Chemical reaction of polychlorinated biphenyls on soils with poly(ethylene glycol)/KOH

Polychlorinated biphenyls (PCB's) with higher chlorination levels have been found to be highly reactive toward poly(ethylene glycol)/KOH under ambient conditions. Artificially contaminated and real world samples of PCB on soils have been reacted with PEG/KOH, affording aryl polyglycols as products. Complete reaction of Aroclor 1260 occurs in less than two weeks in open jars under ambient conditions.     

Destruction/removal of polychlorinated biphenyls from non-polar media. Reaction of PCB with poly (ethylene glycol)/KOH

We have found that polychlorinated biphenyls (PCB's) and other unactivated chlorobenzenes react with poly (ethylene glycols) and potassium hydroxide under mild conditions. Complete reaction with PEG occurs at 75–120°C in under two hours, to produce aryl polyglycols, the products of nucleophilic aromatic substitution. This reaction has been applied to the destruction and removal of PCB's from non-polar media, including transformer oil.     

Sensitized photodegradation of adsorbed polychlorobiphenyls (PCB's)

Polychlorobiphenyls (PCB's) adsorbed on silica gel or montmorillonite were degraded mainly to less chlorinated biphenyls by U.V. irradiation (λ = 254 nm). The photodegradation was considerably enhanced by adding triethylamine to the system. The sensitizing effect can be ascribed, like in solution, to the formation of a charge-transfer complex confirmed by fluorescence quenching experiments.     

Accumulation and elimination kinetics of di-, tri- and tetra chlorobiphenyls by goldfish after dietary and aqueous exposure

Bioaccumulation kinetics of five di-, tri- and tetrachlorobiphenyls from water and food were studied in laboratory experiments with goldfish (Carassius auratus). First order rate constants for uptake from water and clearance were determined after simultaneous administration of the five compounds in constant concentration, and were related to bioconcentration factors obtained in a static fish-water equilibration system. Biomagnification by retention of the PCB's from food was studied in a separate experiment.The difference in clearance rates for the chlorobiphenyls is the main reason for the different bioconcentration and biomagnification factors.Absorption efficiencies from water and food are higher than 40%. Clearance half lives vary from 10 days for 2,5-dichlorobiphenyl to 60 days for 2,3′,4′5-tetrachlorobiphenyl, which is correlalated with the decreasing aqueous solubilities of the compounds. Bioconcentration factors are between 0.4 × 10⁶ and 1.5 × 10⁶, biomagnification factors between 0.2 and 1.7, based on extractable lipids. Substitution of chlorine in the position para to the phenyl-phenyl bond influences hydrophobicity and bioaccumulation of the PCB's more strongly than substitution in ortho position.A kinetic model is developed which accounts for the influence of the lipid content of the fish on the clearance rate of a chemical. Reproducible determination of the bioconcentration potential of environmental chemicals is possible by use of an “internal bioaccumulation standard” in a kinetic test system. Food chain accumulation in fish is likely to be an important process only for persistent chemicals with extremely low water solubility.     

Accumulation of chlorinated hydrocarbon vapours in pine needles

Needles with different ages from four pines have been analysed for PCB's, HCB, α- and γ-HCH, p,p'DDT and DDE. The accumulation found has been discussed and provisional accumulation rates under actual background conditions have been calculated.     

Reaction of polychlorinated biphenyls with mercaptans in non-polar media: Formation of polychlorobiphenyl sulfides

Polychlorinated biphenyls (PCB's) react readily with alkyl mercaptans in non-polar solvents such as toluene or transformer oil. Reactions occur readily with KOH as the base in the presence of a variety of phase transfer catalysts, including phosphonium salts, crown ethers, and poly (ethylene glycols).     

Persistency of highly toxic coplanar PCBs in aquatic ecosystems: uptake and release kinetics of coplanar PCBs in green-lipped mussels (Perna viridis Linnaeus)

The bioaccumulation potential of three highly toxic coplanar PCB isomers [3,3',4,4'-tetrachlorobiphenyl (T(4)CB); 3,3',4,4',5-pentachlorobiphenyl (P(5)CB); and 3,3',4,4',5,5'-hexachlorobiphenyl (H(6)CB)] was investigated using green-lipped mussels (Perna viridis Linnaeus) as a bioindicator, through a transplantation experiment at two locations in Hong Kong waters. By contrast to the relatively rapid uptake and release of many other PCB isomers, the non-ortho chlorine substituted coplanar PCB congeners exhibited slow uptake and clearance. The kinetic parameters of coplanar PCBs based on lipid weight-related data, and the degree of bioaccumulation based on the proportion of coplanar PCBs in total PCBs in mussels, clearly indicate that coplanar PCBs are highly bioaccumulative in lower organisms. On the assumption that mussels are unlikely to be particularly unusual with respect to their bioaccumulation of coplanar PCBs, it appears most likely that these highly toxic and persistent PCB congeners are concentrated by all aquatic organisms, and may reach higher consumers (including humans) in quantities of toxicological concern.     

