Congener profiles of PCBs and PCDD/Fs in Yucheng victims fifteen years after exposure to toxic rice-bran oils and their implications for epidemiologic studies

In 1978-1979, a mass poisoning occurred in central Taiwan from rice-bran oil contaminated by heat-degraded PCBs was later called the Yucheng (oil disease in Chinese). Only a few studies have so far investigated the levels of specific polychlorinated biphenyl (PCB) or polychlorinated dibenzodioxin/furan (PCDD/F) congeners in the Yucheng victims. This study aimed to investigate the serum residual levels of thirty-three PCBs and seventeen 2,3,7,8-substituted PCDD/F congeners in the Yucheng victims 15 years after the exposure. Forty-one blood samples were collected from individual Yucheng victims in 1994-1995. The mean levels of total 33 PCBs and 17 PCDD/Fs were 2468 ng/g lipid (13.3 ng/g sample) and 6550 pg/g lipid (30.9 pg/g sample) respectively. The higher levels were found in PCBs #99, #138, #153, #156, #170, #179, and #180 among 33 PCB congeners, while 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, and OCDD had the higher concentrations among 17 PCDD/F congeners. The total TEQ was contributed in decreasing order by 10 PCDFs (44%), three non-ortho-PCBs (24%), six mono-ortho-PCBs (20%), and seven PCDDs (12%). The mean total PCB levels and TEQ value of the 17 PCDD/Fs in the Yucheng victims 15 years after the toxic exposure were still 9 and 46 times higher than those in the general population in Taiwan. Principle component analysis (PCA) indicated that seven PCB congeners, PCBs #99, #138, #153, #156, #170, #179, and #180, accounted for 73% of the total variances in PCBs. On the other hand, six PCDD/F congeners, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDF, and OCDD, accounted for 97% of the total variances in PCDD/Fs. In addition, PCA revealed that at least three characteristic patterns of congener profiles for PCBs were observed among the Yucheng victims. Similar trend was also observed for PCDD/Fs. These patterns may reflect distinctive exposure scenarios and/or different metabolizing capabilities among the Yucheng victims. We suggest that these patterns, in contrast to total PCB and PCDD/F levels, may be valuable for the future epidemiologic studies when linking exposure with specific health effect.     

Comparison of the concentrations of polychlorinated biphenyls and dioxins in mothers affected by the Yusho incident and their children

Accumulated maternal dioxins are passed onto the fetus and neonate via the placenta and maternal milk. In Japan in 1968, an accidental human exposure to rice oil contaminated with polychlorinated biphenyls (PCBs) and other dioxin-related compounds, such as polychlorinated dibenzofurans (PCDFs), led to development of Yusho oil disease. We investigated differences in blood dioxin concentrations in mother-children pairs affected by the Yusho incident. From 2002 to 2008, blood samples were collected from 26 pairs of Yusho mothers and their children (19 mothers, 26 children). Specific congeners of seven polychlorinated dibenzo-p-dioxins (PCDDs), ten PCDFs, and four non-ortho PCBs were analyzed. The children had significantly lower TEQ concentrations of PCDDs, PCDFs, and coplanar PCBs compared to their mothers. The mother-child difference in blood concentrations varied with the congeners; the largest for 2,3,4,7,8-pentaCDF and the smallest for 1,2,3,4,6,7,8-heptaCDD. The level for 2,3,4,7,8-pentaCDF, which characterizes Yusho oil disease, was approximately 17-30 times higher in the mothers than in the general population, whereas there were no significant differences between children in the formula-fed group and the general population. In contrast, the mean level for 2,3,4,7,8-pentaCDF in the breast-fed group was approximately 1.5 times, (range 0.5-6.5 times) higher than that in the general population. Over 30 years after the Yusho incident, the mean blood dioxin levels in the offspring were only a fraction of the levels in their mothers. This is more consistent with exposure via breast milk than via transplacental transfer in the Yusho incident.     

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.     

