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.     

PCB 77 dechlorination products modulate pro-inflammatory events in vascular endothelial cells

Persistent organic pollutants such as polychlorinated biphenyls (PCBs) are associated with detrimental health outcomes including cardiovascular diseases. Remediation of these compounds is a critical component of environmental policy. Although remediation efforts aim to completely remove toxicants, little is known about the effects of potential remediation byproducts. We previously published that Fe/Pd nanoparticles effectively dechlorinate PCB 77 to biphenyl, thus eliminating PCB-induced endothelial dysfunction using primary vascular endothelial cells. Herein, we analyzed the toxic effects of PCB congener mixtures (representative mixtures of commercial PCBs based on previous dechlorination data) produced at multiple time points during the dechlorination of PCB 77 to biphenyl. Compared with pure PCB 77, exposing endothelial cells to lower chlorinated PCB byproducts led to improved cellular viability, decreased superoxide production, and decreased nuclear factor kappa B activation based on duration of remediation. Presence of the parent compound, PCB 77, led to significant increases in mRNA and protein inflammatory marker expression. These data implicate that PCB dechlorination reduces biological toxicity to vascular endothelial cells.     

Pure non-dioxin-like PCB congeners suppress induction of AhR-dependent endpoints in rat liver cells

The relative potencies of non-ortho-substituted coplanar polychlorinated biphenyl (PCB) congeners to activate the aryl hydrocarbon receptor (AhR) and to cause the AhR-dependent toxic events are essential for their risk assessment. Since some studies suggested that abundant non-dioxin-like PCB congeners (NDL-PCBs) may alter the AhR activation by PCB mixtures and possibly cause non-additive effects, we evaluated potential suppressive effects of NDL-PCBs on AhR activation, using a series of 24 highly purified NDL-PCBs. We investigated their impact on the model AhR agonist-induced luciferase reporter gene expression in rat hepatoma cells and on induction of CYP1A1/1B1 mRNAs and deregulation of AhR-dependent cell proliferation in rat liver epithelial cells. PCBs 128, 138, and 170 significantly suppressed AhR activation (with IC₅₀ values from 1.4 to 5.6 μM), followed by PCBs 28, 47, 52, and 180; additionally, PCBs 122, 153, and 168 showed low but still significant potency to reduce luciferase activity. Detection of CYP1A1 mRNA levels in liver epithelial cells largely confirmed these results for the most abundant NDL-PCBs, whereas the other AhR-dependent events (CYP1B1 mRNA expression, induction of cell proliferation in confluent cells) were less sensitive to NDL-PCBs, thus indicating a more complex regulation of these endpoints. The present data suggest that some NDL-PCBs could modulate overall dioxin-like effects in complex mixtures.     

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.     

Quantifying the global fractionation of polychlorinated biphenyls

Due to the wide range of their physical-chemical properties, polychlorinated biphenyls (PCBs) have played an important role in the derivation of the global fractionation hypothesis, which predicts changes in the composition of persistent organic pollutant mixtures with latitude. Recent historical emission estimates, the derivation of an internally consistent property data set, in combination with a zonally averaged global fate and transport model, allow a quantitative investigation of the compositional shifts PCBs experience as a function of environmental compartment, latitude and time. Model simulations reproduce the higher relative abundance of lighter PCB congeners with increasing latitude, observed in air and soil, and quantify the relative importance of partitioning, persistence and emissions in establishing PCB patterns. Compositional variations consistent with global fractionation, as well as inverted concentration profiles with higher levels in the Arctic than at lower latitudes, are consistent with only minor fractions of the global PCB inventory being transferred northward.     

