PCB Levels Research Articles

Pilot‐scale demonstration of in situ capping of PCB‐containing sediments in the lower Grasse River

AbstractA fish‐consumption advisory is currently in effect in a seven‐mile stretch of the Grasse River in Massena, New York, due to elevated levels of PCBs in fish tissue. One remedial approach that is being evaluated to reduce the PCB levels in fish from the river is in situ capping. An in‐river pilot study was conducted in the summer of 2001 to assess the feasibility of capping PCB‐containing sediments of the river. The study consisted of the construction of a subaqueous cap in a seven‐acre portion of the river using various combinations of capping materials and placement techniques. Optimal results were achieved with a 1:1 sand/topsoil mix released from a clamshell bucket either just above or several feet below the water surface.A longer‐term monitoring program of the capped area commenced in 2002. Results of this monitoring indicated: 1) the in‐place cap has remained intact since installation; 2) no evidence of PCB migration into and through the cap; 3) groundwater advection through the cap is not an important PCB transport mechanism; and 4) macroinvertebrate colonization of the in‐place cap is continuing. Additional follow‐up monitoring in the spring of 2003 indicated that a significant portion of the cap and, in some cases, the underlying sediments had been disturbed in the period following the conclusion of the 2002 monitoring work. An analysis of river conditions in the spring of 2003 indicated that a significant ice jam had formed in the river directly over the capping pilot study area, and that the resulting increase in river velocities and turbulence in the area resulted in the movement of both cap materials and the underlying sediments. The pilot cap was not designed to address ice jam–related forces on the cap, as the occurrence of ice jams in this section of the river had not been known prior to the observations conducted in the spring of 2003. These findings will preclude implementation of the longer‐term monitoring program that had been envisioned for the pilot study. The data collected immediately after cap construction in 2001 and through the first year of monitoring in 2002 serve as the basis for the conclusions presented in this article. It should be recognized that, based on the observation made in the spring of 2003, some of these conclusions are no longer valid for the pilot study area.The occurrence of ice jams in the lower Grasse River and their importance on sediments and PCBs within the system are currently under investigation. © 2003 Wiley Periodicals, Inc.

Passive air sampling of PCBs, PBDEs, and organochlorine pesticides across Europe.

This study presents concurrently sampled ambient air data for a range of persistent organic pollutants at the continental scale. This was achieved using a passive air sampling system, deploying polyurethane foam disks, which was prepared in one laboratory, sealed to prevent contamination, sent out by courier to volunteers participating in different countries, exposed for 6 weeks, collected, resealed, and returned to the laboratory for analysis. Europe was the study area--a region with a history of extensive POPs usage and emission and with marked national differences in population density, the degree of urbanization and industrial/agricultural development. Samplers were deployed at remote/rural/urban locations in 22 countries and analyzed for PCBs, a range of organochlorine pesticides (HCB, alpha-HCH, gamma-HCH, ppDDT, ppDDE), and PBDEs. Calculated air concentrations were in line with those obtained by conventional active air sampling techniques. The geographical pattern of all compounds reflected suspected regional emission patterns and highlighted localized hotspots. PCB and PBDE levels varied by over 2 orders of magnitude; the highest values were detected in areas of high usage and were linked to urbanized areas. HCB was relatively uniformly distributed, reflecting its persistence and high degree of mixing in air. Higher gamma-HCH, ppDDT, and ppDDE levels generally occurred in South and East Europe.

03/02605 Predicting the heating value of MSW with a feed forward neural network: Dong, C. et al. Waste Management, 2003, 23, (2), 103–106

