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.     

Halogenated organic contaminants (HOCs) in sediment from a highly eutrophicated lake, China: Occurrence, distribution and mass inventories

Halogenated organic contaminants (HOCs) including 16 polybrominated diphenyl ethers (PBDEs) and 37 polychlorinated biphenyls (PCBs) were determined in 49 surfacial sediments from Chaohu Lake, a highly eutrophicated lake, China. PBDEs were detected in almost samples with the range of the total concentration (defined as Σ₁₆PBDEs) from 0.84 to 86.6 ng g⁻¹. Compared with the occurrence of PBDEs in Pearl River Delta and Yangtze River Delta in China, lower percentage of BDE-209 over the concentration of Σ₁₆PBDEs was inferred by the high-volume application of penta-BDE mixture product for local domestic furniture purpose. The total concentration of 37 PCBs (Σ₃₇PCBs) ranged from 0.05 to 3.36 ng g⁻¹ with the most detection of PCB-1, -4, -52 and -71. Both the concentrations of Σ₁₆PBDE and Σ₃₇PCB poorly correlated with total organic carbon (TOC), suggesting the significant contribution of phytoplankton organic carbons to sediment TOC. The contamination by PBDEs and PCBs in western region of the lake was significantly more serious than in eastern lake. Our findings about the higher residues of PBDEs and PCBs in sediments at the estuary of Nanfei River compared to the other estuaries also supported the conclusion that urban area (Hefei city) was the main source of PBDEs and PCBs. The comparison with the concentration of HOC in the present study with those in other lacustrine sediments around the world suggested the contamination by PBDEs in Chaohu Lake is at middle of the global concentration range, whereas PCBs is at low end of the global range which could be elucidated by local economic development and historical usage of PBDEs and PCBs. The mass inventories of HOCs in the lake were estimated at 561 and 38 kg, which corresponds to only 0.000006% and 0.0001% of these global historical produce volumes, respectively.     

Spatial distribution of organochlorine contaminants in soil, sediment, and fish in Bikini and Enewetak Atolls of the Marshall Islands, Pacific Ocean

Several nuclear tests were performed at Enewetak and Bikini Atolls in the Marshall Islands between 1946 and 1958. The events at Bikini Atoll involved several ships that were tested for durability during nuclear explosions, and 24 vessels now rest on the bottom of the Bikini lagoon. Nine soil samples were collected from different areas on the two islands of the atoll, and eighteen sediment, nine fish, and one lobster were collected in the vicinity of the sunken ships. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polychlorinated terphenyls (PCTs) in these samples were analyzed using gas chromatography/ion trap mass spectrometry (GC/ITMS). The average recoveries ranged from 78% to 104% for the different PCB congeners. The limits of detection (LOD) for PCBs, PCTs, DDE, DDT, and dieldrin ranged 10-50 pg g⁻¹. Some fish from Enewetak contained PCBs at a concentration range of 37-137 ng g⁻¹, dry weight (dw), and most of the soils from Enewetak showed evidence of PCBs (22-392 ng g⁻¹ dw). Most of the Bikini lagoon sediment samples contained PCBs, and the highest was the one collected from around the Saratoga, an aircraft carrier (1555 ng g⁻¹ dw). Some of the fish samples, most of the soil samples, and only one of the sediment samples contained 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and PCBs. In addition to PCBs, the soils from Enewetak Atoll contained PCTs. PCTs were not detected in the sediment samples from Bikini Atoll. The results suggest local pollution sources of PCBs, PCTs, and OCPs.     

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 (PCBs) in marine fishes from China: Levels, distribution and risk assessment

Muscle tissues of large yellow croakers (Pseudosciaena crocea) and sliver pomfret (Pampus argenteus) from nine coastal cities of East China including Dalian, Tianjin, Qingdao, Shanghai, Zhoushan, Wenzhou, Fuzhou, Quanzhou and Xiamen were analyzed for polychlorinated biphenyl (PCB) concentrations. Thirty-six PCB congeners were quantified in the fishes, of which 11 congeners were dioxin-like PCBs. The total PCB concentrations of the present study were at the low end of the global range, which may be related to the smaller usage and shorter consumption history of PCBs in China. PCBs 18, 29, 52, 66, 101, 104, 138, 153, 180 and 194 were the major constituents found in the fish samples. Regression analysis showed a strong positive correlation (R² = 0.800; p < 0.001) between total dioxin-like PCBs and total PCB concentrations, and that total PCB concentrations explain 80% of the variability in total dioxin-like PCB concentrations. Among the species investigated, significantly higher concentrations of total PCBs were found in croakers than in pomfrets, which may be attributed to their different feeding and living habits. No significant difference in total PCB concentrations among the cities was observed; principal component analysis (PCA) of PCB profiles indicated that PCB pollution came from similar sources in the sampling areas and that there may be other PCB sources in Dalian and Wenzhou. The calculated carcinogenic risks (CRs) from the two species based on a low consumption group and high consumption group were all greater than 10⁻⁶, suggesting that daily exposure to dioxin-like PCBs via fish consumption results in a lifetime cancer risk of greater than one in one million. In contrast, the hazard quotients (HQs) of noncancer risks were all less than unity.     