Ultrasonically-assisted electrocatalytic dechlorination of polychlorinated biphenyls

Commercial mixtures of PCB's (Aroclors) were dechlorinated to biphenyl by ultrasonically-assisted electroreduction with and without soluble catalysts. Ultrasound increased the rate of electrolysis at stirred-mercury-pool electrodes by 2- to 3-fold.     

Comparison of an enzyme-linked immunosorbent assay (ELISA) to gas chromatography (GC)--measurement of polychlorinated biphenyls (PCBs) in selected US fish extracts

The analysis of PCBs in fish tissues by immunoassay methods was evaluated using fish collected from a US monitoring program, the National Contaminant Biomonitoring Program of the US Department of Interior, Fish and Wildlife Service. Selected composite whole fish samples, which represented widely varying concentrations and sources of PCBs, were extracted and subjected to congener PCB analysis by gas chromatography (GC) and total PCB analysis using an ELISA (ePCBs) calibrated against technical Aroclor 1248. PCB congener patterns in these fishes were different from the patterns found in commercial Aroclors or their combinations as demonstrated by principal component analysis of normalized GC congener data. The sum of the PCB congeners measured by GC (total-PCBs) ranged from 37 to 4600 ng/g (wet weight). Concentrations of PCBs as determined by the ELISA method were positively correlated with total-PCBs and the ePCBs/total-PCBs ratios for individual samples ranged from 1 to 6. Ratios of ePCBs/total-PCBs for dilutions of Aroclors 1242, 1254, and 1260 and for matrix spikes range from 0.6 for 1242 to 2.5 for 1254 and 1260. These results suggest that higher chlorinated PCB congeners have higher affinity for the anti-PCB antibodies. Partial least squares with latent variable analysis of GC and ELISA data of selected Aroclors and fish samples also support the conclusion that ELISA derived PCB concentrations are dependent on the degree of chlorination.     

Levels of Persistent Organochlorine Residues in Eggs of Greater Flamingos from the Guadalquivir Marshes (Doñana), Spain

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) residue levels were determined in 53 unhatched eggs from greater roseus flamingos (Phoenicopterus ruber). Eggs were collected in 1996 from the National Park of Doñana (Guadalquivir marshes, Southwest Spain), immediately after one breeding colony abandoned the nesting site due to predator attacks. The main metabolite of p,p′-DDT, p,p′-DDE, was the OCP residue found at higher concentrations, with a geometric mean of 721 ng/g wet weight. Residues of other pesticides, including some hexachlorocyclohexane isomers, hexachlorobenzene, aldrin, heptachlor, and heptachlor-epoxide, were detected at much lower concentrations. The sum of PCBs was 528 ng/g, with PCB congeners #187 and #153 being the most prominent in eggs. The pattern observed in these compounds of industrial origin corresponded more to Aroclor 1260 than to any other commercial mixture. Levels of organochlorine residues indicate a medium degree of exposure, and they are not considered of any concern for the flamingo population. In particular, neither p,p′-DDE nor PCB levels were found to be correlated with the eggshell thickness.     

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.     

Dietary uptake kinetics of polychlorinated biphenyls from sediment-contaminated sandworms in a marine benthic fish (Pseudopleuronectes yokohamae)

To evaluate the dietary uptake of polychlorinated biphenyls (PCBs) from live food, we investigated the dietary uptake and depuration kinetics of PCBs in a marine benthic fish (marbled sole, Pseudopleuronectes yokohamae) by using as food live sandworms (Perinereis nuntia) that were laboratory-exposed to field-collected PCB-contaminated sediment. Marbled sole were fed the PCB-contaminated sandworms for 28 d and then uncontaminated sandworms for 56 d. The assimilation efficiencies (AEs) of 84 PCB congeners via the gastrointestinal tract (GIT) to the muscle of the fish ranged from 0.21 to 0.78; whole-body AEs would be lower than those of muscle because of the lower PCB concentrations, on a lipid basis. The AEs determined in this study were lower than those in other studies that used PCB-spiked commercial pelletized food. The lower AEs found in this study might be attributable to differences in the food administered (live sandworms vs. commercial pellet food), possibly because of low digestibility of sandworm lipids by marbled sole. In addition, the AEs in this study tended to increase with increasing log octanol-water partition coefficients (K_OW) up to about seven, although AEs in the other studies using commercial pelletized food did not increase with increasing log K_OW. This result suggests the co-transport of highly hydrophobic PCB congeners along with lipids and fatty acids from the digested sandworms into the GIT epithelium cells. The growth-corrected half-lives of 26 PCB congeners in the muscle of fish ranged from 20 to 107 d.     

