Systematic analysis and overall toxicity evaluation of dioxins and hexachlorobenzene in human milk

A systematic method for analyzing dioxins (PCDDs, PCDFs and dioxin-like PCBs), hexachlorobenzene (HCB), heptachlor epoxide and beta-hexachlorocyclohexane (HCH) in human milk was developed to determine the residual amount of HCB in human milk and to evaluate the overall toxicity of both dioxins and HCB in human milk. The fractionation behavior of HCB on chromatography with silica gel, alumina, and activated carbon/silica gel, and the concentrated sulfuric acid decomposition method, which is widely used as a dioxin cleanup method, were studied in order to make the preprocessing operation for HCB measurement compatible with that for conventional dioxin measurement. HCB was found to be eluted in the 2% dichloromethane (DCM)/hexane 60 ml fraction from an alumina column. Heptachlor epoxide and a part of beta-HCH were eluted in the 10% DCM/hexane 50 ml fraction from a silica gel column, while the remaining beta-HCH was eluted in the 25% DCM/hexane 60 ml fraction from an activated carbon/silica gel column. Moreover, HCB showed significant correlation with dioxin congeners having high toxicity equivalence factors (TEFs). The results suggest that the exposure route to HCB and its accumulation behavior in the human body are similar to those of the dioxins.     

Residues of dioxins and PCBs in fat of growing pigs and broilers fed contaminated feed

To investigate the kinetics of PCBs and dioxins, 3 week old broilers and 3 month old pigs were fed with a 10-fold diluted feed from the Belgium crisis for one week, followed by a period on clean feed. In the case of broilers this resulted in levels for dioxins, non-ortho and mono-ortho PCBs in fat of 102, 84 and 216 ng TEQ/kg, summarized to 402 ng TEQ/kg. Total levels decreased to 217 and 109 ng TEQ/kg after 1 and 3 weeks on clean feed. Indicator PCB levels decreased from an initial 6.2 mg/kg fat to respectively 3.2 and 1.5 mg/kg. The ratio of indicator PCBs to dioxins TEQs was stable over this period. Levels in back fat of pigs at the end of the exposure period were 26, 15, 82 and 123 ng TEQ/kg for respectively dioxins, non-ortho PCBs, mono-ortho PCBs and the sum. Total TEQ levels decreased to respectively 95, 70, 40, 22 and 12 ng TEQ/kg after 1, 2, 4, 8 or 12 weeks on clean feed. After 12 weeks dioxin levels were around 1 ng TEQ/kg. Indicator PCB levels decreased from 3.48 mg/kg to 2.65, 2.01, 1.25, 0.76 and 0.45 mg/kg fat, again after 1, 2, 4, 8 or 12 weeks on clean feed. Levels of dioxins decreased more rapidly than those of indicator PCBs, also reflected by the ratio of indicator PCBs to dioxins, being 133,000 at the end of the exposure period and 357,000 after week 12. It is concluded that the use of indicator PCBs for dioxins, in the case of a combined exposure, is a safe alternative for screening and in the case of pigs results in an overestimation rather than underestimation of the dioxin levels.     

Estimation of 1999-2004 dietary daily intake of PCDDs, PCDFs and dioxin-like PCBs by a total diet study in metropolitan Tokyo, Japan

A study of the dietary intake of dioxins, consisting of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) through foods retailed in the metropolitan Tokyo area from 1999 to 2004 was carried out by the total diet-market basket method on the basis of food classification (14 groups) and the data on food consumption in the Tokyo region obtained from the Japan Nutrition Survey. The daily intake of dioxins per kg of body weight for a 50 kg average adult body was 2.18 pg TEQ/kg/day in 1999, 1.87 pg TEQ/kg/day in 2000, 1.25 pg TEQ/kg/day in 2001, 1.60 pg TEQ/kg/day in 2002 and 2003 and 1.55 pg TEQ/kg/day in 2004, respectively. These amounts were less than the tolerable daily intake (TDI) of 4 pg TEQ/kg/day for dioxins established in Japan. The dioxins taken daily through fish and shellfish (group 10) accounted for more than 50% of sum WHO-TEQs. In addition, more than 90% of the daily intake of dioxins was taken through fish and shellfish (group 10), meat and eggs (group 11), milk and dairy products (group 12). Also, this study clearly showed that the ratio of dioxin-like PCBs in the daily intake of dioxins was increasing yearly because the reduction rate of dioxin-like PCBs was lower than that of PCDDs and PCDFs in foods.     

