Comparative toxicities of the polychlorinated dibenzofuran (PCDF) and biphenyl (PCB) mixtures which persist in Yusho victims

The toxic Yusho oil contained a mixture of polychlorinated biphenyls (PCBs) which were contaminated by other halogenated aromatics including the highly toxic polychlorinated dibenzofurans (PCDFs). It has been reported that the PCBs and PCDFs which persist in the liver of victims still suffering from Yusho poisoning include the following compounds; 2,3′,4,4′,5-penta-,2,2′,4,4′,5,5′-,2,2′,3′,4,4′,5- and 2,3,3′,4,4′,5-hexa, 2,2′,3,4,4′,5,5′- and 2,2′,3,3′,4,4′,5-heptachlorobiphenyls and the 2,3,7,8-tetra-, 1,2,4,7,8-, 1,2,3,7,8- and 2,3,4,7,8-penta- and 1,2,3,4,7,8-hexachlorodibenzofurans. All of these PCBs and PCDFs have been synthesized and reconstituted to approximate their composition in human liver. A comparison of the dose-response effects of the reconstituted PCB and PCDF mixtures in causing weight loss, thymic atrophy and the induction of cytochrome P-448-dependent monooxygenases indicated that the PCDF mixture was at least 700 times more active than the PCBs. Since the ratio of PCBs/PCDFs persisting in Yusho patients' blood and liver was less than 600:1 and 5:1 respectively, the results suggest that the PCDFs are the major etiologic agent in Yusho poisoning.     

Polychlorinated biphenyl, polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran residues in sediments and fish of the River Nile in the Cairo region

The levels of organohalogenated contaminants, i.e. PCBs, PCDDs and PCDFs were determined in sediment and fish samples collected from different locations in the River Nile, Egypt. Thirty-six sediment and eighteen fish samples were carried out during a period of 12 months from February 2003 to February 2004. Determination of PCBs and dioxins was carried out using a high resolution GC mass spectrometer. The results indicated that the PCB and PCDD/F mean concentrations in sediment samples ranged from 1461 to 2244 and from 240 to 775pgg(-1) dry wt basis, respectively. The mean concentration of PCBs and PCDD/Fs in fish samples were found to be in the range from 695 to 853pgg(-1) fresh wt for PCB congeners and from 27.7 to 121pgg(-1) lipid for total PCDD/Fs. Moreover, the concentrations of both PCBs and PCDD/Fs were found to be different at different locations along the River Nile. It could be concluded that the contamination of the River Nile is within the permissible limits set by the FDA and the Egyptian Standards for fish and shellfish.     

Mixture effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin and polychlorinated biphenyl congeners in rats

Concern of the toxic effects and bioaccumulation of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and polychlorinated biphenyls in the environment continues to be a focus of research in persistent organochlorine contaminants. Groups of five adult female S.D. rats were administered by gavage 0, 2.5, 25, 250 or 1000 ng TCDD/kg body weight/day or TCDD in combination with a mixture of PCB congeners (PCBs) at 2 or 20 microg/kg b.w./day for a period of 28 days. Growth suppression, increased absolute and relative liver weights, and decreased thymic weight were observed in either the 1000 ng TCDD group alone, or the groups receiving a mixture of 1000 ng TCDD + 2 microg PCBs. The TCDD induced increases in liver and thymic weights were not altered by co-administration with PCBs, however, growth suppression appeared to be more pronounced in the group receiving 1000 ng TCDD + 2 microg PCBs than with TCDD alone. Treatment with TCDD at 250 ng and 1000 ng/kg resulted in a significant increase in hepatic microsomal methoxy resorufin-O-demethylase and ethoxy resorufin-O-deethylase activities which were antagonized by co-administration with PCBs. Similarly, effects of 250 ng TCDD on serum cholesterol and liver UDP glucuronosyl transferase activity and ascorbic acid were significantly reduced by co-administration with 20 microg PCBs. Other biochemical effects elicited by treatment with 1000 ng TCDD, but not affected by co-administration with PCBs include the following: increased serum albumin, decreased liver vitamin A, and increased kidney vitamin A and liver microsomal glutathione-S-transferase activity. While decreased hemoglobin, platelet, packed cell volume and red cell indices were observed in TCDD treated rats, no interactive effects were seen. The above results indicate that the mixture effects of PCBs and TCDD may be additive or antagonistic depending on the dose level and endpoints measured. For the purpose of predicting mixture effects, knowledge of mechanisms of action and toxicokinetics is required.     

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid–liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25–25 µg L^?1 of 1.25–20 µg L^?1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.     

