Congener Patterns Research Articles

Patterns and sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in surficial sediments of Lakes Erie and Ontario

This study determines spatial trends and congener patterns of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surficial sediments of Lakes Erie and Ontario. Sediments are enriched in 2378-PCDFs in Lake Ontario, and the PCDD/F concentrations increased from shallow near-shore sediments towards deep-water depositional zone sediments. In Lake Erie, sediments were dominated by octachlorodibenzo-p-dioxin, and the highest PCDD/F concentrations were observed in the western basin and the southern shoreline of the central basin with a decrease towards the eastern basin and the northern shoreline of the central basin. Principal components analysis revealed that chemical manufacture and disposal of chemical waste along the Niagara River has been a major PCDD/F source to Lake Ontario; while PCDD/Fs in Lake Erie are from multiple sources including industrial sources along the Detroit River, major tributaries along the southern shoreline of the lake, and atmospherically-derived material from the upper lakes and connecting channels.

Polychlorinated naphthalenes and other dioxin‐like compounds in Elbe River sediments

Contamination of Elbe River (Germany) sediments with dioxin-like toxicants was investigated following the 500-year flood (flood that statistically occurs once in 500 years) of 2002. It was hypothesized that large amounts of particulate matter from river beds and associated dioxin-like toxicants were mobilized and transported during this flood event. The investigation focused on polychlorinated naphthalenes (PCNs) that have not been determined previously in the Elbe River. The in vitro H4IIE-luc assay was used as an overall measure for toxicants capable of binding to the aryl hydrocarbon receptor (AhR). The assay was combined with congener-specific instrumental analyses and fractionation to quantify PCN contributions to total AhR-mediated activity relative to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). Penta- to octachloronaphthalene concentrations of 30 ng/kg dry weight up to 13 microg/kg dry weight were found in Elbe River sediments downstream of Bitterfeld. Concentrations of penta- to octachloronaphthalenes, however, were only approximately 3 microg/kg dry weight at a site in the vicinity of Bitterfeld, where a level of approximately 3 mg/kg dry weight was reported before the flood. Also, the congener pattern of PCNs at this site changed after the flood, and PCN patterns reported previously for Bitterfeld and assigned to chlor-alkali electrolysis with graphite electrodes could now be observed at the sites from downstream of Bitterfeld and Magdeburg. Whereas PCDD/Fs dominated the dioxin-like activity in the middle and lower Elbe River, PCNs contributed as much as 10% of the total AhR-mediated activity. The contribution of PCBs was less significant (maximum, 0.2%). Thus, in Elbe River sediments, PCNs should be considered as relevant contaminants and be included in future monitoring and risk assessment programs.

Influence of Trophic Position and Spatial Location on Polychlorinated Biphenyl (PCB) Bioaccumulation in a Stream Food Web

We tested the ability of delta15N-derived trophic position (TP) to predict polychlorinated biphenyl (PCB) concentrations in a historically contaminated stream (Twelvemile Creek, SC). We analyzed sediment, four types of organic matter, 27 macroinvertebrate taxa, and 25 fish species from six sites spanning 25 stream km. SigmaPCBs were high across sites (mean fish = 2505 ng g(-1) wet), with little spatial variation in concentrations within a trophic level. SigmaPCBs (wet weight) were significantly positively correlated with TP (r2 = 0.56) and lipids (r2 = 0.44), and concentrations increased 1-2 orders of magnitude among trophic levels. After adjusting for lipids, we calculated a food web magnification factor of 1.6 for SigmaPCBs, which is low compared to marine and lentic food webs. The predictive power of TP for individual congeners increased with Kow (octanol-water partition coefficient), with regression slope approximately 0.48 and r2 approximately 0.70 for Kow > 6.5. The proportion of high Kow compounds increased with distance from the source and with trophic position. Spatial variation in congener patterns was high, in contrast to marine and lentic systems where variation is typically low.

