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.     

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.     

Levels of PCDDs, PCDFs and non-ortho PCBs in serum samples of non-exposed individuals living in Madrid (Spain)

In an attempt to evaluate the background levels of PCDDs, PCDFs and non-ortho PCBs in people living in Madrid (Spain), blood serum samples had been analyzed PCDD, PCDF and coplanar PCB levels from non exposed individuals are reported in this study. Average levels found were 515.29 ppt for total PCDDs, 66.73 ppt for total PCDFs and 85.47 ppt for non-ortho PCBs on a lipid weight basis Calculated I-TEQ values were 8.78 ppt for PCDDs, 6.96 for PCDFs and 7.03 for coplanar PCBs on a lipid weight basis.     

PCDDs, PCDFs and dioxin-like PCBs in food of animal origin (Slovakia)

The levels of 17 toxic polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and 12 non-ortho and mono-ortho polychlorinated biphenyls (PCBs) in 73 foodstuff samples of animal origin collected from shops and small farms in selected districts of Slovak Republic are presented in this paper. The concentrations expressed as WHO-TEQ in analysed samples ranged for PCDDs/PCDFs from 0.25 pg/g fat in pork to 75 pg/g fat in cod liver. The TEQ concentrations of non-ortho PCBs were between 0.007 and 181 pg/g fat and mono-ortho PCBs between 0.0083 and 66.5 pg/g fat. The mean concentrations in freshwater fish and imported species of marine fish were 0.089 pg TEQ/g fresh weight for PCDDs/PCDFs, 0.17 pg TEQ/g fresh weight for non-ortho PCBs and 0.034 pg TEQ/g fresh weight for mono-ortho PCBs. The mean total concentration of PCDDs/PCDFs and dioxin-like PCBs in samples of infant milk formula imported from EU countries was 0.98 pg TEQ/g fat.     

PCDDs/PCDFs and PCBs in water samples from the Three Gorge Reservoir

The Three Gorge Reservoir (TGR) is the largest reservoir in China and its water quality is an important health concern, we have determined the concentrations of PCDDs/PCDFs and PCBs in the water samples collected at three seasons: August 2004, January 2005 and August 2005. The results showed that the average WHO-TEQ of total dioxins-like compounds (PCDDs/PCDFs+PCBs) was 0.06558 pg l(-1), ranged from 0.0008 to 0.32439 pg l(-1), which are much lower than other reported water sources. The main dioxins (PCDDs/PCDFs) are hepta- and octa-chlorinated dibenzo-p-dioxins (CDDs) and chlorinated dibenzofurans (CDFs). Since the levels of dioxins may change after the last water-store stage, the present study provides important data to compare the water quality in the TGR in the future.     

Update of daily intake of PCDDs, PCDFs, and dioxin-like PCBs from food in Japan

Total diet study (TDS) samples of 14 food groups from 16 locations in Japan, collected in 1999 and 2000, were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) to estimate the update of daily intake of these contaminants from food. The mean daily intake of toxic equivalency (TEQ) for an adult weighing 50 kg, calculated at non-detected isomer concentrations equal to zero (ND=0), was estimated to be 2.25 pg TEQ/kg b.w./day. When non-detected isomer concentrations are assumed to be equal to half of the limits of detection (ND=1/2 LOD), the mean daily intake was estimated to be 3.22 pg TEQ/kg b.w./day. These values were below the tolerable daily intake (TDI) of 4 pg TEQ/kg b.w. for PCDD/Fs and dioxin-like PCBs set in Japan. In both the estimates, the mean daily intakes were highest from fish and shellfish (76.9% at ND=0 and 53.9% at ND=1/2 LOD of the total TEQs), followed by those from meat and eggs (15.5% at ND=0 and 11.7% at ND=1/2 LOD of the total TEQs). Congener specific data revealed that these total TEQ levels were dominated by 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3^′,4,4^′,5-PeCB in each case (71.7% at ND=0 and 63.1% at ND=1/2 LOD of the total TEQs). The dioxin-like PCBs (non-ortho and mono-ortho PCBs) accounted for about 50% of these total TEQs. These data will be very useful in the risk assessment of PCDD/Fs and dioxin-like PCBs from food in Japan.     

