Polychlorinated Biphenyl Signatures Research Articles

Concentration-dependent enantioselective accumulation of chiral polychlorinated biphenyls in Nelumbo nucifera Gaertn. root from contaminative sediment.

Nelumbo nucifera Gaertn. (lotus) roots were collected from contaminated sediments which were artificially adding different concentrations of chiral polychlorinated biphenyls (PCBs) to investigate the effect of concentration on the accumulation characteristics and chiral signatures of PCBs in lotus root during its growth period of 150 days. Under high PCB exposure concentration, the biota-sediment accumulation factors (BSAFs) of PCBs 91, 95, and 136 in the lotus root were up to 0.25-0.46 and 8.10-10.5 times higher than those under low-exposure concentration (0.024-0.052). The BSAFs of PCBs 149, 176, and 183 under high-exposure concentration were up to 0.24-0.44, while they were undetected at low concentration. The significant difference observed in the BSAFs based on different concentrations indicates that the lotus root accumulation efficiency toward chiral PCBs increases with the contaminate concentration. Although the (-)-enantiomers of PCBs 91, 95, and 136 wereall preferentially accumulated in lotus root under two exposure concentrations, the extent of the preferential accumulation of (-)-PCB 95 decreased with increasing exposure concentration throughout the whole growth period (30-150 days). In addition, the (-)-enantiomers of PCBs 91 and 136 also showed the same tendency during most of the growth period. Conclusively, the exposure concentrations are an important influence factor on the enantioselective accumulation of chiral PCBs in lotus root.

Toxicokinetics of Chiral PCB 136 and Its Hydroxylated Metabolites in Mice with a Liver-Specific Deletion of Cytochrome P450 Reductase.

Exposure to polychlorinated biphenyls (PCBs) has been implicated in adverse human health effects, including developmental neurotoxicity. Several neurotoxic PCBs are chiral and undergo atropisomeric enrichment in vivo due to atropselective metabolism by cytochrome P450 enzymes. Here we study how the liver-specific deletion of the cytochrome P450 reductase ( cpr) gene alters the toxicokinetics of 2,2',3,3',6,6'-hexachlorobiphenyl (PCB 136) in mice. Male and female mice with a liver-specific deletion of cpr (KO) and congenic wild-type (WT) mice were exposed to a single oral dose of racemic PCB 136 (6.63 mg/kg). Levels and chiral signatures of PCB 136 and its hydroxylated metabolites were determined 1-48 h after PCB exposure in whole blood. Blood levels of PCB 136 were typically higher in M-WT compared to F-WT mice. At the later time points, F-KO mice had significantly higher PCB 136 levels than F-WT mice. 2,2',3',4,6,6'-Hexachlorobiphenyl-3-ol (3-150), 2,2',3,3',6,6'-hexachlorobiphenyl-4-ol (4-136), 2,2',3,3',6,6'-hexachlorobiphenyl-5-ol (5-136), and 4,5-dihydroxy-2,2',3,3',6,6'-hexachlorobiphenyl (4,5-136) were detected in blood, with 5-136 and 4-136 being major metabolites. At later time points, the sum of HO-PCB (∑HO-PCB) levels exceeded PCB 136 levels in the blood; however, higher ∑HO-PCB than PCB 136 levels were observed later in KO than WT mice. PCB 136 and its major metabolites displayed atropisomeric enrichment in a manner that depended on the time point, sex, and genotype. Toxicokinetic analysis revealed sex and genotype-dependent differences in toxicokinetic parameters for PCB 136 atropisomers and its metabolites. The results suggest that mice with a liver-specific deletion of the cpr gene can potentially be used to assess how an altered metabolism of neurotoxic PCB congeners affects neurotoxic outcomes following exposure of the offspring to PCBs via the maternal diet.

Mechanical Treatment of MSWI Fly Ash: A Way Forward to Inhibit PCB Reformation

ABSTRACT Fly ash from municipal solid waste incinerators has been classified as hazardous waste due to the presence of unintentionally-produced Persistent Organic Pollutants (POPs), with Polychlorinated biphenyls (PCB) being a major group among such POPs. Fly ash can be mechanically (MC) treated to destroy organic pollutants before final disposal or reuse. In this study, model fly ash (MFA) doped with 0.2% CuCl2 was artificially prepared and subjected to high intensity ball milling for 0 (original sample), 1, 2, 4, and 8 h of treatment. Furthermore, to explore PCB reformation in the MC treated fly ash, de novo tests were conducted at single reaction time, temperature, and air flow rate. It was found that the sum of PCB, dioxin like PCB, and corresponding International Toxic Equivalent concentrations (∑PCB, ∑dl-PCB and ∑I-TEQ, respectively) were greatly reduced both in gas and in solid phase of MFA after 8 h of treatment. Though chlorination degree successively decreased with prolonged milling, the homologue and isomer signatures of PCB were varied in concentration. Reformation of few isomers was also observed. Results from present study suggest that MC treatment is an effective method to control reformation of pollutants in the long term. However, few suggestions are made for further ongoing research work on MC treatment of fly ash, which are based on surprising results and experimental limitations obtained in this study.

