Synthesis of polychlorinated biphenyls (PCBs) using the Suzuki-coupling

An improved synthesis of polychlorinated biphenyls (PCBs) utilizing a palladium-catalyzed cross-coupling reaction (Suzuki-coupling) is described. The coupling of (chlorinated) aryl boronic acids 1-3 with bromochlorobenzenes 4 using the standard conditions of the Suzuki-coupling gave the desired PCB congeners 5-7 in good to excellent yields. The self-coupling product of the aryl boronic acids is the major impurity of this reaction. 3,4,5-trichlorophenyl derivatives such as 10 can be synthesized by coupling of an aryl boronic acid with the corresponding bromochloroaniline 8. The approach offers the advantage of high selectivity and good yields compared to conventional methods such as the Cadogan reaction and allows the use of less toxic starting materials.     

Immunoassay monitoring of polychlorinated biphenyls (PCBs) in the Great Lakes

Although polychlorinated biphenyls (PCBs) are no longer manufactured, they are still entering the environment. In some compartments of the environment, PCB concentrations are a serious concern. This is especially true in compartments which accumulate PCBs, and in food items consumed by humans and wildlife. Also, there are situations in which management decisions require rapid, sensitive, accurate measurements, which can be made in real time under field conditions. Methods to use an enzyme-linked immunosorbent assay (ELISA) for PCBs were developed and applied to sediments and fish muscle homogenates collected from the Great Lakes. The extraction methods developed can be applied in the field with non-hazardous solvents, in the absence of sophisticated laboratory equipment. The method detection limit for PCBs in dimethyl sulfoxide (DMSO) extracts of sediment was 0.9 mg/kg. For PCBs in isopropanol extracts of fish tissue, the method detection limit was 0.6 mg/kg. The resolution of the ELISA was 0.83 mg/kg at 1.1 mg/kg and 1.6 mg/kg at 1.7 mg/kg, for sediment and fish tissue, respectively.     

A review of polychlorinated biphenyls (PCBs) pollution in indoor air environment

Polychlorinated biphenyls (PCBs) were widely used in industrial production due to the unique physical and chemical properties. As a kind of persistent organic pollutants, the PCBs would lead to environment pollution and cause serious problems for human health. Thus, they have been banned since the 1980s due to the environment pollution in the past years. Indoor air is the most direct and important environment medium to human beings; thus, the PCBs pollution research in indoor air is important for the protection of human health. This paper introduces the industrial application and potential harm of PCBs, summarizes the sampling, extracting, and analytical methods of environment monitoring, and compares the indoor air levels of urban areas with those of industrial areas in different countries according to various reports. This paper can provide a basic summary for PCBs pollution control in the indoor air environment.

Implications: The review of PCBs pollution in indoor air in China is still limited. In this paper, we introduce the industrial application and potential harm of PCBs, summarize the sampling, extracting, and analytical methods of environment monitoring, and compare the indoor air levels of urban areas with industrial areas in different countries according to various reports.     

Effect of metal and glycol on mechanochemical dechlorination of polychlorinated biphenyls (PCBs)

This paper assesses the potential of mechanochemical method with fine metal powder, glycol and alkali for polychlorinated biphenyls (PCBs) removal from waste insulating oil. The effects of relevant parameters, such as kinds of chemicals, rate and time of milling were examined. After each run, the total PCBs content in waste insulating oil was measured. Polyethylene glycol 200, long chain-glycol was more effective than triethylene glycol and ethylene glycol, short chain-glycol as hydrogen donor in mechanochemical dechlorination of PCBs. A maximum of 99.9% PCBs removal (below 2ppm) and 94% total chlorine removal were achieved with the mechanochemical process for 2h.     

A kinetic distribution model of evaporation, biosorption and biodegradation of polychlorinated biphenyls (PCBs) in the suspension of Pseudomonas stutzeri

Kinetics of distribution of PCBs in an active bacterial suspension of Pseudomonas stutzeri was studied by monitoring the evaporated amounts and the concentration remaining in the liquid medium with the biomass. To determine the biodegradation rate constants of the individual congeners of the PCB formulation Delor 103, a model considering biosorption, evaporation, and primary biodegradation constructed previously was used. Rate constants of biodegradation imply that biodegradation of individual congeners is structure-dependent process. Biodegradability decreases with increasing number of chlorine substituents in the molecule, especially if they are in the ortho and para positions. On the other hand, the increasing number of free ortho and meta positions in the biphenyl molecule leads to better biodegradability. For a simple empirical determination of the influence of the chlorine substitution pattern on biodegradability, the di- and trichlorobiphenyl rate constants of biodegradation were analysed.     

