Retention time profiling of all 136 tetra- through octa- chlorinated dibenzo-p-dioxins and dibenzofurans on a variety of Si-Arylene gas chromatographic stationary phases

The applicability of three different Silphenylene Silicone co-polymer (Si-Arylene) GC stationary phases (J&W Scientific DB-5ms, Varian VF-5ms, and VF-Xms) has been evaluated for the separation of all 136 tetra- through the octa- chlorinated dibenzo-p-dioxins (PCDD) and chlorinated dibenzofurans (PCDF) from closely eluting isomers using gas chromatography/high resolution mass spectrometry (GC/HRMS). Their relative performance data are compared to the “conventional” 5% diphenyl 95% dimethylpolysiloxane GC column (Supelco Equity-5) and to each other based on absolute retention times, visualized mass chromatograms, and the separation of 2,3,7,8-substituted isomers. VF-Xms GC column was able to demonstrate a better performance towards separation of 2,3,7,8-substituted PCDD/PCDF compared to other Si-Arylene GC columns tested, where only 2,3,4,7,8-PnCDF can not be resolved from 1,2,3,6,9-PnCDF and 2,3,4,6,7,8-/1,2,3,6,8,9-HxCDF and 1,2,3,7,8,9-/1,2,3,4,8,9-HxCDF can be at least partially resolved. These data suggest that the development of a single GC column for the separation of all 17 2,3,7,8-substituted dioxins and furans is feasible, which therefore could be used as a standard tool for the PCDD/PCDF methods globally including USEPA methods 1613b, 8290A, 8280B, European Standard Method EN 1948, Canadian methods DFPCB-E3418, EPS 1/RM/19, Japanese methods JIS K0311 and JIS K0312. Having one specific GC column to separate all 2,3,7,8-substituted PCDD/PCDF will significantly improve the data quality, comparability by the various methods and assessment techniques while simultaneously leading to a more cost and time efficient operation.     

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.     

Development and validation of a method for analysis of "dioxin-like" PCBs in environmental samples from the steel industry

A method, previously used for determination of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), has been modified for quantitative analysis of "dioxin-like" polychlorobiphenyls (PCBs) in environmental samples from the steel industry. The existing sample clean-up procedure, involving liquid chromatography on multi-layered silica and Florisil columns, has been extended to include a third chromatography stage on a basic alumina stationary phase. The additional clean-up stage is required for PCB analysis in order to eliminate interferences from relatively large concentrations of saturated cyclic and aliphatic hydrocarbons. Samples were analysed for WHO-12 congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) and standard solutions of the method US EPA 1668A. Replicate analysis of method blanks revealed background contamination for PCBs 118, 105 and 77, which are generally abundant in ambient air. These contaminants were taken into account using a subtraction method. The entire procedure was validated by replicate analysis (N = 3) of a certified reference sediment. The RSD for each WHO-12 congener was below 15%, 13C12-labelled PCB internal standard recoveries were in the range 70-95%. A waste dust sample collected in the electrostatic precipitator of a UK sinter plant was analysed for determination of PCDD/Fs and WHO-12 PCBs and exhibited a PCDD/F I-TEQ of 148.5 +/- 21.2 ngkg(-1) and a WHO-TEQ of 7.2 +/- 1.5 ngkg(-1). WHO-12 congeners contributed only 4.6% to the overall TEQ and PCB 126 was the major congener contributing to the WHO-TEQ (96%). The contribution to the overall TEQ of the waste dust sample was mainly attributed to PCDF followed by PCDD, which accounted for 86.6% and 8.7% to the overall TEQ, respectively.     