Changes to polychlorinated biphenyl (PCB) signatures and enantiomer fractions across different tissue types in Guillemots

Two Guillemot carcases were dissected, each providing 12 discrete tissue samples and 3 samples of partially digested food. One hundred and five PCBs from the 209 PCBs determined by GCxGC-ToFMS were detected. The relative proportions of individual PCBs did not vary greatly within tissue types, although the PCB profile from undigested food could be distinguished. Enantiomer fractions (EFs) were determined for CB-95, CB-136 and CB-149 by GC-HRqToFMS. EFs in the partially digested food were near racemic, with high levels of enrichment for E1 CB-95 in the kidneys and liver (EF of 0.80 and 0.84 respectively). This provides some of the clearest evidence to date that fractionation takes place in the organs where metabolic biotransformation and elimination of PCBs occurs. Our findings also confirm the ability of non-lethal sampling techniques, such as collection of small (<1 g) blood samples, to provide PCB signatures that are representative of an individual organism.

Can polychlorinated biphenyl (PCB) signatures and enantiomer fractions be used for source identification and to age date occupational exposure?

Detailed polychlorinated biphenyl (PCB) signatures and chiral Enantiomer Fractions (EFs) of CB-95, CB-136 and CB-149 were measured for 30 workers at a transformer dismantling plant. This was undertaken to identify sources of exposure and investigate changes to the PCB signature and EFs over different exposure periods. Approximately 1.5g of serum was extracted and PCB signatures were created through analysis by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC–TOFMS) and EFs calculated following analysis by gas chromatography with high resolution mass spectrometry (GC–HRMS). A total of 84 PCBs were identified in the serum samples with concentrations of the 7 indicator PCBs ranging from 11–350ngg−1 of serum (1.2–39μgg−1 lipid). The PCB signatures were interpreted using principal component analysis (PCA) which was able to distinguish workers with background or recent minimal exposure from those with prolonged occupational exposure. Occupationally exposed individuals had a similar PCB profile to Aroclor A1260. However, individuals with prolonged exposure had depleted proportions of several PCB congeners that are susceptible to metabolism (CB-95, CB-101 and CB-151) and elevated proportions of PCBs that are resistant to metabolism (CB-74, CB-153, CB-138 and CB-180). The results also identified a third group of workers with elevated proportions of CB-28, CB-60, CB-66, CB-74, CB-105 and CB-118 who appeared to have been exposed to an additional source of PCBs. The results show near complete removal of the CB-95 E2 enantiomer in some samples, indicating that bioselective metabolism or preferential excretion of one enantiomer occurs in humans. By considering PCB concentrations along with detailed congener specific signatures it was possible to identify different exposure sources, and gain an insight into both the magnitude and duration of exposure.

Elevated Levels of Polychlorinated Biphenyls in Plants, Air, and Soils at an E-Waste Site in Southern China and Enantioselective Biotransformation of Chiral PCBs in Plants

E-waste that contains polychlorinated biphenyls (PCBs) is moved across national boundaries, often from industrialized countries in the northern hemisphere, where the items were formerly used, to subtropical and tropical regions in southeastern Asia and Africa. As a result, there is a high likelihood that PCBs will be released into the environment from a primary source due to the elevated temperatures encountered in these low-latitude regions. In the present study, PCBs and enantiomer fractions (EFs) of chiral PCBs (PCB 84, 95, 132, 136, 149, and 183) were analyzed in air, eucalyptus leaves, pine needles, and soil at an e-waste site and a rural site in southern China. The concentrations of PCBs at the e-waste site ranged from 7825 to 76330 pg/m(3), 27.5 to 1993 ng/g, and 24.2 to 12045 ng/g in the air (gas plus particle), plant leaves, and soils, respectively. The atmospheric PCB composition profiles in the present study indicated relatively high abundances of penta- and hexa-PCBs, which were different from those previously observed in the air across China. The Clausius-Clapeyron regression analysis indicated that evaporation from local contaminated surfaces constitutes a primary emission source of PCBs in the air at the e-waste site. The chiral signatures of PCBs in the air at the e-waste site were essentially racemic (mean EFs = (0.484 ± 0.022)-(0.499 ± 0.004) in the gaseous phase) except for PCB 84 (0.420 ± 0.050), indicating that racemic sources dominate the PCB emission in the air. PCB chiral signatures in the soils ((0.422 ± 0.038)-(0.515 ± 0.016)) were similar to those in the air except for PCB 95. However, the chiral PCBs in the plants (especially the eucalyptus leaves) had significantly nonracemic residues ((0.368 ± 0.075)-(0.561 ± 0.045)) compared to those in the air and soil. This finding suggests that enantioselective biotransformation of these atropisomeric PCBs was very likely to occur in the plant leaves, possibly due to metabolism by cytochrome P-450 enzymes in leaves. To our knowledge, this is the first report on the enantioselective metabolism of chiral PCBs in plants under field conditions.

