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.     

Multi-component behavior of fixed-bed adsorption of dioxins by activated carbon fiber

The multi-component behavior of fixed-bed adsorption of dioxins (DXNs) was examined through detailed analyses of the concentration profiles of isomers in fixed-bed activated carbon fiber (ACF). Regularities in both adsorption rates and strengths were clarified. (1) The rate of transfer in the adsorption of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCCDs/DFs) tends to increase with decreasing number of chlorine substituents. Axial dispersion also tends to increase with a decreasing number of chlorine substituents under our experimental conditions. (2) Homologues with the same number of chlorine substituents in PCDDs/DFs have similar adsorption strengths. The adsorption strength of PCDD/DF isomers is probably greater than that of co-planar polychlorinated biphenyls (co-PCB) isomers when the number of chlorine substituents is identical. (3) The adsorption strength of isomers depends on their molecular structure. In PCDDs/DFs the toxic isomers, all of which have vicinal chlorine substituents at the 2, 3, 7 and 8 positions, are relatively strong. It is clear, especially in TeCDDs, that isomers with vicinal chlorine substituents are stronger than isomers without. In co-PCBs, isomers without chlorine substituents at ortho positions are stronger than those with, and (4) A close analogy exists between the adsorption strength order for ACF and the elution order in gas chromatography (GC).     

Emission and chlorination pattern of PCDD/PCDF predicted from indicator parameters

The emission and chlorination pattern of polychlorinated dioxins and dibenzofurans from waste combustion shows a close covariation with that of chlorinated benzenes and phenols. This covariation can be utilized to predict the emission levels of specific isomers as well as the pattern of congeners.     

Apportionment of TEQs from four major dioxin sources in Japan on the basis of five indicative congeners

The major sources of dioxins (polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs)) in the environment in Japan have been considered to be combustion by-products, pentachlorophenol (PCP) formulations, chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations, and PCB products. Data on PCDDs, PCDFs and DL-PCBs from the four sources were analyzed, and indicative congeners whose concentrations were highly correlated with WHO-2006 toxic equivalencies (TEQs) were identified for each source sample. The indicative congeners for combustion by-products, PCP formulations, and CNP formulations were 2,3,4,7,8-pentachlorodibenzofuran, 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin, and 1,2,3,7,8-pentachlorodibenzo-p-dioxin, respectively; for PCB products, the indicative congeners were IUPAC Nos. #126- and #105-pentachlorobiphenyls. Moreover, using the data on PCDDs, PCDFs and DL-PCBs, we developed a set of equations for estimating the apportionment of TEQs from the four sources by using only the concentrations of the above-mentioned five indicative congeners. The equations were used along with the analysis results of different types of environmental samples collected from Japan, to determine the TEQ contributions of the four sources. The obtained values of TEQ contributions seemed to be reasonable. The estimation method was developed by using the data on major dioxin sources in Japan, and therefore, it is generally adaptable to environmental samples from any part of Japan. The method may be usable for regions outside Japan if source identification is carried out and the estimation equations are modified appropriately.     

Effect of reaction time on PCDD and PCDF formation by de novo synthetic reactions under oxygen deficient and rich atmosphere

The effect of reaction time on formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) was studied under laboratory conditions in the system containing municipal waste incineration fly ash, activated carbon and copper chloride dihydrate at 300 degrees C in 99.999% N2 and N2 + 10% O2 atmosphere. The concentrations of tetra- to octa-chlorinated isomers as well as I-TEQ concentrations of toxic congeners are reported. The mechanism of PCDD and PCDF formation from chlorophenols and chlorinated biphenyls is discussed in the light of the time changes of PCDD/PCDF ratios.     

Some pharmacokinetic aspects of PCDDs and PCDFs in mammals after administration of a fly ash extract from a municipal incinerator

Fly ash extracts were fed to male hamster (single dose), male rat (single dose and multiple dose), pregnant and lactating female rat (multiple dose). The retention of four isomers, 2,3,7,8-TCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PnCDD and 2,3,4,7,8-PnCDF, was studied in the liver of the adults, foetuses and liver of the sucklings.

