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.     

Organic chlorine compounds in lake sediments. IV. Dioxins, furans and related chloroaromatic compounds

Polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), polychloronaphthalenes (PCNs) and coplanar PCBs were measured in surface sediments from 18 lake areas in Central Finland. Toxic 2, 3, 7, 8-substituted PCDD and PCDF congeners occurred at low levels (<20 − 230 pg/g dw). PCNs appeared at few ng/g (total PCNs) levels. Pulp mills or any other local sources could not be associated with the sedimented PCDDs, PCDFs and PCNs. Coplanar PCB congeners 77 and 105 (IUPAC Nr) were generally found at 20–550 pg/g levels. The most toxic congener 126 was measured (110 pg/g) only at one area near a local PCB leakage. Pulp mill originated aromatic chlorocompounds which coelute with PCDDs and PCDFs in clean up, probably alkyl polychlorobibenzyls (R-PCBBs) appeared at ng/g levels and showed a clear gradient dowstreams from pulp mill effluent points.     

Relative importance of polychlorinated naphthalenes compared to dioxins, and polychlorinated biphenyls in human serum from Korea: Contribution to TEQs and potential sources

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in human have been studied extensively; however, polychlorinated naphthalenes (PCNs) have been studied less widely. The mean concentrations of PCNs, PCDDs, PCDFs, and PCBs in 61 healthy human volunteers were 2170 pg/g lipid, 452 pg/g lipid, 116 pg/g lipid, and 120 ng/g lipid respectively, and the mean toxic equivalents (TEQs) contributed by PCNs, PCDDs, PCDFs, and PCBs were 5.88, 5.22, 5.48, and 5.33 pg/g lipid, respectively. PCNs contributed to 26.8% of the total TEQs. 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF, PCB126, and hepta-CN-73 accounted for >62% of the total TEQs in the human serum samples. The overall serum PCN homologue profiles of all subjects were dominated by tetra- and penta-CN homologues, and the most predominant individual congener was hepta-CN-73, which contributed 17.5% of the total serum PCN concentration. Enrichment of hepta-CN-73 in the human serum samples might be due to contributors from combustion sources.     

Persistent organic pollutants in Detroit River suspended sediments: polychlorinated dibenzo-p-dioxins and dibenzofurans,dioxin-like polychlorinated biphenyls and polychlorinated naphthalenes

Suspended sediments from the Detroit River were collected in 1999 and 2000 using sediment traps at sites ranging from western Lake Erie to southern Lake St. Clair and analyzed to determine the spatial distributions of contaminants including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), dioxin-like PCBs (DLPCBs) and polychlorinated naphthalenes (PCNs). Concentrations of all three contaminant classes were clearly elevated at sites in the lower reaches of the river in the Trenton Channel. The potential influence of the Trenton Channel as a source of contamination to western Lake Erie was further evidenced by PCDD/PCDF homologue profiles, which indicated a contribution from chemical manufacturing in addition to the normal background combustion profile. Toxic equivalents (TEQs) for PCDDs/PCDFs generally exceeded those for DLPCBs; combined total TEQs in July 2000 for these two compound classes ranged from 2.30 pg/g in southern Lake St. Clair to 306 pg/g at a station just downstream of the outflow of Monguagon Creek in the Trenton Channel. The spatial distribution of PCN contamination was similar to that of PCDDs/PCDFs and DLPCBs, with the highest level of total PCNs (8200 ng/g) detected at a site in the Trenton Channel near Elizabeth Park; TEQs for PCNs in the Trenton Channel ranged from 73 to 3300 pg/g. The data indicate that PCNs represent a significant contribution to dioxin-like biological activity in Detroit River suspended sediments.     

Source determination of highly chlorinated biphenyl isomers in pine needles - comparison to several PCB preparations

The isomer specific composition of 13 technical PCB formulations of different origin and of pine needles was analyzed using GC/MS and HRGC/HRMS. Nonachlorinated biphenyls were identified in 11 among 13 formulations analyzed, with the highest abundance found for highly chlorinated ones (Aroclors 1268 and 1260, Chlorofen, Sovol, Kanechlors 600 and 500, Delor 106, Clophen A60). Decachlorobiphenyl was identified only in Aroclor 1268, Clophen A60, Aroclor 1260 and Chlorofen, comprising, respectively, 8.9, 2.8, 1.3 and 0.82% of the total bulk of nona- and decaCBs detected. Nona- and decaCB were detected in pine needles in Poland with the highest concentrations found at the sites neighboring to a former production sites of the Polish PCB formulations, while in pine needles collected around the Tokyo Bay nona- and decacCB were detected only in four of 10 sites and the concentrations corresponded to those found at the rural areas of Poland.     

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.     