PCB 180 (2,2′,3,4,4′,5,5′-heptachlorobiphenyl) is a persistent and accumulating polychlorinated biphenyl abundantly present in food and the environment. In this study, we used highly purified PCB 180 (dioxinlike impurities: 2.7 ng TEQWHO/g PCB 180) in a 28-day toxicity study in young adult Sprague-Dawley rats. Male and female rats were given total doses of 3, 10, 30, 100, 300, 1000 or 1700 mg/kg b.w. PCB 180 by gavage. Increased liver weights were observed at ≥300 mg/kg b.w. in males and females. No increases in serum ALT or ALP activities were found. A significant increase in liver pentoxyresorufin O-dealkylase (PROD) activity was found in males at ≥10 mg/kg b.w. and in females at ≥30 mg/kg b.w. In both genders, a significant induction of hepatic 7-ethoxyresorufin O-deethylase (EROD) activity was also observed in males at ≥10 mg/kg b.w. and in females at ≥300 mg/kg b.w. Western blotting showed that mainly cytochromes P450 (CYPs) 2B1/2 and 3A1 were induced while slight effects were seen on CYP1A1, CYP1A2 and CYP1B1. However, no induction of CYP1A1, 1A2 and 1B1 was found on the mRNA level, except for a slight effect in females at 1000 mg/kg b.w. Furthermore, hepatic UDP-glucuronosyltransferases (UGTs) 1A1 and 1A6 were markedly induced in males and slightly induced in females. The hepatic concentrations of apolar retinoids were decreased in males at ≥30 mg/kg b.w. and in females at ≥300 mg/kg b.w. Taken together our findings show that pure PCB 180 leads to hepatic changes in a dose range which did not cause CYP1A1 induction but causes centrilobular liver hypertrophy, affects drug-metabolizing enzymes involved in the metabolism of exogenous and endogenous substrates and leads to changes in liver retinoid levels. A benchmark dose (BMD) approach is presented in order to model lowest effective dose levels for these effects. Comparison of PCB 180 liver level related to BMDL5 for hepatic hypertrophy in rats with human data on ‘total′ hepatic PCB levels in individuals without history of specific exposure suggests a relatively small margin of tissue burden in the range of 37-fold. Our results show that the highly pure non dioxin-like PCB 180 exerted strong effects different to dioxin-like compounds and that the low TEQ contamination allowed a characterization of the PCB as non-dioxinlike.

03/02601 Occupational hygiene and health of workers at South Kuzbass open-pit coal mine: Oleshchenko, A. M. et al. Meditsina Truda i Promyshlennaya Ekologiya, 2002, (10), 40–43. (In Russian)

PCB 180 (2,2′,3,4,4′,5,5′-heptachlorobiphenyl) is a persistent and accumulating polychlorinated biphenyl abundantly present in food and the environment. In this study, we used highly purified PCB 180 (dioxinlike impurities: 2.7 ng TEQWHO/g PCB 180) in a 28-day toxicity study in young adult Sprague-Dawley rats. Male and female rats were given total doses of 3, 10, 30, 100, 300, 1000 or 1700 mg/kg b.w. PCB 180 by gavage. Increased liver weights were observed at ≥300 mg/kg b.w. in males and females. No increases in serum ALT or ALP activities were found. A significant increase in liver pentoxyresorufin O-dealkylase (PROD) activity was found in males at ≥10 mg/kg b.w. and in females at ≥30 mg/kg b.w. In both genders, a significant induction of hepatic 7-ethoxyresorufin O-deethylase (EROD) activity was also observed in males at ≥10 mg/kg b.w. and in females at ≥300 mg/kg b.w. Western blotting showed that mainly cytochromes P450 (CYPs) 2B1/2 and 3A1 were induced while slight effects were seen on CYP1A1, CYP1A2 and CYP1B1. However, no induction of CYP1A1, 1A2 and 1B1 was found on the mRNA level, except for a slight effect in females at 1000 mg/kg b.w. Furthermore, hepatic UDP-glucuronosyltransferases (UGTs) 1A1 and 1A6 were markedly induced in males and slightly induced in females. The hepatic concentrations of apolar retinoids were decreased in males at ≥30 mg/kg b.w. and in females at ≥300 mg/kg b.w. Taken together our findings show that pure PCB 180 leads to hepatic changes in a dose range which did not cause CYP1A1 induction but causes centrilobular liver hypertrophy, affects drug-metabolizing enzymes involved in the metabolism of exogenous and endogenous substrates and leads to changes in liver retinoid levels. A benchmark dose (BMD) approach is presented in order to model lowest effective dose levels for these effects. Comparison of PCB 180 liver level related to BMDL5 for hepatic hypertrophy in rats with human data on ‘total′ hepatic PCB levels in individuals without history of specific exposure suggests a relatively small margin of tissue burden in the range of 37-fold. Our results show that the highly pure non dioxin-like PCB 180 exerted strong effects different to dioxin-like compounds and that the low TEQ contamination allowed a characterization of the PCB as non-dioxinlike.

