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.     

Dechlorination pathways of ortho-substituted PCBs by UV irradiation in n-hexane and their correlation to the charge distribution on carbon atom

The photodegradations of 22 individual polychlorinated biphenyl (PCB) congeners (including 21 non-coplanar ortho substituted and one non-ortho substituted) by irradiation with ultraviolet lamp in n-hexane solution were studied. Photoproducts were identified by matching their retention times and mass spectra with those of authentic standards. PCB congener with less than two chlorides was photodegraded within half an hour, if more than three chlorine on ring, the photodechlorination time for PCB needs one and half hours or more, sometimes even longer than 15 h. The half-life of PCB degradation by photodechlorination was much shorter than that by anaerobic biological dechlorination. Charge distribution on carbon atom combined with the monitoring products of individual PCB congeners were used to deduce the photodegradation pathways. The higher the charge distribution for carbon to which chlorine is attached, the easier for photodechlorination to occur. A lot of chlorine atoms attached PCB, the dechlorination was found to occur prior to the carbon with higher charge distribution at the benzene ring with more chlorine atoms attached.     

Polychlorinated biphenyls and dibenzofurans retained in the tissues of a deceased patient with Yucheng in Taiwan

Various tissues from a deceased Yucheng (oil disease) patient were analyzed for individual polychlorinated biphenyl (PCB) and dibenzofuran (PCDF) congeners. With a few exceptions, PCBs with 5 or less chlorine atoms were almost completely excreted from the patient's tissues about two years after the ingestion of the toxic oil. In contrast, most PCB congeners with 6 or more chlorine atoms were retained in the tissues. The intestinal fat contains the highest level of PCBs while the liver contains the highest concentration of PCDFs. The major PCDF congeners retained in the tissues were 1,2,3,4,7,8-hexaCDF, 2,3,4,7,8-pentaCDF, and 1,2,4,7,8-pentaCDF. The former two congeners, especially 2,3,4,7,8-pentaCDF, are very toxic PCDFs; they may play important roles in the etiology of Yucheng.     

Bioaccumulation profiles of polychlorinated biphenyls including coplanar congeners and possible toxicological implications in Baikal seal (Phoca sibirica)

Isomer specific concentrations of individual polychlorinated biphenyls (PCBs) including toxic non-ortho (IUPAC 77, 126, 169), mono-ortho (105, 118, 156) and di-ortho (137, 138, 153, 180) coplanar congeners were determined in the blubber of 40 Baikal seals (Phoca sibirica) and as their fish diet collected from Lake Baikal, Siberia. Residue levels of total PCBs in Baikal seals were noticeably high and comparable to those reported for seals from the North Sea, suggesting the recent usage of this compound in the watershed of Lake Baikal. Non-, mono-, and di-ortho coplanar congeners were also detected in Baikal seals and fish. An approach to estimate bioaccumulation profiles of PCB congeners revealed that the non-ortho PCBs, IUPAC 77, 126 and 169 seemed to be less persistent than other congeners. Furthermore, selective biotransformation of PCB congeners having either meta-para vicinal H atoms or both adjacent chlorinated meta-para and ortho-meta positions has been suggested. Comparison of 2,3,7,8-TCDD toxic equivalents (TEQ) of non-, mono- and di-ortho coplanar congeners in Baikal seals with those for other marine mammals suggested higher enrichment of mono-ortho congeners, particularly IUPAC 105 and 118, which contributed significantly to the total TEQs in Baikal seals. Results imply that the TCDD-like toxicity is relatively serious in Baikal seals, because of the enrichment of these toxic PCB congeners in tissues.     