Distribution of PCDDs, PCDFs and dioxin-like PCBs in the blood, testis and adipose tissue of suckling beef calves

To determine the distribution of persistent organochlorine compounds in beef cattle, concentrations of 2,3,7,8-substituted PCDDs, PCDFs and dioxin-like PCBs were measured in the blood, testes and adipose tissue of four two-month-old Japanese Black calves. Of 29 congeners analyzed, 19, 20 and 28 were detected in the blood, testes and adipose tissue, respectively, of three or all calves. Total toxic equivalents (TEQs) were similar in the testes and adipose tissue, and approximately two times higher than in the blood on a lipid weight basis (P<0.05). More PCDDs and PCDFs had accumulated in the testes than in adipose tissue (P<0.01), but more dioxin-like PCBs were found in adipose tissue than in the testes (P<0.0001). Accumulation patterns in the testes and adipose tissue varied among the congeners of PCDD and PCDF, whereas the patterns were similar in dioxin-like PCBs. In particular, highly substituted PCDD congeners were detected at high concentrations in the testes but at lower concentrations in adipose tissue compared with other congeners. By contrast, accumulation levels of highly substituted PCDFs were lower in both those tissues than the other congeners. In conclusion, it was demonstrated that PCDDs, PCDFs and dioxin-like PCBs leave the circulation and accumulate in the testes and adipose tissue in bovine calves. It was suggested that congeners of PCDD, especially highly substituted PCDDs, and PCDFs have a tendency to accumulate in the testis and dioxin-like PCB congeners accumulate readily in adipose tissue.     

Detailed study on the levels of polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and polychlorinated biphenyls in Yusho rice oil

One bottle of Yusho rice oil was obtained from a Yusho family in 1998. The levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in the causal oil were investigated with two different approaches and the individual concentrations of all the 17 2,3,7,8-substituted PCDD/F and 14 coplanar PCB (Co-PCB) congeners were elucidated for the first time. The concentrations of PCDDs and PCDFs were found to be 0.60 and 8.8 ppm, respectively. For PCBs, more than 130 PCB peaks were observed and a total concentration of 850 ppm including 170 ppm of Co-PCBs was obtained. The toxic equivalents (TEQs) of PCDDs, PCDFs, and Co-PCBs were calculated to be 17, 470, and 120 ppb, respectively. The relative contribution of these classes to the total TEQ in Yusho oil is 3%, 77%, and 20%, respectively, indicating that PCDFs play a major role in the toxicity of Yusho oil. Furthermore, it was confirmed that 2,3,4,7,8-penta-CDF contributes 58% to the total TEQ, supporting the view that this compound is the principal causal agent in Yusho poisoning. It is noteworthy that the most toxic 2,3,7,8-tetra-CDD was newly discovered, although it contributes only 0.1% to the total TEQ. Based on our data, the smallest TEQ intake during the latent period was estimated to be 0.067 mg for Yusho patients. This value is about 60% of that previously reported, suggesting a lower minimum threshold level for the development of the toxic symptoms of Yusho.     

Patterns of PCBs and PCDD/PCDFs in chicken and pork fat following a Belgian food contamination incident

A food contamination incident involving polychlorobiphenyls (PCBs) and PCDD/Fs occurred in 1999 in Belgium. On heavily affected farms, concentrations of PCBs in chicken or pork fat exceeded the Belgium tolerance limit of 200 ng/g lipid weight for the sum of seven marker PCBs. Analysis of contaminated samples showed that the patterns for PCB and PCDD/F congeners differed among feed, chicken fat and pork fat. Lower chlorinated PCBs and polychlorodibenzofurans (PCDFs) including those with high TEFs (PCBs 105, 118, 126 and 2,3,4,7,8-PeCDF) were shown to either bioaccumulate more in chicken fat or to be eliminated more readily in pork. This leads to the possibility that consumption of chicken would result in a higher TEQ human body burden than that from the same consumption of pork. In addition, PCDF congeners with non-2,3,7,8-substitution (e.g., 1,2,4,7,8-PeCDF) were present in chicken fat but absent in pork fat. Since the residue pattern in this commercial episode changes less in the avian species, these results reinforce the value of birds rather than mammals as markers of the source of contamination with persistent organochlorine pollutants.     