Occurrence, possible sources, and temporal trends of polychlorinated dibenzo-p-dioxins and dibenzofurans in water and sediment from the lower Yangtze River basin, Jiangsu and Shanghai areas of Eastern China

The concentrations, compositional profiles, and possible sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) in water column and surface sediment samples from the lower reaches of the Yangtze River were investigated, and the potential risks posed by these chemicals were evaluated. Concentrations of the 17 2,3,7,8-substituted PCDD/PCDF in the water and sediment samples ranged from 0.45 to 10.0 pg TEQ/L (mean 2.34 pg TEQ/L) and from 0.31 to 51 pg TEQ/g dw (mean 5.25 pg TEQ/g dw), respectively. Water and sediments from the Nanjing–Nantong sections of the Yangtze River were found to have elevated PCDD/PCDF levels, and the PCDD/PCDF TEQ concentrations in 13 sediment samples exceeded the probable effect levels (PEL), above which adverse biological effects are likely. Multivariate statistical analysis indicated that the principal PCDD/PCDF contamination source for the water and sediment was the production and use of pentachlorophenol (PCP) or sodium pentachlorophenate (PCP-Na). PCDD/PCDF concentrations were stable over time near the Yangtze River Estuary but had increased sharply in recent decades in the Nanjing–Nantong section, which will have been related to the growth in industrial activities and other anthropogenic PCDD/PCDF sources. Total organic carbon (TOC) and PCDD/PCDF concentrations correlated significantly (R?=?0.474, P?<?0.01), suggesting that TOC plays an important role in the transport and re-distribution of PCDD/PCDF in the Yangtze River basin.     

A comprehensive pollution survey of polychlorinated dibenzo-p-dioxins and dibenzofurans by means of principal component analysis and partial least squares regression

The combined use of principal component analysis and partial least squares regression to the interpretation of polychlorinated dibenzofuran (PCDF) and dibenzo-p-dioxin (PCDD) patterns in crabs are investigated. By exploratory principal component analysis, the PCDFs and the PCDDs are ranked according to their specificity to the emission source. Among the most specific PCDFs to the emission are the 12368/13479-PeCDF and 12478-PeCDF. The 123789-HxCDD isomer is the only specific PCDD to the emission source. Partial least squares regression is used both to explore the determination of sex specific isomers, and in confirmatory analysis by quantitatively relating the pollution waste to the distance from the emission source. 123678-HxCDF is statistically significant for the separation between male and female crabs collected at the same distance from the emission source, while no separation between male and female crabs is evident from 1234789-HpCDF, Octa-CDF, 2,3,7,8-TCDD and Octa-CDD. This observation is somewhat more shaded than what has previously been reported in the literature on differences in male and female crabs. A linear relationship exists between the logtransformed distance and the concentration of PCDFs and PCDDs in male crabs collected between 18 and 33 km from the source. This model underestimates the predicted distance of crabs collected between 33 and 56 km, possible due to a higher sedimentation rate at distances closer to the fjord and the factory.

Although applied to PCDF/PCDD data in this case, the outlined multivariate methods should be applicable to all kind of similar environmental surveys.     

A simplified clean-up procedure for the rapid determination of PCDDs and PCDFs based on retention on activated carbon AX-21

Different 2,3,7,8-substituted polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) were investigated for their retention behaviour on a disposable minicolumn containing activated carbon AX-21. Elution behaviour and recovery were examined, using native and radiolabelled PCDD and PCDF isomers.

A comparison of the total mass chromatograms of PCDDs and PCDFs in an extract from animal adipose tissue, before and after activated carbon treatment, demonstrates the efficiency of this cleanup step with respect to the elimination of interfering compounds.     

Chlorinated dibenzo-p-dioxin and dibenzofuran levels in human adipose tissue and milk samples from the north and south of Vietnam