Behavior of PCNs, PCDDs, PCDFs, and dioxin-like PCBs in the thermal destruction of wastes containing PCNs

In the first known study to characterize the emissions of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) from the thermal treatment of wastes containing PCNs, the formation and decomposition behavior of these pollutants was investigated both at laboratory scale and at plant scale. Exhaust gas measurements from laboratory-scale combustion of rubber belts containing PCNs (FB belts) were used as the basis for calculations predicting that the incremental dioxin toxic equivalency (TEQ) emissions from municipal solid waste (MSW) incinerators would be less than 0.1 ng/m3 N. In order to directly examine co-incineration of FB belts with MSW and to address potential differences between the laboratory experiment and full-scale MSW incinerators, experiments were conducted using a larger scale thermal treatment test facility with sampling and analysis at several points in the thermal treatment process. Congener specific analysis of PCNs clearly showed that both destruction and synthesis simultaneously occurred during combustion in the kiln. Most of the PCNs were destroyed by secondary combustion, and almost all PCNs were removed after flue gas treatment. Almost all PCDDs/DFs were synthesized as by-products of kiln combustion, most of them were destroyed by the secondary combustion, and almost all dioxins (PCDDs/DFs and dl-PCBs) were removed after flue gas treatment. The TEQ emission levels were less than 0.1 ng/m3 N for all plant-scale tests, and differences in TEQ emission levels were very small. Adding wastes containing PCNs to MSW will not influence thermal treatment emissions to the environment from modern solid waste incinerators.     

Dechlorination of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans on fly ash

Dechlorination of commercial mixtures of polychlorinated biphenyls (PCB) as well as polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) on extracted and non-extracted fly ash obtained from municipal waste incinerator (MWI) was studied in closed systems under nitrogen atmosphere at temperatures of 260°C and 340°C. Decomposition results (given as the difference between PCB or PCDD/F molar amounts before and after the experiment (in %) due predominantly to dechlorination reactions) and detoxification data (expressed similarly but related to toxic PCB and PCDD/F congeners only and given in I-TEQ units) are reported. Detoxification of Delor 105/80T at 260°C and 340°C at a loading of 0.65 wt% was 99.48% and 100%, respectively. The decomposition of Delor 103 at 340°C and for the loading of 0.75 wt% corresponded to 99.99%. The detoxification capability of PCDD/Fs on extracted and non-extracted fly ash for loading of 130 and 264 ng/0.4 g of fly ash at 340°C made 96 and 98%, respectively.     

Effects of regional differences in waste composition on the thermal formation of polychlorinated aromatics during incineration

Two artificial wastes (A and B) whose contents reflect regional differences in municipal solid waste composition, were used to investigate the thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) during incineration. Flue gas samples were simultaneously collected at three ports in the post-combustion zone corresponding to flue gas temperatures of 400, 300, and 200 °C. The combustion of Waste B, which had a higher chlorine and metal content than Waste A, produced greater levels of highly-chlorinated homologues, as demonstrated by a higher degree of chlorination. The total concentrations of PCDDs, PCDFs, PCBs, and PCNs formed in the combustion of both wastes increased as temperature decreased along the convector. There were no significant differences in total concentrations between Waste A and Waste B combustion at specific temperatures, with exception of PCDFs at 400 °C. Orthogonal Projections to Latent Structures Discriminant Analysis (OPLS-DA) modeling, used to evaluate the data for all compound groups, suggest that during flue gas quenching at temperatures of 400 °C low-chlorinated homologues are preferentially formed in the presence of copper, which is known to be a very active catalyst for this process. At 300 and 200 °C, the formation of highly-chlorinated homologues is favored.     

Correlation of polychlorinated naphthalenes with polychlorinated dibenzofurans formed from waste incineration

Isomer composition of polychlorinated naphthalenes (PCNs) was measured for municipal waste incinerator fly ash samples and for emission samples produced from soot and copper-deposit experiments conducted at the United States Environmental Protection Agency (US-EPA). Two types of PCN isomer patterns were identified. One pattern contained specific PCN isomers in which chlorine atoms are substituted as if the peri(alpha-) position were dechlorinated from the higher chlorinated PCNs one by one. In another pattern, the isomers had a tendency for the chlorine atoms to assume successive positions on the naphthalene ring, which may be caused by specifically oriented chlorination. Some of these isomers increased, together with several polychlorinated dibenzofuran (PCDF) and a few polychlorinated dibenzo-p-dioxin (PCDD) isomers. The ratios between some specific PCN, PCDF, and PCDD isomers measured for the fly ash samples agree with those obtained from the soot and copper-deposit experiments. The observations suggest that these isomers were formed possibly from de novo synthesis utilizing the carbon structure contained in soot under the catalytic effect of a copper compound. Typical isomers for PCNs and PCDFs produced from incineration emissions were identified.     