The impact of production type and region on polychlorinated biphenyl (PCB), polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in Canadian chicken egg yolks

Chicken eggs from five different production types (conventional, omega-3 enriched, free range, organic and free run) were collected, when available, from three regions (west, central and east) of Canada to determine persistent organic pollutant (POP) concentrations. Total polychlorinated biphenyl (PCB) concentrations (∑37 congeners) in yolks from the eggs ranged from 0.162 ng g⁻¹ lipid to 24.8 ng g⁻¹ lipid (median 1.25 ng g⁻¹ lipid) while the concentration of the sum of the 6 indicator PCBs ranged from 0.100 ng g⁻¹ lipid to 9.33 ng g⁻¹ lipid (median 0.495 ng g⁻¹ lipid). Total polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) concentrations ranged from 2.37 pg g⁻¹ lipid to 382 pg g⁻¹ lipid (median 9.53 pg g⁻¹ lipid). The 2005 WHO toxic equivalency (TEQ) ranged from 0.089 pg TEQ_{PCDD/F+dioxin-like[DL]-PCB} g⁻¹ lipid to 12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid (median 0.342 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). PCB and PCDD/F concentrations were significantly different (p < 0.001) in egg yolks from different regions of collection. In contrast to observations in Europe, PCB and PCDD/F concentrations in Canadian egg yolks were not impacted solely by the production type (e.g., conventional, free range, organic, etc.) used to maintain the laying chickens. Additionally, only one Canadian free range yolk from western Canada (12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid) exceeded the European toxic equivalent concentration limits for eggs (5 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). This differs from observations in Europe where free range/home produced eggs frequently have higher POP concentrations than eggs from other production types. Median PCB dietary intake estimates based on consumption of eggs were less than 10 ng d⁻¹ while median PCDD/F intakes were less than 45 pg d⁻¹.     

The effect of metal catalysts on the formation of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran precursors

The catalytic effects of copper and iron compounds were examined for their behavior in promoting formation of chlorine (Cl₂), the major chlorinating agent of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in an environment simulating that of municipal waste fly ash. Formation of Cl₂ occurred as a result of a metal-catalyzed reaction of HCl with O₂. Catalytic activity was greatest at a temperature of approximately 400 °C, supporting a theory of de novo synthesis of PCDDs and PCDFs on fly ash particles downstream of waste combustion.     

Synthesis of polychlorinated dibenzofuran isomers and their gas chromatographic profiles

Fifty-one polychlorinated dibenzofuran (PCDF) isomers were synthesized by the structure specific methods starting from corresponding chlorophenol and chloronitrobenzene or chlorophenol and chlorodiphenyl iodonium salt. Structures of the synthesized PCDF isomers were confirmed by mass spectrometry and proton magnetic resonance spectroscopy. Gas chromatographic retention times and response factors of the PCDF isomers were determined on the fused silica capillary columns of SP-2330 and OV-101.     

Formation and stability of polychlorinated biphenyl Pickering emulsions

An emulsion stabilized by colloidal suspensions of finely divided solids is known as a Pickering emulsion. The potential for polychlorinated biphenyls (PCBs) to form Pickering emulsions ex situ when in contact with powdered solids, such as clays and metal oxides, is investigated here. Bentonite, iron oxide and magnesium oxide dispersions proved to be robust Pickering emulsion stabilizers, whereas manganese oxide dispersions were not. Batch experiments revealed that emulsions can be formed using a moderately low energy input and can be stabilized with solid concentrations as low as 0.5 wt.%. For the base conditions (volumetric oil fraction (phi(oil))=30 vol.%; solid concentration (chi)=2 wt.%), the formed emulsions were indefinitely stable and the initial average droplet diameters varied from 80 to 258 mum, depending on the solid used in the colloidal dispersion. The average droplet size varied at early time, but for most conditions stabilized to a steady-state value 1 week after preparation. The effect of Ostwald ripening was limited. At greater than 0.5 wt.% concentration, the efficiency of the solid dispersion as a stabilizer was dependant on the volumetric oil fraction but not on the solid concentration. Generally, systems with volumetric oil fractions outside of the 20-70 vol.% range were unstable. The emulsions' droplet stability, average droplet size and size distribution were observed to vary as a function of the amount of energy provided to the system, the volumetric oil fraction, and the concentration of the solid in the aqueous dispersion. It is hypothesized that drilling through fractured rock in the immediate vicinity of dense, non-aqueous phase liquid (DNAPL) PCBs may provide both the energy and solid material necessary to form Pickering emulsions.     