PCDD/F and PCB multi-media ambient concentrations, congener patterns and occurrence in a Mediterranean coastal lagoon (Etang de Thau, France)

Ambient concentrations, congener patterns and multi-media distribution of PCDD/Fs and PCBs were determined in air, water, sediment and mussels in a semi-enclosed marine ecosystem (Thau lagoon, France). Sigma2,3,7,8-PCDD/F and sigma7ICES PCB air concentrations (0.2-1.4 and 31-57 pg m(-3), respectively) were typical of rural areas. Concentrations in the water column were very low for PCDD/Fs (163-476 fg L(-1)) and low for PCBs (138-708 pg L(-1)). PCDD/F and PCB concentrations found in surface sediment (0.15-1.6 and 2.5-33 ng g(-1) d.w., respectively) and mussel (13-21 pg g(-1) d.w. and 10-39 ng g(-1) d.w., respectively) were medium levels. PCDD/F congener patterns observed in air, water particulate phase and sediments were similar suggesting direct coupling among these compartments and atmospheric inputs of PCDD/Fs into the lagoon. Conversely, for the same set of samples, similar patterns were not observed for PCBs in the mentioned compartments.

Temporal Trends, Congener Patterns, and Sources of Octa-, Nona-, and Decabromodiphenyl Ethers (PBDE) and Hexabromocyclododecanes (HBCD) in Swiss Lake Sediments

With the recent ban of pentabromodiphenyl ether (technical PentaBDE) and octabromodiphenyl ether (technical OctaBDE) mixtures in the European Union (EU) and in parts of the United States, decabromodiphenyl ether (technical DecaBDE) remains as the only polybrominated diphenyl ether (PBDE) based flame retardant available, today. The EU risk assessment report for DecaBDE identified a high level of uncertainty associated with the suitability of the current risk assessment approach for secondary poisoning by debromination of DecaBDE to toxic lower brominated diphenylethers. Addressing this still open question, we investigated concentrations and temporal trends of DecaBDE, NonaBDE, and OctaBDE congeners in the sediments of Greifensee, a small lake located in an urban area close to Zürich, Switzerland. PBDE appeared first in sediment layers corresponding to the mid 1970s. While total Tri-HeptaBDE (BDE-28, -47, -99, -100, -153, -154 and -183) concentrations leveled off in the mid 1990s to about 1.6 ng/g dw (dry weight), DecaBDE levels increased steadily to 7.4 ng/g dw in 2001 with a doubling time of 9 years. Hexabromocyclododecanes (HBCD) appeared in Greifensee sediments in the mid 1980s. They are an important class of flame retardants that are being used in increasing amounts, today. As was observed for DecaBDE, HBCD concentrations were continuously increasing to reach 2.5 ng/g dw in 2001. Next to DecaBDE, all 3 NonaBDE congeners (BDE-208, BDE-207, and BDE-206) and at least 7 out of the 12 possible OctaBDE congeners (BDE-202, BDE-201, BDE-197/204, BDE-198/203, BDE-196/200, BDE-205, and BDE-194) were detected in the sediments of Greifensee. Highest concentrations were found in the surface sediments with 7.2, 0.26, 0.14, and 1.6 ng/g dw for Deca-, Nona-, Octa-, and the sum of Tri-HeptaBDE, respectively. While DecaBDE and NonaBDE were found to increase rapidly, the increase of OctaBDE was slower. Congener patterns of Octa- and NonaBDE present in sediments of Greifensee did not change with time. Consequently, there was no evidence for sediment mediated long-term transformation of PBDE within the observed time span of almost 30 years. Despite the high persistence of DecaBDE, environmental debromination occurs, as shown by the detection of a shift in congener patterns of Octa- and NonaBDE in sediments, compared to the respective congener patterns in technical PBDE products. The OctaBDE congener BDE-202 was detected in sediments, representing a transformation product that is not reported in any of the technical PBDE products. Comparison of OctaBDE congener patterns in sediments with OctaBDE congener patterns from known sources reveals that (i) they were distinctively different from the congener patterns in technical PBDE products and (ii) that they were similar to the OctaBDE patterns in house dust and photodegradation products of DecaBDE, suggesting contributions from these sources.