Liver retention was structure dependent and different for both species. Transportation of the isomers via the mother milk was 50–100 times more effective than via the placenta.

After a single intravenous dose of fly ash extract to male rats the elimination of these four isomers was studied in the liver, during a period of 10 days. Elimination rates for 2,3,7,8-TCDD, 1,2,3,7,8-PnCDD and 2,3,4,7,8-PnCDF were in the same range. Pharmacokinetic calculations were done on both tetra congeners, to obtain information about the validity of the published K_e values in the multiple dose experiments with male rats.

For 2,3,7,8-TCDF the K_e value was applicable, but for 2,3,7,8-TCDD the validity of the K_e could not be determined.     

Formation of PCDD/Fs and PCBs in the process of production of 1,4-dichlorobenzene

The occurrence and distribution of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in a typical process of production of 1,4-dichlorobenzene (p-DCB) were investigated systematically in this study. P5CDFs and H6CDFs were the main congeners of PCDD/Fs, while only low levels of other PCDD/Fs were detected in the samples. The concentrations of PCBs were up to 4614 ng/g in the semi-manufactured products, and 1797 ng/g in the product p-DCB. It was also found that high chlorinated PCB congeners increased with the further chlorination. The levels of PCDD/Fs decreased obviously in the purification process, while PCBs could not be removed effectively. Polychlorophenols and other important dioxin precursors (1,4-dichloro-2-phenoxybenzene and 2-phenyl-2',5,5'-trichlorophenol) were also analyzed. Polychlorophenols which ortho- and para-positions of the hydroxyl were substituted by chlorine were the main congeners. In addition, a possible pathway of the formation of PCDD/Fs and PCBs in the production of p-DCB was presented. The results of this article suggest that re-estimation on the risk of using p-DCB products, especially the products for daily use such as mothballs, is expected.     

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.     

Relationship of PCDD/F and Co-PCB concentrations in breast milk with infant birthweights in Tokyo, Japan

OBJECTIVE: To observe how PCDD/F and Co-PCB concentrations in breast milk relate to infant birthweights in Tokyo, Japan. STUDY DESIGN: Breast milk samples were collected from 240 mothers (aged 25-34years old) residing in Tokyo to measure the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs; 14 congeners), polychlorinated dibenzofurans (PCDFs; 15 congeners), and coplanar polychlorinated biphenyls (Co-PCBs; 12 congeners) in the breast milk fat. Individual milk samples (about 50ml) were obtained 30days after delivery, between the months of June and September in 1999 and 2000. The relationship of the infant birthweights with the PCDD/F and Co-PCB concentrations was observed. RESULTS: The birthweights were negatively correlated the concentrations of many of the PCDD/F and Co-PCB congeners, with the mean toxic equivalent quantities (TEQs) of the Co-PCBs, and with the sum of the PCDD, PCDF and Co-PCBs, although their correlation coefficients were less than 0.200. Multiple regression analysis showed octachlorodioxin was statistically significant explanatory variate. CONCLUSIONS: There were slight relationship between the dioxins levels of breast milk and the birthweights of the infants.     

Congener profiles of PCDDs, PCDFs, and dioxin-like PCBs in the breast milk samples in Tokyo, Japan

Exposure to dioxins has raised much public concern recently. We determined the congeners' distribution of polychlorinated-dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in the breast milk samples collected in Tokyo, Japan. Breast milk was taken from 240 mothers, 30 days after delivery in 1999 and 2000 in Tokyo, Japan. The actual concentration and TEQ concentration of PCDDs (14 congeners), PCDFs (15 congeners), and dl-PCBs (12 congeners), and each congener's contribution to the total TEQ level were calculated. Among all the samples, PCDDs accounted for 34.8%, PCDFs accounted for 23.5%, dl-PCBs accounted for 41.7%, which was also similar in the breast milk from the primiparae and secundiparae. The main contributors to the total TEQ with increasing percentages were 2,3,4,7,8-PeCDF, 1,2,3,7,8-PeCDD and 3,3',4,4',5-PCB (#126), and they accounted for more than 65% of the total TEQ. Detailed congener analysis in breast milk samples is effective to understand dioxin sources.     