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.     

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.     

Levels of PCDDs, PCDFs, and PCBs in the blood of the non-occupationally exposed residents living in the vicinity of a chemical plant in the Czech Republic

In 2003, concentrations of altogether 17 PCDD/Fs congeners and 12 non-ortho and mono-ortho dioxin-like PCBs were measured in the blood of 60 randomly selected adults who lived in three settlements surrounding a chemical plant that had been producing chlorinated herbicides (mainly HCHs, HCB, pentachlorophenole, 2,4,5-T) in the 1960's; subjects consuming home-produced animal foods were chosen. Twenty blood donors with similar characteristics from the locality with about 80 km distance were used as control subjects. The factors that influenced the dioxin levels were investigated on the basis of a questionnaire. The aim of our study was to find out whether the residents living in the surroundings of the chemical plant are at a greater exposure risk than the controls. To calculate TEQ values, WHO-TEFs were used. The concentrations of four PCDD and six PCDF congeners were below the LOD in more than 50% of samples. Significantly higher WHO-TEQ levels (p<0.05) were found for PCDDs, PCDFs, or PCBs in all three followed up groups compared with controls. The geometric means of the total TEQ values for PCDD/F/PCBs were 43.8, 50.2, and 40.0 pg/g fat compared to 23.2 pg/g fat in the control. The percentages of TEQ due to the measured congeners in exposed groups were 9-10.3% for PCDDs, 20.5-26.9% for PCDFs, 19.2-23.1% for coplanar and 43.6-47.2% for mono-ortho PCBs. In control, the percentage of TEQ was 11.6, 26.7, 24.1, and 37.5%. PCBs, predominantly PCB156, followed by PCB126 contributed 60 to 70% of the total TEQ value. Positive correlation of the PCDD/PCDF/PCB blood levels with age and with consumption of locally produced eggs was found.     

Human biomonitoring of polychlorinated biphenyls and polychlorinated dibenzodioxins and dibenzofuranes in teachers working in a PCB-contaminated school

Eighteen teachers from a highly contaminated school and 11 teachers from a control school participated in this study. Total polychlorinated biphenyl (PCB) indoor air concentration (six indicator congeners x 5) was beyond 12000 ng/m3 in some rooms of the contaminated school. PCB 28 and PCB 52 were the prevailing congeners. Whole blood was taken from each participant by the local health authority, pooled in two groups and analysed for the six PCB indicator congeners, non-ortho PCBs and polychlorinated dibenzodioxins (PCDD)/polychlorinated dibenzofurans (PCDF). Blood analysis showed elevated mean PCB 28 and PCB 52 levels for the exposed group, however the two groups were almost identical with regard to PCB 101, 138, 153 and 180. Moreover no difference can be observed for the concentration of non-ortho PCBs and PCDD/PCDF. The data support the finding, that heavy indoor air contamination with low chlorinated PCBs causes an increase of PCB 28 and PCB 52 blood levels. However, this increment was small compared to their total PCB load.     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and non-ortho and mono-ortho polychlorinated biphenyls in blood of Yusho patients