Occurrence,profile and possible sources of PCNs in Hong Kong soils,and a comparison with PCBs,PCDDs and PCDFs

Polychlorinated naphthalenes (PCNs) have been proposed for inclusion in the annexes of the Stockholm Convention by the European Union, signifying a probable increase in monitoring PCN levels at a global level. Investigations on PCN levels in the environment of Hong Kong have not been reported. In this preliminary investigation, PCN levels in surface soils samples were determined by isotope dilution HRGC/HRMS techniques, and compared with those of polychlorinated biphenyl (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The concentrations of PCNs in the soil samples were 35–883 pg g^?1 (average, 201; and median, 94 pg g^?1), which were lower than those of PCBs PCDDs and PCDFs. This comparison suggested that PCNs are currently not priority POPs compared with dioxins and PCBs in Hong Kong soils. PCDDs were the most important contributor to the sum of toxic equivalents of PCNs, PCBs, PCDDs and PCDFs. OCDD was the most dominant dioxin congener in Hong Kong surface soils. PCB-118 was the most abundant in 12 dl-PCB congeners. PCN congeners indicating thermal related sources (CN52/60, CN66/67 and CN73) were relatively abundant in their respective homologs, which suggested PCN contamination from thermal sources. The ratio of CN73 to CN74 in soil samples suggested the contribution of PCN contaminations in soils from both thermal-related sources and evaporative emissions of technical PCN mixtures.     

Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

Polychlorinated-naphthalenes, -biphenyls, -dibenzo-p-dioxins, -dibenzofurans and p,p'-DDE in bluefin tuna,swordfish, cormorants and barn swallows from Italy

Concentrations of p,p'-DDE, polychlorinated biphenyl congeners (PCBs), polychlorinated-dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs) and -naphthalenes (PCNs) were measured in bluefin tuna, swordfish, common cormorants, and barn swallows collected from Italy. Average concentrations of PCBs in livers of tuna, swordfish, cormorant, and swallows were 930, 745, 1420 and 1230 ng PCBs g-1, w.w. respectively. p,p'-DDE was found in tuna, swordfish, cormorant, and swallow livers at mean concentrations of 82, 135, 166 and 95 ng DDE g-1, w.w. respectively. PCNs were found in all the samples analyzed, although at concentrations less than those reported for biota from the Baltic Sea. PCBs, particularly, non-ortho coplanar PCBs accounted for 80-90% of the total TEQs in tuna and swordfish. Relative contribution of PCDDs/DFs to TEQs was greater in cormorants and swallows compared to that in fishes. PCDD/DF congeners accounted for up to 80 and 45% of the total TEQs in cormorants and swallows, respectively.     

PCDD/PCDF formation in the chlor-alkali process—laboratory study and comparison with patterns from contaminated sites

Studies on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) during the electrolysis of sodium chloride solution (brine) using graphite or titanium electrodes were carried out at a laboratory scale. High concentrations of PCDFs but no PCDDs were formed in tests using graphite electrodes. With titanium electrodes, PCDFs were only formed when tar pitch was added and mainly originated from the dibenzofuran present in the tar. For the first time, a detailed assessment of the formation of mono- to octachlorinated PCDD/PCDF from tar pitch was investigated. The assessment included of the chlorination steps proved that PCDFs were formed by successive lateral chlorinated from dibenzofuran to MonoCDFs, DiCDFs, and TriCDFs to form the typical known “chlorine pattern” of TetraCDF to OctaCDF with a dominance of 1,2,7,8- and 2,3,7,8-TetraCDFs, 1,2,3,7,8-PentaCDF, and 1,2,3,4,7,8-HexaCDF as marker congeners. The final homologue distributions depended on reaction time and reaction temperature. In addition, electrolysis with non-chlorinated dibenzo-p-dioxins, dibenzofuran, and biphenyl was carried out. As a result, PCDDs, PCDFs, and PCB were formed at comparable yields. Congener patterns in soil samples from a PCDD/F-contaminated site where chlor-alkali electrolysis had been operated for decades in Japan had identical isomer distribution demonstrating the source and contamination potential and risk of these processes. Therefore, sites where in the past 120 years chlor-alkali electrolysis has been operated or where residues from chlor-alkali production or other chlorine using industries have been disposed should be assessed for their pollution level and exposure relevance. The assessment of total organohalogen content revealed that PCDF is only a small fraction of organohalogens in the contaminated soils. For an appropriate risk assessment, also other chlorinated aromatic compounds such as PCBs or PCNs need to be considered.     

Catalyzed dehalogenation of Delor 103 by sodium hydridoaluminate

The complete dechlorination of PCB liquid Delor 103 (42.6% Cl) to biphenyl has been effected in toluene with sodium dihydridobis(2-methoxyethoxo)aluminate (SDMA) in the presence of catalytic amounts of Ni(II) and Co(II) 2,4-pentanedionates at elevated temperatures. Changes in PCB congeners distribution during dechlorination were monitored by GC(ECD) and GC/MS, and the scheme of their transformation was proposed on the basis of site selectivity observed. A kinetic analysis of the reaction is presented.     