Persistent organochlorine pollutants in liver of birds of different trophic levels from coastal areas of Campania, Italy.

Liver samples of 12 species of birds of different trophic levels, collected during the period 1998-2000 from coastal areas of the Campania region, Southern Italy, were analyzed for organochlorine pesticides (OCs), such as dichlorodiphenyltrichloroethane (DDT) and its metabolites, hexachlorobenzene (HCB), gamma-hexachlorocycloexane (gamma-HCH), aldrin, dieldrin, endrin, and the seven PCB "target" congeners, IUPAC Nos. 28, 52, 101, 118, 138, 153 and 180. p,p'-DDE was present in all the samples analyzed, at concentrations ranging from 4 to 4504 ng/g wet wt, which were much higher than those found for HCB, dieldrin, and p,p'-DDD. The concentrations of the others OCs were below the detection limit in all the samples. PCBs were found in all the bird species at levels ranging between 6 and 8431 ng/g wet wt. The hepta-, hexa-, and penta-chlorinated congeners 180, 153, 138, and 118 were predominant since, in almost all the species, they contributed to more than 98% of the total seven determined PCBs. No significant differences in mean concentrations of organochlorine pesticides are detected between single species or between species grouped according to their feeding habits (p > 0.05). However, p,p'-DDE levels were higher in carnivorous species than in omnivorous and insectivorous ones (carnivorous > omnivorous > insectivorous). Concentrations of total PCBs were significantly higher in omnivorous birds than in carnivorous (p < 0.01) and insectivorous ones (p < 0.001), whereas carnivorous birds exhibited significantly higher total PCB levels than insectivorous ones (p < 0.01). Marked differences in total PCB concentrations were found also between single species (from p < 0.05 to p < 0.001). Levels of OCs and PCBs were generally below the thresholds known to affect reproduction, however, mean hepatic concentrations of total PCBs in the yellow-legged herring gull (Larus cachinnans), black-headed gull (Larus ridibundus), and kestrel (Falcus tinnunculus) were far higher than those estimated to elicit immunosuppressive effects and possibly increase susceptibility to parasitoses.

Exposure of Taiwan residents to polychlorinated biphenyl congeners from farmed, ocean-caught, and imported fish.

This study is to assess PCB levels in five frequently consumed fish species in Taiwan, tilapia, milkfish, white pomfret, hairtail, and cod. Seventeen congeners were measured in fillet samples purchased from major markets in northern, central, and southern Taiwan. All 136 samples had traces of PCBs. The median concentrations were 0.18, 0.46, 0.62, 0.69, and 7.34 ng/g wet wt and 1.01, 0.28, 1.14, 5.06, and 19.3 pg-WHO-TEQ/g lipid in tilapia, milkfish, white pomfret, hairtail, and cod samples, respectively. Cod (the imported fish) had the highest wet weight PCB concentrations. The fish caught off-shore (white pomfret and hairtail) had higher levels than the farmed fish (tilapia and milkfish). The congener profiles varied among species. PCB 105/153 and 126 accounted for more than 28% and 53% of the 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (WHO-TEQs) in hairtail and cod, respectively; while PCB 156 was the major TEQ contributor in the other species. The estimated median PCB intake of the general public from consumption of the five species ranged from 0.000023 to 0.048 pg-WHO-TEQ/kg/day. It was also found that samples farmed or caught along the southern coast had higher PCB levels than those from other parts of Taiwan, indicating possible elevated PCB contamination around that area.

Accumulation and lactational transfer of PCBs and pesticides in harbor seals ( Phoca vitulina) from Svalbard, Norway

The harbor seal population on Svalbard, the northernmost breeding site for this species, appears to have a truncated age distribution with older animals being largely absent. PCBs and pesticides were measured in harbor seal males, females, milk and pups from Svalbard to explore whether contaminant exposure or accumulation is a possible cause of premature death for these animals. The levels and patterns of these contaminants were assessed. In addition, transfer of these compounds from females to their pups during lactation was assessed. Both PCB and pesticide levels were low compared to more southern harbor seal populations. Animals from Svalbard contained 5–10 times lower contaminant levels, compared to seals from the Norwegian mainland, and 30 times lower concentrations than those of harbor seals from the Gulf of St. Lawrence in eastern Canada. Ringed seals from Svalbard have contaminant levels that are comparable to the harbor seals, probably because the diet, as well as the metabolic capacity, of the two species is similar at this location. The findings of this study indicate that the early mortality observed for harbor seals on Svalbard, is not likely to be due to contaminant exposure. Female harbor seals transfer a modified contaminant mixture to their pups compared to that found within their own tissues; compounds with higher log K ow, such as some penta-chlorinated PCBs, were selectively transferred into milk. As a result, the contaminant pattern between males and females differed, with penta-chlorinated PCBs more abundant in males than in females. In addition, pups receive a relatively high amount of the less lipophylic compounds and a low amount of the more lipophylic compounds. The similar contaminant pattern in milk and pups suggested that they are probably unable to metabolize contaminants and consequently, accumulate all ingested chemicals.