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho polychlorinated biphenyls (non-ortho PCBs) and mono-ortho polychlorinated biphenyls (mono-ortho PCBs) in blood collected from 279 Yusho patients living in Japan, 92 Yusho-suspected persons living in Japan and 127 normal controls living in Fukuoka Prefecture, and compared among the groups in terms the concentrations of these compounds. The total toxic equivalents (TEQ) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in the bloods of Yusho patients and Yusho-suspected persons were 161.4 and 51.2 pg TEQ/g lipid, respectively and were about 3.5 and 1.1 times higher than those of normal controls, respectively. Although the TEQ concentrations of PCDDs, non-ortho PCBs, and mono-ortho PCBs among Yusho patients, Yusho-suspected persons and normal controls were nearly the same, the PCDFs levels of Yusho patients were significantly higher than those of Yusho-suspected persons and about 10.3 times higher than those of normal controls. In Yusho patients, PCDFs contributed about 65% to the total TEQ concentration. Among the PCDFs congeners for Yusho patients, the concentration of 2,3,4,7,8-pentachlorodibenzofuran (PeCDF) was about 11.3 times higher than that of normal controls. These findings indicated that Yusho patients even now, more than 34 years after the outbreak of Yusho, have much higher blood levels of 2,3,4,7,8-PeCDF in general than do unaffected persons.     

Analysis of polychlorodibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs) in baked-salt food additives in Korea

Thirty-one samples of baked-salt products used in commercial food additives were analyzed for the presence of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Dioxins were highly detected in 12 samples of baked salts. The amount of dioxins found in the samples ranged from 12.47 pg/g to 406.56 pg/g (0.71 pg TEQ/g to 23.51 pg TEQ/g, respectively). The most abundant congeners, as TEQ values, were 2,3,4,7,8-PeCDF; 1,2,3,7,8-PeCDF; and 1,2,3,4,7,8-HxCDF in PCDF congeners and 1,2,3,7,8-PeCDD; 1,2,3,6,7,8-HxCDD; and 1,2,3,7,8,9-HxCDD in PCDD congeners. Meanwhile, PCDDs/PCDFs were analyzed in high-temperature-treated samples of natural sea salt alone and natural sea salt to which di-(2-ethylhexyl)phthalate (DEHP) had been added. In the former case, PCDD/PCDF formation was most evident at temperatures near 450 degrees C, the total amount of dioxins was 90.07 pg/g (6.07 pg TEQ/g), and PCDD congeners comprised less than 50% of the total PCDDs/PCDFs. However, when the latter samples were heated, the total PCDD/PCDF concentration was 512.30 pg/g (21.53 pg TEQ/g), with PCDD congeners comprising over 87% of the total PCDDs/PCDFs.     

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.     

Fate of PCDF/PCB congeners and change of clinical symptoms in patients with Yusho PCB poisoning for 30 years

Two mass-food poisonings called Yusho and Yucheng occurred in Japan and Taiwan in 1968 and 1979, respectively. Blood samples from five Yusho patients and three Yucheng patients were collected several times from 1982 to 1998 and from 1980 to 1995, respectively, and analyzed for polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB) congeners. Fat base concentrations of 2,3,4,7,8-penta-CDF in the Yusho patients, which were responsible for about 70% of the dioxin toxicity, are estimated to be decreased from 60 ppb in 1969 to 800 ppt in 1997 with the median half-life of 2.9 years in the first 15 years after onset and 7.7 years in the next stage of 15 years. Typical Yusho symptoms of acneiform eruption, dermal pigmentation and increased eye discharge were very gradually recovered with lapse of several years. However, enzyme and/or hormone-mediated signs of high serum triglyceride, high serum thyroxin, immunoglobulin disorder and others are persistently maintained for 30 years.     