Congener specific accumulation and toxic assessment of polychlorinated biphenyls in common cormorants, Phalacrocorax carbo, from Lake Biwa, Japan

Isomer-specific accumulation of polychlorinated biphenyls (PCBs) including di-, mono- and non-ortho congeners and hepatic P-450 activities were determined in adult common cormorants from Lake Biwa, Japan. The mean total PCB levels in male and female birds were 7.2 +/- 6.1 and 2.1 +/- 0.74 microg g(-1) wet wt, respectively, in the liver. The highly biomagnified congeners were IUPAC 126, 153, 169, 180 and 194, whereas a higher degree of biotransformation could be observed in both meta-para chlorine unsubstituted congeners in the cormorant liver. The estimated metabolic index also showed that common cormorants had higher PB-type enzyme activities than some avian and marine mammals but poor MC-type enzyme activities. The concentrations of non-ortho coplanar congeners were in the order of IUPAC 126 > IUPAC 169 > IUPAC 77 with mean values 6.1 +/- 5.9, 1.3 +/- 1.4 and 0.43 +/- 0.26 ng g(-1) wet wt, respectively. The calculated mean 2,3,7,8-TCDD toxic equivalent (TEQ) concentration in cormorants was 1.8 +/- 1.7 ng g(-1) wet wt and was dominated by IUPAC 118, followed by IUPAC 126. A significant increase of ethoxyresorufin-O-deethylase (EROD) and pentoxyresorufin-O-deethylase (PROD) activities was observed with estimated TEQ of PCBs in the cormorants, suggesting that the current contamination level is sufficient for altering their biochemical responses.     

Distribution characteristics of PCBs in the sediments of the lower Nakdong River, Korea

The objective of this study is to investigate the distribution characteristics of polychlorinated biphenyl (PCB) congeners in sediments of the lower Nakdong River of Korea. The sediments were collected using a grab sampler in May 1999. PCBs were extracted in the Soxhlet extractor and cleaned by using adsorption chromatographic techniques and concentrated sulfuric acid. A HP6890 gas chromatograph equipped with an electron capture detector was used for quantification. The results of congener specific analysis showed that the total concentration is ranged over 1.1-141 ng/g dry weight. The levels of PCB congeners are significantly correlated with the total organic carbons (TOC) in the sediments. The major fractions of PCBs in these sediments are congeners containing 4, 5 or 6 chlorine atoms per biphenyl molecule.     

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.     

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.     

Highly toxic coplanar PCBs: occurrence, source, persistency and toxic implications to wildlife and humans

Isomer-specific determinations of PCB congeners in a wide variety of animal species such as fish, marine mammals (whale, dolphin and porpoise) and terrestrial mammals (dog, cat and human) revealed the environmental occurrence of highly toxic coplanar 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) within a range of few pg g(-1) to several ten ng g(-1) in fat tissues (except fish) on a wet weight basis. Detection of these toxic residues in wild specimens collected from remote areas such as the North Pacific suggests the already widespread distribution of coplanar PCBs as in the case of general PCB pollution. The clear positive correlations between concentrations of total PCBs and each of the three coplanar PCBs obtained in all mammals analysed suggest that the sources of coplanar PCB contamination to the environment are mainly commercial PCB preparations. Comparison of the composition of three toxic coplanar PCBs in commercial PCB mixtures and in the various animals indicates the relative metabolisability of these congeners as follows: 3,3',4,4'-T4CB>3,3',4,4',5-P5CB>3,3',4,4',5,5'-H6CB. Moreover, marine mammals seem to have lower potency to metabolise the coplanar PCBs in comparison with terrestrial mammals. In human adipose tissues, the concentrations of coplanar PCBs were found to be much higher than 2,3,7,8-tetrachlorodibenzo-p-dioxin (T(4)CDD), 2,3,4,7,8-pentachlorodibenzofuran (P(5)CDF) and other toxic congeners. 'T(4)CDD-equivalent' analysis based on the enzyme induction potencies and the residues of these toxic chemicals indicates that 3,3',4,4',5-P(5)CB may impose a greater toxic threat than dioxins and furans to the humans and probably to wildlife also.     