PRELIMINARY OBSERVATIONS ON ENDOCRINE DISRUPTING EFFECTS OF POLYCHLORINATED BIPHENYLS (PCBS) IN THE POPULATION EXPOSED TO HEAVY ENVIRONMENTAL POLLUTION

A chemical factory, Chemko, at Strazske, East Slovakia, produced 21,500 tons PCBs during 1959–1984. Large amounts of PCBs contaminated the environment due to poor technological and preventive measures. Up to 20-times higher PCB levels were found in ambient air samples close to the Chemko landfill site and highly contaminated effluent canal. Some preliminary results of a complex study of PCB health effects are: We examined 1010 adult subjects from the polluted area [PA] and 1040 subjects from control area [CA]. The mean serum level of the sum of PCBs (ng/g, lipid adjusted) in the PA (378 specimens) was 2738 and in CA (1038 specimens) 871. Thyroid volume by ultrasound (mean±SD) was significantly higher in PA (10.77±5.09 ml, 90 % = 16.6 ml) than in CA (8.99±4.11 ml; 90 % 13.3 ml; P < 0.001) and the same was true for free thyroxine [FT4] (2.04±0.37 vs. 1.91±0.37 pmol/L) and total triiodothyronine [TT3] (17.04±3.12 vs. 15.99±2.58 nmol/L). In PA also significantly higher frequency of positive antithyroperoxidase antibodies [anti-TPO] was found in males (52,7 % vs. 7.9 %-P < 0.001) as well as in females (32.0 % vs. 24.5 %-P < 0.001). However, after 4 decades of heavy exposure the average level of thyrotropin and the prevalence of abnormally increased levels (>4.0 mU/L) in both areas was the same which shows a normal thyroid function. It was concluded that, in spite of increased thyroid volume, FT4 and FT3 level and positive anti-TPO frequency, the thyroid function in great majority of exposed subjects was normal, but presumably the set points of individual short and long feedback loops were shifted which resulted in a new final steady state. After a long-term exposure of population presumably only the sequels or remnants a previous long-term process may be found. A total of 478 8–9 years old school children were recruited (119 boys and 116 girls born and living in the PA and 124 boys and 119 girls in the CA). Comparison of performance of psychological tests showed differences between areas in tests of sensomotor reactions, in short memory, and in tests of high mental processes, in favor of CA. Three main types of developmental defects of tooth enamel were recorded in children: demarcated opacities, diffuse opacities, and hypoplasia. Preliminary results showed that the percentage of children with at least one permanent tooth affected by enamel defects was 66% in the PA compared to 55% in the CA group. After finishing all analyses, for each subject will be available a large amount of data: on various organochiorines serum concentrations and their metabolites, on toxic metals serum concentrations, on thyroid status, cognitive processes, dental status, concentrations, on thyroid status, cognitive processes, dental status, hearing impairment, cytochrome P450 enzymes and xenoestrogenic activities. This will make possible exposure-effect hypothesis testing using multifactorial analysis.

A comparison of organic contaminants in two high Arctic lake ecosystems, Bjørnøya (Bear Island), Norway

