Higher Chlorinated Biphenyls Research Articles

Strategy for Remediation of Polychlorinated Biphenyls-Contaminated Soil Through Redox Management Based on Electronegativity of the Contaminants.

Literature review reveals that Persistent Organic Pollutants (POPs), such as polychlorinated biphenyls (PCBs), are electron deficient compounds due to the presence of highly electronegative groups. Hence, they are more amenable to anaerobic biodegradation rather than oxidative metabolism. However, the studies on PCBs bioremediation are more inclined towards aerobic treatment. Besides, the past studies are mainly centered on screening and application of PCB-degrading microorganisms. In our opinion the degradative capacity is already present in the native microflora, and choice of electron donor is of paramount importance for faster reductive metabolism of PCBs. In this study, the use of methanol as electron donor with cow dung as the general microbial inoculum resulted in high specific rate of degradation (0.0542-0.0637 /day) for high-chlorinated biphenyls. The % removal of PCBs ranged between 67.7 and 71.7%. It may be the first study on the application of methanol as a cheap electron donor for PCBs biodegradation without bioaugmentation with specifically selected microorganisms.

Characterization of newly synthesized starch coated Fe/Cu nanoparticles and its dechlorination efficiency on the low and high chlorinated biphenyls

New starch coated zero-valent Fe/Cu nanoparticles were synthesized by borate reduction method. The surface profile of synthesized nanoparticles was studied by atomic force microscopy (AFM) imaging. Comparison of Infra red (IR) spectra of soluble starch and starch coated Fe/Cu nanoparticle revealed the complex formation between Fe/Cu nanoparticles and soluble starch. X-ray diffraction pattern and Energy-dispersive X-ray spectroscopy (EDX) spectrum analysis exposed the composition of starch coated Fe/Cu nanoparticles. SEM imaging determined the size of Fe/Cu nanoparticle which was fallen into the size of 48 to 70 nm. In this study, the capability of starch coated Fe/Cu nanoparticle to degrade the low and high chlorinated biphenyls were studied extensively. It was observed that soluble starch and β-cyclodextrin have enhanced the polychlorinated biphenyl (PCB) degradation by preventing iron nano-agglomeration and making the PCB as a soluble form, respectively. The dechlorination was further confirmed by the estimation of released chloride ion during the PCB degradation. The present study suggested that this new method could be an efficient and reliable method to treat PCB contaminated soil and sediments.

Occurrence, distribution, and dechlorination of polychlorinated biphenyls and health risk assessment in Selangor River basin.

Polychlorinated biphenyls (PCBs) were monitored in surface water collected in the Selangor River basin, Malaysia, to identify the occurrence, distribution, and dechlorination process as well as to assess the potential adverse effects to the Malaysian population. Ten PCB homologs (i.e., mono-CBs to deca-CBs) were quantitated by using gas chromatography-mass spectrometry (GC/MS). The total concentration of PCBs in the 10 sampling sites ranged from limit of detection to 7.67ngL-1. The higher chlorinated biphenyls (tetra-CBs to deca-CBs) were almost not detected in most of the sampling sites, whereas lower chlorinated biphenyls (mono-CBs, di-CBs, and tri-CBs) dominated more than 90% of the 10 homologs in all the sampling sites. Therefore, the PCB load was estimated to be negligible during the sampling period because PCBs have an extremely long half-life. The PCBs, particularly higher chlorinated biphenyls, could be thoroughly dechlorinated to mono-CBs to tri-CBs by microbial decomposition in sediment or could still be accumulated in the sediment. The lower chlorinated biphenyls, however, could be resuspended or desorbed from the sediment because they have faster desorption rates and higher solubility, compared to the higher chlorinated biphenyls. The health risk for the Malaysia population by PCB intake that was estimated from the local fish consumption (7.2ngkg-1 bwday-1) and tap water consumption (1.5×10-3-3.1×10-3ngkg-1 bwday-1) based on the detected PCB levels in the surface water was considered to be minimal. The hazard quotient based on the tolerable daily intake (20ngkg-1 bwday-1) was estimated at 0.36.

