Process-diagnostic patterns of chlorobiphenyl congeners in two radiochronologically characterized sediment cores from the northern Baffin Bay.

Polychlorinated biphenyl (PCB) patterns were interpreted in two radioisotopically constrained sediment cores from the Arctic ocean in order to seek clues about their large-scale environmental fates. Low but clearly measurable fluxes of individual PCB congeners were observed in deeper layer sediments, corresponding to the past 170 years, in a single dated core from the Baffin Bay shelf. Fluxes of the dominant individual congeners in the surface sediments were 20-100 pg m(-2) d(-1). Combining these data with the sediment data from the Arctic Monitoring and Assessment Program, it appears that the PCB distribution in Arctic surface sediments is governed by the organic carbon (OC) content of the sediments. The historical development of the PCB congener fingerprint suggests that the modern sediments are enriched in medium-chlorinated congeners, implying that there are at least two significant, but distinctly different, sink processes acting on the PCB pool. The relative abundance of light-to-heavy congeners, in mid-shelf marine sediments of similar ages, between 40 degrees N and 76 degrees N latitude suggests a northward dilution of PCBs which is stronger attenuated for heavier congeners, consistent with a temperature-driven global fractionation process. The significant presence of PCB in historical archives pre-dating the organochlorine society, as observed in this and several previous studies, awaits a fuller explanation.     

PCB accumulation and tissue distribution in cave salamander (Proteus anguinus anguinus, Amphibia, Urodela) in the polluted karstic hinterland of the Krupa River, Slovenia

For over two decades, a manufacturer of electrical capacitors disposed of its waste within the karstic hinterland of the Krupa River (Slovenia) resulting in the surroundings becomming heavily polluted with PCB. Albeit the extent of the contamination has been known since 1983 and the Krupa River has become one of the most PCB polluted river in Europe, the effects on the cave fauna of the region remain unknown. The most famous cave dweller of the Krupa hinterland is the endemic cave salamander Proteus anguinus anguinus. In this study we determine the levels of PCB in the tissues of the Proteus and in river sediments. The total concentration of PCB in individual tissue samples from specimens of the Krupa spring was between 165.59 μg g⁻¹ and 1560.20 μg g⁻¹ dry wt, which is at least 28-times higher than those from an unpolluted site. The kidneys contained the lowest concentration, while the highest concentration was in subcutaneous fat and tissues with high lipid contents like visceral fat and liver. Total PCB concentrations in sediment samples from the Krupa River were between 5.47 and 59.20 μg g⁻¹ dry wt showing that a high burden of PCB still remains in the region. The most abundant PCB congeners in all analyzed samples were di-ortho substituted (PCB #101, #118, #138 and #158), but higher proportion of mono-ortho PCB was present in sediments. The ability of Proteus to survive a high PCB loading in its environment and especially in its tissues is remarkable. Its partial elimination of low chlorinated and mono-ortho substituted congeners is also reported.     

Bioavailability of PCBs from field-collected sediments: application of Tenax extraction and matrix-SPME techniques

Two chemical approaches, Tenax extraction and matrix solid phase microextraction (matrix-SPME), were evaluated for their potential to improve the prediction of bioavailability by equilibrium partitioning theory (EPT) across sediments with various characteristics. Biota-sediment accumulation factors (BSAFs) and body residues were quantified by exposing Lumbriculus variegatus to three PCB-contaminated field sediments. The concentration of PCBs in biota was positively correlated to the total PCB sediment concentration, the PCB concentration in the rapidly desorbing fraction estimated using Tenax extraction, and the PCB concentration on the SPME fibers. Results showed EPT was acceptable for estimating bioavailability from the tested sediments with sum PCB BSAFs of 1.18-2.47; however, it overestimated PCB bioavailability from sandy sediment. Both Tenax extraction and matrix-SPME, which take sequestration into account, reduced variability in prediction of PCB bioavailability across sediments, including the sandy sediment, and could be used as cost- and time-efficient alternatives for bioassay. Matrix-SPME was considered the better technique due to its ability to directly predict PCB body residues in the exposed biota and its potential use with in situ applications in the field.     