Congener pattern of hexabromobiphenyls in marine biota from different proveniences

Blubber of seals, harbour porpoises and fish originating from the North Sea, the Baltic Sea, as well as coastal waters of Iceland and North America were analyzed for residues of polybrominated biphenyls. According to GC/ECNI-MS, hexabromobiphenyls (hexaBBs) dominated in the samples, followed by pentabromobiphenyls (pentaBBs) and heptabromobiphenyls (heptaBBs), whereas octabromobiphenyls (octaBBs) were only detected in selected samples and nonabromobiphenyls (nonaBBs) and PBB 209 were not found at all. Eleven peaks of hexaBBs—two peaks might have been each composed of two congeners, respectively—were detected in the different samples. The hexaBB pattern in samples of Iceland was a mixture of the pattern determined in samples from North America and continental Europe. In samples from the European continent, the major congener in technical hexabromobiphenyl, PBB 153, accounted for 11–37% of the hexaBBs. Other prominent isomers were PBB 155 (7.1–64%) and PBB 154 (11–33%), followed by PBB 133 as well as PBB 132 and/or PBB 146. Most of these PBBs were determined for the first time in marine biota and must be metabolites of higher brominated PBBs since they were not present in any technical product. PBB 153 was dominant in blubber of marine mammals from North America (92–96%). Blubber of harbour porpoises and also seal milk showed more peaks, which is indicative of a lower capability of biotransforming PBBs. It is concluded from this and other studies that PBB residues in North America are mainly originating from technical hexabromobiphenyl, while the bulk of the PBB residues in the European marine samples originated from technical octa- and decabromobiphenyl. Finally, it is evident from this study that a global ban of PBBs should not only be restricted to hexabromobiphenyls, but also needs to include higher brominated mixtures.

Dietary exposure to brominated flame retardants correlates with male blood levels in a selected group of Norwegians with a wide range of seafood consumption

This study investigates dietary exposure and serum levels of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in a group of Norwegians (n = 184) with a wide range of seafood consumption (4-455 g/day). Mean dietary exposure to Sum 5 PBDEs (1.5 ng/kg body weight/day) is among the highest reported. Since concentrations in foods were similar to those found elsewhere in Europe, this may be explained by high seafood consumption among Norwegians. Oily fish was the main dietary contributor both to Sum PBDEs and to the considerably lower HBCD intake (0.3 ng/kg body weight/day). Milk products appeared to contribute most to the BDE-209 intake (1.4 ng/kg body weight/day). BDE-209 and HBCD exposures are based on few food samples and need to be confirmed. Serum levels (mean Sum 7 PBDEs = 5.2 ng/g lipid) and congener patterns (BDE-47 > BDE-153 > BDE-99) were comparable with other European reports. Correlations between individual congeners were higher for the calculated dietary exposure than for serum levels. Further, significant but weak correlations were found between dietary exposure and serum levels for Sum PBDEs, BDE-47, and BDE-28 in males. This indicates that other sources in addition to diet need to be addressed.

Modeling of DR CALUX ® bioassay response to screen PCDDs, PCDFs, and dioxin-like PCBs in farm milk from dairy herds

A recent issue in the EU legislation is the evaluation of the toxicologically-equivalent contribution of dioxin-like polychlorobiphenyls (DL-PCBs) in addition to that coming from polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs) as contaminants in foods for a total of 29 congeners. This fact is determining the need to revise analytical criteria both for confirmatory and screening analysis. In this work, a modeling was developed to check the reliability of the outcomes of the DR CALUX ® bioassay when applied to farm milk samples characterized by large differences in congener patterns. To reproduce some field conditions where DL-PCB contributions up to 90% of total WHO-TEQs (HRGC-HRMS assessment) were recorded in dairy products, goat milk samples from a common bulk were fortified at different TEQ levels with mixtures containing either PCDDs and PCDFs or non- ortho substituted DL-PCBs. Fortification ranged approximately 4.5–15 pgWHO-TEQ/g fat. Based on the results, DR CALUX ® relative potency value (REP) of DL-PCB 126 was estimated 0.061 against the canonical WHO-TEF of 0.1. The value of 0.061 together with the other DR CALUX ® REPs from the literature for the remaining 28 congeners were used to model DR CALUX ® response (C-TEQs) in milk samples with different congener patterns. The theoretical underestimation of DR CALUX ® data could be mitigated by correcting the latter with the linear correlation experimentally obtained between C-TEQs and the WHO-TEQs. Under these conditions, the use as calibrants of reference samples with different analytical patterns could help those laboratories involved in a high throughput routine to set the most appropriate decision limits to optimize screening output.