Polychlorinated biphenyls in Narragansett Bay surface sediments

Polychlorinated biphenyls (PCBs) were evaluated in 41 surface sediments collected from Narragansett Bay, RI in 1997-1998. Highest concentrations of total PCBs (1760 ng/g) were in rivers at the head of the bay and the values decreased southward toward the mouth of the bay, with elevated concentrations in some of the coves. The PCB levels in approximately 43% of the samples exceeded the effects range median (ERM) guideline [Environ. Manage. 19 (1995) 81] indicating possible adverse biological effects at these stations. Principal component analysis (PCA) of the surface sediment PCBs separated the Taunton River samples from the rest of the samples. This result suggests that this river has a different PCB composition and sources than the other areas investigated. It also showed that this river has a limited influence on other bay stations as the adjacent samples downstream did not have the same chemical signature. Congener ratios derived from the PCA were useful in distinguishing stations that had different sources of PCBs than the bulk of the bay sediments. Although Aroclor 1268 and 1270 accounted for <1% of all PCB production, their major components, CB206 and CB209, account for 3-6% of the CBs in most bay samples. This may reflect more local use of these Aroclor mixtures and/or be indicative of their relative stability, compared to less chlorinated mixtures. Using linear alkyl benzenes (LABs) as a marker for sewage derived PCBs suggested that up to 95% of the PCBs at the most contaminated sites in the Seekonk, Providence, and Taunton Rivers were sewage derived. This analysis also showed that there is a high background level (167 ng/g) of PCBs in the Seekonk and Providence River, while the Taunton River had a relatively low background level (23.7 ng/g). At the furthest stations south in the Providence River, the sewage derived PCBs only accounted for 23% of the total which suggests that PCB associated with sewage particles are rapidly deposited and are therefore not the most significant source of these compounds to the lower reaches of Narragansett Bay.     

The developmental neurotoxicity of legacy vs. contemporary polychlorinated biphenyls (PCBs): similarities and differences

Although banned from production for decades, PCBs remain a significant risk to human health. A primary target of concern is the developing brain. Epidemiological studies link PCB exposures in utero or during infancy to increased risk of neuropsychiatric deficits in children. Nonclinical studies of legacy congeners found in PCB mixtures synthesized prior to the ban on PCB production suggest that non-dioxin-like (NDL) congeners are predominantly responsible for the developmental neurotoxicity associated with PCB exposures. Mechanistic studies suggest that NDL PCBs alter neurodevelopment via ryanodine receptor-dependent effects on dendritic arborization. Lightly chlorinated congeners, which were not present in the industrial mixtures synthesized prior to the ban on PCB production, have emerged as contemporary environmental contaminants, but there is a paucity of data regarding their potential developmental neurotoxicity. PCB 11, a prevalent contemporary congener, is found in the serum of children and their mothers, as well as in the serum of pregnant women at increased risk for having a child diagnosed with a neurodevelopmental disorder (NDD). Recent data demonstrates that PCB 11 modulates neuronal morphogenesis via mechanisms that are convergent with and divergent from those implicated in the developmental neurotoxicity of legacy NDL PCBs. This review summarizes these data and discusses their relevance to adverse neurodevelopmental outcomes in humans.

     

Concentration levels and congener profiles of polychlorinated biphenyls, pentachlorobenzene, and hexachlorobenzene in commercial pigments

The concentration levels and congener profiles of polychlorinated biphenyls (PCBs), pentachlorobenzene (PeCBz), and hexachlorobenzene (HxCBz) were assessed in commercially available organic pigments. Among the azo-type pigments tested, PCB-11, which is synthesized from 3,3′-dichlorobendizine, and PCB-52, which is synthesized from 2,2′,5,5′-tetrachlorobendizine, were the major congeners detected. It is speculated that these were byproducts of chlorobendizine, which has a very similar structure. The total PCB concentrations in this type of pigment ranged from 0.0070 to 740 mg/kg. Among the phthalocyanine-type pigments, highly chlorinated PCBs, mainly composed of PCB-209, PeCBz, and HxCBz were detected. Their concentration levels ranged from 0.011 to 2.5 mg/kg, 0.0035 to 8.4 mg/kg, and 0.027 to 75 mg/kg, respectively. It is suggested that PeCBz and HxCBz were formed as byproducts and converted into PCBs at the time of synthesizing the phthalocyanine green. For the polycyclic-type pigments that were assessed, a distinctive PCB congener profile was detected that suggested an impact of their raw materials and the organic solvent used in the pigment synthesis. PCB pollution from PCB-11, PCB-52, and PCB-209 pigments is of particular concern; therefore, the monthly variations in atmospheric concentrations of these pollutants were measured in an urban area (Sapporo city) and an industrial area (Muroran city). The study detected a certain level of PCB-11, which is not included in PCB technical mixtures, and revealed continuing PCB pollution originating from pigments in the ambient air.     