Development of a simple selective SFE method for the determination of desorption behaviour of PCBs in two Swedish sediments

A simple selective supercritical fluid extraction (SFE) method was developed for the determination of desorption behaviour of PCBs in sediments. This method was applied to determine the distribution of individual PCB congeners among sites of differing bonding strengths in two Swedish sediments (Lake J?rnsj?n and Baltic bay Orserumsviken). Four different PCB fractions were distinguished in each sediment by applying consecutively harsher supercritical fluid extraction conditions on the same sample. Even though the two sediments had completely different textures, they showed very similar extraction behaviour. It was shown that, in both sediments, a major part of the PCBs (58% and 65%, respectively) were located at "fast sites", from which they were extractable already with the mildest extraction conditions (60 min, 40 degrees C and 120 bar). Only a small fraction of the PCBs were so tightly bound to the sediments (located at "slow sites"), that they could be extracted only under the harshest conditions (60 min, 150 degrees C and 400 bar). Information of this kind should be of great value for the determination of bioavailability of pollutants in sediments and soils, and it is the author's belief that this technique has the potential to develop into a powerful tool in environmental risk assessment.     

PCBQ: Computerized quantification of total PCB and congeners in environmental samples

Computerized methodologies for the quantification of total PCBs, PCB in Aroclor mixtures and individual PCB congeners in environmental samples are presented. The method for total PCBs is based on a multiple-linear regression analysis using data from capillary gas chromatography of Arocolor standards. PCB congeners were identified and their weight percentages determined in Aroclor mixtures by GC/MS. PCB congeners and total PCBs were accurately quantified in predetermined test data and environmental samples.     

Why biota still accumulate high levels of PCB after removal of PCB contaminated sediments in a Norwegian fjord

Accumulation of polychlorinated biphenyls (PCBs) in blue mussels (Mytilus edulis) and semipermeable membrane devices (SPMDs) was still high after the removal of PCB contaminated sediments from a Norwegian fjord by dredging. The accumulation of low chlorinated PCB congeners with a low octanol water-partitioning coefficient (K_ow) in blue mussels and SPMDs was higher than for the highly chlorinated congeners with a high K_ow. The accumulation of low chlorinated congeners was also higher in a lightly contaminated area compared to a highly contaminated area. That dredging the contaminated sediments was unsuccessful in lowering PCB levels in the biota may be for the following reasons: (1) Due to the low solubility of PCBs in the water it is possible that a decrease in the sediment concentration of PCB would leave the water concentrations of PCB unchanged. (2) Removal of the fine organic sediments may also play an important role, since a seabed with coarse inorganic material has a lesser ability to bind PCB. (3) The dredging may whirl up fine contaminated particles that eventually settles on the seabed producing a thin contaminated sediment layer that determine the water concentration. (4) Bioaccumulation in blue mussels and in the SPMDs occurs mostly from PCB dissolved in the water column. Since the water concentration of PCB is unchanged by the dredging, the accumulation in SPMDs and mussels is the same as before dredging. Further monitoring need to be carried out to report the long-term effect of the dredging.     

Formation pathways of polychlorinated dibenzofurans (PCDFs) in sediments contaminated with PCBs during the thermal desorption process

Thermal desorption has attracted considerable interest as a remediation technology for the removal of dioxins and polychlorinated biphenyls (PCBs) from contaminated soils and sediments. Although several research groups have confirmed that polychlorinated dibenzofurans (PCDFs) are formed from PCBs during the thermal desorption of sediments contaminated with PCB, the formation pathways remain poorly understood. Herein, thermal desorption has been used to develop a greater understanding of the formation pathways of PCDFs from sediments contaminated with PCBs. PCB decomposition experiments of sediments contaminated with PCBs were performed over 5 min at 450 °C with a gas composition of 10% O(2)/90% N(2), either in the absence (Run 1) or presence (Run 2-4) of one of three different (13)C(12)-labeled PCB individual standards. The results of Run 1 showed that 99.96% of PCBs and 98.40% of polychlorinated dibenzo-p-dioxins (PCDDs) in the treated sediments had decomposed, whereas the concentration levels of PCDFs had increased by a factor of 31. The addition of different (13)C(12)-labeled PCBs to the sediment sample yielded different (13)C(12)-PCDFs isomer patterns, with formation pathways including loss of ortho-Cl(2), loss of HCl involving a 2,3-chlorine shift, loss of ortho-H(2) and dechlorination.     