Levels of PCDDs, PCDFs and dioxin-like PCBs in raw cow's milk collected in France in 2006

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) as well as polychlorinated biphenyls (PCBs) are widespread environmental contaminants. A French national survey was carried out in April 2006 to assess the concentrations of PCDD/Fs and dioxin-like PCBs (DL-PCBs) in raw cow's milk. A random sampling scheme stratified by region was applied to collect 239 raw milk samples from 93 plants belonging to 17 dairy companies. Compared to a previous survey led in 1998 analyzing half-skimmed drinking milk in France, the PCDD/Fs level was cut by half, with an average concentration of 0.33 pg toxic equivalent (TEQ)/g fat in 2006. The mean DL-PCBs concentration was 0.57 pg TEQ/g fat and subsequently the sum of PCDD/Fs and DL-PCBs was 0.90 pg/g fat, values below the thresholds defined by the European Union regulations.     

Levels of PCDDs and PCDFs in two kinds of fast foods in Korea

We initiated an attempt to gather preliminary Korean fast food data on the concentrations, whole weight and international toxic equivalent (TEQ), in two kinds of fast foods, hamburger and fried chicken. The levels of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) in hamburgers are detected to be lower than in fried chickens. Total TEQ level of PCDDs in fried chicken is 47.45 times higher than in hamburger. In case of PCDFs, it is 48.61 times. Even though these are compared to the only one brand and three samples each, we think that these high levels of PCDDs/PCDFs in fried chicken are very important data because of the potentially increasing daily intake. If we continue to survey for PCDDs/PCDFs in fast foods more even, especially fried chicken, these data will be useful to calculate the estimated daily intake of TEQ levels of PCDDs/PCDFs in Korea.     

Levels of PBDEs, PCDDs, PCDFs, and coplanar PCBs in edible fish from California coastal waters

The levels of polychlorinated dibenzo-dioxins (PCDDs), polychlorinated dibenzo-furans (PCDFs), coplanar polychlorinated biphenyls (coPCBs), and polybrominated diphenyl ethers (PBDEs) were measured in fish collected from San Francisco Bay in 2000 and from the California coast in 2001. The samples were composites of only the edible portions of the fish (skin on, skin off, or whole body minus head and guts) of comparable size and from distinct geographical areas. Sixty-five composite samples were analyzed for PCDD/PCDF/coPCBs, and 43 composite samples were analyzed for PBDEs. For all fish of all species from all sampling areas, the mean concentration of the sum of BDEs 47, 99, 100, 153, and 154 was 302 ng/g lipid weight, with BDE 47>100>99 approximately 154>153. For all fish of all species from all sampling areas, the mean PCDD/PCDF International Toxic Equivalent (I-TEQ) was 33.1 pg/g lipid. For the three coPCBs (77, 126, 169), the mean I-TEQ for all fish of all species from all sampling areas was 109 pg/g lipid. The highest concentrations of both PCDD/PCDF/coPCBs and PBDEs were found in the highly populated areas of San Francisco Bay, the Los Angeles area, and San Diego Bay.     

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

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

Levels and profiles of PCDDs,PCDFs and cPCBs in Belgian breast milk. Estimation of infant intake

Congener-specific analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 20 non-pooled breast milk samples collected in or close to an industrial area of Wallonia (Belgium). PCDD/F concentrations ranged between 16.0 and 52.1 pg TEQ/g fat, with a mean value of 29.4 pg TEQ/g fat. If coplanar PCBs (77, 126, 169) are included in TEQ calculations, levels ranged between 22.2 and 100.2 pg TEQ/g fat, with a mean value of 40.8 pg TEQ/g fat. It appears that 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and PCB-126 account for more than 90% of the TEQ. Estimated PCDD/F dietary intake is 76 pg TEQ/kg body weight (bw)/day. This value is almost 20 times higher than the World Health Organization tolerable daily intake. A value of 103 pg TEQ/kg bw/day represents the intake of PCDDs, PCDFs and cPCBs (no mono-ortho PCBs included).     