Depletion of selected polychlorinated biphenyl, dibenzodioxin, and dibenzofuran congeners in farmed rainbow trout (Oncorhynchus mykiss): a hint for safer fish farming

Farmed fish can be exposed to persistent organic contaminants--such as polychlorinated biphenyls (PCBs), dibenzodioxins (PCDDs), and dibenzofurans (PCDFs)--via feed, this eventually resulting in accumulation levels of health concern. To study the correlation between feed contamination, chemical accumulation in fish muscle (fillet), and chemical depletion, an all-vegetal base (or blank) feed was prepared and fortified with a commercial PCB mixture (Aroclor 1254) and six PCDD and PCDF congeners (namely, 2,3,7,8-T(4)CDD, 2,3,7,8-T(4)CDF, 1,2,3,7,8-P(5)CDD, 1,2,3,7,8-P(5)CDF, O(8)CDD, and O(8)CDF) to reproduce realistic low, medium, and high contamination levels. After a 1-month exposure, trout (Oncorhynchus mykiss) were fed with the blank feed and sacrificed every 0.5 months over a 3-month period from exposure end; fillet specimens were sampled at each time. In all groups, the average fish weight increased linearly through the observation period. The chemical diminishing patterns observed were due to the combined effect of clearance and growth dilution: for 10 PCB and four PCDD and PCDF congeners, patterns were described with an empirical one-compartment (fish muscle) model. The canonical pseudo-first-order kinetic equation used was also modified into the form C=[C(0)exp(-k(C)t)] (m(W)t+1)(-1) to distinguish between the contributions to depletion from clearance, exp(-k(C)t), and growth dilution, (m(W)t+1)(-1). Most mean clearance half-life (HL(C)) estimates appear to be greater than 4 months, in a number of cases reaching magnitudes well over 10 months or even negative, thus clearly indicating a non-negligible contribution from a second compartment. Based on means and their 95% confidence intervals, the depletion HL(D) estimates of the 14 selected congeners seem to be comprised between 1.2-3.4 and 1.0-5.0 months, respectively: these values, accounting for both clearance and growth dilution, provide an indication of the relevance of a blank feed as a management option to reduce the overall PCB, PCDD, and PCDF content in farmed trout. Due to a lack of bioaccumulation, O(8)CDD and O(8)CDF yielded no results for evaluation, whereas for many PCB congeners results were insufficient for empirical modelling.     

Coating effects on the glass adsorption of polychlorinated biphenyl (PCB) congeners

The effects of coating materials on polychlorinated biphenyl (PCB) adsorption in aqueous solution were assessed in an attempt to minimize PCB sorption loss during sampling processes. A coating material, which enhances PCB adsorption and allows adsorbed PCBs to be readily extracted by solvents, can act as a sampling concentrator to reduce PCB losses from both adsorption and evaporation. Several coating materials were evaluated, including paraffin oil, silicone oil, dimethyldichlorosilane (Sylon-CT), Prosil 28^® and polydimethylsiloxane (PDS) with viscosity 0.65, 50 (PDS 50), and 500 (PDS 500) cSt. PDS and silicone oil enhanced adsorption for all five congeners examined (IUPAC No. 28, 52, 101, 138, and 180). Sylon-CT, paraffin oil and Prosil 28^® had inconsistent effects on adsorption of different congeners. Desorption of adsorbed PCBs onto all coating types was assessed. The recovery efficiency of extracting PCBs with solvents was enhanced greatly with all coatings as opposed to non-coated surfaces, with the exception of paraffin oil. Coating with silicon oil, PDS 50, and 500 resulted in virtually 100% recovery of adsorbed PCBs. It was also found that Teflon containers were poor substitutes for glass containers and failed to minimize PCB losses. Among the materials studied, the best coating that could be used as a sampling concentrator was PDS 500.     

The effects of pruning and nodal adventitious roots on polychlorinated biphenyl uptake by Cucurbita pepo grown in field conditions

Two cultivation techniques (i-pruning and ii-nodal adventitious root encouragement) were investigated for their ability to increase PCB phytoextraction by Cucurbita pepo ssp pepo cv. Howden (pumpkin) plants in situ at a contaminated industrial site in Ontario (Aroclor 1248, mean soil [PCB] = 5.6 μg g⁻¹). Pruning was implemented to increase plant biomass close to the root where PCB concentration is known to be highest. This treatment was found to have no effect on final shoot biomass or PCB concentration. However, material pruned from the plant is not included in the final shoot biomass. The encouragement of nodal adventitious roots at stem nodes did significantly increase the PCB concentration in the primary stem, while not affecting shoot biomass. Both techniques are easily applied cultivation practices that may be implemented to decrease phytoextraction treatment time.     