Persistence and fate of polychlorinated biphenyls (PCBs) in sewage sludge-amended agricultural soils

Four metal enriched sewage sludges containing different concentrations of polychlorinated biphenyls (PCBs) were applied to two field soils in the UK in 1968. Samples of the sludges, sludge-amended soils and soils from untreated control plots were stored and analysed retrospectively. Sludge concentrations ranged from 1 to 7 mg SigmaPCB kg(-1). The pattern of PCBs was similar in three of the four sludges, with congeners 14, 18, 28 and 52 present at the highest concentrations. The fourth sludge contained higher amounts of congeners 149, 153, 138 and 180. SigmaPCB concentrations in control plot soil have declined over the last 20 years, indicating a reduction in atmospheric deposition inputs of PCBs to the soil. SigmaPCB concentrations also declined on the sludge-amended plots, reaching control plot concentrations (30-60 microg SigmaPCB kg(-1)) in the late-1980s. Half-lives ranged from < 1 to 8.5 years for congeners 18, 28 and SigmaPCB. Biodegradation and/or the formation of reversibly sorbed soil PCB residues could not account for the losses observed. Volatilisation is implicated as the most important loss process on both the control and sludge-amended plots. Using the fugacity approach, congener concentrations in soils at Luddington were predicted still to have not reached equilibrium with the air. Further losses to the atmosphere are likely.     

Increased deposition of polychlorinated biphenyls (PCBs) under an AC high-voltage power line

There is considerable public concern regarding the potential risks to health of electromagnetic fields in general and high-voltage power lines in particular. As epidemiological findings are not supported by a clearly defined mechanism of direct magnetic field interactions with the human body, potential indirect effects are of interest. It has been suggested that an increased exposure to chemical pollutants could occur near high-voltage power lines due to formation and deposition of charged aerosols. The current study reports empirical evidence that seems to support this hypothesis. The deposition of 18 congeners of polychlorinated biphenyls (PCBs) was studied by collecting samples of pine needles under a 400 kV AC power line and at reference sites in the vicinity. Compared to the reference sites, the average deposition of PCB congeners under the power line was almost double. This difference between the two groups of samples was statistically significant. While it is premature to draw any conclusions regarding the human exposure near high-voltage power lines, the issue deserves attention and further investigations.     

Biostimulation of the autochthonous microbial community for the depletion of polychlorinated biphenyls (PCBs) in contaminated sediments

In this study, the effect of the biostimulation of the autochthonous microbial community on the depletion of polychlorinated biphenyls (PCBs) in historically contaminated sediments (6.260?±?9.3 10^?3?μg PCB/ g dry weight) has been observed. Biostimulation consisted of (1) the amendment of an electron donor to favor the dehalogenation of the high-chlorinated PCBs and (2) the vegetation of sediments with Sparganium sp. plants to promote the oxidation of the low-chlorinated PCBs by rhizodegradation. The effects of the treatments have been analyzed in terms of both PCB depletion and changes of the autochthonous bacterial community structure. The relative abundance of selected bacterial groups with reference to untreated sediments has been evaluated by quantitative real-time PCR. The amendment of acetate determined the enrichment of anaerobic dechlorinators like Dehalococcoides sp. Vegetation with Sparganium sp. plants determined the enrichment of either (3) the dechlorinators, Dehalococcoides and the Chloroflexi o-17/DF-1 strains or (4) the Acidobacteria, β-Proteobacteria, Actinobacteria, α-Proteobacteria, Bacteroidetes, and Firmicutes. The combination of the two biostimulation strategy determined the 91.5 % of abatement of the initial PCB content.     

Painted surfaces--important sources of polychlorinated biphenyls (PCBs) contamination to the urban and marine environment

A study of a large number of samples of flaking old paint from various buildings in Bergen, Norway (N = 68) suggests that paint may be the most important contemporary source of PCBs in this urban environment with concentrations of PCB₇ up to 3.39 g/kg. Twenty-three of the samples were collected from a single building, and the concentrations were found to vary over 3 orders of magnitude. In addition, 16 concrete samples from a large bridge previously coated with PCB-containing paint were collected and separated into outer- and inner samples indicating that PCBs are still present in high concentrations subsequent to renovation. PCBs were found in several categories of paint from wooden and concrete buildings, potentially introduced to the environment by natural weathering, renovation, and volatilization. Consequently, this dispersion may lead to increased levels of PCBs in urban atmospheres, soils, and harbor sediments where high concentrations have resulted in Governmental advice against consumption of certain seafood.     

