Polychlorinated dibenzo-p-dioxins,dibenzofurans and polychlorinated biphenyls in polar bear,penguin and south polar skua

Concentrations of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (DFs) and non- and mono-ortho-substituted polychlorinated biphenyls (dioxin-like PCBs) were measured in livers of polar bears from the Alaskan Arctic and in eggs of Adelie penguin and south polar skua and weddell seal liver, fish and krill from Antarctica. This is one of the first reports to document the concentrations of PCDDs/DFs in polar bear livers from Alaska, and in penguin and skua eggs from Antarctica. Concentrations of total PCDD/DFs in livers of polar bears ranged from 8 to 66 (mean: 26) pg/g, on a lipid weight basis. Concentrations of total PCDD/DFs in Antarctic samples were in the increasing order on a lipid weight basis; weddell seal liver (8.9 pg/g) < fish (11-17 pg/g) < krill (27 pg/g) > penguin eggs (30 ng/g) > seal liver (57 ng/g) > fishes (6.2 ng/g) > krill (0.9 ng/g). Concentrations of 2378-tetrachlorodibenzo-p-dioxin equivalents (TEQs) calculated based on the WHO TEFs were higher in the eggs of polar skua (mean: 344: range: 220-650 pg/g, lipid wt.) from Antarctica than in polar bear livers from Alaska (mean: 120; range: 69-192 pg/g). In general, concentrations of PCDFs were greater than those of PCDDs in polar organisms. 23478-PeCDF is one of the dominant congener found in several samples. Concentrations of TEQs in polar bear livers and skua eggs were close to those that may cause adverse health effects. Dioxin-like PCBs, particularly, non-ortho coplanar PCBs were the major contributors to TEQ concentrations in penguin and skua eggs whereas mono-ortho PCBs accounted for a major portion of TEQs in polar bear livers.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, naphthalenes and polybrominated diphenyl ethers in the edible fish caught from the Baltic Sea and lakes in Finland

A total of 156 fish composite samples were collected from five areas of the Baltic Sea and from three lakes and analysed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polybrominated diphenyl ethers (PBDEs). The European Union's maximum permissible level for PCDD/Fs, 4 pg WHO-TEQ/g fresh weight (fw), was exceeded in salmon, river lamprey and Baltic herring. In other species from the Baltic Sea, the 90th percentile was 3.42 pg WHO(PCDD/F)-TEQ/g fw. In the lake fish, the concentrations of PCDD/Fs, PCBs and PCNs were only 29-46% of those in the same species caught from the Baltic Sea, whereas the concentrations of PBDEs in the lake fish were as high as in the Baltic Sea fish. Dioxin-like PCBs contributed to the total dioxin-like toxicity of PCBs and PCDD/Fs by 49+/-12% in all the analysed samples.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice plants: possible contaminated pathways

Uptake of dioxins was confirmed in rice plants. We determined (i) dioxin concentrations and isomer profiles in leaf+stem samples of rice plants grown in three soils with different dioxin concentrations and isomer profiles and (ii) temporal changes in dioxin concentrations and isomer profiles in rice grown in a paddy field on which agricultural chemicals containing dioxin impurities had been used in previous years. Principal-component and chemical mass-balance analyses of the data showed that dioxin concentrations and isomer profiles in the rice grown in the different soils were similar, even though the dioxin concentrations and isomer profiles of the soils were different. However, the dioxin concentrations in the rice were influenced by dioxin levels in the atmospheric gas phase. Changes in dioxin levels during the growing period of the rice were also strongly influenced by adhesion of the soil to plant components during the early stage of growth, but gradually the influence of the atmospheric gas phase became predominant. Calculated dietary uptake estimates indicated that, even in rice grown in Japan on soil contaminated with high concentrations of dioxins, the amount of dioxins ingested by humans from rice is extremely small, and the amount of dioxins ingested by livestock from forage rice is similar to that for other forage crops.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice straw smoke and their origins in Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) contained in the smoke generated from rice straw burning in post-harvest paddy fields in Japan were analyzed to determine their congener profiles. Both the apportionment of toxic equivalent (TEQ) by using indicative congeners and the comparison of the homolog profiles showed that the PCDDs/PCDFs/DL-PCBs present in the rice-straw smoke were greatly influenced by those present as impurities in pentachlorophenol (PCP) and chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations that had been widely used as herbicides in paddy fields in Japan. Further, in order to investigate the effects of paddy-field soil on the PCDDs/PCDFs/DL-PCBs present in rice-straw smoke, PCDD/PCDF/DL-PCB homolog profiles of rice straw, rice-straw smoke and paddy-field soil were compared. Rice-straw smoke was generated by burning rice straw on a stainless-steel tray in a laboratory. The results suggested that the herbicides-originated PCDDs/PCDFs/DL-PCBs and the atmospheric PCDDs/PCDFs/DL-PCBs contributed predominantly to the presence of PCDDs/PCDFs/DL-PCBs in the rice-straw smoke while the contribution of PCDDs/PCDFs/DL-PCBs formed during rice straw burning was relatively minimal. The major sources of the PCDDs/PCDFs/DL-PCBs found in the rice-straw smoke were attributed primarily to the paddy-field soil adhered to the rice straw surface and secondarily to the air taken by the rice straw. The principal component analysis supported these conclusions. It is concluded that rice straw burning at paddy fields acts as a driving force in the transfer of PCDDs/PCDFs/DL-PCBs from paddy-field soil to the atmosphere.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans and polychlorinated biphenyls levels in human breast milk from different regions of Turkey