Although 2,3,7,8-TCDD has been found to be extremely toxic to a variety of laboratory aminals, human epidemiology studies, where exposure to 2,3,7,8-TCDD has been less well characterized than in animal toxicologic studies, have been less conclusive in characterizing the extent of toxicity. In order to determine whether the newly refined techniques of human adipose tissue biopsy including isomer specific and sensitive measurement of PCDDs and PCDFs might be able to assist in finding populations within the same country with high and low levels of dioxins, adipose tissue samples were taken and levels analyzed from the north and south of Vietnam. It seemed reasonable, based on previous work, that high levels of 2,3,7,8-TCDD might still be found in adipose tissue in selected patients living in areas sprayed with Agent Orange and other 2,3,7,8-TCDD containing herbicides, and that lower levels should be found in patients not exposed to 2,3,7,8-TCDD from herbicides or other sources, such as persons who had always resided in the north of Vietnam. Of 9 specimens from patients hospitalized in Hanoi who had never been south, none had detectable adipose tissue levels of 2,3,7,8-TCDD at a detection limit of 2 or 3 ppt on a wet weight basis. Of 15 specimens from Ho Chi Minh City hospitalized patients the mean of positive specimens (12 of 15) was 28 on a lipid basis. The mean of the positive values from the south is about 2 to 3 times higher than found in the North American Continent control patients where the mean is about 6–10 ppt and much higher than in the north of Vietnam. In the northern specimens, the levels were non-detectable with a sensitivity of between 2 and 3 ppt. Other PCDD and PCDF isomers not found in Agent Orange, the penta- through octachlorinated dibenzo-dioxins and dibenzofurans, were similar in isomer type and quantity in the south of Vietnam to what we previously reported in North America. Adipose tissue from the north of Vietnam contained the lowest levels of four through eight chlorinated dioxins and furans thus far reported. The initial data suggests that populations exist in the south of Vietnam with elevated levels of 2,3,7,8-TCDD at the present time, fourteen years after the last known 2,3,7,8-TCDD (Agent Orange) application, superimposed on a preexisting body burden of dioxins and dibenzofurans from sources other than Agent Orange such as technical grade pentachlorophenol or products of incineration contaminated with higher chlorinated PCDDs or PCDFs. In light of the recent finding that unexpected levels of PCDDs and PCDFs exist in the general adult population of industrialized countries, ca. 1,000 to 1,200 ppt, wet weight of total dioxin and furan isomers in adipose tissues, it seems reasonable that the extent of human toxicity of dioxins may be more readily characterized in Vietnam than in industrialized countries. Because 2,3,7,8-TCDD was applied in 1962–1970, although not yet cleaned up, the levels of 2,3,7,8-TCDD in the environment, the food chain, and in humans, would be expected to decrease with time. Therefore, if studies are not initiated in a timely fashion, the opportunity to better characterize the extent of the toxicity of TCDD to humans as well as the persistence of TCDD in the environment in Vietnam may be lost.     

Levels of PCBs, PCDDs and PCDFs in commercial butter samples in Spain

Feasibility of three different extraction methods for the simultaneous determination of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in butter is discussed. The method based on liquid-liquid extraction with water of the non fatty solids from butter dissolved in hexane was found to be the most efficient for the determination of the lipid content and the levels of the investigated pollutants. This method was used to evaluate the background levels of PCBs, PCDDs and PCDFs in butters commercially available in Spain. Broad ranges of PCB, specifically, PCDD and PCDF concentrations were found in the different brands analysed. Levels, profiles and patterns of these pollutants in butter were compared with those previously reported for different Spanish dairy products. The toxic tetra-equivalents of 2,3,7,8-TCDD (1-TEQ) averages for PCDDs and PCDFs in the 21 butter samples analysed were 0.41 and 0.70 pg/g fat basis, respectively. These values were similar or lower than those cited in the literature for other countries.     

Ambient air concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans in Ohio: Sources and health risk assessment

PCDD and PCDF were measured in air samples collected in Ohio in 1987. No 2,3,7,8-TCDD was detected in any of the samples with a detection limits of less than 240 fg/m³. Using a chemical mass balance model applied to PCDD/PCDF congener group profiles, major potential sources of these compounds to the atmosphere in Ohio were determined to be municipal solid waste combustion, and sewage sludge combustion. Cancer risk calculations for inhalation of PCDD/PCDF in ambient air in Ohio are approximately 10–6. Given the current knowledge of the health effects of exposure to PCDD/PCDF in air, there is no appreciable risk to public health for the levels of these compounds found in ambient air in Ohio.     