Biodegradation of PCBs by ligninolytic fungi and characterization of the degradation products

The aim of the present study was to compare the degrading capabilities of eight ligninolytic fungal representatives towards a technical mixture of polychlorinated biphenyls (Delor 103). Axenic cultures of the fungi, either in complex or N-limited liquid media, were spiked with the technical mixture of Delor 103. All of the fungal strains were able to degrade the pollutant significantly after 6weeks of incubation in both media. Outstanding results were achieved by the treatment with Pleurotus ostreatus, which removed 98.4% and 99.6% of the PCB mixture in complex and mineral media, respectively. This fungus was the only one capable of breaking down penta- and hexachlorinated biphenyls in the complex medium. Ecotoxicological assays performed with the luminescent bacterium Vibrio fischeri demonstrated that all of the fungal strains employed in this study were able to remove the toxicity only temporarily (e.g., after 28d of incubation), while P. ostreatus was capable of suppressing the toxicity associated to PCBs along the whole incubation period in both media. We also performed an extensive set of qualitative GC/MS analyses and chlorinated derivatives of hydroxy- and methoxy-biphenyls were detected along with monoaromatic structures, i.e. chlorobenzoic acids, chlorobenzaldehydes and chlorobenzyl alcohols. This results indicate that both intracellular (cytochrome P-450 monooxigenase, aryl-alcohol dehydrogenase and aryl-aldehyde dehydrogenase) and extracellular (ligninolytic enzymes) enzymatic systems could be involved in the biotransformation of PCB by ligninolytic fungi. The data from this work also document that the fungi are able to degrade further the main metabolites on the PCB pathway (i.e. chlorobenzoic acids) simultaneously with PCBs.     

Development and calibration of epiphytic lichens as saltfall biomonitors--dry-deposition modelling

Blubber collected from beluga whales and ringed seals during subsistence hunts in the southern Baffin Island region of the Canadian Arctic were analysed for polychlorinated naphthalenes and eight planar PCB congeners (mono-ortho PCBs: 105, 114, 118 and 156; non-ortho PCBs: 77, 81, 126, 169). SigmaPCN (3-7 Cl) concentrations in blubber ranged from 35.9-383 pg/g (lipid weight; lw) in beluga and 35.4-71.3 pg/g (lw) in ringed seal. These represent the first measurements of PCNs in marine mammals in the Canadian Arctic, mammals which are an important part of the traditional diet of the indigenous population. SigmaCoplPCB concentrations were much higher, ranging from 15.5-317 ng/g (lw) in beluga whale blubber and 16.5-40.9 ng/g (lw) in ringed seal blubber. PCNs and coplanar PCBs both exhibit dioxin-like toxicity. Although average sigmaPCN concentrations were less than 1% of sigmaCoplPCBs, PCNs contribute up to 11% of TEQ relative to the coplanar PCBs based on TEFs determined by H4IIE enzyme assays.     

Dependence of GC-RRTs on the solvent-accessible surface area of dioxins and related compounds

The correlation between gas chromatograph relative retention times (GC-RRTs) of dioxins and related compounds, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated naphthalenes (PCNs), and their solvent-accessible surface area (SAS) was analyzed for congeners and isomers. GC-RRTs were linearly dependent on SAS for congeners while there was little dependence for isomers. However, by using classification parameters, Nad-Cl, Nad-H, N1,9Cl, and NalphaCl, based on the substitution positions and patterns of chlorine and/or hydrogen atoms bound to the molecular skeleton, a linear relationship was found among isomers. Furthermore, the GC-RRTs of CDD, CDF, and CN isomers, which are planar, decreased despite increasing SAS, and this tendency was enhanced with the above classification. The retention behavior was explained in terms of the effective enhancement of molecular hydrophobicity caused by an increase in the number of adjacent chlorine pairs.     

Metabolic pathways of polychlorinated biphenyls degradation by Pseudomonas sp. 2

Polychlorinated biphenyls (PCBs) included with the commercial mixture Delor 103 were degraded by immobilized cells of aerobic bacterial strain Pseudomonas sp. 2. The ability of the strain to metabolise selected tri- and tetrachlorobiphenyls, and the site of primary attack of the biphenyl skeleton were investigated. It was observed that the amount of residual PCBs was 1-48% of the original PCBs after three weeks of incubation. Identified metabolites indicate that the used bacterial strain attacks the biphenyl skeleton at the 2,3- and 3,4-positions, and it is also able to dehalogenate PCBs. Metabolic pathways of degradation of individual congeners were proposed. Transformation of 2,4- and 2,5-dichlorobenzoic acids by Pseudomonas sp. 2 was also observed.