Human breast milk offers the optimal nutrition for all infants and have been widely used in biomonitoring programs to assess human exposure to lipophylic environmental contaminants such as polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB). There are no previous reports from Turkey on chemically determined levels of PCDDs, PCDFs, and PCBs in human breast milk expressed as World Health Organization (WHO) toxic equivalents (TEQ). To get an overview of the levels of these contaminants in Turkish human milk, samples from 51 Turkish women living in the Ankara, İstanbul, Antalya, Kahramanmaraş, and Afyon provinces were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) throughout 2007. The mean concentrations of WHO_PCDD/F-TEQ and WHO_PCB-TEQ of all samples from the five regions were 7.5 and 3.1 pg g⁻¹ on a lipid basis, respectively. PCDD/F concentrations ranged between 0.78 and 29.3 pg WHO-TEQ g⁻¹ fat (1.7 and 36.2 pg WHO-TEQ g⁻¹ fat, respectively, including PCB). Of the five studied locations, the lowest levels of ∑TEQs (PCDD/F + PCB) were found in the Afyon (6.8 pg WHO-TEQ g⁻¹ fat) and the highest in the Antalya (15.6 pg WHO-TEQ g⁻¹ fat) province. The results have been discussed in terms of regions and PCDD/F and PCBs for which analyses had been made. The mean levels of PCDD/Fs and PCBs in Turkish human milk are comparable to that found in other countries.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in River Po sediments

The River Po is the main Italian river draining one of the most populated and industrialised regions in Italy. As part of a monitoring project to assess environmental quality in the River Po, we measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in bottom sediments collected along the whole course of the river, from the spring to the delta, downstream from the confluence of its main tributaries. The aim was to investigate the level of contamination in the main Italian river and the contribution of contaminant loads from the subbasins. Composite sediment samples were collected in summer and winter surveys in low-flow water conditions and analysed by HRGC-HRMS for PCDD and PCDF homologue groups and for the 2,3,7,8-substituted congeners. The spatial trend observed in the Po River for PCDD and PCDF concentrations varied depending on the load of contaminants received from the tributaries and the processes of sedimentation. The sum of PCDD and PCDF concentrations, and the toxic equivalent content, ranged from 121 to 814 and from 1.3 to 13 ng/kg dry weight sediment, respectively. These levels of contamination seem lower than in the sediments of rivers draining highly industrialised areas. The PCDD and PCDF homologue profiles in all the samples were very similar, suggesting a common source of this contamination in the River Po. Principal component analysis suggested that widespread sources, such as urban runoff and domestic wastewaters, are probably the main cause of these levels of PCDDs and PCDFs.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in plywood combustion gas

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/DF) levels in plywood combustion gas were investigated for the effects of ammonium chloride (NH4Cl) and paint. For combustion systems in which neither NH4Cl nor paint were present in the plywood samples, total amounts of PCDD/DFs in the combustion gas were in the order of 35-529 ng/Nm3, and were higher in the systems with softwood trees than broadleaf ones, depending on the Cl concentrations. For the systems with added NH4Cl and no paint, and those without NH4Cl but were painted, higher PCDD/ DF rates were observed at combustion temperatures of 270 degrees C and 500 degrees C, respectively. However, for the systems with both NH4Cl and paint, their amounts in the range of 0.6-13 ng/Nm3 were the lowest in all systems. The PCDD/DF abundance profiles were similar to their patterns in pentachlorophenol (PCP). Furthermore, it was found that the 2,3,7,8-chlorine substituted penta- and hexa-CDDs contributed more than other 2,3,7,8-chlorine substitutes to toxicity equivalency (TEQ).     

Polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and non-ortho,mono-ortho chlorine substituted biphenyls in Japanese human liver and adipose tissue

We measured PCDDs/DFs levels in Japanese human livers and adipose tissues in 1999, and TEQ were calculated with WHO TEF. The mean total levels of PCDDs/DFs in livers and adipose tissues were 57 pg TEQ/g on a lipid basis and 49 pg TEQ/g on a lipid basis, respectively. 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, 2,3,4,6,7,8-HxCDF, 1,2,3,7,8,9-HxCDF and 1,2,3,4,6,7,8-HpCDF concentrations in livers considerably differed from those in 1989 (p < 0.05). The mean non-ortho-chlorine substituted biphenyls levels showed 20 pg TEQ/g on a lipid basis and 17 pg TEQ/g on a lipid basis in livers and adipose tissues, respectively. In livers, the mean of 3,3',4,4'-TCB concentrations was 131 pg/g on a lipid basis, and 7.7-fold higher than that in 1989. The mean total mono-ortho-chlorine substituted biphenyls level was 13.0 pg TEQ/g on a lipid basis in livers and 21.6 pg TEQ/g on a lipid basis in adipose tissues. 3,3',4,4',5-PeCB and 3,3',4,4',5,5'-HxCB levels decreased in adipose tissues, and 3,3',4,4',5-PeCB level only decreased in livers. PCDDs, PCDFs, and mono- and non-ortho-chlorine substituted biphenyls levels may have decreased in livers and adipose tissues because of a governmental policy on dioxins discharge for the decade. Then, we estimated the correlations of PCDDs, PCDFs and the related compound levels between livers and adipose tissues. The correlative PCDDs congeners may have had a similar behavior to that between liver and adipose tissue. On the contrary, most PCDFs isomers may have different behavior between liver and adipose tissue, while 2',3,4,4',5-PeCB (IUPAC No. 123) may also have a different behavior between liver and adipose tissue.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in marine mammals in the Canadian North

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in pooled samples of ringed seal (Phoca hispida) blubber, beluga (Delphinapterus leucas) blubber and polar bear (Ursus maritimus) liver and fat from several areas throughout the Canadian north and compared to mean PCB and HCB levels in the same samples. All seal samples, and all but one polar bear sample, had detectable 2,3,7,8-TCDD at concentrations ranging from 2 to 37 ng/kg, but TCDD was not found in beluga blubber (< 2 ng/kg). All seal samples and one of three beluga samples contained 2,3,7,8-TCDF at levels of 2 to 7 ng/kg, but TCDF was not found in any bear sample. TCDF must therefore be cleared rapidly by polar bears. No other PCDF congeners were found at detection limits of 4 to 8 ng/kg. OCDD concentrations in seal blubber and polar bear samples ranged from not detected (< 8 ng/kg) to 43 ng/kg. No apparent biomagnification of TCDD, OCDD or TCDF occurred from seal to bear fat, similar to previous findings for DDT, and unlike SigmaPCBs and HCB which biomagnified 6- to 17-fold. Highest concentrations of 2,3,7,8-TCDD and OCDD in seals and bears were found in the central Canadian Arctic Archipelago, and lowest were found in Hudson Bay, the reverse of PCB concentration distribution. The reason for higher levels of TCDD and OCDD in the Arctic than in the sub-Arctic is suggested to be trans-polar movement of aerosols with combustion-related origins in Eurasia. Levels of 2,3,7,8-TCDF were more evenly distributed throughout the North, and were positively correlated with PCB, but not with HCB or 2,3,7,8-TCDD levels in seals.     

Absorption of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans by breast-fed infants

The absorption of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans was studied in four breast-fed infants. The absorption was measured by comparing the estimated total intake and the excretion in faeces, during 48 hours, at three different time points; 1, 2 and 3 months post parta. The levels of the analysed compounds in the human milk are typical for Sweden, i.e 20 ppt toxic equivalents for the dibenzo-p-dioxins and dibenzofurans and for the polychlorinated biphenyls 16 ppt toxic equivalents. For most of the congeners the absorption is found to be over 95%. Higher excretion is noticed for heptachlorinated and octachlorinated dioxins.     

Dechlorination of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans on fly ash

Dechlorination of commercial mixtures of polychlorinated biphenyls (PCB) as well as polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) on extracted and non-extracted fly ash obtained from municipal waste incinerator (MWI) was studied in closed systems under nitrogen atmosphere at temperatures of 260°C and 340°C. Decomposition results (given as the difference between PCB or PCDD/F molar amounts before and after the experiment (in %) due predominantly to dechlorination reactions) and detoxification data (expressed similarly but related to toxic PCB and PCDD/F congeners only and given in I-TEQ units) are reported. Detoxification of Delor 105/80T at 260°C and 340°C at a loading of 0.65 wt% was 99.48% and 100%, respectively. The decomposition of Delor 103 at 340°C and for the loading of 0.75 wt% corresponded to 99.99%. The detoxification capability of PCDD/Fs on extracted and non-extracted fly ash for loading of 130 and 264 ng/0.4 g of fly ash at 340°C made 96 and 98%, respectively.     