Determination of PCBs, PCDDs and PCDFs in insulating oil samples from stored Chinese electrical capacitors by HRGC/HRMS

Homologue and congener profiles of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in commercial PCBs formulations are key information for the source identification of PCBs contamination as well as for the risk assessment caused by potential exposure. The isotope dilution technology in combination with high resolution gas chromatography-high resolution mass spectrometry (HRGC/HRMS) has made the accurate determination of such profiles possible. So far, various commercial PCB formulations except Chinese products have been successfully determined. Two PCBs containing insulating oil samples from stored Chinese electrical capacitors have been determined with the same methodology for comparability. The total concentration PCBs in two oil samples were 790 000 μg g⁻¹ and 720 000 μg g⁻¹, respectively. TriCBs, TetraCBs, and DiCBs were found to be most abundant. Concentration of dioxins contamination in two samples is 650-670 ngTEQ g⁻¹, of which 69-71 ngTEQ g⁻¹ from PCDD/Fs with the predominant congeners of 1,2,7,8-TeCDF; 2,3,7,8-TeCDF; 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDF. The contributions of DL-PCBs in total TEQ in both samples were more than 85%. The dioxin-like toxicity in insulating oils contained in electrical capacitors could be considered receive attention as an important dioxins source if such wastes are not managed in an environmentally sound manner.     

Synthesis of hydroxylated PCB metabolites with the Suzuki-coupling

An improved synthesis of hydroxylated polychlorinated biphenyls (PCBs) which are structurally related to the major hydroxy PCB congeners identified in human plasma is described. The coupling of (chlorinated) aryl boronic acids with bromochloro anisoles using the standard conditions of the Suzuki coupling gave the desired hydroxylated PCB metabolites in good to excellent yields. 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.     

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.     

Distribution, source and risk assessment of polychlorinated biphenyls (PCBs) in urban soils of Beijing, China

The concentration of PCBs in urban soils of Beijing across six land types including business districts (BD), cultural and educational areas (CE), classical gardens (CG), public green (PG), residential areas (RA), and roadsides (RD) was investigated. The total concentrations of PCBs ranged from below method detection limit (M.D.L.) to 37.11 × 10⁻³ mg kg⁻¹ dry weight (mean: 11.70 × 10⁻³ mg kg⁻¹; median: 13.28 × 10⁻³ mg kg⁻¹), which was at a medium level compared with other cities around the world. In general, the levels of PCBs decreased from the center of Beijing city to the suburb, suggesting the increasing PCBs concentrations with the age of the urban area. For different types of land use, the highest level of PCBs was observed in CG soils which have the oldest age, and the homologue profiles were similar, which were predominated by lowly chlorinated congeners including di-, tri- and tetra-CBs. Principal component analysis indicated that local sources such as Aroclor 1016, 1242, and 1248 were important sources in addition to long-range transport of PCBs all over the world. Although the toxic equivalency (TEQ) concentrations of dioxin-like PCBs in all soil samples of Beijing were higher than those in other urban areas of China, they met the Canadian soil quality standard.     