Levels of persistent organochlorine residues in eggs of greater flamingos from the Guadalquivir marshes (Doñana), Spain

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) residue levels were determined in 53 unhatched eggs from greater roseus flamingos (Phoenicopterus ruber). Eggs were collected in 1996 from the National Park of Do?ana (Guadalquivir marshes, Southwest Spain), immediately after one breeding colony abandoned the nesting site due to predator attacks. The main metabolite of p,p'-DDT, p,p'-DDE, was the OCP residue found at higher concentrations, with a geometric mean of 721 ng/g wet weight. Residues of other pesticides, including some hexachlorocyclohexane isomers, hexachlorobenzene, aldrin, heptachlor, and heptachlor-epoxide, were detected at much lower concentrations. The sum of PCBs was 528 ng/g, with PCB congeners #187 and #153 being the most prominent in eggs. The pattern observed in these compounds of industrial origin corresponded more to Aroclor 1260 than to any other commercial mixture. Levels of organochlorine residues indicate a medium degree of exposure, and they are not considered of any concern for the flamingo population. In particular, neither p,p'-DDE nor PCB levels were found to be correlated with the eggshell thickness.     

Distribution patterns of nitrobenzenes and polychlorinated biphenyls in water, suspended particulate matter and sediment from mid- and down-stream of the Yellow River (China)

Samples of water, suspended particulate matter (SPM) and sediment were collected from mid- and down-stream of the Yellow River. The distribution and concentration of 10 nitroaromatic compounds and polychlorinated biphenyls (PCBs) were extensively studied. The total concentration of 10 nitrobenzenes (SigmaNBs) varied from 0.269 to 9.052 microg l(-1) in water, from 2.916 to 164.4 microg kg(-1) dry weight in SPM, and from 0.954 to 14.72 microg kg(-1) dry weight in sediment. PCBs associated with the sediments, measured as the summed responses of Aroclor 1242, 1248, 1254, 1260 (in comparison to those of a standard 1:1:1:1 mixture), were found to be in the range of non-detectable to 5.98 microg kg(-1). In the samples collected, various PCB congeners showed similar distribution characteristics with congeners containing 3-5 chlorine atoms accounting for more than 96.4% of total PCB. In most of the samples, PCB concentrations occurred in the order: TetraCB > TriCB > PentaCB. Levels of SigmaNBs in the Yellow River were relatively low in comparison with values reported from other river and marine systems, and PCB levels were comparatively low. Relative to the PCBs, SigmaNBs showed significantly more difference among the various stations, presumably due to the influence of different pollution sources. No obvious correlation was observed between the pollutant concentrations and either the TOC or the grain size of the sediments.     

Vorkommen chlorierter Kohlenwasserstoffe in ausgewählten Umweltproben Nordgriechenlands (Xanthi)

Residues of persistent chlorinated hydrocarbons HCB, BHC isomers, Heptachlor and -epoxide, DDE, Aldrin, Dieldrin and PCBshave been analysed in selected environmental samples soil, grass roots, pine-needles, hen's eggs and sheep's milk from Northern Greece (Xanthi). Almost all samples have shown residues in a range of 0,1 – 10 ppb except eggs and milk, which have been partially contaminated with HCB (approx. 20 ppb), DDE (approx. 40 ppb) and Dieldrin (approx. 30 – 40 ppb) related to freshweight. The contamination levels have been in the same order of magnitude as in environmental samples from Germany except PCBs, which have been accumulated in German samples tendencially higher. All residues detected have been significantly lower than the limits allowed in food stuffs.     

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.     

PCB congener-specific analysis: A critical evaluation of toxic levels in biota

Despite the fact that PCB congeners exhibit very different biochemical activities, it has been necessary, due to former difficulties in separation and quantitation, to assess toxic hazard to tissues in terms of the concentration of the PCB mixture present. This approach is justifiable provided that a dynamic equilibrium is established among all tissues for each congener. Recent biochemical studies, involving individual congeners indicate that this may not always be the case. Toxic PCB congeners, isostereomers of TCDD, are electron acceptors capable of binding to cytoplasmic protein (Ah receptor) and other cellular macromolecules associated with a particular tissue. Specific Congener analysis of snapping turtle tissues has indicated the possible selective disposition of 2,3,3′, 4,4′-pentachlorobiphenyl in the testes, a situation which may lead to a surreptious decrease in the population of that species, considering the longevity and wide distribution of these reptiles.     