An evaluation of factors affecting alumina selectivity for the isomer specific determination of 2,3,7,8-tetrachlorodibenzodioxin

Fully activated basic alumina has previously been shown to have the ability to give quantitative separation of tetrachlorodibenzo-p-dioxins (TCDDs) from polychlorinated biphenyls (PCBs) using a 12% chloroform in hexane solution. Further separation of 2,3,7,8-TCDD from other tetra isomers can be accomplished by use of 100% n-butyl chloride, 15% methylene chloride in hexane or 40% chloroform in hexane. A more complete comparison of basic alumina with acidic and neutral alumina has now been carried out. Additionally, an evaluation of this procedure for use with the other 2,3,7,8- substituted furans and dioxins has been made. Lewis base oxygen sites of the dioxin and furan molecules were used to explain the interactions observed. The alumina surface is believed to provide randomly spaced aluminum sites which act as Lewis acids in the adsorption process.     

PCDD/F and PCB history in dated sediments of a rural lake

Concentrations of polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and biphenyls (PCB) were analysed from a sediment core, which had been sampled from a remote lake in Finland. The deepest subsamples were analysed from a depth of 4.0 m, and were more than 8000 years old. At the surface of the sediment core, low levels of industrial background contamination were detected. The sum of 2,3,7,8-substituted PCDD/Fs was 35 ng/kg d.w. (dry weight), or 1.2 ng/kg d.w. in WHO's toxicity equivalent, WHO-TEQ. The annual accumulation rate of 2,3,7,8-substituted PCDD/Fs was 1.26 ng m(-2) a(-1). Deeper in the core, PCDD/F concentrations ranged between 2.11 and 11.1 ng/kg d.w. (0.24 and 1.70 ng/kg d.w. WHO-TEQ) and the accumulation rate was 0.11 ng m(-2) a(-1). A characteristic PCDD/F congener profile was found in all pre-industrial sediment layers. The order of concentrations was OCDD > 1,2,3,4,6,7,8-HpCDD > 1,2,3,7,8,9-HxCDD > 1,2,3,4,7,8-HxCDD > 2,3,7,8-TCDD, and concentrations of 2,3,7,8-chlorinated dibenzofurans were below the detection limit. Similar congener profiles have previously been described in samples for which natural PCDD/F formation has been proposed. PCBs were present at low levels in all of the sediment samples. The sum of the PCB concentrations of the sediment subsamples ranged between 50 and 2540 ng/kg d.w., and the three predominant congeners in the core were PCBs 18, 52, and 110.     

The dioxin/POPs legacy of pesticide production in Hamburg: Part 2—waste deposits and remediation of Georgswerder landfill

α-HCH, β-HCH, and γ-HCH (lindane) were listed as persistent organic pollutants in the Stockholm Convention. Therefore, they need to be globally addressed including the wastes remaining from historic use and production. While at most lindane production sites the unintentionally produced 85 % HCH waste isomers have been deposited, at a former pesticide factory in Hamburg-Moorfleet HCH waste isomers have been recycled from 1953 to 1984 by thermal decomposition to chlorobenzenes and resulted in high polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran (PCDD/PCDF)-contaminated residues. The management of the PCDD/PCDF-contaminated waste from the former pesticide factory in Hamburg has been assessed and quantified. Based on past accredited PCDD/PCDF measurements, the registered 3,700 tonnes of disposed thermal HCH decomposition residue contained 333 to 854 kg of PCDD/PCDF toxicity equivalent (I-TEQ) in 53–102 tonnes total sum of PCDD/PCDF. The wastes have been deposited together with other wastes in landfills in Hamburg and other parts of Germany. For the Georgswerder landfill (Hamburg), where approximately 50 % of the PCDD/PCDF is disposed, current and previous situation and remediation activities are described. While PCDD/PCDF leaching from the landfill is controlled and incinerated, more water soluble organochlorines (vinyl chloride, cis-1,2-dichlorethene, chlorobenzenes) and benzene remain as a challenge for groundwater management. A comprehensive aftercare program has been established and will need to be operated by future generations including renewal of containment systems. Former lindane/HCH productions need—in addition to HCH deposits—to be assessed for possible recycling practice of HCH and related PCDD/PCDF-containing deposits. This could systematically be addressed within the Stockholm Convention implementation.     