Polychlorinated biphenyls (PCBs) in sediments in Hong Kong: a congener-specific approach to the study of coplanar PCBs in aquatic ecosystems

Patterns of contamination by polychlorinated biphenyls (PCBs) were investigated in fourteen samples of coastal sediments from Hong Kong. Congener-specific analyses revealed nine sediment samples from Junk Bay to contain PCBs at concentrations ranging from 31 to 2200 ng g(-1) dry weight, concentrations generally increasing with distance north in the Bay. By contrast, five sediments from the Tolo area to the north-east of Hong Kong exhibited total PCB levels of only 6.6 to 45 ng g(-) dry weight. The patterns of relative abundance of PCB congeners in the northern Junk Bay sediments suggested the existence of ongoing source(s) of PCBs in this area; biphenyls of lower chlorination were present at high concentration in these samples. Three coplanar PCBs (3', 4, 4'-tetrachlorobiphenyl; 3,3',4,4',5-pentachlorobiphenyl; and 3,3',4,4',5,5'-hexachlorobiphenyl) were found to be present in Junk Bay sediments; these are highly toxic and are cause for concern in aquatic environments. The abundance of the three coplanar PCBs in the sediments studied was similar to that in commercial PCB mixtures, suggesting that these congeners are not enriched over other PCBs by the sediments of coastal ecosystems. It is concluded that the preferential enrichment of coplanar PCBs occurs in the biosphere, rather than in sediments.     

PCB dechlorination hotspots and reductive dehalogenase genes in sediments from a contaminated wastewater lagoon

Polychlorinated biphenyls (PCBs) are a class of persistent organic pollutants that are distributed worldwide. Although industrial PCB production has stopped, legacy contamination can be traced to several different commercial mixtures (e.g., Aroclors in the USA). Despite their persistence, PCBs are subject to naturally occurring biodegradation processes, although the microbes and enzymes involved are poorly understood. The biodegradation potential of PCB-contaminated sediments in a wastewater lagoon located in Virginia (USA) was studied. Total PCB concentrations in sediments ranged from 6.34 to 12,700 mg/kg. PCB congener profiles in sediment sample were similar to Aroclor 1248; however, PCB congener profiles at several locations showed evidence of dechlorination. The sediment microbial community structure varied among samples but was dominated by Proteobacteria and Firmicutes. The relative abundance of putative dechlorinating Chloroflexi (including Dehalococcoides sp.) was 0.01–0.19% among the sediment samples, with Dehalococcoides sp. representing 0.6–14.8% of this group. Other possible PCB dechlorinators present included the Clostridia and the Geobacteraceae. A PCR survey for potential PCB reductive dehalogenase genes (RDases) yielded 11 sequences related to RDase genes in PCB-respiring Dehalococcoides mccartyi strain CG5 and PCB-dechlorinating D. mccartyi strain CBDB1. This is the first study to retrieve potential PCB RDase genes from unenriched PCB-contaminated sediments.     

Seasonal variation of the distribution of PCBs in sediments and biota in a PCB-contaminated estuary

To elucidate the effects of seasonal variation of precipitation on the distribution of polychlorinated biphenyls (PCBs) in estuarine sediments and benthic feeders, PCB concentrations of river surface sediments and mullet fish (Liza macrolepis) were investigated in the estuary of Er-Jen River near former PCB contamination sites before and after each wet season from 2002 to 2004. Analyses of grain size distribution and organic matter revealed that the pre-existing surface sediments were covered by and mixed with the soil particulates brought by surface runoff after each wet season. Obvious increment of PCB content and significantly elevated fraction (p < 0.005) of light PCBs of the river mouth’s sediments after each wet season indicated that the invading particles were rich in unweathered PCBs. PCBs previously buried in the surface soil of heavily contaminated sites were flushed into this estuary through surface runoff. The precipitation altered the PCB patterns in sediment organic matter, the dietary source of mullet, and consequently changed that of mullets accordingly, which all possessed significant greater fraction of light PCBs. In this study, it was demonstrated that seasonal summer precipitation affected the distribution of PCBs on surface sediments and the mullets of this estuary. PCB residuals retained in this region still pose potential threats to biota resided here.     