2,2′,3,3′,6,6′-Hexachlorobiphenyl (PCB 136) Is Enantioselectively Oxidized to Hydroxylated Metabolites by Rat Liver Microsomes

Developmental exposure to multiple ortho-substituted polychlorinated biphenyls (PCBs) causes adverse neurodevelopmental outcomes in laboratory animals and humans by mechanisms involving the sensitization of Ryanodine receptors (RyRs). In the case of PCB 136, the sensitization of RyR is enantiospecific, with only (-)-PCB 136 being active. However, the role of enantioselective metabolism in the developmental neurotoxicity of PCB 136 is poorly understood. The present study employed hepatic microsomes from phenobarbital (PB)-, dexamethasone (DEX)- and corn oil (VEH)-treated male Sprague-Dawley rats to investigate the hypothesis that PCB 136 atropisomers are enantioselectively metabolized by P450 enzymes to potentially neurotoxic, hydroxylated PCB 136 metabolites. The results demonstrated the time- and isoform-dependent formation of three metabolites, with 5-OH-PCB 136 (2,2',3,3',6,6'-hexachlorobiphenyl-5-ol) being the major metabolite. The formation of 5-OH-PCB 136 increased with the activity of P450 2B enzymes in the microsomal preparation, which is consistent with PCB 136 metabolism by rat P450 2B1. The minor metabolite 4-OH-PCB 136 (2,2',3,3',6,6'-hexachlorobiphenyl-4-ol) was produced by a currently unidentified P450 enzyme. An enantiomeric enrichment of (-)-PCB 136 was observed in microsomal incubations due to the preferential metabolism of (+)-PCB 136 to the corresponding 5-OH-PCB 136 atropisomer. 4-OH-PCB 136 displayed an enrichment of the atropisomer formed from (-)-PCB 136; however, the enrichment of this metabolite atropisomer did not affect the enantiomeric enrichment of the parent PCB because 4-OH-PCB 136 is only a minor metabolite. Although the formation of 5- and 4-OH-PCB 136 atropisomers increased with time, the enantioselective formation of the OH-PCB metabolites resulted in constant enantiomeric enrichment, especially at later incubation times. These observations not only demonstrate that the chiral signatures of PCBs and their metabolites in wildlife and humans are due to metabolism by P450 enzymes but also suggest that the enantioselective formation of neurotoxic PCB 136 metabolites, such as 4-OH-PCB 136, may play a role in the developmental neurotoxicity of PCBs.

Concentrations and chiral signatures of POPs in soils and sediments: A comparative urban versus rural study in Canada and UK

Surface soils and sediments were collected in Toronto, Canada to investigate the concentrations and enantiomeric signatures of urban versus rural locations. Samples were analyzed for polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs) and organochlorine pesticides (OCs). In soils, the sum of 10 PCB congeners (∑PCB 28, 52, 95, 101, 118, 136, 138, 149, 153, 180) and 15 PAHs (∑PAHs) ranged from 0.76–58 to 58–3200 ng g −1, respectively. The most abundant OCs detected were DDTs, followed by chlordanes and endosulfans. ∑PAHs exhibited an urban–rural gradient of up to 60 times but a gradient was not observed for ∑PCBs and OCs which may reflect local sources of these chemicals. In sediments, ∑PCBs and ∑PAHs ranged from 0.03–23 ng g −1 to 42–3300 ng g −1, respectively. ∑PCBs, ∑PAHs, chlordanes and DDTs exhibited weak urban–rural gradients. Chiral signatures of PCB 95, 136, 149, trans-chlordane (TC), cis-chlordane (CC) and o, p-DDT were characterized to study the enantiomeric degradation in urban versus rural areas and its relation to contaminant levels. Supplementary to these data, we also report on the chiral signatures of PCBs in UK lake sediments from a variety of urban and rural locations. The extent of enantiomeric degradation was expressed as the enantiomeric excess (EE%) which is defined as 100 × ( E1 − E2)/( E1 + E2), where E1 is always the most abundant enantiomer and E2 is the least abundant enantiomer. The EE% of PCB 149 in the UK sediments was negatively correlated ( p < 0.05) with ∑PAHs suggesting either more recent emissions of this PCB congener in the more contaminated urban locations and hence a more racemic signature or less enantiomeric degradation of the congener in more contaminated urban soils. However, no significant correlation was observed between EE% of any of the chiral chemicals and contaminant levels in the Toronto soils.