Lake Ellasjøen and Lake Øyangen are two high Arctic lake ecosystem located on the island Bjørnøya (74°30′ N, 19°00′ E) in the Barents Sea. High levels of persistent organic pollutants (POPs), especially PCB and p, p′-DDE, were found in sediment and biota from Lake Ellasjøen while levels were several times lower in Lake Øyangen. Stable isotope signatures (δ 15N) in comparable organisms (e.g. zooplankton, Arctic char) collected from both the lakes were also significantly different. The values of δ 15N were 6–10‰ higher in the organisms from Ellasjøen than from Øyangen. In both Ellasjøen and Øyangen, a statistically significant correlation ( P<0.05) was found between the levels of PCB and DDT, and δ 15N values in organisms indicating enhanced bioaccumulation for higher trophical level lake organisms. As the lakes on Bjørnøya are remote, more than 500 km from any known point source, the presence of POPs is most likely the result of long-range transport of contaminants to the area. The observed higher contaminant concentrations associated with the Ellasjøen ecosystem is attributed to two factors. Ellasjøen is located in the southern, mountainous part of Bjørnøya and it is likely that this area receives more precipitation, and thereby more airborne contaminants, than the flatter areas further north on the island (i.e. the area around Øyangen). In addition, higher δ 15N-levels in organisms from Ellasjøen as compared to Øyangen indicate the input of guano from seabirds using the lake as a resting area as an additional source of POPs to Ellasjøen.

Seabird eggs as bioindicators of chemical contamination in Chile

Seabird eggs were used as bioindicators of chemical contamination in Chile. Brown-hooded Gull ( Larus maculipennis), Kelp Gull ( Larus dominicanus), Trudeau's Tern ( Sterna trudeaui), Neotropic Cormorant ( Phalacrocorax brasilianus), and Pink-footed Shearwater ( Puffinus creatopus) eggs were sampled at different breeding sites during the 1990s. Mercury and organochlorines (PCBs, DDT, HCB, HCH, and PCP) were quantified to reveal the interspecific differences, spatial and temporal trends in contamination levels. Trudeau's Tern displayed the highest levels of mercury (486 ng g −1 wet weight). The highest ΣDDT concentrations were measured in Brown-hooded Gulls (726 ng g −1). PCB levels were similar among the species (102–236 ng g −1), but the composition of the PCB mixture was different in Pink-footed Shearwaters. With the exception of the Brown-hooded Gull, all species studied presented similar and low levels of organochlorines (ΣOHa). Residues of PCB and related compounds were not detected in any of the seabird eggs analyzed in Chile. Geographical variation was low, although levels of industrial chemicals were slightly higher in eggs from Concepción Bay, and agricultural chemicals in eggs from Valdivia. Also interannual variation was low, but some evidence was found of decreasing levels in gull eggs throughout the time of the study. The causes of the low levels and small variability in space and time of environmental chemicals in Chilean seabirds are discussed. We propose the use of seabirds in future monitoring of the development of chemical contamination in Chile.

The PCB pollution of Lake Iseo (N. Italy) and the role of biomagnification in the pelagic food web

Several models of varying complexity have been used to predict pollutant concentrations in the higher levels of the food web from those in lower levels, but the role of the biomagnification process in aquatic food chains is still controversial. We used the fugacity-based approach to verify the transfer of PCBs through the pelagic food chain of Lake Iseo (N. Italy), sampling several zebra mussel specimens and some fish belonging of different trophic levels. The zebra mussel seems to be a suitable starting species for modelling the bioaccumulation process through the trophic web, not only because its physiological characteristics and population size do not change much with time (as do algae and zooplankton) but also because it takes up toxicants exclusively from the water, as shown by the application of two predictive trophic models commonly used. The data provided by one of those models were in good agreement with our experimental data on fish in Lake Iseo, that show a not negligible uptake from food for the top predator species (pike and perch) with an increase of about three times in comparison with the PCB levels measured in the zebra mussel specimens.

Dioxin, dibenzofuran, and coplanar PCB levels in Laotian blood and milk from agent orange-sprayed and nonsprayed areas, 2001.

Agent Orange, a phenoxyherbicide contaminated with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), was used by American military forces during the United States-Vietnam war between 1962 and 1971 primarily as a defoliant to destroy forests where enemy troops might find cover. Agent Orange was used mainly in Vietnam, but also to a lesser extent in Laos and Cambodia. In Laos, there have been no prior studies of TCDD contamination from Agent Orange, despite known defoliation and documented records of Agent Orange spraying. This article presents findings of TCDD in human blood and milk from two geographic areas in Laos: Vientiane, a nonsprayed area, and Sepone, an Agent Orange-sprayed area. German and Canadian laboratories used high-resolution gas chromatography-mass spectrometry to measure 7 dioxin, 10 dibenzofuran, and 4 non-ortho or coplanar polychlorinated biphenyls in Laotian blood and milk samples. Most subjects tested in this Laos Ministry of Health Study showed low dioxin and dibenzofuran levels, consistent with what would be expected in a primarily rural nonindustrial country. These findings are consistent with relatively low dioxin and dibenzofuran levels recently found in food from these same areas. The chemically and toxicologically related non-ortho PCBs were measured but were found at low levels compared to specimens from other countries, presumably because of less industrialization and industrial pollution in Laos.