Distributions of polyhalogenated compounds in Hudson River (New York, USA) fish in relation to human uses along the river

PCBs (as Aroclor concentrations) have been extensively examined in fish along the Hudson River, but other xenobiotic chemicals in fish have had limited assessment. This study determined concentrations and congener distributions of polybrominated diphenyl ethers (PBDEs), polybrominated and polychlorinated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs and PCDD/Fs), and polychlorinated biphenyls (PCBs) in smallmouth bass and striped bass taken from a 385 km reach of the Hudson River. Concentrations of PBDEs and PCBs in smallmouth bass, and PCBs in striped bass, were positively related to human uses of the compounds in the basin. Generally low levels of PCDD/Fs were found. One striped bass, however, contained elevated 2,3,7,8-TCDD, indicating exposure to a known source in the adjacent Newark Bay-Passaic River basin. PBDDs were generally below detection. PBDFs were present in four of 18 smallmouth bass, but were not detected in striped bass. Dioxin-like PCBs contribute most to 2,3,7,8-TCDD toxic equivalents in 29 of 30 samples.     

Concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans and non-ortho substituted biphenyls in polar bear milk from Svalbard (Norway)

Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and non-ortho substituted biphenyls (PCB, CB) were determined in 6 polar bear milk samples from Svalbard (Norway). For these compounds, no data for polar bears have been reported before from this region. Most of the PCDD/PCDF congeners were found at detectable levels. Concentrations expressed as 2,3,7,8-TCDD equivalents (Nordic model) were in the order of 1–3 pg/g⁻¹ fat (0.2–1.6 pg ml⁻¹ milk) which is comparable with ringed and harp seal blubber from the same region. On whole milk basis, concentrations were similar to those found in human milk. An estimation of the daily uptake via milk showed that the intake is lower for polar bears compared to humans. As in human milk, relatively high levels of OCDD were found in some polar bear milk samples. The PCDD/PCDF congener pattern in the milk was different to that found in polar bear fat from the Canadian Arctic. Non-ortho substituted PCB levels in polar bear milk were similar to those found in polar bear fat from the Canadian North. However, CB 77 or 169 dominated in the milk while CB 126 was the most abundant congener in fat. PCDD/PCDF levels expressed as 2,3,7,8-TE were highly correlated with the fat content of the milk. No correlation between CB and PCDD/PCDF concentrations was found. Some data indicate that PCDD/PCDF concentrations in polar bear milk decrease with increasing time after delivery.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in eggs of eight avian species from Dongting Lake, China

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in eggs of eight avian species collected from Dongting Lake of China to assess residue levels, accumulation patterns, and toxic potential in different avian species. Concentrations of total 2,3,7,8-substituted PCDD/Fs were in the range of 10.8-182pgg(-1) lipid weight. Eggs of great egret and lesser pied kingfisher contained higher levels of PCDD/Fs than eggs of other species, indicating the specific exposure and accumulation of PCDD/Fs relating to feeding habits and the life span. PCDD/Fs congener patterns varied among species. The patterns of PCDD/Fs in the eggs may be influenced by feeding habits, specific elimination, and metabolism. In general, concentrations of PCDDs were higher than those of PCDFs in avian eggs. On basis of lipid weight, total 2,3,7,8-TCDD toxic equivalents (TEQs) calculated based on the WHO TEFs for birds ranged from 2.04 to 42.0pgg(-1); and on basis of wet weight, total WHO-TEQs ranged from 0.19 to 1.59pgg(-1). 2,3,7,8-TCDF, 2,3,4,7,8-PeCDF, 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD were the major contributors to TEQ concentration in most avian eggs, whereas 1,2,3,4,7,8-HxCDD also accounted for a major portion of TEQs in eggs of azure-winged magpie. Values of TEQs in avian eggs were lower than toxic threshold values, implying risk reduction and natural restoration of PCDD/Fs contamination in Dongting Lake region.     