Comparability of world-wide analytical data of PCDDs, PCDFs and non-ortho PCBs in samples of chicken, butter and salmon

It was the primary objective of the present study to elucidate, from a chemical analytical point of view, the comparability of dioxin determinations and the consequences concerning the data on levels in food reported world-wide. To do so, an international intercalibration study on the determination of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like PCBs in three natural food items was performed between March and June 2000. Samples of chicken, butter and salmon, collected in Norway, where sent to 42 laboratories and analysed for 20 PCDDs/PCDFs/non-ortho PCBs. The study generated congener-specific data for the three food matrixes both on wet weight and lipid basis. The reported data from 37 laboratories, in 15 countries, were statistically analysed in order to determine the congener-specific comparability as well as the comparability based on a toxic equivalency value (TEQ). Based on the reported data the mean relative standard deviations (mean RSD) for the WHO98-TEQDFP measurements were found to range from 36% to 57% the three foods. For chicken, the consensus level was 1.2 ppt TEQ on lipid basis, and the reported levels by 24 laboratories were between 0.53 and 2.2 ppt. For butter, the consensus was 0.55 ppt TEQ. 27 laboratories reported levels from 0.18 up to 1.5 ppt. For the salmon, sample levels of 5.9 to 38 ppt TEQ (by 25 laboratories) was reported where 15 ppt was the consensus value. It can thus be concluded that the world-wide data on dioxins, at background levels in foods, are not direct numerically comparable due to inherent analytical reasons. Up to 50% deviations are expected when interlaboratory dioxin results for foods are compared.     

PCDDs, PCDFs, dioxin-like PCBs and indicator PCBs in soil from five selected areas in Slovakia

There is a lack of information regarding persistent organic pollutants (POPs) in soil from Slovakia. This paper reports the concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), 12 dioxin-like polychlorinated biphenyls (dl-PCBs) and 6 indicator PCBs associated with 32 soil samples collected in 2007 from areas in the vicinity up to several kilometres from four selected industrial PCDD/F sources in Slovakia and one background area.The results show that the total WHO₁₉₉₈-PCDD/F/dl-PCB-TEQ concentrations varied from 0.34 to 18.05 pg g⁻¹ dry weight (dw) and the average total TEQ concentrations in samples collected at the Šala, Košice, Krompachy and Dubová areas were 3.18, 2.64, 7.80, and 3.19 pg g⁻¹ dw respectively. The average of the total WHO₁₉₉₈-TEQ values in three soil samples representing the background Starina area was 0.66 pg g⁻¹ dw. The predominant contaminants among 2,3,7,8-substituted PCDD/Fs, dl-PCB, and indicator PCBs was OCDD, PCB 118, and PCB 153 respectively. The major contributors to the TEQ were 2,3,4,7,8-PeCDF, PCB 126, 1,2,3,7,8-PeCDD, PCB 156 and 1,2,3,4,7,8-HxCDF + 1,2,3,4,7,9-HxCDF in descending order.     

PCDDs and PCDFs in food samples from Catalonia, Spain. An assessment of dietary intake

Food samples from local markets and supermarkets of Tarragona (Catalonia, Spain) were analyzed for PCDD/F concentrations. On lipid basis, PCDD/F levels in meat, fish, eggs, and fats and oils were similar or lower than those found in other countries. By contrast, in general terms PCDD/F levels in milk, vegetables, and cereals showed higher levels than those previously reported. The total dietary PCDD/F intake by the population of Tarragona was estimated to be 210 pg I-TEQ/day. This value is higher than the dietary intake of PCDD/Fs found in a number of surveys from other countries. However, when total dietary intake of PCDD/Fs was calculated including only fish and seafood, meat, milk and dairy products, eggs, and fats and oils, a dietary intake of PCDD/Fs of 117 pg I-TEQ/day was obtained. This intake is in the same range than that reported for different regions and countries. The results of the present study show that food groups such as vegetables, fruits, and cereals should not be excluded to estimate the total dietary intake of PCDD/Fs by general populations, especially in those countries and/or regions in which their consumptions are notable.     

Degradation half-life times of PCDDs, PCDFs and PCBs for environmental fate modeling

Literature search of the knowledge on the degradation of persistent organic pollutants (POPs) in environmental compartments air, water, soil and sediment was done in purpose to find properties of POPs of interest for modeling. One degradation process, hydrolysis (chemical degradation), was omitted as negligibly slow for POPs studied. The other two, photolysis and biodegradation processes, were considered separately in purpose to develop estimation procedures. The estimates can be given as pseudo first-order rate constants kP for photolysis and kB for biodegradation. For each compartment, an overall degradation rate is k(tot) = kP + kB and lifetime t(1/2) = ln 2/k(tot). The latter values, lifetimes in each compartment, will be used as input parameters to the Baltic Sea model.     