Immunologic effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides in Japanese infants

Effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides on lymphocyte subsets were investigated in the peripheral blood from 101 Japanese infants with approximately 10 months of age. Perinatal exposure to these organochlorine compounds were estimated by their contamination levels in the breast milk of the mothers. Lymphocyte subsets such as CD16+, HLA-DR+, CD4+, CD4+8+, CD8+, CD3+ and CD20+ cells in peripheral venous blood were assessed in a subgroup of 92 infants. Greater exposures to HCE, chlordane and dioxins were significantly associated with the increase in the percentages of CD8+ and CD3+ T lymphocytes and CD4+/CD8+ T cell ratios, respectively. In addition, higher HCH exposure was also associated with a decrease in the percentage of HLA-DR+ T lymphocytes. Furthermore effects of dioxins, DDT and PCBs on the percentage of CD16+ T lymphocyte were more pronounced by the combined exposure of dioxins and PCBs or by the combined exposure of DDT and PCBs. Effects of HCE on the percentages of CD8+ T lymphocyte were also more pronounced by the combined exposure of HCE and chlordane. In conclusion, our study suggests that greater exposures to dioxins, PCBs and organochlorine pesticides determined in this study (except dieldrin) influence the immune system of Japanese infant, although the clinical significance of these changes is uncertain.     

Combined approaches to determine the impact of wood fire on PCDD/F and PCB contamination of the environment: a case study

Fires might be the source of persistent organic pollutants (POPs) such as dioxins, furans (PCDD/Fs) and/or polychlorobiphenyls (PCBs) in the environment. In the perspective of defining legal responsibilities a thorough characterization of the impact of such an event should be carried out. However, such characterization is not easy as the environment integrates both local and diffuse sources of such molecules. Thus, a combined approach, which includes gathering field surveys, modeling and laboratory experiments, should be conducted. The objective of this work is to illustrate different approaches to give sufficient insight to determine the actual impact of wood fire on the environment. The work was carried out at the vicinity of a burnt down parcel. The fired material was a mixture of wood and PCB-contaminated soils as the site was a former pyralene-disposal site. Modeling, soil and lichen sampling and experimental combustion were carried out to delineate the contamination for each chemical and to define the area within the fire that was responsible for the environmental contamination. Concentrations of PCDD/F and PCBs were very high on the burnt plot. The combined approach determined that the furans were the predominant compounds in the smoke emitted by the fire. Based on this tracer, it was possible to demonstrate that in terms of environmental contamination of PCDD/F, the impact of the fire was restricted to a 2 km radius from the burnt down plot. For PCBs, no specific tracer was identified. In this case, the delineation of the impact could only be empirical, based on the total concentration of the chemicals.     

Concentration of Organochlorine Pollutants in Surface Waters of the Central European Biosphere Reserve Krivoklatsko (8 pp)