PCDD/PCDF emissions from small firing systems in households

This report presents results of emission measurements of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in the flue gas of seven oil, nine gas, and two wood firing systems under laboratory conditions. The burn rate of the combustion was in the range of the rated useful heat output. Two additional test series varied the amount of combustion air and thus the heat output. The PCDD/PCDF emissions for oil- and gas-fired boilers are in the range of 0.0020-0.0142 ng I-TEQ/m3 (referring to 3% O2 in the dry flue gas). No correlation between the combustion technique and the PCDD/PCDF emissions could be established. In the tests with the wood-fired furnaces PCDD/PCDF concentrations in the flue gas ranging from 0.014 to 0.076 ng I-TEQ/m3 (referring to 13% O2 in the dry flue gas) were found. A significant correlation between the firing rate of the heating insert and the measured PCDD/PCDF concentrations was found. On examination of three typical 2,3,7,8-CDD/CDF congener profiles, a comparable pattern could be observed with natural gas and light fuel oil. The congener distribution for wood combustion is considerably different.     

Polychlorinated dibenzodioxins and dibenzofurans in butter from different states in Australia

Nine samples of butter from producers in various states of Australia were analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Detectable concentrations of 2,3,7,8-chlorine substituted PCDD/Fs were found in all samples. The mean PCDD/F concentration expressed as 2,3,7,8-TCDD equivalents (TEQs) was 0.19 pg TEQ g-1 fat. The highest concentration (0.46 pg TEQ g-1 fat) was observable in a sample from Victoria which is the most densely populated state. Overall the results indicate that PCDD/F concentrations in dairy products from Australia are low in comparison to the levels in dairy products of industrialized countries on the Northern Hemisphere. As expected, this study provides evidence that the environmental and consequently the human body burden of PCDD/Fs to be relatively low in Australia.     

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.     

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.     

Levels and congener distributions of PCDDs,PCDFs and non-ortho PCBs in Belgian foodstuffs--assessment of dietary intake

Congener-specific analyses of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs) and 4 non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 197 foodstuffs samples of animal origin from Belgium during years 2000 and 2001. All investigated matrices (except horse) present background levels lower than the Belgian non-commercialization value of 5 pg TEQ/g fat. Pork was the meat containing the lowest concentration of both PCDD/Fs and cPCBs. The mean background concentration of 2,3,7,8-TCDD toxicity equivalent in milk was 1.1 pg/g of fat, with a congener distribution typical of non-contaminated milk. The relative contribution of 2,3,7,8-TCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF to the PCDD/Fs TEQ was 85+/-7.9% for all investigated matrices. The cPCBs contribution to the total TEQ was 47+/-19.0% for products of terrestrial species and 69+/-20.0% for aquatic species. Once the contribution of cPCBs was added to the TEQ, few foodstuffs such as horse, sheep, beef, eggs and cheese presented levels above the future European guidelines that currently only include PCDD/Fs but will be re-evaluated later in order to include 'dioxin-like' PCBs. Based on levels measured in the samples, the estimation of the dietary intake was 65.3 pg WHO-TEQ/day for PCDD/Fs only (1.00 pg WHO-TEQ/kg bw/day, for a 65 kg person) and 132.9 pg WHO-TEQ/day if cPCBs were included (2.04 pg WHO-TEQ/kg bw/day, for a 65 kg person). Meat (mainly beef), dairy products, and fish each account for roughly one third of the intake.