Trend studies of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans in human milk

Human milk has been used in studies of long-term changes in the concentrations of organochlorine contaminants in mothers from the Stockholm region. The previously observed decline (1972 to 1985) in the levels of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) seems to have ceased for certain compounds since the levels were about the same in samples collected in 1985 and 1989. Calculating with the proposed toxicity equivalency factors for the different congeners of PCDDs, PCDFs and PCBs it is seen that the congeners of PCBs contribute more to the possible toxicity than those of PCDDs and PCDFs. The mono-ortho substituted congener 2,3′,4,4′,5-pentachlorobiphenyl (IUPAC No. 118) contributes with the largest part.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in paddy soils and river sediments in Akita, Japan

Paddy soils and sediments from the Yoneshirogawa, Omonogawa, and Koyoshigawa River Basins in Akita were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The levels and compositions in those samples including soils from non-agricultural areas (non-agricultural soils) were investigated using isomer-specific analysis to determine characteristic sources. The PCDD/PCDF compositions in the samples were compared with respect to possible sources. The PCDD/PCDF concentrations in paddy soils were much higher than those in the non-agricultural soils and much higher than those found in other parts of Japan. Although PCDD/PCDFs were ubiquitous in sediments from river sources to mouths of the respective river basins, those concentrations were much lower than those from paddy soils and non-agricultural soils, and from other parts of Japan. Comparison of PCDD/PCDF homologues and isomer compositions for samples indicated that compositions of paddy soils and sediments, except for those from river sources, had similar characteristics to PCDD/PCDFs originating from impurities in herbicides, 2,4,6-trichlorophenyl 4-nitrophenyl ether (CNP) and pentachlorophenol (PCP), and that compositions of river-source sediments and non-agricultural soils resembled those of atmospheric depositions. Results of statistical analyses suggest that PCDD/PCDF contamination of paddy soils and sediments is attributable mainly to three sources: CNP, PCP, and atmospheric deposition. Results of this study also demonstrate that CNP and PCP are not only important contaminants of local areas of Japan, but that they exist throughout Akita, in northern Japan. We therefore conclude that PCDD/PCDF pollution caused by those compounds has a widespread influence on paddy soils and river sediments in Japan.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in soils and sediments from Daliao River Basin, China

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) were analyzed in surface sediments and top soils collected from 30 sites in Daliao River Basin. The concentrations of PCDD/F ranged from 0.28 to 29.01 ng TEQ kg(-1) dw (mean value, 7.45 ng TEQ kg(-1)dw) in sediments, and from 0.31 to 53.05 ng TEQ kg(-1)dw (mean value, 7.00 ng TEQ kg(-1)dw) in soils. PCDD/F pollution in sediments from the mid- and downstream sections of Hun River was found to be relatively heavy, and the levels of PCDD/F contamination in paddy soils were generally higher than those of upland soils. Using multivariate statistical analysis, the PCDD/F homologue and congener profiles of all soil and sediment samples were compared with those of suspected PCDD/F sources. The results showed that, PCDD/F contamination in most sediments of Hun River should mainly originated from the production of organochlorine chemicals, while metal smelting was the important potential source of PCDD/F in the drainage area of Taizi River. PCDD/F contamination in paddy soils should be simultaneously attributed to the polluted water irrigation and the organochlorine pesticide application.     

Polychlorinated dibenzo-p-dioxins, -dibenzofurans, and biphenyls in domestic animal food stuff and their fat

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzo-p-dioxins (PCDFs) and dioxin-like coplanar PCBs and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) were measured in domestic animal related samples such as feed ingredient, mixed feed and animal fat from Japan. The mean concentration of total PCDDs, PCDFs and coplanar PCBs in fish oil was 17000pg g-1 lipid wt, which 9- to 30-fold greater than that from other animal originated ingredients. Mixed feed for chicken and chicken fat contained greater total PCDDs, PCDFs, coplanar PCBs concentrations (190 and 2100pg g-1 lipid wt) compared to those for pig (120 and 320pg g-1 lipid wt). WHO-TEQs were ranged 0.39-13, 0.15-0.22 and 0.73-2.8pg g-1 lipid wt for ingredients, mixed feeds and animal fats, respectively. Greater biomagnification factor was noticed for congeners 1,2,3,7,8-PeCDD, 1,2,3,6,7,8-HxCDD, 2,3,7,8-TCDF and 1,2,3,4,7,8-HxCDF in chicken and pig fat. Biomagnification factors for both mono- and non-ortho coplanar PCBs were greater in chicken fat compared to those in pig fat.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in paper making from a pulp mill in China

An extensive investigation on the input, formation and fate of PCDD/Fs in a pulp mill using reeds as raw materials in China was carried out. The main PCDD/Fs input in the production process came from reeds, which may be contaminated by PCDD/Fs from sodium pentachlorophenate to control snailborne schistosomiasis. High levels of I-TEQ in the products were observed.