A review on human exposure to brominated flame retardants—particularly polybrominated diphenyl ethers

Brominated flame retardants (BFRs) have been and are still heavily used as additive or reactive chemicals in polymers and textiles. Only a few of the BFRs have been assessed in human subjects with a major data set on internal exposures to polybrominated diphenyl ethers (PBDEs). Increasing PBDE levels have been observed in mothers' milk from Sweden as well as in blood from Germany and Norway. The levels are in general lower than PCB levels. However, the PBDE concentrations found in the North Americans are considerably higher compared to European subjects. The PBDEs are dominated by 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47). Decabromodiphenyl ether (BDE-209) is reported both in the general population and in occupationally exposed persons showing the bioavailability of this high molecular weight compound. While the lower and medium brominated diphenyl ethers are persistent, BDE-209 has a fairly short half-life of approximately 2 weeks. Tetrabromobisphenol A (TBBPA) is readily eliminated in humans showing a half-life of about 2 days. Still, TBBPA is accumulated in humans but a continuous exposure to this BFR is required to maintain a certain level in the human subject. TBBPA has not been detected in the general population but in people exposed at work. The current review addresses human exposure routes and levels of BFRs.

Neonatal and childhood teeth in relation to perinatal exposure to polychlorinated biphenyls and dibenzofurans: observations of the Yucheng children in Taiwan

In order to determine the effect of perinatal polychlorinated biphenyls and dibenzofurans (PCBs/PCDFs) exposure on neonatal and childhood teeth in Yucheng children, we carried out complete dental examinations on 73 Yucheng children born to mothers who ingested high levels of PCBs/PCDFs and 75 matched controls, aged 7–11 years, in 1992. Ten of 73 (10%) exposed children were reported to have borne teeth during the neonatal period, while none of the controls did. The exposed group also had a significantly higher percentage of teeth with congenitally missing tooth germ compared to the controls (29 vs 2.7%) or rotation (19 vs 2.7%). The percentages of developmental defects increased significantly with increasing maternal serum PCB levels, childhood PCB and PCDF levels, and the duration of breast feeding. The maternal PCB level clearly played a more important role in an increased risk of neonatal teeth and developmental defects. The defects were apparent from the lowest tertile, with a total PCB level of <10 ppb in maternal serum measured nearest to childbirth. The number of permanent teeth tended to be less in exposed children than in the control group from the age of 11years onwards. Our present study has demonstrated for the first time a dose-response relationship between perinatal PCBs/PCDFs exposure and dental defects.

POPs in edible clams from different Italian and European markets and possible human health risk

Human intake of persistent organic pollutants (POPs) occurs primarily through diet and fish and other seafood represent the principal means of contamination. Despite this, few legal limits have been established to protect human health from the various chemicals that are alleged to be carcinogenic or endocrine disruptor compounds. Several pools of edible clams ( Tapes philippinarum and Venus gallina) bought in different Italian and European markets were examined in order to perform a risk assessment of some of these contaminants and also to identify possible health issues. POP concentrations in the soft tissues of mollusks varied considerably among source farming sites, particularly in the Venice Lagoon. Some POPs (DDTs, HCB and HCHs) showed very low concentrations and no risk for human health, in line with the limits established by European law. In contrast, PAHs could represent a potential hazard for human health and PCB levels in the most contaminated sites reached or even exceed the Minimal Risk Level as set by the ATSDR for human consumption, even if all the samples did not exceed the PCB limits in edible seafood as set by the FDA.