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.     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and polychlorinated biphenyls in blood and breast milk collected from pregnant women in Sapporo City, Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), and non-dioxin-like PCBs in paired samples of blood and breast milk collected from 67 secundiparas in Sapporo City, Japan, and combined this data with those of the 30 secundiparas previously measured. The arithmetic mean total toxic equivalents (TEQ-WHO) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the 97 secundiparous subjects were 3.0-23 (mean: 13, median: 14) and 2.7-20 (mean: 8.6, median: 8.5) pg TEQ g⁻¹ lipid, respectively. The sums of the concentrations of 56 non-dioxin-like PCB congeners that were measured in the subjects’ blood and breast milk were 16-326 (mean: 107, median: 100) and 12-252 (mean: 73, median: 67) ng g⁻¹ lipid, respectively. The partitioning ratios of individual congeners of PCDDs, PCDFs, dioxin-like PCBs, and non-dioxin-like PCBs from blood to breast milk in secundiparas were almost the same as those of primiparas that have been recently reported, suggesting that the partitioning ratios of these compounds from maternal blood to breast milk in women is little affected by delivery. Furthermore, the partition of PCB congeners with chlorine at the 2-, 3-, 4′-, and 5-positions or the 2-, 4-, 4′-, and 5-positions of the biphenyl ring from the blood to the breast milk tended to occur at a higher level than that of other congeners. In particular, the levels of tetraCB-74 and hexaCB-146 in the breast milk for both primiparous and secundiparous mothers were slightly higher than those in the blood.     

Concentrations of polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans,and polychlorinated biphenyls in blood and breast milk collected from pregnant women in Sapporo City,Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), and non-dioxin-like PCBs in paired samples of blood and breast milk collected from 67 secundiparas in Sapporo City, Japan, and combined this data with those of the 30 secundiparas previously measured. The arithmetic mean total toxic equivalents (TEQ-WHO) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the 97 secundiparous subjects were 3.0–23 (mean: 13, median: 14) and 2.7–20 (mean: 8.6, median: 8.5) pg TEQ g⁻¹ lipid, respectively. The sums of the concentrations of 56 non-dioxin-like PCB congeners that were measured in the subjects’ blood and breast milk were 16–326 (mean: 107, median: 100) and 12–252 (mean: 73, median: 67) ng g⁻¹ lipid, respectively. The partitioning ratios of individual congeners of PCDDs, PCDFs, dioxin-like PCBs, and non-dioxin-like PCBs from blood to breast milk in secundiparas were almost the same as those of primiparas that have been recently reported, suggesting that the partitioning ratios of these compounds from maternal blood to breast milk in women is little affected by delivery. Furthermore, the partition of PCB congeners with chlorine at the 2-, 3-, 4′-, and 5-positions or the 2-, 4-, 4′-, and 5-positions of the biphenyl ring from the blood to the breast milk tended to occur at a higher level than that of other congeners. In particular, the levels of tetraCB-74 and hexaCB-146 in the breast milk for both primiparous and secundiparous mothers were slightly higher than those in the blood.     

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.     

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.     

Mechanism of the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans from chlorophenols in gas phase reactions

The pyrolysis of chlorinated phenates at a temperature of about 280 degrees C results in the formation of definite chlorinated dibenzodioxin (PCDD) congeners [1-3]. It is shown that in gas phase reactions chlorophenols react in the presence of oxygen above 340 degrees C not only to PCDD but also to chlorinated dibenzofurans (PCDF). The mechanism of this reaction of chlorophenols to PCDD and PCDF was elucidated. In a first step phenoxyradicals are formed which are capable of forming PCDDs and PCDFs. This is confirmed by the oxygen dependency of the reaction. In an argon atmosphere no dimerization of chlorophenols could be observed at 420 degrees C. By the identification of intermediates and by analyzing the PCDF isomers formed from individual chlorophenols the reaction pathway is elucidated. As intermediates in the formation of PCDFs polychlorinated dihydroxybiphenyls (DOHB) were identified. These are most likely formed by the dimerization of two phenoxy radicals at the hydrogen substituted carbons in ortho-positions under simultaneous movement of the hydrogen atoms to the phenolic oxygen PCDDs are formed in the gas phase via ortho-phenoxyphenols (POP) analogous to the pyrolysis of phenates, but due to the radical mechanism in the first condensation step to POPs not only a chlorine atom is capable for substitution but also the hydrogen atoms. The formation of the DOHBs and their condensation to PCDFs and hydroxylated PCDFs as well as the ratio of PCDD to PCDF formed show a strong dependency on the reaction temperature, the substitution pattern of the chlorophenols and the oxygen concentration.