Geographic specificity of Aroclor 1268 in bottlenose dolphins (Tursiops truncatus) frequenting the Turtle/Brunswick River Estuary, Georgia (USA)

Coastal marine resources are at risk from anthropogenic contaminants, including legacy persistent organic pollutants (POPs) with half-lives of decades or more. To determine if polychlorinated biphenyl (PCB) signatures can be used to distinguish among local populations of inshore bottlenose dolphins ( Tursiops truncatus) along the southeastern U.S. coast, blubber from free-ranging and stranded animals were collected along the Georgia coast in 2004 and analyzed for PCB congeners using gas chromatography with electron capture and negative chemical ionization mass spectrometric detection (GC-ECD and GC-NCI-MS). Mean total PCB concentrations (77 ± 34 μg/g lipid) were more than 10 fold higher and congener distributions were highly enriched in Cl 7–Cl 10 homologs in free-ranging animals from the Turtle/Brunswick River estuary (TBRE) compared with strandings samples from Savannah area estuaries 90 km to the north. Using principal components analysis (PCA), the Aroclor 1268 signature associated with TBRE animals was distinct from that observed in Savannah area animals, and also from those in animals biopsied in other southeastern U.S estuaries. Moreover, PCB signatures in dolphin blubber closely resembled those in local preferred prey fish species, strengthening the hypothesis that inshore T. truncatus populations exhibit long-term fidelity to specific estuaries and making them excellent sentinels for assessing the impact of stressors on coastal ecosystem health.

Chiral Source Apportionment of Polychlorinated Biphenyls to the Hudson River Estuary Atmosphere and Food Web

The New York/New Jersey Harbor Estuary is subject to significant contamination of polychlorinated biphenyls (PCBs) from numerous sources, including the historically contaminated Upper Hudson River, stormwater runoff and sewer overflows, and atmospheric deposition from PCBs originating from the surrounding urban area. However, the relative importance of these sources to the estuary's food web is not fully understood. Sources of PCBs to the estuary were apportioned using chiral signatures of PCBs in air, water, total suspended matter, phytoplankton, and sediment. PCBs 91, 95, 136, and 149 were racemic in the atmosphere of the estuary. However, the other phases contained nonracemic PCB 95 and to a lesser extent PCB 149. Thus, the predominant atmospheric source of these congeners is likely unweathered local pollution and not volatilization from the estuary. The similarity in chiral signatures in the other phases is consistent with dynamic contaminant exchange among them. Chiral signatures in the dissolved phase and total suspended matter were correlated with Upper Hudson discharge, suggesting thatthe delivery of nonracemic contaminated sediment from the Upper Hudson, not the atmosphere, controls phytoplankton uptake of some PCBs. Thus, measures to control PCB contamination in the Upper Hudson should be effective in reducing loadings to the estuary's aquatic ecosystem.

Congener-Specific Survey for Polychlorinated Biphenlys in Sediments of Industrialized Bays in Korea: Regional Characteristics and Pollution Sources

Areas of the Korean coastline with heavy industry and major harbors were investigated for polychlorinated biphenyl (PCB) pollution. This investigation paid attention to variations in the PCB congener patterns for a possible source of contamination. Surface sediments from 49 sites were sampled. Although the occurrence of PCBs in coastal marine environment correlates well with shipping and industrial activities, the contribution from shipping activities is considerable because of its enormous economical importance in Korea. The highest concentrations were found in harbors with heavy ship traffic and ship construction. Principal component analysis (PCA) of congener-specific composition of PCBs revealed distinct regional patterns, especially in a harbor and steel manufacturing area. PCB signatures with enhanced higher chlorinated congeners were typical for harbors with shipping activities and correlated well with commercial formulations that were formerly used in ship painting. Lower chlorinated congeners with up to five chlorines were significantly abundant in steel works zones which differed from harbor zones. This distinction was consistent with the congener patterns in the ambient air and the effluent of the steel works as well as in the nearby surface sediments. This study identified steel manufacturing as a recent and ongoing emission source of PCBs in Korea's coastal zone.