Concentration changes of PCDDs, PCDFs, and dioxin-like PCBs in human breast milk samples as shown by a follow-up survey

Breast milk is known to discharge dioxins from the human body. However, to date, no direct comparison has been made of the concentrations of dioxin analogues in breast milk obtained from identical population after successive deliveries. We present here follow-up survey results of PCDDs, PCDFs, and dioxin-like PCBs concentrations in human breast milk samples from 35 women living in Tokyo from whom samples had been obtained and analyzed to determine the corresponding concentrations in the past. The average concentrations of total PCDDs, PCDFs, dioxin-like PCBs were 8.5, 5.5, 11 TEQ pg/g fat for the first samples and 5.4, 4.0, 6.6 TEQ pg/g fat for the second samples, respectively. The degrees of reduction of total PCDDs and total dioxin-like PCBs were higher than that of total PCDFs because 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3',4,4',5-PeCB (#126), which were the predominant congeners among PCDDs, PCDFs, and dioxin-like PCBs, respectively, had different degrees of reduction. Moreover we observed a significant increase of the concentrations of PCDDs, PCDFs, and dioxin-like PCBs in samples from three women in this follow-up survey, and the patterns of increased isomers differed among the three samples. It was conjectured that the increase of the concentrations was due mainly to dietary intake between deliveries. It is important for pregnant women to have a balanced diet to mitigate the exposure of infants to these chemicals.     

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.     

PCDDs, PCDFs, PCBs and DDE in edible marine species from the Adriatic Sea

Edible marine species from several areas of the Adriatic sea were analyzed for their content in persistent organic pollutants (POPs), such as polychlorinated dibenzodioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and pp'-DDE (dichlorodiphenyldichloroethylene), a metabolite of the organochlorine pesticide dichlorodiphenyltrichloroethane (DDT). On the whole, PCDD/F contamination levels were low. In general, I-TEQ findings were greater for those species at higher levels in the trophic web (mackerel > red mullet > anchovy). Contamination levels were within 0.23 and 1.07 pg TEQ/g fw (fresh weight) in the aforesaid species, while all remaining species exhibited contamination levels ranging from approximately 0.07 to 0.25 pg TEQ/g fw. Besides, TEQ cumulative findings in species from the northern area were in general greater than those from the central and southern areas. PCB cumulative findings in the samples also revealed a detectable difference in contamination levels in species obtained from the northern, central, and southern sampling sites, between 7.6 and 177, 2.3 and 157, and 4.5 and 94 ng/g fw, respectively. The greatest PCB concentrations were found in mackerel (94-177 ng/g fw). Finally, DDE concentration levels varied from 0.7 to 32.4 ng/g fw. The highest levels of contamination were found in mackerel, red mullet and anchovy (17.7-32.4 ng/g fw, 8.1-9.8 ng/g fw, and 6.4-11.9 ng/g fw, respectively).     

Levels, profile and pattern of PCDDs and PCDFs in samples related to the production and use of chlorine

Analyses of sludge from graphite electrodes used in the chloralkali process show total levels of PCDFs as high as 650000 pg/g sludge. The levels of tetra-, penta-and hexaCDFs were found to be approximately the same. The levels for the corresponding PCDDs were below the detection level. The dominating congeners within each group are the toxic 2,3,7,8-substituted PCDFs at levels of 340000 pg/g, This typical pattern, called the “chloralkali pattern” can also be found in soil samples taken at another chloralkali plant. The typical pattern can also be identified in a solution of ferric chloride. Traces of “chloralkali pattern” are identified in a sludge sample from the drinking water purification plant, the source for PCDFs in the sludge is unknown.     

High variation of PCDDs, PCDFs, and dioxin-like PCBs ratio in cooked food from the first total diet survey in Taiwan

This study determined the levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in 240 individual food samples, belonging to 37 different foodstuffs in first total diet study (TDS) in Taiwan. The foods were collected from markets located in eight cities or counties around Taiwan. The food was cooked in a laboratory according to recipes typically used in Taiwan. In this study, PCDD/Fs were lower than the limits proposed by the European Union (EU) regulation for commercialized food, except for a notable PCDD/Fs level in ducks (3.660 pg WHO-TEQ/g, fat) obtained from central Taiwan. We hypothesize the duck meat might be probably polluted via emission of a fly ash recycling plant located near the duck farms. In addition to fish, most foods had high PCDD/Fs to dl-PCBs ratio. Needle fish and sea perch had relatively lower PCDD/Fs and dl-PCBs levels compared with those in other fish. Data from this study can be utilized for further consideration about dietary intake.