Emissions of polychlorinated biphenyls (PCBs) from sludge drying beds to the atmosphere in Chicago

Ambient air PCB concentrations in the Lake Calumet region in Southeast Chicago have been found to be significantly higher than in nearby non-urban areas. This area is highly industrialized and also contains municipal sludge drying facilities and landfills. In an effort to quantify the importance of the sludge drying facilities to the elevated concentrations, upwind/downwind air samples from the Calumet East sludge drying bed were obtained between April and October 2002. For these samples, the downwind minus upwind (downwind-upwind) concentration varied from 0.33 to 1.27ngm(-3) for non-northeast (NE) direction winds suggesting sludge drying is a source of PCBs to the atmosphere. However, the upwind concentrations were higher than the downwind for winds from the NE of the sampling site suggesting more significant source(s), possibly Lake Calumet or the so called "Cluster site" NE of the sludge drying beds. Flux chamber experiments carried out during the sampling period measured average PCB fluxes of 210ngm(-2)h(-1) (range 43-910ngm(-2)h(-1)) which resulted in an overall flux of 0.005kgday (d)(-1) ( approximately 2kgyr(-1)). A developed regression equation between moisture content and sludge concentration estimated higher PCB losses of 0.26kgd(-1) ( approximately 95kgyr(-1)). Although these two approaches yielded different values, they both indicate that the emission from the Calumet East sludge drying beds were of minimal importance when compared to the total estimated amount of 2-70kgd(-1) (700-2100kgyr(-1)) of PCBs entering the Chicago atmosphere.     

Records of polychlorinated biphenyls (PCBs) in sediments of four remote Chilean Andean Lakes

Sediment cores from four Chilean lakes along the Andes Chain (Chungará, Laja, Castor and Venus) were analysed in order to investigate PCB concentrations and distributions in sediment samples. Sediment cores were analysed for PCBs using gas chromatography (GC-ECD/MS) and radioisotopically dated using 210Pb. Organic carbon content (OC) and 210Pb fluxes were also measured. Results showed that sediment PCB concentrations (ngg(-1) d.w.) at Lake Chungará (1.2 +/- 1) in northern Chile, Laja (5 +/- 4) in central, and in Lake Castor (3.5 +/- 4) in southern Chile (the eastern side of the Andes Mountain) were lower than sediments collected from Lake Venus (64 +/- 30) located in southern Chile (the western side) which contained 15-fold higher concentrations of PCBs. The percentage (%) of organic carbon was variable and showed a high range of values in the sediment fluctuating from 2% (Lake Laja) to 22% (Lake Chungará). Analysis of 210Pb fluxes, presented a decrease trend following Lake Laja>Castor>Chungará with a positive correlation with rainfall at each site. Sedimentation rates in Lake Castor (1846 gm(-2)yr(-1)) were higher than at Chungará (748 gm(-2)yr(-1)) and Lake Laja (508 gm(-2)yr(-1)). Focusing factor (FF) is used as a tool to elucidate PCB input in the aquatic ecosystem. FF were lower (<1) for the shallower lakes (Lakes Chungará and Castor). This study provides background levels of PCBs at remote lakes in Chile. Differences in geographical characteristics (orographic effect) might play an important role in the arrival of PCBs, particularly into the southern lakes. PCB fluxes indicated deposition of PCBs in recent sediments is higher than in previous years with peaks of PCB between 1991 and 1998. The continuing increase of PCB inputs in remote Chilean lakes, could be associated with long range atmospheric transport (LRAT).     

Relationships between steric factors and bioconcentration of polychlorinated biphenyls (PCB's) by the sea mullet (Mugil cephalus Linnaeus)

Isolation of the polychlorinated biphenyls (PCB's) from sea mullet (Mugil cephalus) collected in the Brisbane River estuary indicated that these corresponded approximately to the Arochlor Grade 1260, although minor amounts of Grade 1254 were present. However the composition of the isolates similar to the 1260 Grade in all cases exhibited marked differences between the proportions of individual components present in the original mixture as compared to the mixture found in the fish. The number of chlorines in a PCB compound has an influence on bioconcentration, but with isomers it is suggested that variable uptake of the different PCB's occurs principally as a result of steric effects relating to the orientation of the two phenyl rings and the patterns of substitution of chlorine. A Steric Effect Coefficient has been empirically developed which correlates closely with relative uptake of PCB isomers.     