Behavior and source characteristic of PCBS in urban ambient air of Yokohama, Japan

To understand the behavior and sources of polychlorinated biphenyls (PCBs) in ambient air, gaseous and particulate phase concentrations were measured at Yokohama City, Japan, during March 2002 and February 2003. The concentration of total PCB and TEQ ranged from 62 to 250 pg/m(3) and from 2 to 14 fgTEQ/m(3), respectively. The gas-particle partition coefficient (K(p)) was obtained as a function of temperature. The relationship between the partition coefficient and the sub-cooled liquid vapor pressure (P(L)) was also established (coefficients of determination for log K(p) versus log P(L) plot were >0.76, except for three samples). As a result, the partition ratio of gaseous and particulate phase PCBs can be estimated for an arbitrary temperature. Principal component analysis (PCA) was applied to the source identification of PCBs in ambient air. The concentrations of 122 congeners between tetra-CBs and deca-CB were used as input variables, and three PCs with eigenvalue more than 10 were obtained. The principal component 1 (PC 1) accounted for 43.4% of the total variance, and was interpreted as volatilization from PCB products and/or sites polluted by PCBs. The concentrations of PCB congeners were strongly related with PC 1 which showed high correlation with temperature. PC 2 accounted for 22.3%, and was interpreted as PCBs from incineration sources, while PC 3 accounted for 10.8%, but could not be interpreted.     

Study of the distribution of the polychlorinated biphenyls in the milk fat globule by supercritical fluid extraction

The distribution of polychlorinated biphenyls (PCBs) in the milk fat globule has been studied by sequential extraction of four different lipidic fractions from powdered full-fat milk with supercritical carbon dioxide. Extractions were carried out in the dynamic mode in the pressure range 13.6-23.3 MPa at a temperature of 50 degrees C. The levels of PCBs and short-chain triglycerides (SCT), medium-chain triglycerides (MCT) and long-chain triglycerides (LCT), as well as the cholesterol in these four supercritical fluid extraction (SFE) fractions were determined. Extracts obtained at lower pressures were found to be enriched in PCBs, SCT, MCT and cholesterol, while the concentrations of all these analytes decreased for subsequent extractions. Satisfactory quadratic correlations were found between the PCB and SCT and MCT levels (r2 in the range 0.9-0.999), and between the PCB and cholesterol levels (r2 in the range 0.8-0.999, except for PCB 105) determined in the SFE fractions. These results suggested a similar distribution of the PCBs and the cholesterol in the milk fat globule. This conclusion was also supported by the comparison of the PCBs and the cholesterol chemical structures as well as by the total PCB levels determined by SFE to those obtained by using different extraction methods. The classical requirement for the analysis of this kind of lipophilic pollutants of an exhaustive extraction of the lipids of the matrix to ensure their quantitative recovery has been revised.     

Concentrations and gas/particle partitioning of PCBs in Chicago

Thirty seven air samples were collected in Chicago, IL from June to October 1995 and analyzed for gas and particle concentrations of polychlorinated biphenyls (PCBs). Lower molecular weight (MW) PCBs dominated the samples and on average 95% of the Sigma50PCB concentration (gas+particulate) was in the vapor phase. Sigma50PCB concentrations were classified based on prevailing winds (lake and land). The Sigma50PCB concentration varied between 0.42 and 5.21 ng/m3 (1.80+/-1.70 ng/m3) for lake and 0.53 and 8.31 ng/m3 (2.41+/-2.15 ng/m3) for land wind directions. Back trajectory analyses suggested that SW of Chicago can be an important local or regional source sector for PCBs. Partitioning between gas and particulate phases was modeled using the Junge-Pankow model. The measured particle phase concentrations for low MW PCBs were lower than those predicted by the model while the opposite was observed for high MW PCBs. Plots of gas/particle partition coefficient (log Kp) vs. subcooled liquid vapor pressure (log pL(0)) had reasonable correlations for individual samples but the slope varied among the samples. Samples that originated from over the lake had higher slopes than samples that originated from over the land.     