Levels of PCDD/Fs,PCBs and PBDEs in breast milk of women living in the vicinity of a hazardous waste incinerator: Assessment of the temporal trend

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in previous surveys carried out in the same area in 1998 (baseline study), 2002 and 2007. The current total concentrations of 2,3,7,8-chlorinated PCDD/Fs in breast milk ranged from 18 to 126 pg g⁻¹ fat (1.1–12.3 pg WHO₂₀₀₅-TEQ_PCDD/F), while the total levels of PCBs ranged from 27 to 405 pg g⁻¹ fat (0.7–5.3 pg WHO₂₀₀₅-TEQ_PCB). In turn, PBDE concentrations (sum of 15 congeners) ranged 0.3–5.1 g g⁻¹ fat, with a mean value of 1.3 ng g⁻¹ fat. A general decrease in the concentrations for PCDD/Fs, both planar and total PCBs, and PBDEs in breast milk was observed. The levels of PCDD/Fs, PCBs, and PBDEs in milk of women living in urban zones were higher than those corresponding to industrial zones (41%, 26%, and 8%, respectively). For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants that we have also observed in recent studies carried out in the same area of study.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

Spatial character of polychlorinated biphenyls from soil and respirable particulate matter in Taiyuan, China

As one of China’s great metropolises, Taiyuan is affected by heavy chemical industry and manufacture of chemical products, and faces pollution from polychlorinated biphenyls (PCBs). Therefore, this study was conducted to determine the PCB concentrations in various environmental media in Taiyuan. We collected 15 soil samples, 34 respirable particulate matter (PM) samples (17 of PM_2.5 and 17 of PM₁₀) from urban areas of Taiyuan, and measured a total of 144 PCB congeners (including some coeluting PCB congeners). The total PCB concentrations were 51–4.7 × 10³ pg g⁻¹ in soil, 27–1.4 × 10² pg m⁻³ in PM_2.5 and 16–1.9 × 10² pg m⁻³ in PM₁₀. Of the PCB homologues, the dominant PCBs detected in the various media were all tri-CBs. Soil was relatively the most polluted media. Furthermore, principal-component analysis revealed that the major PCB source in Taiyuan may be associated with the main commercial PCB through long-range transmission. Toxic equivalency (TEQ) concentrations (based on ten dioxin-like PCBs) ranged from N.D. to 5.9 × 10⁻³ pg-WHO TEQ g⁻¹ in soil, 2.0 × 10⁻⁴–3.4 × 10⁻³ pg-WHO TEQ m⁻³ and 1.0 × 10⁻⁴–1.2 × 10⁻³ pg-WHO TEQ m⁻³ in PM_2.5 and PM₁₀, respectively. In previous studies, PCBs were not a severe component of contaminant in Taiyuan; however, this study suggested there is a potential threat of human exposure to PCBs for residents of Taiyuan.     

Assessment of the daily intake of 62 polychlorinated biphenyls from dietary exposure in South Korea

The dietary intake of polychlorinated biphenyls (PCBs) was estimated using the sum of 62 PCB congeners (∑₆₂PCBs), including seven indicator PCBs and 12 dioxin-like PCBs, in the South Korea. In this study, 200 individual food samples belonging to 40 different foodstuffs were investigated to estimate the distribution of PCB congeners in five sampling cities. PCB exposure was estimated using Korean dietary habits as established by the National Health and Nutrition Examination Survey (NHANES). The PCB concentrations in rice, the most frequently consumed food in Korea, was relatively low in whole food samples. The mean PCB levels measured in fish were the highest in this study, but each fish is consumed in relatively small amounts by the general population. Therefore, the daily dietary intake should also be considered with regard to human exposure to PCBs, especially with the consumption of contaminated foods. Dioxin-like PCB levels were also calculated using TEF values that were established in 2005. The average levels (pg TEQ/g) were 0.0002 for rice and 0.0098 for fish. The dioxin-like PCBs accounted for a relatively small percentage of the total PCBs, compared to previous studies. According to our research, the health risks associated with exposure to PCBs could be estimated using the tolerable daily intake (TDI) of the general population.     

Accelerated delivery of polychlorinated biphenyls (PCBs) in recent sediments near a large seabird colony in Arctic Canada

Polychlorinated biphenyls (PCBs) were measured in sediment cores from ponds located near a large seabird colony at Cape Vera, Devon Island, Arctic Canada. Surface sediment PCB concentrations were ∼5× greater in seabird-affected sites relative to a nearby control pond and were correlated with independent indicators of seabird activity including, sedimentary δ¹⁵N and lakewater chlorophyll a and cadmium concentrations. PCB fluxes were amongst the highest recorded from the High Arctic, ranging from 290 to 2400 ng m⁻² yr⁻¹. Despite a widespread ban of PCBs in the mid-1970s, PCB accumulation rates in our cores increased, with the highest values recorded in the most recent sediments. Possible mechanisms for the recent PCB increases include a vertical flux step driven by seabird-delivered nutrients and/or delayed loading of PCBs from the catchment into the ponds. The high PCB levels recorded in the seabird-affected sites suggest that seabird colonies are exposing coastal ecosystems to elevated levels of contaminants.     