Dramatic Changes in the Temporal Trends of Polybrominated Diphenyl Ethers (PBDEs) in Herring Gull Eggs From the Laurentian Great Lakes: 1982–2006

DecaBDE is a current-use, commercial formulation of an additive, polybrominated diphenyl ether (PBDE) flame retardant composed of > 97% 2,2',3,3',4,4',5,5',6,6'-decabromoDE (BDE-209). Of the 43 PBDE congeners monitored, we report on the temporal trends (1982-2006) of quantifiable PBDEs, and specifically BDE-209, in pooled samples of herring gull (Larus argentatus) eggs from seven colonies spanning the Laurentian Great Lakes. BDE-209 concentrations in 2006 egg pools ranged from 4.5 to 20 ng/g wet weight (ww) and constituted 0.6-4.5% of sigma39PBDE concentrations among colonies, whereas sigma(octa)BDE and sigma(nona)BDE concentrations constituted from 0.5 to 2.2% and 0.3 to 1.1%, respectively. From 1982 to 2006, the BDE-209 doubling times ranged from 2.1 to 3.0 years, whereas for sigma(octa)BDEs and sigma(nona)BDEs, the mean doubling times ranged from 3.0 to 11 years and 2.4 to 5.3 years, respectively. The source of the octa- and nona-BDE congeners, e.g., BDE-207 and BDE-197, are the result of BDE-209 debromination, and they are either formed metabolically in Great Lakes herring gulls and/or bioaccumulated from the diet and subsequently transferred to their eggs. In contrast to BDE-209 and the octa- and nona-BDEs, congeners derived mainly from PentaBDE and OctaBDE mixtures, e.g., BDE-47, -99, and -100, showed rapid increases up until 2000; however, there was no increasing trend post-2000. The data illustrates that PBDE concentrations and congener pattern trends in the Great Lakes herring gull eggs have dramatically changed between 1995 and 2006. Regardless of BDE-209 not fitting the pervasive criteria as a persistent and bioaccumulative substance, it is clearly of increasing concern in Great Lake herring gulls, and provides evidence that regulation of DecaBDE formulations is warranted.

Occurrence and Biomagnification of Polychlorinated Naphthalenes and Non- and Mono-ortho PCBs in Lake Ontario Sediment and Biota

Biota and surface sediments collected from Lake Ontario were analyzed for polychlorinated naphthalenes (PCNs) and non- and mono-ortho-substituted polychlorinated biphenyls (n/ m-o-PCBs) to compare bioaccumulation behavior of these classes of dioxin-like chemicals in a food web from the Great Lakes. Mean sigmaPCN concentrations (tri-octaCN) ranged from 14 +/- 9 pg/g in plankton to 3500 +/- 3200 pg/g (wet weight) in lake trout while sediments contained from 21 to 38 ng/g (dry weight). Principal components analysis of PCN congener patterns indicated that chlorine substitution determined which congeners favored accumulation (e.g., CN-42, -52, -60, -66, -67, and -73), while others may be subject to metabolism. The bioaccumulative congeners exhibited similar trophic magnification factors (TMFs; 1.23-1.42) and biomagnification factors (BMFs; 5.5-8.6) to the n/m-o-PCBs for the trout/weighted diet relation, although BMFs for a benthic feeding relationship (slimy sculpin/Diporeia) indicated that the n/m-o-PCBs were more bioavailablethroughthe benthic pathway. PCNs contribute significantly to the burden of dioxin-like compounds in Lake Ontario biota, contributing between 12 and 22% of total PCN + PCB TEQ in lake trout and up to 69% in benthic organisms.

Atmospheric levels and distribution of dioxin-like polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the vicinity of an iron and steel making plant

Polyurethane foam disk passive air samplers (PAS) were deployed in a steel complex, and in residential and semi-rural areas of a city in Southern Korea between January and April 2006. Dioxin-like polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were monitored to investigate the influence of the steel complex on the residential and semi-rural areas. The average levels of ∑ 12PCB (26.2; 6.1–61.8 pg m −3) and ∑ 9PBDE (25.2; 9.0–61.6 pg m −3) in the steel complex were higher than those of neighboring areas, indicating that the steel complex is a major source of both chemical groups. No significant difference in the congener patterns for the different areas suggests that the study area is commonly affected by the same sources. Elevated air concentrations at the eastern sites of the city and relatively low concentrations at the residential area close to the steel complex were observed. According to air dispersion modeling, the major wind direction plays a key role in determining this spatial distribution of PCBs and PBDEs. Consequently, the levels of these chemicals at the residential area might not be strongly influenced by the emissions from the steel complex. This study suggests that the combination of passive air sampling and air dispersion modeling is a useful tool for assessing source–receptor relationships of persistent organic pollutants (POPs) on a local scale.