Modeling polychlorinated biphenyl sorption isotherms for soot and coal

Sorption isotherms (pg-ng/L) were measured for 11 polychlorinated biphenyls (PCBs) of varying molecular planarity from aqueous solution to two carbonaceous geosorbents, anthracite coal and traffic soot. All isotherms were reasonably log-log-linear, but smooth for traffic soot and staircase-shaped for coal, to which sorption was stronger and more nonlinear. The isotherms were modeled using seven sorption models, including Freundlich, (dual) Langmuir, and Polanyi-Dubinin-Manes (PDM). PDM provided the best combination of reliability and mechanistically-interpretable parameters. The PDM normalizing factor Z appeared to correlate negatively with sorbate molecular volume, dependent on the degree of molecular planarity. The modeling results supported the hypothesis that maximum adsorption capacities (Q_max) correlate positively with the sorbent’s specific surface area. Q_max did not decrease with increasing sorbate molecular size, and adsorption affinities clearly differed between the sorbents. Sorption was consistently stronger but not less linear for planar than for nonplanar PCBs, suggesting surface rather than pore sorption.     

Organic carbon effects on aerobic polychlorinated biphenyl removal and bacterial community composition in soils and sediments

Certain organic compounds, including biphenyl and salicylic acid, stimulate polychlorinated biphenyl (PCB) degradation by microorganisms in some environments. However, the usefulness of these amendments for improving PCB removal by microorganisms from diverse habitats has not been extensively explored. This study evaluated the effects of biphenyl, salicylic acid, and glucose on changes in aerobic PCB removal and bacterial communities from an agricultural soil, a wetland peat soil, a river sediment, and a mixture of these samples. PCB removal patterns were significantly different between soils and sediments amended with carbon compounds: (i) terrestrial soil microorganisms removed more PCBs than river sediment microorganisms, particularly with regard to PCBs with >4 chlorine substituents, (ii) glucose-supplemented, agricultural soil microorganisms removed more hexachlorobiphenyl than unsupplemented samples, (iii) biphenyl-supplemented, river sediment microorganisms removed more di- and tri-chlorobiphenyls than unamended samples. Carbon amendments also caused unique shifts in soil and sediment bacterial communities, as determined by specific changes in bacterial 16S rRNA denaturing gradient gel electrophoresis banding patterns. These results indicate that organic carbon amendments had site-specific effects on bacterial populations and PCB removal. Further work is needed to more accurately characterize PCB degrading communities and functional gene expression in diverse types of environments to better understand how they respond to bioremediation treatments.     

Dechlorination of polychlorinated biphenyl congeners by anaerobic microorganisms from river sediment.

The microbial dechlorination of seven kinds of polychlorinated biphenyls (PCBs) by anaerobic microorganisms from river sediment was investigated. Dechlorination rates were found to be affected by the chlorine level of PCB congeners; dechlorination rates decreased as chlorine levels increased. Dechlorination rates were fastest under methanogenic conditions and slowest under nitrate-reducing conditions. The addition of individual electron donors (acetate, pyruvate, and lactate) enhanced the dechlorination of PCB congeners under methanogenic and sulfate-reducing conditions but delayed the dechlorination of PCB congeners under nitrate-reducing conditions. PCB congener dechlorination also was delayed by the addition of various polycyclic aromatic hydrocarbons (PAHs) under three reducing conditions and by surfactants, such as brij30, triton SN70, and triton N101. The results suggest that methanogen, sulfate-reducing bacteria, and nitrate-reducing bacteria all are involved in the dechlorination of PCB congeners.     

Determination of 2,3,7,8-TCDD toxic equivalent factors (TEFs): support for the use of the in vitro AHH induction assay

The in vitro induction of the cytochrome P₁-450-dependent monooxygenases, aryl hydrocarbon hydroxylase (AHH) or ethoxyresorufin O-deethylase (EROD) by 2,3,7,8-TCDD and related toxic halogenated aryl hydrocarbons in rat hepatoma H-4-II E cells has been developed as a short term quantitative bioassay for these toxic chemicals. There was a linear correlation between the -log EC₅₀ (in vitro) AHH induction vs the -log ED₅₀ (in vivo) for body weight loss, thymic atrophy, hepatic AHH and EROD induction in the rat for several polychlorinated biphenyl, dibenzo-p-dioxin and dibenzofuran congeners and mixtures. These data clearly support the utility of the in vitro AHH induction assay as a short term test system for quantitating the “toxic or 2,3,7,8-TCDD equivalents” in an extract containing toxic halogenated aromatics. The bioassay method is rapid, relatively accurate and much more cost effective than conventional analytical methods such as gas-chromatography-mass spectrometry from which it is difficult to determine the levels of 2,3,7,8-TCDD equivalents in specific analytes.     

