to the breeding population. Congener-specific analysis of PCBs in failed and deserted dipper eggs during 1990-93 revealed that geometric mean concentrations were four to 20 times higher along the Mule than elsewhere in Wales, UK. PCB signatures also varied highly significantly from other locations, with congeners 138, 153 and 180 dominant at the contaminated site, but 118 or 170 more frequent in eggs elsewhere. Subsequent analysis of surface runoff confirmed a small breaker's yard as a point source. Neither laying dates, clutch-sizes, brood-sizes, nest failure nor hatching failure along the contaminated Mule (n=46 breeding attempts and 218 eggs) differed significantly from dippers along adjacent reference rivers (n=82 breeding attempts and 315 eggs) or Welsh rivers as a whole (n=332 breeding attempts and 1534 eggs). Subsequent recaptures of breeding dippers ringed initially as nestlings were nearly identical between the Mule (7.7% of 182 nestlings), the reference set (7.5% of 323 nestlings) and all other Welsh rivers (7.3% of 2821 nestlings). These data illustrate the value of congener-specific analysis of bird's eggs in indicating local PCB sources. The data show also that PCBs can occur in dipper eggs at total concentrations of 0.49 (geometric mean)-1.29 (upper quartile) microg g(-1) wet mass without effects on breeding performance and survival. These values are below those at which biochemical or reproductive effects on other passerines have been detected, but above current concentrations in any other population of European dippers for which PCB data are available. Population effects by PCBs on European dippers are therefore unlikely. Survivors from locally contaminated sites like that in our study might allow field assessments of second-generation effects on breeding performance in wild birds that have developed under PCB exposure.     

Reproductive success and chlorinated hydrocarbon contamination of resident great blue herons (Ardea herodias) from coastal British Columbia,Canada, 1977 to 2000

Over the period 1977-2000, eggs of Pacific great blue heron (Ardea herodias fannini) were collected from 23 colonies along the southern coast of British Columbia, Canada, and analyzed for persistent organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs). Concentrations of OC pesticides in eggs declined sharply in the late 1970s, after which there were minimal changes. The sums of PCB congeners were not reduced appreciably during the 1980s and 1990s, but Aroclor 1260 concentrations suggested a sharp decline in PCB contamination of eggs in the late 1970s, similar to that shown for OC pesticides. Eggs collected along or near the Fraser River delta showed higher levels of most pesticides compared to other monitored colonies. Although the delta lands support a long-standing agricultural economy, the primary factors influencing OC levels in the delta colonies were thought to be driven by estuarine processes. We suggest two possible influencing factors were: 1) a greater rate of bioaccumulation in the estuary due to the deposition of particulates collected over a vast area encompassed by the Fraser River watershed; or 2) a higher rate of biomagnification in the estuary due to species differences at lower trophic levels of the heron food chain. Eggs from urban colonies contained higher levels of PCBs. The congener pattern was not clearly different from that observed in less contaminated eggs from rural and pulp mill-influenced colonies, except that colonies in Vancouver had greater proportions of PCB-66, suggesting a local source of Aroclor 1242. Productivity in the coastal heron colonies was highly variable over the period of study, with 71% of recorded colony-wide reproductive failures occurring in colonies near pulp mills. However, the predominant factors influencing reproductive success were probably disturbance by humans and bald eagles, combined with loss and degradation of nesting habitat, and not sublethal toxicity.     