Microbial transformation and degradation of polychlorinated biphenyls

This paper reviews the potential of microorganisms to transform polychlorinated biphenyls (PCBs). In anaerobic environments, higher chlorinated biphenyls can undergo reductive dehalogenation. Meta- and para-chlorines in PCB congeners are more susceptible to dechlorination than ortho-chlorines. Anaerobes catalyzing PCB dechlorination have not been isolated in pure culture but there is strong evidence from enrichment cultures that some Dehalococcoides spp. and other microorganisms within the Chloroflexi phylum can grow by linking the oxidation of H(2) to the reductive dechlorination of PCBs. Lower chlorinated biphenyls can be co-metabolized aerobically. Some aerobes can also grow by utilizing PCB congeners containing only one or two chlorines as sole carbon/energy source. An example is the growth of Burkholderia cepacia by transformation of 4-chlorobiphenyl to chlorobenzoates. The latter compounds are susceptible to aerobic mineralization. Higher chlorinated biphenyls therefore are potentially fully biodegradable in a sequence of reductive dechlorination followed by aerobic mineralization of the lower chlorinated products.

Metabolic activation of PCBs to carcinogens in vivo—A review

Many higher-chlorinated biphenyls, persistent and predominant in foods, are active as promoters in hepatocarcinogenesis. Lower-chlorinated biphenyls, predominating in indoor and outdoor air, are more readily metabolized and therefore shorter lived, ‘episodic’ contaminants. Thus inhalation of such lower-chlorinated biphenyls may expose humans to reactive, possibly genotoxic/carcinogenic intermediates. Lower-chlorinated biphenyls may be metabolized via arene-oxides to mono- and di-hydroxylated intermediates and further to (semi)quinones, highly reactive intermediates. Covalently bound lower-chlorinated biphenyls have been detected in rodent tissues in vivo. We recently showed using the modified Solt–Farber foci assay that several mono- to tetrachlorinated biphenyls have initiating activity in the livers of rats. In a follow-up study of PCB3 (4-chlorobiphenyl) metabolites, only one monohydroxy- and one quinoid-metabolite showed initiating activity, indicating that the metabolic activation of PCB3 proceeds via hydroxylation and oxidation to the 3,4-quinone, the ultimate carcinogen. Since cancer initiation is based on genotoxic event(s), we hypothesized that PCB3 and/or its metabolite(s) are mutagenic in rat liver in vivo. To investigate this, BigBlue ® rats, transgenic for the lacI reporter gene, were exposed to PCB3 and 4-hydroxy-PCB3 (4-HO-PCB3). In male rats the mutant frequency (MF) of lacI in the liver was significantly elevated and the mutation spectrum differed significantly from the control. 4-HO-PCB3 caused a non-significant ( p = 0.115) doubling of the MF compared to the control. These studies prove that lower halogenated biphenyls may be metabolically activated in vivo to genotoxic and initiating intermediates.

Study of transportation and distribution of PCBs using an ecologically simulated growth chamber

This study was designed to investigate the transportation, distribution, and bioaccumulation of PCBs in various environmental media and compartments using an ecologically simulated growth chamber. Spatial and temporal trends of PCBs in the growth chamber were discussed. The release of PCB congeners in soil was affected by the amount of rainfall with the transporting direction moving away from PCBs contaminated point. Two pathways of PCBs accumulation in plants were the uptake of roots and the deposition on shoots/leaves. There were 29 PCB congeners been found in the lalang grass. Higher concentrations of lower chlorinated PCBs were identified than higher chlorinated PCBs because of relatively higher vapor pressure for lower chlorinated congeners. After 10 months of monitoring, PCBs were detected in water samples which were contributed by the release of PCBs from leached soil. Analysis of sediment showed that the percentages of low- and mid-chlorinated biphenyls were decreased 1% and 13%, respectively compared to the increase (14%) of high-chlorinated biphenyls. The increase of high-chlorinated PCBs was possibly caused by their low hydrophilicity which had resulted higher adsorption rate in sediment. All of five species of fish had been found significant amount of PCBs accumulation (∑PCBs: 21.7–102.1 μg/g-lipid). The concentrations of PCBs in fish were varied significantly among species. The range of bioaccumulation factors (BAFs) among different species of fish could be as much as 5 times depending on the consumption habits of fish. The mass balance of PCBs distribution in the growth chamber was also discussed.