Sources of polychlorinated biphenyl blank contamination and their impact on fingerprinting

Abstract

The development of high-resolution mass spectrometry methods for the measurement of polychlorinated biphenyls (PCBs) in environmental samples has dramatically reduced detection limits, leading to problems obtaining clean blanks. When PCBs are detected in samples at concentrations similar to the blanks, blank contamination must be addressed before fingerprinting and source apportionment through positive matrix factorization (PMF) can be successful. We tested a variety of blank correction methods using data from a study of water column concentrations of PCBs in the Spokane River, where concentrations of Σ₂₀₉PCBs in whole water samples averaged 171?pg/L without blank correction and Σ₂₀₉PCBs in the blanks averaged 88?pg/L. The results suggest that subtracting blank masses from sample masses can lead to erroneous results. Instead, censoring at one times the batch-specific blank level is a better approach. The sources of PCBs in field and method blanks were investigated by examining their congener profiles via PMF. The results suggest that commercial PCB formulations (in the US, Aroclors) continue to be the primary source of PCBs in blanks forty years after PCB production and use were banned in the United States. Other sources of PCBs to blanks include PCB 11 from pigments; PCBs 44?+?47?+?65, 45?+?51, and 68 arising from polymers cured using bis(2,4-dichlorobenzoyl) peroxide; and PCBs 1, 2, 3, 4, 8, 15 and others arising from silicone products derived from phenylsiloxanes, such as silicone-based adhesives.     

Atmospheric polychlorinated biphenyl concentrations and apparent degradation in coastal New Jersey

To characterize the atmospheric dynamics and behavior of organic compounds in the NY–NJ Harbor Estuary, atmospheric concentrations of polychlorinated biphenyls (PCBs) were measured at coastal, suburban and urban sites in New Jersey in 1997–1999. ∑PCB concentrations at the suburban site varied from 86 to 2300 pg m⁻³ and from 84 to 1100 pg m⁻³ at the coastal site. Although the temporal trends of total concentrations were significantly different at the three sites (p<0.01), PCB congener profiles revealed similar patterns (r²>0.90, p<0.001) implicating a dominant emission type and/or process. Temperature explained >50% of the total variability in ln[PCB] at both sites. Atmospheric concentrations at the suburban site increased when winds blew from an eastnortheast vector, while increased wind speeds led to a slight dilution. Wind speed and direction were not significantly correlated with the concentrations measured at the coastal site. Temporal changes in congener distribution at the suburban site are consistent with the preferential atmospheric removal of 3–5 Cl-biphenyls by hydroxyl radical attack with estimated half-lives of 0.7–1.8 years.     

Accumulation and tissue distribution of selected polychlorinated biphenyl congeners in chickens

During one to three consecutive periods of 2 weeks, broiler chickens (n = 108) received test dies to which different amount of PCBs (7 congeners) were added. The relationship between exposure time and accumulation of individual congeners in different chicken tissues, such as breast, thigh and abdominal fat tissue, was observed. In all tissues, the vast majority of the PCB accumulation occurred during the first 2 weeks of exposures. After that, PCB concentrations only increased in the abdominal fat tissue of the animals. The individual PCBs were distributed differently in the various tissues. While CBs 28, 118, 138, 153 and 180 accumulated in the chickens, CBs 52 and 101 were metabolized, but no methyl sulphone metabolites of these congeners could be detected. Our results provide information on the absorption, tissue distribution and biotransformation of the individual PCB congeners and confirm the structure-activity relationships for metabolism of PCBs in birds, which are different from those in fish or mammalian species.     

Atmospheric oxidation mechanisms of polychlorinated dibenzo-p-dioxins are different from those of benzene and dibenzofuran: a theoretical prediction

The reaction mechanisms of dibenzo-p-dioxin (DD) and 2,3,7,8-TCDD with OH radical have been studied using density functional theory calculations. Under the atmospheric conditions, ca 42% of DD + OH reaction proceeds as formation of DD − OH-β adduct, which will react with O₂ slowly; while the rest will proceed as formation of DD − OH-γ adduct, which will decompose to the substituted phenoxy radical P1 by the fused-ring C-O bond cleavage. For 2,3,7,8-TCDD + OH, the reaction will predominantly form the substituted phenoxy radical P2. The reaction mechanisms are drastically different from the peroxy mechanism for the atmospheric oxidations of benzene and dibenzofuran.