Seasonal influences on PCB retention and biotransformation in fish

There is extensive evidence that fish from waters with polychlorinated biphenyls (PCB)-contaminated sediments accumulate PCBs and related chemicals and that people who eat fish from contaminated waters have higher body burdens of PCBs and PCB metabolites than those who do not. PCBs and their metabolites are potentially toxic; thus, it is important to human health to understand the uptake, biotransformation, and elimination of PCBs in fish since these processes determine the extent of accumulation. The intestinal uptake of PCBs present in the diet of fish into fish tissues is a process that is influenced by the lipid composition of the diet. Biotransformation of PCBs in fish, as in mammals, facilitates elimination, although many PCB congeners are recalcitrant to biotransformation in fish and mammals. Sequential biotransformation of PCBs by cytochrome P450 and conjugation pathways is even less efficient in fish than in mammalian species, thus contributing to the retention of PCBs in fish tissues. A very important factor influencing overall PCB disposition in fish is water temperature. Seasonal changes in water temperature produce adaptive physiological and biochemical changes in fish. While uptake of PCBs from the diet is similar in fish acclimated to winter or summer temperatures, there is evidence that elimination of PCBs occurs much more slowly when the fish is acclimated at low temperatures than at warmer temperatures. Research to date suggests that the processes of elimination of PCBs are modulated by several factors in fish including seasonal changes in water temperature. Thus, the body burden of PCBs in fish from a contaminated location is likely to vary with season.     

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.     

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.     

Influence of activated carbon amendment on the accumulation and elimination of PCBs in the earthworm Eisenia fetida

In this study we investigated the use of activated carbon (AC) as a soil amendment for reducing bioavailability of polychlorinated biphenyls (PCBs) to the earthworm Eisenia fetida. Artificial soil was contaminated with PCBs and used in bioaccumulation experiments fresh or after aging for 19 months. PCB bioaccumulation in earthworms was reduced by 68% when AC was placed as a layer without mixing and by 94% when AC was manually mixed into the soil. Aging of the same AC mixed soil for 19 months resulted in an overall reduction of 99% in PCB biouptake. AC-treated aged soil also showed two orders of magnitude lower equilibrium aqueous concentrations of PCBs compared to untreated aged soils. The findings from this study indicate that application of engineered sorbents like AC to PCB impacted soils may greatly reduce PCB uptake at the base of the terrestrial food chain.     

Polychlorinated biphenyls in broiler diets: their digestibility and incorporation in body tissues

The influence of dietary amounts of polychlorinated biphenyls (PCBs) was studied on performance, apparent PCB digestibility and PCB accumulation in broiler chickens that were maintained until 42 days of age. Dietary concentrations of supplemented PCBs, based on the sum of seven reference congeners, ranged from 0 to 12 ng/g, which was below the legal maximum of 200 ng PCBs/g fat in Belgian feeds. PCB ingestion did not significantly affect body weight and feed intake. Apparent PCB digestibility was not influenced by dietary levels of added fat varying between 4% and 8%, but was significantly higher in broilers fed diets containing added PCBs. Accumulation of PCBs in the fat fraction of abdominal adipose tissue and breast and thigh muscle greatly depended upon PCB intake. However, PCB contents in the various body fat fractions within the same animal differed, even within muscle tissues, indicating an unequal PCB distribution in body fats.     

Polychlorinated biphenyl distribution and faecal excretion in rats fed wheat bran