Organochlorine contaminants and eggshell thinning in grebes from prairie Canada

Eggs of five species of grebe were collected from Manitoba, Saskatchewan and Alberta during 1982-1987: red-necked (Podiceps grisegena), horned (P. auritus), eared (P. caspicus), western (Aechmophorus occidentalis) and pied-billed (Podilymbus podiceps). DDE and PCBs were present in all samples analyzed, whereas dieldrin, mirex and oxychlordane were occasionally present at low levels. Mercury was present at low levels in all samples for which it was analyzed. Red-necked grebes nesting in Manitoba had the highest contaminant levels and, assuming that contaminant burdens were accumulated principally on the wintering grounds, the mean PCB:DDE ratio (3.1) indicated that these birds and those from sites in central and eastern Saskatchewan probably wintered on the Atlantic coast. Overall low contaminant levels and a low mean PCB:DDE ratio (1.4) in the eggs of red-necked grebes breeding in Alberta and western Saskatchewan suggested that these birds wintered on the Pacific coast. A similar pattern was apparent in horned and eared grebes. Concentrations of DDE and PCB were both significantly correlated with Ratcliffe index (shell thickness), and were strongly correlated with each other. Ratcliffe indices were determined for historical collections of red-necked grebe eggs. Eggshell thickness of grebes nesting in Manitoba declined significantly during the years following the introduction of DDT (post-1947) and has only recovered partially since it was banned in 1972. The Alberta-breeding population did not appear to have undergone any significant decrease in shell thickness.     

The role of DDE,PCB, coplanar PCB and eggshell parameters for reproduction in the white-tailed sea eagle (Haliaeetus albicilla) in Sweden

The reproduction of white-tailed sea eagles was monitored in 1964-1999 in 3 differently contaminated sub-populations: Baltic Sea coast (Bp), inland central Sweden (Ip) and Lapland (Lp). 249 dead eggs from 205 clutches were obtained for analyses of DDE and PCBs and for eggshell measurements. A desiccation index (Di) value was calculated for each egg as a measure of water loss through the shell. In the highly contaminated Bp, p,p'-DDE concentrations in the eggs decreased continuously and 5-fold during the study period and PCB concentrations decreased 3-fold from the mid 1980s. The PCB pattern changed slightly over time towards more high-chlorinated congeners but the relative toxicity of the PCB mixture, expressed as 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ), remained constant and TEQ can be assumed to have decreased in a similar way as PCB over time. Productivity (P), shell thickness (St), shell index (Si) and Di increased over time in the Bp but no change in Di or productivity occurred in the Lp, where residue concentrations were 5-8 times lower. P of the Bp was not correlated to St or Si but was negatively correlated to Di, DDE and PCB. An S-shaped dose-response relationship was indicated between P and DDE. After 1988, when the PCB/DDE ratio was considerably higher than previously, PCB but not DDE concentrations were significantly higher in eggs with dead embryos as compared to undeveloped eggs, implying lethal concentrations of PCB, and a LOEL of 320 pg g-1 TEQ is suggested for embryo mortality. In a subset of 21 eggs, representing productive and unproductive females, analyzed for a selection of coplanar PCB congeners, tris(4-chlorophenyl) methanol and bis(4-chlorophenyl) sulphone, there was no evidence for a correlation between P and any of these compounds. A reduction in residue concentrations in old females did not lead to increased P or improved Di-values, indicating a remaining effect from a previous, higher exposure to contaminants. The inability to reproduce included a high rate of undeveloped eggs, indicating effects at a prezygotic stage. P showed the strongest correlation with Di, and Di was most strongly correlated to DDE. Thus, the remaining effect of previous exposure resulted in a stronger correlation to the symptom (Di) rather than to the suggested causative agent (DDE). LOEL values for depressed P were estimated at 120 micrograms g-1 DDE and 500 micrograms g-1 PCB (lipid basis). It is concluded that the major reason for depressed P during the study period was DDE, but that effects also from PCB were largely concealed by the effects from DDE.     

Formation of polychlorobiphenyls in silicone rubber

In silicone rubber crosslinked with bis(2,4-dichlorobenzoyl) peroxide (DCBP) as initiator about 0.1% of DCBP is converted into polychlorobiphenyls (PCBs). The PCB content in silicone rubber determined by high resolution gas chromatography (HRGC) after its destruction by HF is around 10 mg/kg. 29 PCB congeners were detected. Instead of the expected PCB-47, lower chlorinated congeners are predominant. Some possible pathways of their origin are presented.