Background, Aim and Scope The article is focused on dioxin, furan, PCB and organochlorine pesticide monitoring in the surface waters of the Central European, protected natural reserve Krivoklatsko, under the UNESCO programme Man and Biosphere. Persistent compounds are presently transported via different means throughout the entire world. This contamination varies significantly between sites. This raises the question of what constitutes the naturally occurring background levels of POPs in natural, unpolluted areas, but which are close to industrialised regions. Information of real background POP contamination can be of high value for risk assessment management of those sites evidently polluted and for the defining of de-contamination limits. Preserved areas should not be seen as isolated regions in which the impacts of human activities and natural factors are either unexpected or overlooked. Every ambient region, even those protected by a law or other means, are still closely connected to neighbouring human developed and impacted areas, and are therefore subject to this anthropogenic contamination. These areas adjacent to natural reserves are sources of diverse substances, via entry of air, water, soil and/or biota. After an extended period of industrial activities, organochlorine pollutants, even those emitted in trace concentrations have reached detectable levels. For future research and for the assessment of environmental changes, present levels of contamination would be of high importance. This work publishes data of the contamination with organochlorine pollutants of this natural region, where biodiversity and ecological functions are of the highest order. Materials and Methods: Semipermeable membrane devices (SPMDs) were utilised as the sampling system. SPMDs were deployed in two small creeks and one water reservoir selected in the central part of the Krivoklatsko Natural Reserve, where it could be expected that any possible contamination by POPs would be lowest. The exposed SPMDs were analysed both for chemical contents of POPs and for toxicity properties. The chemical analyses of dibenzo-dioxins, dibenzo-furans, PCBs and OCPs were analysed by GC/MS/MS on GCQ or PolarisQ (Thermoquest). Toxicity bioassays were performed on the alga Desmodesmus subspicatus, bacteria Vibrio fischeri and crustacean Daphnia magna. All toxicity data were expressed as the effective volume Vtox. Vtox is a toxicity parameter, the determination of which is independent of SPMD deployment time and pre-treatment dilution (unlike, for example, the EC50 of the SPMD extract). Results: The following chemical parameters were monitored: 1) tetra, penta, hexa and hepta dibenzo-p-dioxins and furans; 2) all those detectable from tri- through deca-polychloriated biphenyls (PCBs) and 3) a group of organochlorine pesticides: hexachlorobenzene and isomers of hexachlorocyclohexane, DDE, DDD and DDT. The concentrations of dioxins and furans on the assessed sites varied from under detection levels up to 7 pg.l-1; PCBs were detected in a sum concentration up to 2.8 ng.l-1; and organochlorine pesticides up to 346 pg.l-1. The responses of bioassays used were very low, with the values obtained for Vtox being under 0.03 l/d. Discussion: Toxicity testing showed no toxicity responses, demonstrating that the system used is in coherence with the ecological status of the assessed sites. Values of Vtox were under the critical value – showing no toxicity. The PCA of chemical analysis data and toxicity responses resulted in no correlations between these two groups of parameters. This demonstrated that the present level of contamination has had no direct adverse effects on the biota. Conclusions: The concentration values of six EPA-listed, toxic dioxins and sums of tetra-hepta dioxins; nine EPA toxic dibenzofurans and the sums of tetra-hepta bibenzofurans are presented together with all tri-deka PCBs and organochlorine pesticides (alfa-, beta-, gama-, delta-HCH, HCB, opDDE, ppDDE, opDDD, ppDDD, opDDT, ppDDT). These values represent possible current regional natural background values of these substances monitored within the Central European region, with no recorded adverse effects on the freshwater ecosystem (up until the present time). Recommendations and Perspectives: Assessment of dioxins, furans and other organochlorine compounds within natural reserves can be important for the monitoring of human-induced impacts on preserved areas. No systematic monitoring of these substances in areas not directly affected by industry has generally been realised. There is a paucity of data of the presence of any of these substances within natural regions. Further monitoring of contamination of both soil and biota by dioxins and furans in preserve regions is needed and can be used for future monitoring of man-made activities and/or accidents. Semipermeable membrane devices proved to be a very good sampling system for the monitoring of trace concentrations of ambient organochlorine compounds. Toxicity evaluation using the Vtox concept demonstrated that those localities assessed expressed no toxicity.     