Concentrations of polybrominated diphenyl ethers, organochlorine compounds and nitro musks in mother's milk from Germany (Bavaria)

The aim of this study was to determine a new spectrum of substances that will be selected for future breast milk monitoring in Bavaria, Germany. Up to now, the analysis of breast milk in Bavaria was limited to selected organochlorine pesticides (OCP) and polychlorinated biphenyls (PCB). Information on background levels of toxicologically interesting substances, such as dioxins and dioxin-like polychlorinated biphenyls (dl-PCB) or on flame retardants, such as polybrominated diphenyl ethers (PBDE) are very limited or not available for Bavaria. We present here levels on OCP, some nitro musks, indicator PCB, polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and dl-PCB concentrations in breast milk collected at 12 weeks post-partum of 43 primiparous mothers living in Bavaria. The average concentrations of PCDD, PCDF and dl-PCB were 4.98, 4.93 and 9.92 pg WHO-TEQ g(-1) lipid, respectively. The mean contribution of PCDD, PCDF, non-ortho and mono-ortho PCB to the total WHO-TEQ is consistently about 25% each. Furthermore the concentration on PBDE in breast milk at two sampling points, 12 weeks and 16 weeks after delivery, were determined. Overall, 19 PBDE congeners were analysed, however the level of 12 PBDE congeners were below the limit of detection. BDE-153 and BDE-47 were the predominant congeners accounting for about 66% of the total PBDE. The means of the total concentrations of PBDE (five congeners) at the first and second sampling point were 1.90 and 2.03 ng g(-1) lipid, respectively. Based on our results the overall concentrations of the analysed substances in milk samples from Bavaria are consistent with the levels of breast milk samples of other European countries reflecting the low background body burden of these compounds.     

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.     

PCDD/Fs and PCBs in Baltic herring during the 1990s

Baltic herring samples caught from the Baltic Sea during the spring periods of 1993-1994 and 1999 were analysed for polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and polychlorinated biphenyls (PCB). For analyses, 1570 individual herring were combined to 120 pools. Correlations between concentrations of congeners 1,2,3,7,8-PeCDD, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, and 2,3,4,6,7,8-HxCDF, and age of herring were the strongest (r>0.8) followed by correlations between PCB congeners PCB 105, 118, 126, 156, 169 and 180 (r>0.7), and age of herring. Due to higher fat percentage in herring in the Gulf of Bothnia the concentrations of PCDD/Fs and PCBs on fresh weight (fw) basis were higher than in herring in the Gulf of Finland. The concentrations of WHO(PCDD/F)-TEQs ranged from 1 to 27 pg/g fw, depending on the age and catchment area of herring, and concentrations of WHO(PCB)-TEQs reached 32 pg/g fw. Between the two studied time points no clear downward trend in concentrations was observed.     

Organochlorine pesticides and polychlorinated biphenyl congeners in wild terrestrial mammals and birds from Chubu region, Japan: Interspecies comparison of the residue levels and compositions

In order to understand the residue levels of organochlorine compounds (OCs) and their accumulation patterns in wildlife inhabiting Chubu region, Japan, the concentrations of polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), DDT compounds (DDTs) and hexachlorobenzene (HCB) were measured in 8 species of terrestrial mammals and 10 species of birds. In view of feeding habits, the contamination levels of OCs were found to be higher in omnivorous mammals than in herbivorous ones, and in fish-eating ones and raptores than in omnivorous birds. In fox and dog, PCB-180 (2, 2′, 3, 4, 4′, 5, 5′-heptachlorobiphenyl) was the most dominant PCB congener, while in the other species PCB-153 (2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl) was the most persistent. The ratios of lower chlorinated PCB congeners (tri- to tetra-) to total PCBs were larger in fish-eating birds than in the other birds. The results indicate that the compositions of PCB congeners would reflect the differences of feeding habits and xenobiotic metabolizing systems among each species.     