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.     

The air-water exchange of polychlorinated biphenyls and polybrominated diphenyl ethers at an urban lake, a receipt water body for the effluent from a municipal sewage treatment plant

The effluents and sludge from municipal sewage treatment plants (MSTPs) are considered as potential sources of many contaminants to the ambient environments. In the present work, the air-water exchange of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) was studied using passive air samplers at an urban lake, which receives the effluents from a MSTP in Beijing, China. The concentrations of PCBs and PBDEs in atmosphere were in the range 15.5-108 ng sample⁻¹ and 2.37-27.8 ng sample⁻¹, respectively, during the sampling period (August, 2007-July, 2008). The predominant PCBs and PBDEs were lowly halogenated congeners. The calculation for the exchange fluxes of PCBs and PBDEs using fugacity model showed that, the net exchange fluxes in different seasons were closely related to the halogen number of different congeners. Except for CBs-28 and 52, the net exchange fluxes was mainly directed from air to water for most of predominant congeners, which implied that the lower chlorinated CBs were dominated by volatilization process rather than the dry/wet depositions and diffusion between air-water interface, additionally, for heavy congeners, the dry/wet deposition process was an important source of PCBs and PBDEs in this lake.     

Organochlorine,PCB, PAH,and metal concentrations in eggs of loggerhead sea turtles (Caretta caretta) from northwest Florida,USA

Abstract

Composite samples of unhatched and physically unaltered loggerhead sea turtle, Caretta caretta, eggs collected from 20 nests along northwest Florida were analyzed for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and metals. Chemical analyses revealed that turtle eggs contained detectable amounts of metals, PAHs, and PCBs. Only one OCP, p, p'‐DDD, was detected, and its presence was restricted to eggs from two nesting sites. None of the PCB concentrations exceeded the Food and Drug Administration's (FDA) action limit. Concentrations of dioxin‐like PCB congeners, 105, 118, and 126, and total PCBs were also detected and are contributors to the toxic burden of loggerhead sea turtle eggs. Concentrations of PAHs, 1,2,5,6‐dibenzanthracene, 1‐methyl naphthalene, Cl‐naphthalene and naphthalene were variable at nesting sites. Comparison of mean metal burdens in eggs from different beaches suggested that no uniform geographic gradients exist. Presence of OCPs, PCBs, PAHs and metals and their additive or synergistic toxicity is a concern to loggerhead sea turtle eggs; however, additive or synergistic impacts for loggerhead sea turtles are largely undocumented.     

Reductive dechlorination for remediation of polychlorinated biphenyls

Technologies such as thermal, oxidative, reductive, and microbial methods for the remediation of polychlorinated biphenyls (PCBs) have previously been reviewed. Based on energy consumption, formation of PCDD/F, and remediation efficiency, reductive methods have emerged as being advantageous for remediation of PCBs. However, many new developments in this field have not been systematically reviewed. Therefore, reductive technologies published in the last decade related to remediation of PCBs will be reviewed here. Three categories, including catalytic hydrodechlorination with H₂, Fe-based reductive dechlorination, and other reductive dechlorination methods (e.g., hydrogen-transfer dechlorination, base-catalyzed dechlorination, and sodium dispersion) are specifically reviewed. In addition, the advantages of each remediation technology are discussed. In this review, 108 articles are referenced.     

Concentrations of polychlorinated biphenyls in water from US Lake Ontario tributaries between 2004 and 2008

Research on the environmental fate and transport of PCBs in Lake Ontario basin depends, among other aspects, on the availability of representative data sets for upstream sources, but data are lacking for most US Lake Ontario tributaries. In this study, water samples were collected between September 2004 and October 2008 from five tributaries and were analyzed for 209 polychlorinated biphenyls (PCB) with high-resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) following EPA Method 1668A. Total PCB concentrations ranged between 0.31 and 42.75 ng L⁻¹. Congeners between Di and Hexa PCBs accounted between 70 and 99% of the total PCB. The tributary with highest PCB concentrations presented similar pattern and percentage levels to Aroclor 1242. Total average loads for the sampling events ranged between 1.85 g d⁻¹ and 59.08 g d⁻¹. PCB concentrations were evaluated against other variables and other studies (including different matrices) to better understand their transport. The methodology used is reliable to assess PCB contamination in surface water.