Polychlorinated biphenyls (PCBs) and hydroxy-PCBs in adipose tissue of women in Southeast Spain

Polychlorinated biphenyls (PCBs) and hydroxylated PCBs (OH-PCBs) were investigated in human adipose tissue samples collected from 20 women undergoing surgery. Mean sum of PCB and sum of OH-PCB levels were 737 ng/g of lipid and 8 pg/g of lipid, respectively. Among PCBs, congeners 180, 153, 138 and 170 were the most frequent and abundant, and together constituted 72% of the total amount of PCBs in adipose tissue. The PCB congener pattern and the frequencies and concentrations of non-dioxin-like and non-hydroxylated congeners observed in adipose tissue were similar in distribution and order of magnitude to the profile previously published in Spain but lower than that found in other European countries. Among OH-PCB congeners studied, 4-OH-PCB 107/118 was found at the highest concentrations followed by 3′-OH-PCB 180 and 3-OH-PCB 138. To date, no information on levels of PCB metabolites in the Spanish population is available for comparison. These three predominant OH-PCBs contributed 97% of all OH-PCBs. Twelve dioxin-like PCBs contributed around 8% of the total PCB exposure, and all were present in all study subjects. Further research is required to determine trends in human exposure to PCBs and OH-PCBs and how existing banning measures affect exposure.

Anaerobic transformation of polybrominated biphenyls with the goal of identifying unknown hexabromobiphenyls in Baltic cod liver

Polybrominated biphenyls (PBBs) have been introduced as flame retardants in 1970. Despite decreasing application rates since the mid-1970s, PBB residues are still reported in the environment. Furthermore, environmental PBB residues often do not match the PBB pattern in technical products. To get insights into the structures of environmentally-relevant PBBs, the congener patterns of technical hexabromobiphenyl (THBB), octabromobiphenyl (TOBB), synthesized PBB 209 were compared to PBB residues in a cod liver sample from the Baltic Sea. The most relevant PBB congeners in Baltic cod liver were not present in the technical products and therefore most likely metabolites. For this reason, TOBB and HPLC-fractions obtained from this technical product were incubated with super-reduced cyanocobalamine. Reductive debromination was found to be the predominant transformation process. Bromine substituents in ortho-positions proved to be more recalcitrant, and several of the unknown PBBs were tri- and tetra- ortho substituted congeners. Furthermore, the key-PBBs determined in Baltic cod liver were formed during this process. The most important hexabromobiphenyl in Baltic cod liver was identified as PBB 155 by parallel synthesis. PBB 155 which was not detected in the technical PBB product analyzed was suggested as an indicator PBB congener suited to decide whether PBB residues originate from the previous use of THBB (low relative abundance of PBB 155) or TOBB/TDBB (high relative abundance of PBB 155). The latter scenario was found to be valid for the Baltic cod liver sample. Thus, PBBs in the Baltic Sea appeared to originate from partially-weathered residues of PBB 209.

Case Report: Human Exposure to Dioxins from Clay

ContextFor the general population, the dominant source of exposure to dioxin-like compounds is food. As part of the University of Michigan Dioxin Exposure Study (UMDES), we measured selected polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) in serum of 946 subjects who were a representative sample of the general population in five Michigan counties.Case presentationThe total toxic equivalency (TEQ; based on 2005 World Health Organization toxic equivalency factors) of serum from the index case was 211 ppt on a lipid-adjusted basis, which was the highest value observed in the UMDES study population. This subject had no apparent opportunity for exposure to dioxins, except that she had lived on property with soil contaminated with dioxins for almost 30 years, and had been a ceramics hobbyist for > 30 years. Soil from her property and clay that she used for ceramics were both contaminated with dioxins, but the congener patterns differed.DiscussionThe congener patterns in this subject’s serum, soil, and ceramic clay suggest strongly that the dioxin contamination in clay and not soil was the dominant source of dioxin contamination in her serum.Relevance to public health practice: It appears that ceramic clay, in particular the process of firing clay with unvented kilns, can be a significant nonfood and nonindustrial source of human exposure to dioxins among ceramics hobbyists. The extent of human exposure from ceramic clay is unclear, but it may be widespread. Further work is needed to more precisely characterize the routes of exposure.