Changes in Chlorinated Organic Pollutants and Heavy Metal Content of Sediments during Pyrolysis (7 pp)

Background There has been an increasing concern about the treatment and disposal of contaminated sediment from dredged river, harbor or estuary due to the accumulated toxic organics such as dioxins and inorganics particularly heavy metals like Cr, Pb, Zn, Cu, Hg and Cd. However, considering the huge amount of materials and financial costs involved, any candidate technology must ultimately result to reusable residual by-products. This can only be made possible if the toxic pollutants are removed or stabilized in the raw sediment and then fed back into the materials cycle. Currently, we are developing a pyrolysis process for the commercial-scale cleanup of dioxins and heavy metal-contaminated river sediment to yield reusable char for various economical applications. In this connection, this paper describes our preliminary investigation into the extent of dioxins and heavy metal volatilization from actual contaminated sediment. The stabilization of certain metallic species particularly Cr ions was studied. Methods Laboratory scale pyrolysis experiments were conducted using a special horizontal lab-scale pyrolyzer. Sediment samples from Shanghai Suzhou Creek and Tagonoura Harbor were pyrolyzed in the reactor under nitrogen gas at 800°C and different retention times of 30, 60 and 90 min. A constant heating rate of 10°C min-1 was employed. The pyrolysis gas was first allowed to pass through a cold trap to condense the tar. Uncondensed gases were then channeled through a column containing an adsorbent (XAD-2 Resin) for dioxins. Heavy metal concentrations in the initial and final sediment residues were analyzed by ICP (Nippon Jarrel-Ash) following their acid and alkali (for Cr6+) digestion. Dioxins content of the pyrolysis char, tar, and exhaust gases in the dioxin adsorbent were also determined. For comparative purpose, thermal treatment under air flow was conducted. Results The data for the removal of heavy metals from Suzhou Creek sediment showed very significant reductions in Pb, Zn and Cr6+ content of the sediment at this condition. Percentage removals were 42.4%, 60.8% and 42.2%, respectively. The disappearance of Cr6+ was due to reduction reactions rather than volatilization since the total Cr content remained almost unchanged. Other heavy metals such as Cu, Fe and Ni showed very minimal reductions. Nonetheless, Toxicity Characteristics Leaching Procedure (TCLP) tests confirmed that these residual heavy metals were rather stable in the pyrolysis char. Reduction of toxic Cr6+ at 42.2% has also been achieved by pyrolysis (with N2) as opposed to the more than 580 % increase in Cr6+ observed during thermal oxidation (with air). Discussion Pyrolysis also remove toxic organics particularly dioxins from the sediment. For the total dioxins, removal percentage of 99.9999% was achieved even at the lowest retention time of 30 min. Almost all polychlorinated dibenzo-p-dioxine (PCDDs) and polychlorinated dibenzo-furans (PCDFs) were removed at any retention time. The TEQs detected from the solid residues were mainly contributed by dioxin-like PCBs, yet these were present in relatively trace quantities. At the shortest retention time of 30 min, only 0.000085 pg-TEQ g-1 of polychlorinated biphenyls (PCBs) was detected in the pyrolysis char. Furthermore, the residual PCBs have very low toxicity ratings and none of the highly toxic PCBs, which were initially present in the sediment such as 3,3',4,4',5-PeCB and 3,3',4,4'5,5'-HxCB, were detected in the char. Results further confirmed that most of the dioxins that were removed were transferred to the gas phase so that volatilization may be considered as the main mechanism for their removal. Conclusion Some heavy metals particularly Pb and Zn can be volatilized under N2 pyrolysis at 800oC. Pyrolysis also prevented the formation of more toxic Cr6+ ions and at the same time resulted to its reduction by around 42.2% contrast to the 580% increase during thermal oxidation. PCDDs and PCDFs have been removed and were not formed in the solid products over the retention time range of 30-90 min at 800°C. Dioxin-like PCBs mostly remained and a retention time of 30 min was found sufficient for its maximum removal. Recommendations and Perspective . With the above results, a temperature of 800oC at a retention time of 30 min is sufficient for the removal of total dioxins and some heavy metals by volatilization. It is however necessary to destroy the dioxins as well as recover heavy metals in the gas phase. Stability of remaining heavy metals in the char also needs to be confirmed by leaching tests. These are the major concerns, which we are currently evaluating to establish the feasibility of our proposed large scale pyrolysis system for sediment treatment.     