Background levels of non-ortho-substituted (coplanar) polychlorinated biphenyls in human serum of Missouri residents

This study characterizes the levels of polychlorinated biphenyls (PCB) congeners PCB 77, PCB 81, PCB 126, and PCB 169, in a group of 150 men and women with no documented exposure to PCBs. Its purpose is to provide current referent levels of coplanar PCBs in Missouri residents and to compare those levels to levels reported in the literature from the United States and other countries. Although this study used an extensive questionnaire assessing potential sources of exposure, no positive relations were found between these exposure sources and participants' PCB levels. The PCB levels for the four congeners measured were lower than any reported in the literature. PCBs 126 and 169 are only two of the dioxin-like congeners; however, their contribution makes up 11% of the total TEQ. Age was significantly related to PCB 126 and PCB 169. For every one-year increase in age, both PCB congeners increased by approximately 0.4 parts per trillion (ppt). There was no gender difference for PCB 126; however, PCB 169 levels were 3 ppt higher in males than females.     

PCB congener selective biodegradation by the white rot fungus Pleurotus ostreatus in contaminated soil

Six strains of white rot fungi were tested for their biodegradation ability of low chlorinated polychlorinated biphenyl (PCB) commercial mixture (Delor 103) in real soil system. Phanerochaete chrysosporium and Trametes versicolor did not show any ability to degrade PCBs in soil. On the contrary, four strains of Pleurotus ostreatus were able to remove about 40% of Delor 103 in two months. All P. ostreatus strains decomposed PCBs selectively with the preference for congeners with chlorine atoms in ortho > meta > para position. Degradation efficiency decreased with increasing number of chlorination.     

Determination of coplanar and ortho substituted PCBs in some sewage sludges of Switzerland using HRGC/ECD and HRGC/MSD

The three most toxic coplanar PCB congeners PCB 77, 126 and 169 as well as 7 mono-and di-ortho-PCBs (PCB 28, 52, 101, 118, 153, 138, 180) were measured in 19 sewage sludges. Concentrations of the coplanar PCBs ranged between 231–5050 ng/kg dw for PCB 77, 43–1511 ng/kg dw for PCB 126 and 29–273 ng/kg dw for PCB 169. Comparable results were obtained with mass selective detection in the single ion monitoring mode (MSD-SIM) except for PCB 169, where MSD-SIM was less sensitive than ECD. The sum of the 7 mono-and di-ortho-PCBs, which are routinely measured as representatives of the PCB fraction, reached levels between 43–550 μg/kg dw and agreed well with results previously obtained in our laboratory. Based on our data, a selective accumulation of the coplanar PCBs could not be observed. Sludges that received industrial effluents clearly showed higher PCB levels than rural ones. Finally, calculation of TEQ equivalents of the coplanar PCBs in the sewage sludges revealed that, based on application rates normally used in Switzerland, the contribution of the sludges to soil pollution seems to be of minor importance.     

Analysis of some polyhalogenated organic pollutants in sediment and sewage sludge

A laminated sediment core collected in the southern part of the Baltic Proper was analysed for DDT compounds, polychlorinated biphenyls (PCB) including the coplanar congeners, polybrominated diphenyl ethers (PBDE) and polychlorinated naphthalenes (PCN). Two sewage sludge samples were also analysed for the same compounds.

The results of the sediment analyses indicate the presence of PCB, DDT and PBDE compounds in sediment layers dating from the 1950s and later. Neither coplanar PCB nor PCN were detected at any level of the sediment core. The PCB concentrations indicate a slight increase in levels during the last decades, while there were no changes in the levels of DDT compounds. In contrast, TeBDE levels increase 4- to 8-fold and one PeBDE congeners levels increase 10- to 20-fold. The results of sewage sludge analyses showed the concentration of the individual PBDE to be at about the same level as for the individual PCB congeners. The congener pattern in sludge samples indicates low-chlorinated products to be the main PCN source.     