Analyses of known and new types of polyhalogenated aromatic substances in oven ash from recycled aluminium production

Persistent aromatic bromine, chlorine and mixed chlorine-bromine compounds were analysed from recycled aluminium smelter (ALS) ashes to explore the impact of brominated flame retardants (BFR) on their formation. Polybrominated diphenyl ethers (PBDE) were the most abundant original BFRs found. Induction furnace ash contained tetra- to octa-BDEs about 2000 ng g −1 in similar congener ratios as the original scrap, but contents of nona- and deca-BDEs were only 25 and 5 ng g −1 indicating their significant degradation in ALS process. In the most non-polar fraction, PCB levels and profiles were similar as earlier ALS ash samples in 1990s. The highest PCB level measured was that of deca-CB (450 ng g −1) in the induction furnace ash. In this fraction, bromo compounds were non-detectable (<5 ng g −1). Fraction of the most polar compounds (from reversed toluene elution of carbon column (“dioxin fraction”) contained PCDDs, PCDFs and polychlorinated dibenzothiophenes (PCDTs) in similar amounts and congener profiles as earlier investigated ALS ash samples. Bromine-containing dioxin and furan congeners were not detected. From individual PCDDs and PCDFs, octaCDF was the most abundant (205 ng g −1) in induction furnace ash. In this fraction, the original BFR, tetrabromo-bisphenol-A, was identified. Its level in the induction furnace ash was approximated to be 388 ng g −1. In addition, 12 novel brominated and chlorinated compounds were found as abundant (8–441 ng g −1 in the induction furnace ash) contaminants from the fraction. Four of them were bisphenol derivatives, five biphenylols, then octachlorofluorenone (OCFL) and octachlorobiphenylene (OCBP). Their structures or structure types were deduced from total low-resolution EI mass spectra by theoretical isotope cluster simulation (ICLU) and through known fragmentation rules.

Organohalogens and metals in marine fish and mussels and some relationships to biological variables at reference localities in Norway

The main goals of this study were to define, for the Norwegian coast, “high background” levels of micropollutants routinely monitored within the the Oslo and Paris Commission Joint Assessment and Monitoring Programme, and to reassess the present Norwegian reference levels used as the basis for a classification of environmental quality. The indicator organisms analysed as bulked/individual samples were cod ( Gadus morhua, n≈1170; n≈240 for organochlorines), dab ( Limanda limanda, n≈75), plaice ( Pleuronectes platessa, n≈55) lemon sole ( Microstomus kitt, n≈13). and blue mussels ( Mytilus edulis, n≈200) collected between 1991–2000. Based on the 90–95 percentiles of measurements at localities far from point sources, we propose for liver of cod a reference level for ΣPCB 7 (CBs 28, 52, 101, 118, 138, 153 and 180) of 500 μg kg −1 w.w. and further for DDE 200 μg kg −1, ΣHCHs 30 μg kg −1, HCB 20 and OCS 5 μg kg −1 w.w. In the same order the proposed reference levels for liver of dab are: 150, 60, 15, 5, and 2 μg kg −1 w.w.; and for the soft body of mussels: 3, 1, 1, 0.1 and 0.1 μg kg −1 wet weight. Reference levels of metals are 0.1 mg Hg kg −1 w.w. in fish fillet, and for Hg, Cd, Pb, Zn, Cu in mussels 0.2, 2, 3, 200 and 10 mg kg −1 d.w., respectively. Hg in fillet of cod and dab were positively correlated with length and weight. PCB levels in liver of cod and dab showed a positive but weak correlation with length, whereas no co-variation was found between PCBs and liver fat. The results of introductory recordings of polychlorinated dibenzo- p-dioxins/dibenzofurans, polychlorinated naphtalenes, Toxaphene and brominated flame retardants in liver of cod from reference sites are also presented.

PCB and PCDD/F totals, TEQs, and congener patterns in Korean coastal marine environments, 1987, 1988, 1990, and 1996-1999.

Various mussel and oyster samples and select top sediment samples were taken over 27 industrial and pristine coastal sites form South Korea's west, south, and east coasts. Site-specific total PCB, PCDD/F, and organochlorine TEQ levels in biota were 1-306 ng/g ww, 3-9,400 pg/g ww, and 0.3-200 pg/g ww, respectively. Temporal trends showed a general decrease in total TEQ with an increase in TEQ contribution by PCDD/Fs at most locations over the past decade. Linear regression was used to establish a relationship between each contaminant total and the respective TEQ contribution. Principal component analysis was used to model the congener-specific PCB and PCDD/F data, and two three-component models were developed that describe the congener-specific patterns based on the variance between samples over the entire data set. Unique PCDD/F patterns were identified and discussed with respect to outliers identified in the previously established TEQ regressions and a distinct PCDD/F pattern was found that related to a single industrial source (i.e., steel mill). PCB patterns were explored in relation to those of common commercial mixtures of PCBs (i.e., Aroclors) and patterns were discussed with respect to TEQ. It was found that sites with relatively high PCB-TEQs showed an Aroclor 1254-like contamination.