Polychlorinated biphenyls (PCBs) are abundant and persistent environmental contaminants, which tend to accumulate through the food chain. Because of the toxic potential of these compounds, body burden should be kept as low as possible e.g. by taking dietary measures. In the present report, the effect of wheat bran consumption on absorption of dietary PCBs as well as on excretion of previously absorbed PCBs was investigated in rats. Moreover, the accumulation of 7 reference PCB congeners in liver and abdominal adipose tissue was studied. Faecal excretion of dietary PCBs was significantly higher in rats fed wheat bran compared to its placebo. As a result, apparent PCB digestibility was diminished, but not enough to significantly affect PCB accumulation in liver and abdominal adipose tissue. Furthermore, excretion of previously absorbed PCBs following switching of the rats to a control diet without added PCBs was enhanced by wheat bran fibre intake, although to a much lesser extent than excretion of PCBs originating directly from the diet. Consequently, stimulation of PCB clearance from liver and abdominal adipose tissue due to wheat bran consumption was not detectable. Although no preferential absorption of PCB congeners was observed, PCB patterns in tissues obviously differed from the dietary PCB pattern. This was mainly due to PCBs 52 and 101, which were metabolised in the body. Moreover, reduced levels of PCB 138 were found in liver, while PCB 28 and 138 were predominantly present in adipose tissue. The experiment also demonstrated that PCB redistribution from the liver to the adipose tissue occurs.     

Polychlorinated biphenyls contamination in urban soil of Shanghai: level, compositional profiles and source identification

Surface soil samples taken from 55 sampling sites at the urban areas of Shanghai were collected and analyzed for the occurrence of 144 polychlorinated biphenyls (PCBs) by GC-μECD. The results showed that totally 74 PCB congeners were identified and the mean concentration of total PCBs was 3057 ng kg⁻¹ with a range of 232 to 11325 ng kg⁻¹. Compared with the related reports, the level of PCBs contamination in this study was approximately equal to the global background value in soils, but higher than Chinese background for rural and urban soils. According to the compositional profiles of PCBs homologues, a higher proportion of low chlorinated (from tri-CBs to hexa-CBs) was observed. The results indicated that PCB15 + 13, PCB18, PCB28, PCB104 + 47 and PCB153 were the most dominant congeners among the identified PCBs. Through homologues analysis, cluster analysis and principal component analysis (PCA), it was found that PCBs were stretched from mixed local sources, and appeared to be mostly originated by Aroclor 1260- and 1254-like mixtures as well as some samples influenced by Aroclor 1232 and 1242. The correlation analysis showed the relatively good correlation among the PCB homologues and soil total organic carbon (TOC), suggesting important influence of soil TOC on PCBs contamination in soil matrix in Shanghai region. The toxic equivalency (TEQ) concentrations of these six dioxin-like PCBs detected in urban soil samples range from 2.71 to 24.9 pg kg⁻¹-PCDDeq with a mean 8.18 pg kg⁻¹-PCDDeq.     

Mussels as bioindicators of PCB pollution: a case study on uptake and release of PCB isomers and congeners in green-lipped mussels (Perna viridis) in Hong Kong waters

The uptake and release of PCB isomers and congeners were examined in green-lipped mussels (Perna viridis) through a transplantation experiment in two locations in Hong Kong waters. Rapid rates of uptake and release of relatively less lipophilic lower-chlorinated PCBs were observed in the mussels, indicating that the primary mechanism of bioaccumulation of lipophilic pollutants in P. viridis complies with the concept of equilibrium partitioning. Thus, data for contaminant concentrations are most appropriately based upon lipid weights of samples when using mussels as bioindicators of aquatic PCB pollution. Considering the kinetic parameters of PCBs based on lipid weight-related data, it is concluded that P. viridis has the ability to respond rapidly to changes in ambient levels of PCBs. This is significant in determining the usefulness and limitations of mussels as bioindicators for monitoring programmes investigating aquatic pollution by PCBs.     

Immunohistochemical detection of polychlorinated biphenyls in field collected damselfish (Abudefduf sordidus; Pomacentridae) embryos and larvae

Antibodies against polychlorinated biphenyls (PCBs) were used to determine if immunohistochemical methods could detect PCBs in embryos and larvae of a territorial coral reef fish (Abudefduf sordidus; Pomacentridae) collected from Johnston Atoll, Central Pacific Ocean. Sites with differing levels of contamination were sampled, one with relatively high sediment PCB concentrations of up to 389.0 ng/g and another with low PCB concentrations of only 0.5 ng/g. Immunostaining suggested that PCB concentrations were higher in fish larvae from the PCB contaminated site and that PCB concentrations within abnormal embryos were higher than normal embryos from the same nest. This technique will be useful for detecting exposed populations in the field and assessing correlations with adverse effects, particularly in potential indicator organisms such as Abudefduf sordidus.