Digestibility, retention and incorporation of low-level dietary PCB contents in laying hens

Polychlorinated biphenyls (PCBs) are persistent and hazardous environmental contaminants, which tend to bioaccumulate in the food chain. In the present report the long-term effect of low-level dietary PCB concentrations was studied on performance, egg quality, apparent PCB digestibility, apparent PCB retention and PCB accumulation in laying hens that were fed experimental diets for 41 weeks. The tested dietary concentrations of supplemented PCBs, based on the sum of seven reference congeners, were 0, 1.5 and 6 ng/g. PCB ingestion did not significantly affect performance or egg quality parameters. The PCB concentration in egg yolk reached a nearly constant level after approximately 40 and 70 days of consumption of the diets containing 1.5 and 6 ng PCBs/g, respectively. Apparent faecal PCB digestibility and apparent retention were not influenced by dietary levels of added fat varying between 1.5% and 4.5%, but were significantly higher in hens fed diets containing added PCBs. Moreover, apparent PCB digestibility and retention increased significantly with age. Among the seven individual PCB congeners, no systematically significant differences with regard to apparent faecal digestibility were observed throughout the experiment. Accumulation of PCBs in the fat fraction of egg yolk, abdominal adipose tissue and thigh and breast muscle greatly depended upon PCB intake, but never exceeded the maximally allowed concentration of 200 ng/g. As PCBs 52 and 101 were hardly found in egg yolks and hen tissues, it was concluded that both congeners were greatly metabolised. Comparison of relative contents of individual PCB congeners revealed that PCBs 118, 138 and 153 were preferentially incorporated in yolk and body tissues.     

Spatial distribution and source apportionment of PCBs in sediments around İzmit industrial complexes, Turkey

The spatial distribution, degree of pollution and major sources of PCBs were evaluated in surficial sediments within the heavily urbanized and industrialized ?zmit Bay and its main freshwater inputs. ΣPCB concentrations range from 2.90 to 85.4ngg(-1) in marine sediments and from ND to 47.7ngg(-1) in freshwater sediments. Results suggest that high concentrations of ΣPCBs were localized around a chlor-alkali plant and an industry that handles bulk liquid, dry and drummed chemicals, and petroleum products in the Bay. Using a chemical mass balance receptor model (CMB), major sources of PCBs in the region were investigated. The CMB model identified Aroclor 1254 and 1260 to be the major PCB sources in marine sediments and the less chlorinated Aroclor 1248 and 1242 as the major PCB sources in freshwater sediments. The potential sources for the PCBs were briefly discussed in terms of their use in various industrial applications.     

Polychlorinated biphenyls (PCBs) and Polybrominated Diphenyl Ethers (PBDEs) in surface sediments from Monastir Bay (Tunisia,Central Mediterranean): Occurrence,distribution and seasonal variations

An assessment of PCB and PBDE contamination of surface sediments in Monastir Bay was carried out in two contrasted seasons of the year. Samples were collected from 5 sites and analyzed for the ∑₇ marker PCBs (i.e. PCBs 28, 52, 101, 118, 138, 153 and 180) and ∑₄ PBDE congeners (PBDEs 47, 99, 119 and 153) by GC/ECD. Concentrations of both PCBs and PBDEs showed seasonal variations. PCB concentrations were in the range of 3.1–9.3 ng g⁻¹ and 1.1–8.1 ng g⁻¹ in wet and dry season respectively, and sediments were considered moderately contaminated with PCBs. All PCBs analyzed were detected in surface sediments. PCB 153 and 52 congeners showed the highest relative abundance in both winter and summer. PBDE concentrations ranged from not detect to 0.1 ng g⁻¹, with only BDE-47 congener detected in sediments and only in winter. Analysis of spatial and seasonal variations indicated that PCB distribution is governed by hydrodynamics and temporal variability of inputs. While the PCB contamination appeared to be mainly land-based, PBDEs are suspected to originate from atmospheric deposition.     