Polychlorinated biphenyl congener patterns in tree swallows (Tachycineta bicolor) nesting in the Housatonic River watershed, western Massachusetts, USA, using a novel statistical approach

A novel application of a commonly used statistical approach was used to examine differences in polychlorinated biphenyl (PCB) congener patterns among locations and sample matrices in tree swallows (Tachycineta bicolor) nesting in the Housatonic River watershed in western Massachusetts, USA. The most prevalent PCB congeners in tree swallow tissue samples from the Housatonic River watershed were Ballsmitter Zell numbers 153, 138, 180, 187, 149, 101, and 170. These congeners were seven of the eight most prevalent congeners in Aroclor 1260, the PCB mixture that was the primary source of contamination in the Housatonic River system. Using paired-Euclidean distances and tolerance limits, it was demonstrated that congener patterns in swallow tissues from sites on the main stem of the Housatonic River were more similar to one another than to two sites upstream of the contamination or from a nearby reference area. The congener patterns also differed between the reference area and the two upstream tributaries and between the two tributaries. These pattern differences were the same in both pipper (eggs or just hatched nestlings) and 12-day-old nestling samples. Lower-chlorinated congeners appeared to be metabolized in nestlings and pippers compared to diet, and metabolized more in pippers compared to nestlings. Euclidean distances and tolerance limits provide a simple and statistically valid method to compare PCB congener patterns among groups.     

A numerical study on the seasonal variability of polychlorinated biphenyls from the atmosphere in the East China Sea

A three-dimensional/high-resolution transport model for persistent organic pollutants (POPs) has been developed for the East China Sea (ECS). The POPs model has four compartments (gaseous, dissolved, phytoplankton-bound, and detritus-bound phases) and includes processes for diffusive air-water exchange, phytoplankton uptake/depuration to POPs, decomposition of dissolved phase, vertical sinking of phytoplankton, detritus production by phytoplankton mortality, and vertical sinking and decomposition of detritus. The POPs model is coupled with an ocean circulation model that can reproduce the seasonal variation in physical variables to represent the advection and diffusion of POPs. We applied the POPs model to the polychlorinated biphenyl congener 153 (PCB 153) from the atmosphere and examined the behavior of PCB 153 in the ocean. The model showed a remarkable seasonal variability of PCB 153. Concentrations in the dissolved and particulate phases are high in winter (January-March) and low in summer (July-September). In coastal regions, where chlorophyll a concentration is high, horizontal and vertical distributions in the dissolved and particulate PCB 153 concentrations are strongly affected by phytoplankton uptake. The sensitivity experiments on the dynamics of PCB 153 suggested that a change of Henry’s law constant associated with water temperature is the major factor controlling the seasonal variability of PCB 153. The model-based yearly mass balance of PCB 153 in the ECS indicated that most of the atmospheric input (35.5 kg year⁻¹) is removed by the horizontal advection outside the ECS (19.0 kg year⁻¹) and accumulates to the sea bottom by vertical sinking (15.7 kg year⁻¹). For comparison with PCB 153, we also conducted simulations for PCB 52, 101, and 180. The seasonal variations are similar to that of PCB 153. The mass balance of PCB 52 that has short half-life time and less hydrophobic property shows the different results compared with PCB 101, 153, and 180.     

Atropisomers of 2,2′,3,3′,6,6′-hexachlorobiphenyl (PCB 136) exhibit stereoselective effects on activation of nuclear receptors in vitro

PCB 136 is an environmentally relevant chiral PCB congener, which has been found in vivo to be present in form of rotational isomers (atropisomers). Its atropselective biotransformation or neurotoxic effects linked with sensitization of ryanodine receptor suggest that it might interact also with other intracellular receptors in a stereospecific manner. However, possible atropselective effects of PCB 136 on nuclear receptor transactivation remain unknown. Therefore, in this study, atropselective effects of PCB 136 on nuclear receptors controlling endocrine signaling and/or expression of xenobiotic and steroid hormone catabolism were investigated. PCB136 atropisomers were found to exert differential effects on estrogen receptor (ER) activation; (+)-PCB 136 was estrogenic, while (?)-PCB 136 was antiestrogenic. In contrast, inhibition of androgen receptor (AR) activity was not stereospecific. Both PCB136 stereoisomers induced the constitutive androgen receptor (CAR)-dependent gene expression; however, no significant stereospecificity of PCB 136 atropisomers was observed. PCB136 was a partial inducer of the pregnane X receptor (PXR)-dependent gene expression. Here, (?)-PCB 136 was a significantly more potent inducer of PXR activity than (+)-PCB 136. Taken together, the present results indicate that at least two nuclear receptors participating in endocrine regulation or metabolism, ER and PXR, could be regulated in an atropselective manner by chiral PCB 136. The enantioselective enrichment of PCB atropisomers in animal and human tissues may thus have significant consequences for endocrine-disrupting effects of chiral ortho-substituted PCB congeners.