Übertragung potenziell schädlicher Organochlorverbindungen durch mütterliches Stillen im Verlauf der ersten 6 Lebensmonate

Despite a decline of 70 to 90 % during the past 20 years, many presumed carcinogenic and teratogenic organochlorine compounds (OC) are still present in our biosphere and accumulate in our food-chain. They are prenatally transmitted from mother to fetus, and mother's milk due to its high lipid content is an elimination pathway of special importance in all mammals. It was the aim of the present study to investigate whether breast-feeding increases the body pollution of human infants with OC during the first six months of life. The study was approved by the committee on Biomedical Research of the Heinrich Heine University Düsseldorf, Germany. With written informed consent of the parents, blood samples were taken from 10 breast-fed and bottle-fed infants at the age of six weeks and six months, respectively. Three higher chlorinated PCB (polychlorinated biphenyls) congeners (IUPAC nos. 138, 153, and 180), HCB, and DDE, the main metabolite of DDT in mammals, were analyzed with capillary gas chromatography with electron capture detection. Reliability was tested with gas chromatography-mass spectrometry. Furthermore, the sum of the three higher chlorinated biphenyls (SigmaPCB) was calculated. There were no differences between the study groups of breast-fed and bottle-fed infants with regard to sex distribution, gestational age, birth weight, age of the mothers, and smoking behavior of the parents. However, serum concentrations of all OC were significantly higher (p < 0.0001) in breast-fed than in bottle-fed infants as early as at six weeks of age, and their concentrations nearly doubled until the age of six months (median [microg/L]; A = six weeks; B = six months): PCB 138, A: 0.40 vs. 0.09; B: 0.72 vs. 0.07; PCB 153, A: 0.57 vs. 0.11; B: 0.99 vs. 0.09; PCB 180, A: 0.33 vs. 0.04; B: 0.58 vs. 0.02; Sigma PCB, A: 1.19 vs. 0.29; B: 2.28 vs. 0.18; HCB, A: 0.13 vs. 0.04; B: 0.43 vs. 0.07; DDE, A: 1.05 vs. 0.18 ; B: 1.90 vs. 0.19. Breast-feeding significantly increases the serum concentration of our infants with different OC within the first six months of life, which leads to a body burden with OC, in this amount last measured in the mid-1980 s in Germany. In face of these results, common recommendations for breast-feeding should be reconsidered, taken into account the availability of infants formula (industrial vs. Third World countries).

Differential accumulation of low-chlorinated (Delor 103) and high-chlorinated (Delor 106) biphenyls in human placental tissue and opposite effects on conversion of DHEA to E2

Objective Polychlorinated biphenyls (PCBs) and related compounds elicit a diverse spectrum of toxic responses. Additionally, they are able to pass through the human placenta. The aim of the presented data was to compare the action of low-chlorinated (Delor 103) and (Delor 106) high-chlorinated biphenyls on placental steroidogenesis. Methods Explants of human placental tissue were used to test differences in PCBs accumulation and influence on placental steroidogenesis. Delor 103 or 106, were added daily for six days at a dose of 200 pg from day 0 to day 6 of culture. The media in the control and experimental groups were changed every day, and collected and frozen for steroid analysis by RIA. Determinations of PCBs of tissue and medium were analysed by GC/MS/MS. Results Delor 103 was found at a higher level in the tissue than Delor 106. The first day of exposure to Delor 103 had no effect on the conversion of dehydroepiandrosterone (DHEA) to estradiol (E2) while there was a 2-fold decrease in E2 secretion from days 3 to 6. Conversely, Delor 106 caused an immediate increase in E2 secretion, which was maintained at higher levels throughout the exposure period. Conclusion Differences between the accumulation of lower chlorinated and higher chlorinated biphenyls in human placental tissue and in the properties of the congeners can have multiple effects that may intensify or counteract the effects on uterine contraction by PCBs.

Species and organ dependence of PCB contamination in fish, foxes, roe deer, and humans.