Polychlorinated biphenyls (PCBs) in sediments in Hong Kong: a congener-specific approach to the study of coplanar PCBs in aquatic ecosystems

Patterns of contamination by polychlorinated biphenyls (PCBs) were investigated in fourteen samples of coastal sediments from Hong Kong. Congener-specific analyses revealed nine sediment samples from Junk Bay to contain PCBs at concentrations ranging from 31 to 2200 ng g(-1) dry weight, concentrations generally increasing with distance north in the Bay. By contrast, five sediments from the Tolo area to the north-east of Hong Kong exhibited total PCB levels of only 6.6 to 45 ng g(-) dry weight. The patterns of relative abundance of PCB congeners in the northern Junk Bay sediments suggested the existence of ongoing source(s) of PCBs in this area; biphenyls of lower chlorination were present at high concentration in these samples. Three coplanar PCBs (3', 4, 4'-tetrachlorobiphenyl; 3,3',4,4',5-pentachlorobiphenyl; and 3,3',4,4',5,5'-hexachlorobiphenyl) were found to be present in Junk Bay sediments; these are highly toxic and are cause for concern in aquatic environments. The abundance of the three coplanar PCBs in the sediments studied was similar to that in commercial PCB mixtures, suggesting that these congeners are not enriched over other PCBs by the sediments of coastal ecosystems. It is concluded that the preferential enrichment of coplanar PCBs occurs in the biosphere, rather than in sediments.     

Prediction of the bioconcentration factor of PCBs in fish using the molecular connectivity index and fragment constant models.

Models based on molecular connectivity index (MCI) and fragment constant (FC) method were developed for prediction of the bioconcentration factor (BCF) for polychlorobiphenyls (PCBs) in fish. The mean residuals for the MCI and FC models were 0.195 and 0.223 log units, respectively. The two models were then compared in terms of their mean residuals. In addition to the chlorine atom substitution number, other important structural features exhibiting a significant influence on the BCFs of PCB congeners were discussed and incorporated to the models. These features include the degree of the ortho-substitution, the presence of chlorine pairs in the three- and five- positions, and the crowding of chlorine atoms on the phenyl ring.     

Comparison of seven indicator PCBs and three coplanar PCBs in beef, pork, and chicken fat

The risk assessment of polychlorinated biphenyls (PCBs) is difficult since complex congeners were used in many industrial applications for a long period of time and the residue monitoring in foods of animal origin and the environment were not established in comparable systems. The relationships of determined concentrations in indicator PCB congeners (mono- and di-ortho PCBs) and coplanar PCB congeners (non-ortho PCBs) in livestock products are presented in this study. The concentrations of seven indicator PCBs were compared with three coplanar PCBs in beef, pork, and chicken fat. Distributions of concentration for the indicator PCBs in three different animal species were similar except for that of PCB-118 (2,3',4,4',5-pentachlorobiphenyl) in pork fat. The congeners with the highest concentration were PCB-138 (2,2',3,4,4',5'-hexachlorobiphenyl) in beef and pork fat and PCB-28 (2,4,4'-trichlorobiphenyl) in chicken fat. The bioaccumulation and metabolism of PCBs in animal species represent different congener profiles in livestock products. The percentage of the total concentration of three coplanar PCBs was about 2% of the total concentration of the seven indicator PCBs. Relatively high concentration of mono-ortho and di-ortho PCBs in fat samples of livestock products may be calculated with the concentration of coplanar PCBs that can be usually determined on a sequential procedure with dioxin analysis. Therefore, the relationship of the amounts between seven indicator PCBs and three coplanar PCBs may be useful to derive the composition and level of contaminants in beef, pork, and chicken.     

Biodegradation of coplanar polychlorinated biphenyls by anaerobic microorganisms from estuarine sediments.

In this study, we investigated the biodegradability of biphenyl and 5 congeners (one non-planar and four coplanar) of polychlorinated biphenyl (PCB). Biphenyl, the non-planar congener 2,3',4',5-tetrachlorobiphenyl (25-34 CB), and the four coplanar congeners 3,3',4,4'-tetrachlorobiphenyl (34-34 CB), 3,4,4',5-tetrachlorobiphenyl (345-4 CB), 3,3',4,4',5-pentachlorobiphenyl (345-34 CB), and 3,3',4,4',5,5'-hexachlorobiphenyl (345-345 CB) were amended at a concentration of 10 mg/L into anoxic sediment slurries collected from the estuaries of the Tansui River and the Erjen River. During 2 years' incubation under sulfidogenic conditions, biphenyl was persistent, while all other chlorinated congeners, except for 345-345 CB, were dechlorinated with or without a lag period in sediment slurries collected from both rivers. Dechlorination of coplanar and non-planar congeners began with para chlorine removal. All para chlorines from the mono-, di-, and trichlorobiphenyl groups could be removed by sediment slurries from both rivers. Microbial communities in sediment from the Erjen River additionally fostered meta-dechlorination activity, but only after removal of all the para chlorines. Addition of Tween 20 (0.05%, v/v) into sediment slurries from the Tansui River did not enhance dechlorination rates or extents, but the addition of toluene- or 3-chlorobenzoate-adapted sediments enhanced dechlorination of 34-34 CB and 345-4 CB.     