Differential uptake for dioxin-like compounds by zucchini subspecies

The zucchini (Cucurbita pepo) cultivars 'Patty Green', 'Black Beauty', and 'Gold Rush' were cultivated on weathered dioxin-contaminated soil in pots, and concentrations of the 29 dioxin-like compounds that were assigned WHO-TEFs, three non-toxic polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), and two non-dioxin-like polychlorinated biphenyls (PCBs) were analyzed. Toxic equivalent (TEQ) values accumulated in 'Black Beauty' and 'Gold Rush' were about 180 times higher than those in 'Patty Green'. The bioconcentration factor (BCF) based on total mass concentration of the twelve dioxin-like PCBs was higher than those of the seven PCDDs and ten PCDFs in all the cultivars. The BCFs for PCDD and PCDF congeners were negatively correlated with octanol-water partition coefficients in all the plants. No correlations were observed in PCB congeners in the high accumulators, although in 'Patty Green' the BCFs for PCB congeners were significantly correlated with octanol-water partition coefficients. Our findings suggest that the high accumulators had unknown, unique mechanisms for uptake of PCBs, whereas PCDDs and PCDFs were absorbed based on their physicochemical properties.     

Effect of solid waste landfill organic pollutants on groundwater in three areas of Sicily (Italy) characterized by different vulnerability

The aim of this study was to obtain information on the presence and levels of hazardous organic pollutants in groundwater located close to solid waste landfills. Eighty-two environmental contaminants, including 16 polycyclic aromatic hydrocarbons (PAHs), 20 volatile organic compounds (VOCs), 29 polychlorinated biphenyls (PCBs), 7 dioxins (polychlorinated dibenzo-p-dioxins, PCDDs) and 10 furans (polychlorinated dibenzofurans, PCDFs) were monitored in areas characterised by different geological environments surrounding three municipal solid waste landfills (Palermo, Siculiana and Ragusa) in Sicily (Italy) in three sampling campaigns. The total concentrations of the 16 PAHs were always below the legal threshold. Overall, the Fl/Fl + Py diagnostic ratio revealed that PAHs had a petrogenic origin. VOC levels, except for two notable exceptions near Palermo landfill, were always below the legal limit. As concerns PCB levels, several samples were found positive with levels exceeding the legal limits. It is worth noting that the % PCB distribution differs from that of commercial compositions. In parallel, some samples of groundwater containing PCDDs and PCDFs exceeding the legal threshold were also found. Among the 17 congeners monitored, the most abundant were the highest molecular weight ones.

     

PCDD/PCDF, dl-PCB and PBDE serum levels of Slovak general population

Blood serum specimens from 81 non-occupationally exposed adults residing in four areas close to municipal and waste incinerators as well as metallurgical industry plant and 44 adult subjects coming from control area of Slovakia were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polybrominated diphenylethers (PBDEs). The concentration of total WHO(98)TEQ PCDD/F/dl-PCBs in whole group of donors from areas where known sources causing dioxin contamination are present was significantly higher than in control group of donors (p<0.001). Correlation between the age of donors and PCDD/F and dl-PCB levels was confirmed (Spearman's r(PCDD/Fs)=0.543, r(dl-PCBs)=0.521, p<0.001). Furthermore, this study presents first results concerning the PBDE congeners in human serum of Slovak general population. The total concentration (congeners 28, 47, 99, 100, 153, 154, 183) in control group was approximately 1.5-times higher in comparison to that of residents coming from areas with supposed environmental pollution. The most abundant congeners in all samples were BDE-47 and BDE-153 with median values of 0.24 ng g(-1) lipid and 0.23ngg(-1) lipid, respectively. The positive association between PBDE values and age of donors was not found.