Polychlorinated biphenyls in surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in East China Sea

The spatial distribution and source of polychlorinated biphenyls (PCBs) in 30 surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in Eastern China were analysed. Total concentrations of PCBs ranged from 9.33 to 19.60 ng g⁻¹ dry weight for all the sampling stations. The observed PCB levels were lower than those in areas of high urbanisation or contamination in the bay. Low-chlorinated PCBs, dominated by tri-PCB, were identified as the prevalent contaminate of surface sediments, and the top three PCB congeners were lighter chlorinated congeners (PCB 8, PCB 18 and PCB 28). These results were in agreement with the fact that tri-PCB compounds are the dominant contaminants in China. The result of the principal component analysis revealed that all samples were similar in composition to Aroclor 1242, suggesting they might originate from electrical capacitors and transformers. The levels of PCBs were significantly correlated with the total organic carbon in the sediments.     

Distribution characteristics of PCBs in the sediments of the lower Nakdong River, Korea

The objective of this study is to investigate the distribution characteristics of polychlorinated biphenyl (PCB) congeners in sediments of the lower Nakdong River of Korea. The sediments were collected using a grab sampler in May 1999. PCBs were extracted in the Soxhlet extractor and cleaned by using adsorption chromatographic techniques and concentrated sulfuric acid. A HP6890 gas chromatograph equipped with an electron capture detector was used for quantification. The results of congener specific analysis showed that the total concentration is ranged over 1.1-141 ng/g dry weight. The levels of PCB congeners are significantly correlated with the total organic carbons (TOC) in the sediments. The major fractions of PCBs in these sediments are congeners containing 4, 5 or 6 chlorine atoms per biphenyl molecule.     

Pesticides and PCBs in sediments and fish from the Salton Sea, California, USA

The Salton Sea, the largest manmade lake in California, is officially designated by the State of California as an agricultural drainage reservoir. The purpose of this study was to determine organochlorine and organophosphorous pesticides, as well as polychlorinated biphenyl (PCB) concentrations in sediments and fish tissues in the Salton Sea and evaluate the relative ecological risk of these compounds. Sediment samples were taken during 2000-2001 and fish tissues (Tilapia mossambique, Cynoscion xanthulu) were collected in May 2001. All samples were analyzed for 12 chlorinated pesticides, 6 organophosphorus pesticides, and 55 polychlorinated biphenyl (PCB) congeners. SigmaDichlorodiphenyltrichloroethane (SigmaDDT) and total PCB concentrations observed in sediments ranged from 10 to 40 and 116 to 304 ng/g dry wt, respectively. DDT/DDD ratios in sediments and fish tissues of the northern Sea in 2001 indicated recent DDT exposure. Lindane, dieldrin, dichlorodiphenylethane (DDE) and total PCB concentrations detected in sediments exceeded probable effect levels established for freshwater ecosystems, and pp-DDE and total PCB concentrations were higher than effect range-median values developed for marine and estuarine sediments. In fish liver, concentrations of endrin and SigmaDDT exceeded threshold effect level established for invertebrates. SigmaDDT concentrations detected in fish tissues were higher than threshold concentrations for the protection of wildlife consumers of aquatic biota. DDE concentrations in fish muscles tissues were above the 50 ng/g concentration threshold for the protection of predatory birds. Dimethoate, diazinon, malathion, chlorpyrifos, disulfoton varied from < or = 0.15 to 9.5 ng/g dry wt in sediments and from < or = 0.1 to 80.3 ng/g wet wt in fish tissues. Disulfoton was found in relatively high concentrations (up to 80.3 ng/g) in all organs from Tilapia and Corvina. These results demonstrate continued contamination of specific organochlorine compounds in sediments and resident fish species of the Salton Sea.     