Snapping Turtles (Chelydra serpentina) as Bioindicators in Canadian Areas of Concern in the Great Lakes Basin. 1. Polybrominated Diphenyl Ethers, Polychlorinated Biphenyls, and Organochlorine Pesticides in Eggs

We examined the concentrations and spatial patterns of congeners of PBDEs, PCBs, and organochlorine pesticides in snapping turtle (Chelydra serpentina) eggs from Areas of Concern (AOCs) on the Canadian shores of Lake Ontario, St. Lawrence River, and connecting channels. Eggs from Lyons Creek (Niagara River AOC) reflected a local PCB source over a range of 7.5 km (3.2-10.8) from the Welland Canal. PCB contamination in eggs declined with increasing distance from the Welland Canal, whereas the relative contribution of congeners associated with Aroclor 1248/1254 increased with sigma PCB concentrations. Compared to turtle eggs from other sites in Lake Erie and Lake Ontario, eggs from Lyons Creek and Snye Marsh had PCB congener patterns that reflected a strong contribution from Aroclor 1254. PCBs in the eggs were associated with industrial sources and reflected the composition of different Aroclor technical mixtures. Organochlorine pesticides in eggs tended to be highest at Hamilton Harbour and Bay of Quinte AOCs, and were dominated by DDE, sigma chlordane, and mirex. In contrast, PBDE congener patterns in turtle eggs resembled PentaBDE technical formulations regardless of absolute concentrations or location, and were largely associated with urban environments.

Polybrominated Diphenyl Ethers in Seafood Products of South China

South China is probably one of the heaviest polybrominated diphenyl ether (PBDE) polluted regions in the world, thanks to the presence of huge and rapidly growing electronics manufacturing industries, as well as several of the world's largest e-waste recycling sites in the region. In the present work, a wide variety of nonfish seafood products collected from South China was analyzed for PBDE residues. The concentrations of PBDEs in seafood products were highly species-specific, and the magnitude of PBDE pollution was moderate in South China compared to the global levels. Congener patterns of PBDEs in seafood samples suggested that seafood products are prone to accumulating low-brominated congeners, and possible metabolic debromination of BDE-99 to BDE-47 could occur in certain organisms, such as crabs and mantis shrimp. Generally, the congener profile was dominated by BDE-209, and to a lesser extent by BDE-47 and BDE-99, which was consistent with the fact that Deca-BDE is mass-produced in China and with previous sediment results from the same area. The occurrence of BDE-209 in aquatic species from South China suggests that BDE-209 appears to be more bioavailable than previously thought, and the environmental fate and safety of BDE-209 require further investigation and call for a thorough reassessment.

Polybrominated diphenyl ethers in domestic indoor dust from Canada, New Zealand, United Kingdom and United States

Because of the similarities in European and North American dietary exposure, it has been suggested that the order of magnitude higher body burdens in North Americans may be due to international variations in exposure via ingestion of indoor dust. Furthermore, ingestion of indoor dust has been suggested as a possible source of PBDEs in the blood serum of New Zealanders. Hence, polybrominated diphenyl ethers (PBDEs) were measured in domestic indoor dust from: Amarillo/Austin, Texas, US; Birmingham, UK; Toronto, Canada; and Wellington, New Zealand. Concentrations of BDE 209 in two UK samples were – at 520,000 and 100,000 ng g−1 – the highest ever recorded in a domestic (or office) indoor dust sample. Median concentrations in ng g−1 were: in Canada 620 and 560 for Σtri–hexa-BDEs and BDE 209 respectively; in New Zealand 96, BDE 209 not determined; in the UK 59 and 2,800; and in the US 1600 and 1300. With respect to BDE 209, concentrations were in the order: UK∼US>Canada. For Σtri–hexa-BDEs, the order of concentrations was US∼Canada≫New Zealand∼UK. Combined with principal component analysis of congener patterns, this suggests that, while North American dusts are contaminated by both Deca- and Penta-BDE commercial formulations, UK dusts are contaminated predominantly by Deca-BDE. The Octa-BDE formulation appears of minimal importance in accordance with available market demand figures. Despite the commercial formulations of PBDEs never having been manufactured in, nor imported into New Zealand, their presence in dusts from that country suggests international trade in PBDE-containing goods is an important pathway effecting their global distribution.