According to previous experimental results, PCBs are deposited in muscle fat in animals and in humans, although they also reach the brain, the liver, and the lungs. The aim of the present study was to determine the concentrations of the so-called "indicator PCBs" (PCB nos. 28, 52, 101, 138, 153, 180), as described by the German ordinance for maximum concentrations of contaminants in foodstuffs, in muscle tissue, liver, and brain of four different species: fish, fox, roe deer, and humans, all exposed to PCBs directly in their environment. Potential target organs for the accumulation of these congeners were also to be identified. Furthermore, the organs or tissues were to be identified in which PCBs are accumulated, and unusual patterns of accumulation or breakdown of particular PCBs, for example the "dioxin-like PCBs" (coplanar PCBs) determined. For humans, the lungs were also included in these studies. Statistical comparison of PCB concentrations in samples from wild animals and humans showed that in spite of its relatively high fat concentration, brain tissue in all of the species examined (with the exception of fish) appeared to be better protected against accumulation of PCB than liver or muscle tissue. This protection may be the result of the blood-brain barrier, as witnessed by the relatively uniform concentration of PCBs throughout the various organs of fish, since the blood-brain barrier of fish is considerably less efficient than that of mammals. No peculiarities were found in regard to distribution of the coplanar PCBs over the other congeners in this study. This applies to the brain and other organs or tissues of the four species that were examined. Accumulations of PCBs and coplanar PCBs in the liver were only found in fox and roe deer. In contrast, humans were found to have accumulations of the high-chlorinated biphenyls studied here as well as PCB no. 118 in muscle tissue fat and not in the liver. Unexpectedly, low-chlorinated biphenyls were found to accumulate in the human lung. The results of this study show that the lung represents a target organ for the accumulation of potentially metabolically activated low-chlorinated biphenyls, indicating that the possible biological effects of PCBs on the lungs will need to receive more attention in the future.

Isomer-specific analysis of polychlorinated biphenyls and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) in red fox and human adipose tissue from central Italy.

The general exposure of humans and foxes to polychlorinated biphenyls (PCBs) and DDT in Italy was determined by analysis of adipose tissue samples collected from 1991-1992. sigma PCB concentrations varied between 1.0 and 2.6 micrograms/g (wet wt.). sigma DDT concentrations ranged from 1.6 to 5.0 micrograms/g (wet wt.). About thirty-five PCB congeners were identified in most samples. PCB congeners of IUPAC Nos. 138, 153, and 180 were the most abundant compounds, accounting for an average of 50% of the sigma PCBs in humans and 64% in foxes. Generally, higher chlorinated biphenyls and those with a 2,4,5-chlorine substitution in one ring and at least one substitution in the 4-position of the other ring were preferentially accumulated. Coplanar PCB congeners were detected at considerable concentrations and there is no sign of decline in their concentrations with respect to previously reported data. IUPAC Nos. 118, 156 and 126 were the main contributors to toxicity in humans and foxes. The significant contribution of mono-ortho congeners in humans and non-ortho congeners in foxes suggests that differences in metabolic potential may affect the PCB toxicity pattern.

PCB congeners in human milk in Germany from 1984/85 and 1990/91

Studies of so-called bioindicators clearly show the impact of environmental legislation on PCB contamination of the environment and of the food chain in the Federal Republic of Germany. This is evident from the results of studies performed in our laboratory on samples of muscle tissue from foxes that were submitted for post-mortem examination in the years 1983, 1987 and 1991. Whereas the concentration of low-chlorinated congeners of high-chlorinated biphenyls, with the exception of PCB no. 101, decreased. This trend may also be responsible for changes in the otherwise stable PCB concentrations in human milk. Consequently, in the study describe here, milk samples from 1990/91, from women in Middle-Hesse, Germany, were examined and the results compared to samples stemming from 1984/85. 11 refs., 3 tabs.

Degradation of PCBs by ferric ion, hydrogen peroxide and UV light

AbstractA 1‐g/L two‐phase mixture of the commercial PCB oil Aroclor 1242 in acidified water at 66°C was degraded by a photoassisted Fenton‐type reaction consisting of Fe3+, H2O2, and UV light (300‐400 nm). Up to 88% PCB removal and 85% dechlorination were obtained, without attempts at optimization. The order of reactivity was di‐ &gt; tri‐&gt; tetra‐ ‐ – higher chlorinated biphenyls, but the selectivity was weak. Perfluorinated surfactants added to increase PCB solubility or rates of dissolution had a detrimental effect on degradation. Minimal reaction was observed at room temperature.