Measurements of selected PCBs in open urban ambient air of Madrid (Spain)

The focus of this study was to characterize the concentration levels of selected PCBs and compare them to compiled data in order to contribute to the international database. The sampling site is located in the outskirts of Madrid and can be considered an open urban area. 32 samples of air were taken from February 1998 to June 1998 by using a high volume air sampler. Glass fiber filters and polyurethane foam (PUF) were used to collect the paniculate and gas phase material, respectively. PUF plugs were Soxhlet extracted and filters were ultrasonically extracted by using pesticide-grade hexane and dichloromethane, respectively. The cleanup procedure was carried out on a florisil column with hexane and hexane/dichloromethane as elution solvents. GC/MS in a selected ion monitoring mode was used for quantification and 29 selected PCBs congeners were analyzed.     

Polychlorinated biphenyl, polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran residues in sediments and fish of the River Nile in the Cairo region

The levels of organohalogenated contaminants, i.e. PCBs, PCDDs and PCDFs were determined in sediment and fish samples collected from different locations in the River Nile, Egypt. Thirty-six sediment and eighteen fish samples were carried out during a period of 12 months from February 2003 to February 2004. Determination of PCBs and dioxins was carried out using a high resolution GC mass spectrometer. The results indicated that the PCB and PCDD/F mean concentrations in sediment samples ranged from 1461 to 2244 and from 240 to 775pgg(-1) dry wt basis, respectively. The mean concentration of PCBs and PCDD/Fs in fish samples were found to be in the range from 695 to 853pgg(-1) fresh wt for PCB congeners and from 27.7 to 121pgg(-1) lipid for total PCDD/Fs. Moreover, the concentrations of both PCBs and PCDD/Fs were found to be different at different locations along the River Nile. It could be concluded that the contamination of the River Nile is within the permissible limits set by the FDA and the Egyptian Standards for fish and shellfish.     

Human milk survey for dioxins in the general population in Japan

BACKGROUND: Much attention has been paid to the level of dioxins in breast milk in Japan but few large-scale studies have been conducted on the subject. METHODS: From 1997 to 2002, we collected 839 samples of breast milk from primiparas residing throughout Japan. Starting in 1999, breast milk was also collected from secundiparas. Seven isomers of polychlorinated dibenzo-p-dioxins (PCDDs), 10 of polychlorinated dibenzofurans (PCDFs), 4 of coplanar polychlorinated biphenyls (Co-PCBs) and 8 of mono-orthochlorinated polychlorinated biphenyls (mono-ortho PCBs) were analyzed by employing gas chromatography and mass spectrometry. A correlation between the level of dioxins in human milk and the age of the mothers was noted for the primiparas and the secundiparas; and the levels were compared between the first and the second deliveries. Grouped by parity and prefecture in each year, observations were also made on the trends in these levels. Dioxin levels are shown by using geometric means because their distributions were skewed to the left. RESULTS: The sum of PCDDs and PCDFs, Co-PCBs, mono-ortho PCBs, and total dioxins in the breast milk of primiparas were 13.9, 5.4, 3.4, and 22.7 pg TEQ/g fat, respectively. In the samples obtained from secundiparas, these levels were 63-68 percents of those taken from the primiparas. The correlation coefficients between the PCDDs/DFs, Co-PCBs, mono-ortho PCBs, and total dioxins and the age of the primiparas were 0.19, 0.17, 0.36, and 0.24, respectively. All these correlations were statistically significant (p < 0.001). The positive correlations between these contaminants and the age of the secundiparas were also examined. The total dioxins as well as PCDDs/DFs, Co-PCBs, and mono-ortho PCBs in the breast milk of the primiparas declined significantly between 1998 and 2002 (regression coefficients: -0.04, -0.05, -0.03, and -0.03, respectively). However, no significant decline in these levels was observed when sorted by prefectures. CONCLUSIONS: Much attention should be paid to the age and parity of nursing mothers when investigating the relationship between the level of dioxins in breast milk and the body burden of infants.     