Chlorinated hydrocarbon contamination in osprey eggs and nestlings from the Canadian Great Lakes basin, 1991-1995.

Populations of osprey (Pandion haliaetus) in the Great Lakes basin declined dramatically during the 1950s-1970s due largely to adverse effects of persistent chlorinated hydrocarbons, ingested in their fish prey, on eggshell thickness and adult survival. Nevertheless, these contaminants were not measured in osprey tissues during the decades of decline on the Canadian Great Lakes. Between 1991 and 1995, we monitored recovering osprey populations on the Great Lakes, including Georgian Bay and the St. Marys River area on Lake Huron and the St. Lawrence Islands National Park, as well as at two inland sites within the basin. Current OC levels, even from the most contaminated lakes, were typically lower than those associated with reproductive effects. DDE levels in fresh eggs averaged 1.2-2.9 microg/g, well below the 4.2 microg/g level associated with significant eggshell thinning and shell breakage. Nevertheless, a proportion of eggs from all study areas did exceed this level. PCB levels in eggs seldom exceeded 5 microg/g except in one lake of high breeding density in the Kawartha Lakes inland study area, where the mean sum PCB level was 7.1 microg/g and the maximum concentration measured was 26.5 microg/g. On average, mean reproductive output (0.78-2.75 young per occupied nest) of breeding populations in Great Lakes basin study areas exceeded the threshold of 0.8 young thought necessary to maintain stable populations. We concluded that, although eggs and especially nestling plasma, are useful in reflecting local contaminant levels, ospreys are relatively insensitive, at least at the population level, to health effects of current levels of chlorinated hydrocarbons on the Canadian Great Lakes.

Quantitative dynamics of PCB transfer from mother to pup during lactation in UK grey seals Halichoerus grypus

PCB contamination was measured in the milk and serum of grey seal Halichoerus grypus mothers and in the serum of their pups sampled from 2 to 5 times between parturition and weaning on the Isle of May, Scotland, in 1998 and 2000. Blubber biopsies were also taken from the lactating females at early and late lactation in 2000. Concentrations of PCBs in milk stayed constant during the first part of lactation (0.31 +/- 0.17 mug g milk(-1)) and then increased at late lactation (0.67 +/- 0.42 mug g milk(-1)). Curiously, it did not follow the changes of milk lipid content, which increased at early lactation and then stayed constant until the end of the nursing period. As a result, even when expressed per unit of milk lipids, PCBs underwent a rise at the end of lactation. The changes in milk PCBs were accompanied by similar dynamics in maternal serum as well as in pup serum. Increased concentrations of PCBs at late lactation in serum and milk may be explained in part by the changes observed in maternal blubber. PCB levels increased significantly between early and late lactation in inner blubber, suggesting that PCBs are less easily mobilised from blubber than lipids. At late lactation, the retention capacity of the reduced blubber layer for PCBs might have reached its maximum. The mobilization of less polar lipids from blubber might also occur at this stage. In both cases, this could result in a higher mobilization of PCBs at this time. While inner blubber was significantly less concentrated than outer blubber at early lactation (1.26 +/- 0.72 mug g lipids(-1) in inner blubber vs 3.16 +/- 1.34 mug g lipids(-1) in outer blubber), these variations disappeared at late lactation (3.24 +/- 2.60 mug g lipids(-1) in inner blubber vs 3.59 +/- 1.46 mug g(-1) lipids in outer blubber). Newborn pups already had significantly higher serum levels of PCBs than their mothers, revealing an important placental transfer (11.9 +/- 7.0 ng ml serum(-1) in pups vs 6.7 +/- 3.5 ng ml serum(-1) in mothers). These differences were even greater in late lactation, due to the ingestion of milk (27.9 +/- 18.1 ng ml serum(-1) in pups vs 12.2 +/- 7.2 ng ml serum(-1) in mothers). As lactation progressed, PCB levels in pup serum increased exponentially as compared to the levels in the serum of their mothers.