Source characterization and risk of exposure to atmospheric polychlorinated biphenyls (PCBs) in Ghana

With recent evidence that persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) are emerging in environmental media in some developing countries that otherwise have sparing production and usage history, it has become important to identify such contemporary source factors of PCBs and the risks this may pose, in line with the global consensus on POP management and elimination. The present study investigated contaminations from atmospheric PCBs in Ghana, deciphered source factors, and accessed risk of exposure to dioxin-like PCBs (DL-PCBs). Atmospheric PCBs were monitored by deployment of PUF-disk passive air samplers (PAS) at several sites across Ghana for 56 days. Atmospheric ∑₁₉₀PCB concentration in Ghana ranged from 0.28 ng/m³ in Kumasi to 4.64 ng/m³ at Agbogbloshie, a suburb in Accra noted for informal electronic waste (e-waste) recycling activities. As high as 11.10 ng/m³ of PCB concentration was measured in plumes from uncontrolled open burning of e-wastes at Agbogbloshie. Applying statistical source characterization tools, it emerged that e-wastes were a major contributor to the environmental burden of atmospheric PCBs in Ghana. The risk of DL-PCB toxicity via inhalation in the Agbogbloshie area was 4.2 pg TEQ/day, within similar order of magnitude of an estimated risk of 3.85 pg TEQ/day faced by e-waste workers working averagely for 8 h per day. It is suggested that elimination of e-waste sites would help to significantly reduce PCB-related toxicity issues in Ghana.

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Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in breast milk from the Pacific Northwest

Breast milk samples from 40 first-time mothers from the Pacific Northwest of the US and Canada were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). Total PBDEs (summation operator PBDEs), calculated by summing values for the 12 PBDEs congeners analyzed, ranged from 6 to 321 ppb (lipid weight) (mean=96 ppb; median=50 ppb). In approximately 40% of the women (15/40), summation operator PBDEs>100 ppb lw in their milk, and four samples had levels >250 ppb lw. PBDE 47 was the dominant congener in most samples, whereas PBDE 153 was predominant in a few (3/40). summation operator PCBs were calculated by summing values for the 82 PCB congeners analyzed, and ranged from 49 to 415 ppb (lipid weight) (mean=147 ppb; median=126 ppb). approximately 30% of the mothers (13/40) have summation operator PBDEs> summation operator PCBs in their milk samples, and approximately 65% (25/40) have BDE 47>PCB 153 in breast milk samples, with BDE 47 averaging 3-fold greater levels than PCB 153. Clearly, the lower brominated PBDEs are surpassing PCBs as a major environmental concern in North America, and are likely affecting significant portions of the populations in these regions. PBDEs have become a major persistent organic pollutant. However, there are no positive correlations between levels of summation operator PBDEs and summation operator PCBs, or between levels of PBDE 47 and PCB 153, suggesting there may be some differences in exposure pathways for PBDEs and PCBs in humans.     

A new hybrid system of QSAR models for predicting bioconcentration factors (BCF)

The aim was to develop a reliable and practical quantitative structure-activity relationship (QSAR) model validated by strict conditions for predicting bioconcentration factors (BCF). We built up several QSAR models starting from a large data set of 473 heterogeneous chemicals, based on multiple linear regression (MLR), radial basis function neural network (RBFNN) and support vector machine (SVM) methods. To improve the results, we also applied a hybrid model, which gave better prediction than single models. All models were statistically analysed using strict criteria, including an external test set. The outliers were also examined to understand better in which cases large errors were to be expected and to improve the predictive models. The models offer more robust tools for regulatory purposes, on the basis of the statistical results and the quality check on the input data.     

A national survey of polybrominated diphenyl ethers (PBDEs) and indicator polychlorinated biphenyls (PCBs) in Chinese mothers' milk