Phytoremediation to increase the degradation of PCBs and PCDD/Fs

Phytoremediation is already regarded as an efficient technique to remove or degrade various pollutants in soils, water and sediments. However, hydrophobic organic molecules such as PAHs, PCBs and PCDD/Fs are much less responsive to bioremediation strategies than, for example, BTEX or LAS. PCDD/Fs and PCBs represent 3 prominent groups of persistent organic pollutants that share common chemical, toxicological and environmental properties. Their widespread presence in the environment may be explained by their chemical and biological stability. This review considers their fate and dissipation mechanisms. It is then possible to identify major sinks and to understand biological activities useful for remediation. Public health and economic priorities lead to the conclusion that alternative techniques to physical treatments are required. This review focuses on particular problems encountered in biodegradation and bioavailability of PCDD/Fs and PCBs. It highlights the potential and limitations of plants and micro-organisms as bioremediation agents and summarises how plants can be used to augment bacterial activity. Phytoremediation is shown to provide some new possibilities in reducing risks associated with dioxins and PCBs.     

Certification of a long-term sampling system for PCDFs and PCDDs in the flue gas from industrial facilities

AMESA (adsorption method for sampling of dioxins) is a fully automatic system for long term monitoring of dioxin emissions from industrial processes based on the adsorption method. The system has been tested and undergoing a certification procedure according to the German guidelines for certification of systems for continuous monitoring of special substances. The certification covered parameters such as disposability of the system, reproducibility of the results and comparability of the sampling method with German and European standard methods. Furthermore break through, blanks and sample storability were investigated. The results prove that AMESA is a state of the art sampling system for continuous monitoring of dioxin/furan emissions.     

Determination of PCBs, PCDDs and PCDFs in insulating oil samples from stored Chinese electrical capacitors by HRGC/HRMS

Homologue and congener profiles of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in commercial PCBs formulations are key information for the source identification of PCBs contamination as well as for the risk assessment caused by potential exposure. The isotope dilution technology in combination with high resolution gas chromatography-high resolution mass spectrometry (HRGC/HRMS) has made the accurate determination of such profiles possible. So far, various commercial PCB formulations except Chinese products have been successfully determined. Two PCBs containing insulating oil samples from stored Chinese electrical capacitors have been determined with the same methodology for comparability. The total concentration PCBs in two oil samples were 790 000 μg g⁻¹ and 720 000 μg g⁻¹, respectively. TriCBs, TetraCBs, and DiCBs were found to be most abundant. Concentration of dioxins contamination in two samples is 650-670 ngTEQ g⁻¹, of which 69-71 ngTEQ g⁻¹ from PCDD/Fs with the predominant congeners of 1,2,7,8-TeCDF; 2,3,7,8-TeCDF; 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDF. The contributions of DL-PCBs in total TEQ in both samples were more than 85%. The dioxin-like toxicity in insulating oils contained in electrical capacitors could be considered receive attention as an important dioxins source if such wastes are not managed in an environmentally sound manner.     