Microbial dechlorination of polychlorinated biphenyls in anaerobic sewage sludge.

The potential of a chlorophenol (CP)-adapted consortium to dechlorinate polychlorinated biphenyls (PCBs) in sewage sludge was investigated. Results show that dechlorination rates differed significantly depending on sludge source and PCB congener. Higher total solid concentrations in sewage sludge and higher concentrations of chlorine in PCB resulted in slower dechlorination rates. No significant difference was found for 2,3,4,5-CB dechlorination from pH 6.0 to pH 8.0; however, dechlorination did not occur at pH 9.0 during a 41-day incubation period. Results show that at concentrations of 1 to 10 mg/L, the higher the PCB concentration, the faster the dechlorination rate. In addition, dechlorination rates were in the following order: methanogenic conditions > sulfate-reducing conditions > denitrifying conditions. The addition of acetate, lactate, pyruvate, and ferric chloride decreased lag times and enhanced dechlorination; however, the addition of manganese dioxide had an inhibitory effect. Dechlorination rates were also enhanced by the addition of PCB congeners, including 2,3,4-CB, 2,3,4,5-CB and 2,3,4,5,6-CB in mixture. Overall results show that the CP-adapted consortium has the potential to enhance PCB dechlorination. The optimal dechlorination conditions presented in this paper may be used as a reference for feasibility studies of PCB removal from sludge.     

Occurrence and accumulation of organochlorine contaminants in swordfish from Mediterranean Sea: a case study

Polychlorinated biphenyls including coplanar congeners and DDT compounds were measured in the liver of a teleost species: namely, Xiphias gladius. PCB concentrations (median: 1121 ng/g lipid wt) were comparable with DDT levels (median: 1236 ng/g lipid wt). PCBs revealed a profile dominated by hexa-, penta- and heptachlorinated congeners. Among DDTs, the compound in the greatest concentration was p,p'-DDE, representing 70% of the total DDT burden, followed by o,p'-DDT>p,p'-DDT>p,p'-DDD=o,p'-DDD. Mean total 2,3,7,8-TCDD equivalent of five coplanar PCBs was 8.83 pg/g lipid weight. The isomers with higher TEQs values were non-ortho congeners than mono-ortho ones.     

A survey of PCB congeners in U.K. cows'' milk

Samples of unpasteurised bulked milk, taken directly from ten herds of dairy cattle on rural and urban farms in the north west of England on five separate sampling occasions, were analysed for a range of PCB congeners. ΣPCB concentrations (sum of 37 congeners) ranged from 3.4–16.4 ng/g milk fat with a mean ΣPCB concentration of 8.4 ng/g milk fat. The dominating congeners were 118, 153, 138 and 180, which contributed 15%, 20%, 17% and 9% of the ΣPCB load respectively. The chlorine pattern of the congeners which made moderate or major contributions to the ΣPCB concentration were typically substituted at both para positions (4, 4′), while the PCB congeners not detected in the milk had at least one ring that was not 4-substituted. These results indicate the 4,4′ substitution pattern as being the key to PCB persistence in cows. It is estimated that consumption of typical daily intakes of milk with the PCB concentrations measured in this study would contribute 11 % of the average daily ΣPCB intake for individuals in the UK. This contribution would increase to 30% when exposure through the consumption of dairy products prepared from such milk (e.g. cheese, butter) is taken into account. It is estimated that the inclusion of the TEF assigned PCBs would typically increase the TEQ rating of cows' milk by approximately 40% over that attributed to PCDD/Fs alone.