Seven polybrominated diphenyl ethers (PBDEs) congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154 and BDE-183) and six indicator polychlorinated biphenyls (PCBs) congeners (CB-28, CB-52, CB-101, CB-138, CB-153 and CB-180) were measured in 24 pooled human milk samples comprised of 1237 individual samples from 12 provinces in China. The samples were taken to estimate the background body burden of general population and assess nursing infant exposure via human milk in China. The median concentrations of ∑₇PBDEs and ∑₆PCBs were 1.49 and 10.50 ng g⁻¹ lipid weight (lw), respectively. BDE-28, BDE-47 and BDE-153 were predominant PBDE congeners accounting for nearly 70% of ∑₇PBDEs. As for indicator PCBs, CB-153 was the most abundant congener, followed by CB-138. In our study, there was no significantly statistical relationship between concentrations of PBDEs in milk samples and maternal age as well as dietary habits. ∑₇PBDEs did not correlate to ∑₆PCBs in Chinese mothers’ milk. The human exposure to indicator PCBs in China was found to be significantly determined by maternal age, dietary habits and geographical factors. It is suggested that Chinese general population is probably exposed to PBDEs with multiple sources and pathways. The estimated daily intakes (EDI) of BDE-47, BDE-99 and BDE-153 for the Chinese nursing infant were much lower than corresponding threshold reference values suggested by USEPA.     

A new hybrid system of QSAR models for predicting bioconcentration factors (BCF)

The aim was to develop a reliable and practical quantitative structure–activity relationship (QSAR) model validated by strict conditions for predicting bioconcentration factors (BCF). We built up several QSAR models starting from a large data set of 473 heterogeneous chemicals, based on multiple linear regression (MLR), radial basis function neural network (RBFNN) and support vector machine (SVM) methods. To improve the results, we also applied a hybrid model, which gave better prediction than single models. All models were statistically analysed using strict criteria, including an external test set. The outliers were also examined to understand better in which cases large errors were to be expected and to improve the predictive models. The models offer more robust tools for regulatory purposes, on the basis of the statistical results and the quality check on the input data.     

Assessment of polychlorinated biphenyls (PCBs) in cheese from Rio Grande do Sul, Brazil

Polychlorinated biphenyls (PCBs) are among the most toxic environmental pollutants. Food, especially animal based, has been described as the major source for human exposure to PCBs. We investigated PCB levels (congeners 10, 28, 52, 153, 138, and 180) in cheese from 14 cities of Rio Grande do Sul, Brazil. The fat was extracted using sodium sulfate and petroleum ether, and PCBs purification was conducted using florisil and hexane. The identification and quantification were made in a gas chromatograph with microelectron capture detector (GC-microECD). PCB congeners were found (lower bound data as ngg(-1) fat) in the following rank: 52 (15.75)>180 (4.91)>28 (3.43)>153 (3.00)>10 (2.38)>138 (1.37). Summation operatorPCB contamination ranged from 0 to 78.32 ngg(-1) fat. Differences in PCB levels between industrialized (33.32 ngg(-1) fat) and homemade (26.58 ngg(-1) fat) cheese and between two different regions (36.19 vs. 26.95 ngg(-1) fat) were not statistically significant. For university students, the estimated daily intake (EDI) of PCBs from cheese ranged from 0 to 3.13 pgkg(-1) b.w. EDI was significantly higher for industrialized than homemade cheese, and for cheese from Mountain/Porto Alegre region than from Santa Maria/South/Western region. No sample exceeded maximum level of PCBs allowed in dairy products in the European Community.     

Accumulation of hydroxylated polychlorinated biphenyls (OH-PCBs) and implications for PCBs metabolic capacities in three porpoise species

The present study investigated polychlorinated biphenyls (PCBs) and hydroxylated metabolites of PCBs (OH-PCBs) in blood from three porpoise species: finless porpoises (Neophocaena phocaenoides), harbor porpoises (Phocoena phocoena), and Dall’s porpoises (Phocoenoides dalli). The porpoises were found stranded or were bycaught along the Japanese coast. Concentrations of OH-PCB were the highest in Dall’s porpoises (58 pg g⁻¹ wet wt), second highest in finless porpoises (20 pg g⁻¹ wet wt), and lowest in harbor porpoises (8.3 pg g⁻¹ wet wt). The concentrations in Dall’s porpoises were significantly higher than the concentrations in finless porpoises and harbor porpoises (p < 0.05 and p < 0.01, respectively). There was a positive correlation between PCB and OH-PCB concentrations (r = 0.67, p < 0.001), suggesting the possible concentration-dependent induction of CYP enzymes. The three porpoise species may have exceptionally low metabolic capacities compared with other marine and terrestrial mammals, because low OH-PCB/PCB concentration ratios were found, which were 0.0016 for Dall’s porpoises, 0.0013 for harbor porpoises, and 0.00058 for finless porpoises. Distinct differences in the OH-PCB congener patterns were observed for the three species, even though they are taxonomically closely related.