Estimation of effects of dioxins and dioxin-like PCBs on wildlife population--a case study on common cormorant

We presented a method for quantitatively evaluating the effects of chemical pollutants in the environment on a wildlife population. We expressed the effects of exposure to dioxins and dioxin-like PCBs in Tokyo Bay sediment on a common cormorant (Phalacrocorax carbo) population in two ways. One was the changes in the intrinsic growth rate, and the other was the changes in the gross population size. The effects of exposure to the compounds were estimated by using the method of population ecology and available field data. Common cormorant population at Shinobazu Pond in Tokyo, Japan during 1974-1986 was selected as the target population. Intrinsic growth rate or gross size of the population based on the calculated residual level of dioxins and dioxin-like PCBs in the period was estimated to decrease to 89% or 85% of that without exposure to the compounds, respectively.     

Risk assessment of dioxins and dioxin-like PCBs in food--comments by the German Federal Environmental Agency

Human health risk assessments for dioxins and dioxin-like PCBs (with the exception of the one by US-EPA) recommend health based exposure limits within the range of 1-4 pg WHO-TEQ/kg bw per day. As all humans are exposed to measurable levels of dioxins and related substances, the determination of the tolerated daily intake is a very significant decision and may influence limit values guiding risk reduction measures and target levels. The proposed TDI has to protect all human subpopulations. In the case of dioxin this is particularly important as the exposure of infants through breast-feeding may exceed the exposure of adults by one or two orders of magnitude. An overview of recently recommended limit values (WHO, SCF, JECFA) for PCDDs, PCDFs and dioxin-like PCBs using WHO-TEFs shows the common feature that the values were derived only from non carcinogenic endpoints. In November 2000 the Scientific Committee on Food of the European Commission published an 'Opinion of the SCF on the Risk Assessment of Dioxins and Dioxin-like PCBs in Food' [SCF, Scientific Committee on Food 2000. Opinion of the SCF on the risk assessment of dioxins and dioxin-like PCBs in food. European Commission, Brussels, Adopted on November 2000 http://europa.eu.int/comm/food/fs/sc/scf/out78_en.pdf]. On the basis of this extensive review of data and experimental results the Committee recommended a temporary tolerable weekly intake (t-TWI) of 7 pg WHO-TEQ/kg bw. Only six months later the SCF carried out a re-evaluation of its t-TWI from November 2000. The reconsideration of 'pivotal studies' led to the situation that the re-assessment is now based only on rat studies which investigated only reproductive effects only on male offspring and, in addition, three of these studies are single dose studies at gestational day 15. Applying an overall uncertainty factor of 10 to the LOAEL derived estimated human daily intakes (EHDI) the SCF concluded that 14 pg/kg bw per week should be considered as a tolerable intake for 2,3,7,8-TCDD. The SCF stated that on a body weight basis, the dioxin intake of breast-fed infants has been estimated to be one to two orders of magnitude higher than the average adult intake. Recent German data suggest that the body burden of formerly breast-fed children aged 9-11 is still about 30% higher than those of their formula-fed age-mates. As breast-feeding has measurable benefits for neurological and immunological development, formula feeding cannot be recommended as an alternative to lower dioxin intake. So the only remaining way to lower the dioxin uptake is to drastically reduce the background exposure of the general population. It is acknowledged that any recommendation of a precise number for a TDI is flawed by uncertainties and the possibility of different weight being given to the studies of relevance. The determination of the TDI has influence on all regulatory limit values that are based on the TDI value. A higher TDI lowers the level of protection for humans. It is proposed by the German Federal Environmental Agency that the TDI should be reassessed in a process transparent to the public and on the basis of all relevant endpoints from animal experiments and human epidemiology, including the assessment of cancer risks.     