Occurrence and possible sources of polychlorinated biphenyls in surface sediments from the Wuhan reach of the Yangtze River, China

Twenty-seven surface sediment samples were collected from the mainstream and eight tributaries of the Wuhan reach of the Yangtze River, China, in 2005, in order to assess the distribution, possible sources, and potential risk of polychlorinated biphenyls (PCBs) in the environment. The total concentrations of PCBs (the sum of 39 congeners) ranged from 1.2 to 45.1 ng g⁻¹ dry weight, with a mean value of 9.2 ng g⁻¹. Sediment samples with the highest PCB concentrations came from the tributary sites, which are closer to PCB sources. Conversely, PCB concentrations in the sediment from the mainstream sites of Yangtze River were relatively low. The observed PCB levels were higher than those found in the sediments of other rivers in China, but lower than those in river sediments from other urban areas and harbors around the world. Low-chlorinated PCBs, dominated by tetra-PCBs and penta-PCBs, were identified as being prevalent in the surface sediments. Correlation analyses between the PCBs and the geochemistry and heavy metal content of the sediments suggest that the washing of these compounds from the land into the river by floods and heavy rains, or industrial wastewater and domestic sewage, may be the major sources of the PCBs. According to established sediment quality guidelines, the risk of adverse biological effects from the levels of PCBs recorded at most of the studied sites should be insignificant, although the higher concentrations at other sites could cause acute biological damage.     

Routine analysis of hydrocarbons, PCB and PAH in marine sediments using supercritical CO2 extraction

Automated Supercritical Fluid Extraction (SFE), using CO2, was tested and optimised for routine analysis of hydrocarbons (THC), polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) in marine sediments. The aim of the exercise was to reduce the amount of solvents used and to reduce the manual handling time for each sample. The sediments contained elemental sulphur, which was removed during the extraction step using activated Cu. Similar recoveries and reproducibility where found for THC when conventional solvent extractions and SFE where compared. Modifying the CO2 with methanol was necessary to obtain extraction recoveries similar to conventional extraction methods for PCB and PAH.     

Spatial variations and correlations in the distribution of PCDDs, PCDFs and related compounds in sediments from the river Rhine — Western Europe

PCDDs, PCDFs and some related aromatic compounds were determined isomer specifically in sediments from the river Rhine and its tributaries, in order to study sources and environmental fate of these compounds. Additionally, waste water effluents from industries that unintentionally might coproduce PCDDs or PCDFs were analyzed. In all sediments and in some waste water effluents these compounds could be detected. Variations of the isomeric patterns of the PCDFs enabled a distinct industrial area, that was associated with PCB contamination to be identified. The contamination of sediments and organisms from the Dutch river Rhine delta with these compounds mainly could be attributed to the transboundary pollution of the river Rhine.     

Bioaccumulation of PCBs in the cuttlefish Sepia officinalis from seawater, sediment and food pathways

The cuttlefish Sepia officinalis was selected as a model cephalopod to study PCB bioaccumulation via seawater, sediments and food. Newly hatched, juvenile cuttlefish were exposed for 17 days to environmentally realistic concentrations of (14)C-labeled 2,2',4,4',5,5'-hexachlorobiphenyl (PCB#153) (18 ng PCB l(-1) seawater; 30 ng PCB g(-1) dry wt sediments; Artemia salina exposed to 18 ng PCB l(-1) seawater). Accumulation of PCB#153 was followed in three body compartments: digestive gland, cuttlebone and the combined remaining tissues. Results showed that (1) uptake kinetics were source- and body compartment-dependent, (2) for each body compartment, the accumulation was far greater when S. officinalis was exposed via seawater, (3) the cuttlebone accumulated little of the contaminant regardless of the source, and (4) the PCB congener showed a similar distribution pattern among the different body compartments following exposure to contaminated seawater, sediment or food with the lowest concentrations in the cuttlebone and the highest in the remaining tissues. The use of radiotracer techniques allowed delineating PCB kinetics in small whole organisms as well as in their separate tissues. The results underscore the enhanced ability of cephalopods to concentrate organic pollutants such as PCBs, and raise the question of potential risk to their predators in contaminated areas.