Degradation of PCB congeners by bacterial strains

Biological in situ methods are options for the remediation of contaminated sites. An approach to quantify biodegradation by soil bacteria was developed, combining experiment with mathematical modelling. We performed in vitro assays to investigate the potential and kinetics of the wild-type degrader, Burkholderia sp. strain LB400 (expressing bph) and the genetically modified Pseudomonas fluorescens strains F113pcb and F113L::1180 (expressing bph under different promoters) to metabolise individual congeners of polychlorinated biphenyls (PCBs). Kinetics of metabolism was analysed using the Monod model. Results revealed similar patterns of degradable PCB congeners for LB400 and F113L::1180. The degree of PCB degradation was comparable for LB400 and F113L::1180 but was much lower for F113rifpcb. In additional mesocosm experiments with PCB-contaminated soil, the F113 derivatives demonstrated a good survival ability in willow (Salix sp.) rhizosphere. Strain F113L::1180 in combination with willow plants is expected to degrade a large spectrum of PCB congeners in soil. The data from the experiments were used to calculate the time scale of the degradation process in a PCB-contaminated soil. The uncertainty of the model predictions due to the uncertainties of experimental removal velocities and bacterial cell density in soil was quantified.

Biodegradative potential and characterization of psychrotolerant polychlorinated biphenyl-degrading marine bacteria isolated from a coastal station in the Terra Nova Bay (Ross Sea, Antarctica)

Antarctic marine bacteria were screened for their ability to degrade polychlorinated biphenyls (PCB) as the sole carbon and energy source at both 4 °C and 15 °C. PCB-degrading isolates (7.1%) were identified by sequencing their 16S rDNA as Pseudoalteromonas, Psychrobacter and Arthrobacter members. One representative isolate per genera was selected for evaluating the biodegradative potential under laboratory scale and phenotypically characterized. Removal of individual PCB congeners was between 35.6% and 79.8% at 4 °C and between 0.4% and 82.8% at 15 °C. Differences in the removal patterns of PCB congeners were observed in relation to the phylogenetic affiliation: Arthrobacter isolate showed similar biodegradation efficiencies when growing at 4 °C and 15 °C, while Pseudoalteromonas better degraded PCBs at 15 °C. No biodegradation was detected for Psychrobacter isolate at 4 °C. Results obtained highlight the occurrence of PCB-degrading bacteria in Antarctic seawater and suggest the potential exploitation of autochthonous bacteria for PCB bioremediation in cold marine environments.

Seasonal and spatial character of PCBs in a chemical industrial zone of Shanghai, China

As one of China's great metropolises, Shanghai is suffering from the impact of manufacture and the use of chemical industrial products, and it faces serious pollution from polychlorinated biphenyls (PCBs). Therefore, in this study, in order to assess the seasonal and spatial character of contamination from chemical industrial zones, the concentrations of PCBs have been measured in various environmental media, including soil, leaves, and atmospheric particulate samples collected in a chemical industrial zone of Shanghai and compared with samples from presumably unpolluted sites of rural areas. In soils, the PCB concentrations ranged from 0.5 ng g(-1) (unpolluted site) to 586.85 ng g(-1) (chlor-alkali industry site). The concentrations of PCBs in evergreen leaves ranged from 0.3 ng g(-1) to 32.46 ng g(-1), and more chlorinated biphenyls congeners, such as penta-biphenyls and hexa-biphenyls, were the dominant contributors in winter and spring. Seasonal differences and the constitution patterns of congeners might be affected by the temperature and industrial activities. The PCB concentrations in the leaves of deciduous trees increase over time as the leaves grow. The PCB concentration in atmospheric particulates was in the range of 9.22-14.15 x 10(3)pg m(-3), which might be the result of influence from climate and industrial activities. The relativity of PCB contents among the environmental media was discussed. The results in this paper provide an important profile of the current contamination status of a key chemical industrial zone in China.