Dioxins, dioxin-like PCBs and chloroorganic contaminants in herring, Clupea harengus, from different fishing grounds of the Baltic Sea

The contaminant levels of dioxins, dioxin-like PCBs and a range of chloroorganic compounds have been determined in relation to various fishing grounds of the Baltic Sea. Sampling covered an area from the Skagerrak to the coast of Latvia. The data are compared with herring from fishing grounds in the North Sea and west of the British Isles. Also the temporal trend of the dioxin levels in the edible part of herring landed around the Island of Rügen is given from commercial samples collected between 1996 and 2004. A continuous increase of the dioxin concentrations was observed from west to east. Lowest concentrations of 0.199 ng WHO-PCDD/F-TEQ kg(-1)wet weight were found in herring fillets west of the British Isles. Highest level of 6.972 ng WHO-PCCD/F-TEQ kg(-1)w.w. was analysed in fillets off the coast of Latvia. Results showed also a spatial dependence of the WHO-TEQ ratio dioxins:dioxin-like PCBs and of the dioxin congener profile. Only the DDT group of various chloroorganic compounds determined, showed a dependence from the fishing ground. A clear temporal tendency could not be deduced from the data.     

PCBs, dioxins and furans in Hooded Merganser (Lophodytes cucullatus), Common Merganser (Mergus merganser) and mink (Mustela vison) collected along the St. Maurice River near La Tuque, Quebec

A pulp and paper mill located in La Tuque on the St.Maurice River, Quebec, and using the kraft bleaching process was historically the largest pulp and paper industry point source of chlorinated dibenzo-p-dioxins and dibenzofurans in Quebec. A study was undertaken to document the bioaccumulation of PCBs, dioxins and furans in piscivorous birds and mammals in this area. Hooded and Common Merganser eggs were collected in nest boxes along the St.Maurice River and Common Merganser fledglings were collected at two sites on the river. Wild minks were trapped along the St.Maurice River and in a control area upstream. Analysis of pooled merganser eggs showed contamination with dioxins, furans and PCBs. Liver samples of fledglings were contaminated with 2,3,7,8-tetrachlorodibenzofuran at the downstream site. Analysis of mink livers showed a significant higher contamination with dioxins and furans in some downstream samples compared with the upstream samples.     

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.     

Modified clean-up for PBDD,PBDF and PBDE with an active carbon column--its application to sediments

A clean-up method for polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs) and diphenyl ethers (PBDEs) was modified using combinations of multi-layered silica gel, Florisil and active carbon columns. By using active carbon column chromatography in the final procedure, PBDEs were well separated from PBDD/Fs in an elution test with reference standards. We report the application of this method to sediment samples taken from industrialized areas in Japan. These sediments contained PBDEs ranging in concentration from 13 to 2394 pg/g, dry wt. PBDEs did not interfere with the quantification of PBDD/Fs. In addition, PBDEs found in the PBDD/F fraction did not interfere with the identification of PBDFs using the HRGC/HRMS separation method. Some 2,3,7,8-tetra- to hexabrominated dioxins and furans were also detected in the sediment samples.     

Assessment of the daily intake of 62 polychlorinated biphenyls from dietary exposure in South Korea

The dietary intake of polychlorinated biphenyls (PCBs) was estimated using the sum of 62 PCB congeners (∑₆₂PCBs), including seven indicator PCBs and 12 dioxin-like PCBs, in the South Korea. In this study, 200 individual food samples belonging to 40 different foodstuffs were investigated to estimate the distribution of PCB congeners in five sampling cities. PCB exposure was estimated using Korean dietary habits as established by the National Health and Nutrition Examination Survey (NHANES). The PCB concentrations in rice, the most frequently consumed food in Korea, was relatively low in whole food samples. The mean PCB levels measured in fish were the highest in this study, but each fish is consumed in relatively small amounts by the general population. Therefore, the daily dietary intake should also be considered with regard to human exposure to PCBs, especially with the consumption of contaminated foods. Dioxin-like PCB levels were also calculated using TEF values that were established in 2005. The average levels (pg TEQ/g) were 0.0002 for rice and 0.0098 for fish. The dioxin-like PCBs accounted for a relatively small percentage of the total PCBs, compared to previous studies. According to our research, the health risks associated with exposure to PCBs could be estimated using the tolerable daily intake (TDI) of the general population.