Polychlorierte Biphenyle (PCB) in Fischen aus Teichwirtschaften und Nachkl�rteichen

The concentrations of six selected single polychlorinated biphenyl (PCB) congeners, for which legal tolerance levels became valid in 1988, and the congener no. 49 (2,2',4,5'-tetrachlorobiphenyl) were determined in the muscle tissue of 58 fishes from fish hatcheries and in 17 fishes from settle ponds. The fish were taken from flowing waters in the years 1986 and 1987. High and low chlorinated biphenyls were present in each sample, but the concentration of the low chlorinated biphenyls was distinctly lower than that of the higher chlorinated ones. Nevertheless these results demonstrate the intake of components of low chlorinated technical PCB mixtures in the environment and food chains. Compared with the investigations carried out in 1980/81 in fishes from fish hatcheries, a decrease of PCB contamination in the muscle tissues with regard to the technical mixture Clophen A 60 was observed. This is in accordance with the results our team obtained a short time previously in muscle tissue from foxes and in food-stuffs. The concentration of all PCB congeners determined in the muscle tissue from fish of settle ponds was significantly higher than in the tissue from fish taken from hatcheries. Thus, the PCB content depends on the PCB load in different environments. Therefore, fishes can be useful as bioindicators for the intake of low and high chlorinated PCB congeners in aquatic ecosystems.

Polychlorierte Biphenyle: Bestimmung der Einzelkomponenten in Rohmilch und kontaminierten Futtermitteln

Since 1980, 2145 samples of raw milk from producers in the district of Freiburg have been analysed for polychlorinated biphenyls (PCB) during a monitoring programme. In 1983, we started to search for the source of PCB, whenever milk was contaminated above the average value (above 0.2 mg/kg fat, calculated as Clophen A60). In 7 cases, previous coats of paint in the silos proved to be the cause of the PCB contamination. Five samples of milk and 4 corresponding silages as well as 1 sample of wood (from a cowshed) were investigated for all of the individual PCB components included in the technical mixtures of Clophen A30 and A60. Two samples of silages contained both low and high chlorinated biphenyls, whereas low chlorinated biphenyls (di-, tri-, and tetrachlorinated biphenyls) were not detected in the corresponding milk samples. Pentachlorinated biphenyls were only detected in the range of 1%-2%. In the samples of wood and corresponding milk, a different PCB pattern appeared. There were remarkably high percentages of hepta- and octachlorinated biphenyls as well as a lower percentage of hexachlorinated biphenyls. The exact PCB content of the milk, determined by the addition of all single components, proved to be approximately half the value obtained by the usual calculation based on the evaluation of the three main peaks of the technical PCB mixture (Clophen A60). During 1984-1987, 607 samples of raw milk were analysed for six single PCB components, for which legal tolerance levels became valid in 1988.(ABSTRACT TRUNCATED AT 250 WORDS)

Comparative toxicities of chlorinated biphenyls on sea urchin egg fertilisation and embryogenesis

The aim of this study was to compare the biological actions of selected chlorinated biphenyls (CB's) (with different degrees of chlorine substitution), using the sea urchin test system, for their ability to affect fertilisation, embryogenesis and mitotic activity. Sea urchin embryos were exposed to the test agents throughout larval development or for shorter intervals (e.g. before or after hatching). Sperm or eggs were exposed before fertilisation, thereafter the contaminants were removed from embryo cultures. The results showed maximal activities from medium-chlorinated (tetra- and hexachloro-substituted) compounds, as compared to low- and high-chlorinated biphenyls (mono-, di- and octachloro-substituted), at nominal levels ranging from 10 −6 m to 10 −5 m . This held true for the different parameters and treatment schedules. Developmental defects were only detected following post hatching exposure of embryos to CB's, whereas pre-hatching exposure failed to reveal any embryological or cytogenetic abnormalities.

Comparative effects of commercial Aroclors on rat liver enzyme activities

Hepatic DNA, RNA, protein and p-nitroanisole O-demethylase, aniline hydroxylase, nonspecific carboxylesterase, bromosulphophthalein-glutathione (BSP-GSH) conjugating enzyme and p-nitrophenol UDPglucuronyl transferase activities were measured in young Wistar male rats which had received intraperitoneal injections (50 mg/kg) of biphenyl and Aroclors 1016, 1221, 1232, 1242, 1248, 1254 and 1260, dissolved in peanut oil, for 3 consecutive days and assayed 96 h after the last injection. Biphenyl and all the Aroclors caused the same degree of enhancement of BSP-GSH conjugating enzyme. Decreased DNA content, increased RNA and protein content and the other enzymatic activities were related to the percent weight of chlorine and the chlorobiphenyl composition of the Aroclors. More marked effects were observed with the highly chlorinated Aroclor 1248, 1254, and 1260 mixtures which contained predominantly tetra-, penta-, hexa-, and higher-chlorinated biphenyls.