Large-scale fires and time trends of PCDDS/DFs in sediments

Drastic increases in PCDDs/DFs concentrations were identified in the uppermost layers of a sediment core sample taken from the coastal area of Kobe City. As large-scale fires caused by the Great Hanshin-Awaji earthquake were deemed to be a possible cause, we performed additional sampling of sediment cores and surface sediment samples, estimating the total amount of PCDDs/DFs released from fires and presuming the load to sediments by individual transport routes, such as air and water, using an air diffusion model to investigate the influence of fires. The total amount of PCDDs/DFs released from fires was estimated at 2000 g-total PCDDs/DFs, 22 g-TEQ. Increases in PCDDs/DFs generated in fires were principally transported through water rather than air. If 20% of the total PCDDs/DFs formed in fires had entered water, it would correspond to the entire increase of PCDDs/DFs concentration in sediment cores.     

Estimation of sources and inflow of dioxins and polycyclic aromatic hydrocarbons from the sediment core of Lake Suwa, Japan

To elucidate the historical changes in polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), coplanar polychlorinated biphenyl (co-PCB), and polycyclic aromatic hydrocarbon (PAH) inflows in Lake Suwa, their concentrations in the sediment core were analyzed in 5 cm interval. The maximum concentrations (depth cm) of PCDDs/DFs, co-PCBs, and PAHs were 25.2 ng/g dry (30-35 cm), 19.0 ng/g dry (30-35 cm), and 738, 795 ng/g dry (50-55 cm, 30-35 cm), respectively. Age and sedimentation rate of the sediment were estimated from the vertical changes in apparent density. Deposition rate of dioxins and PAHs were calculated from the concentration and sedimentation rate of the sediment. The results indicate that large amounts of dioxins and PAHs flowed into the lake in flood stage compared to normal stage.     

Specific biomagnification of polychlorinated dibenzo-p-dioxins and dibenzofurans in tufted ducks (Aythya fuligula), common cormorants (Phalacrocorax carbo) and their prey from Lake Shinji,Japan

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) were detected in waterfowl such as common cormorants, tufted ducks, and their prey, namely fish and bivalves from Lake Shinji, Japan. The concentration of total PCDDs/DFs-TEQ was found to be higher in the muscle tissues of common cormorants than in those of tufted ducks. The results of hierarchical cluster analysis implied that the residue distribution pattern of PCDD/DF homologues was considerably different between these two species. Furthermore, biomagnification factors (BMFs) were estimated from bivalves as prey to tufted duck muscles as target organs. Despite the highest concentrations of 1,3,6,8- and 1,3,7,9-TeCDD in tufted ducks and their prey, however, the BMFs of these isomers were calculated to be lower than those of the toxic 2,3,7,8-substituted PCDDs/DFs. On the other hand, log BMF of toxic 2,3,7,8-substituted PCDDs/DFs were significantly higher for lower chlorinated isomers than those of the higher chlorinated isomers. The biota-sediment accumulation factors (BSAFs) of PCDDs/DFs were also estimated using shijimi clam and fish samples against sediment from Lake Shinji. The average BSAFs were estimated and ranged from 4.0×10⁻³ to 2.2×10⁻¹ and 2.0×10⁻⁴ to 2.0×10⁻¹ for bivalve and fish samples, respectively. Based on calculated BMFs and BSAFs, the total PCDD/DF-TEQ levels in the tufted duck were estimated to have been lowest (2.0 pg TEQ/g dry weight basis) in 1947 and highest (9.8 pg TEQ/g) in 1971.     

Concentrations and accumulation profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans in aquatic tissues, and ambient air from South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), including 2378-substituted isomers were present in samples of shellfish and fish, and ambient air collected from Masan Bay, and Masan City, South Korea. Total concentrations of PCDDs/DFs in mussel and clam were 750 pg g(-1), lipid weight (lw), and 3418 pg g(-1), lw, respectively. Total concentrations of PCDDs/DFs in mullet, gizzard and flounder were 52, 82, and 122 pg g(-1), lw, respectively. Shellfish tissues contained a greater number of PCDD/DF isomers, contributing greater total concentrations of PCDDs/DFs compared to fish collected from the same locations. The predominance of 2378-substituted PCDDs/DFs in fish is represented in greater total concentrations of 2378-TeCDD equivalents (TEQs), whereas there was very limited occurrence of 2378-substituted isomers in shellfish. TEQ concentrations in samples of mussel and clam were 0.97 and 12 pg g(-1), lw, respectively. Total TEQs in mullet, gizzard and flounder were 12, 22 and 18 pg g(-1), lw, respectively. In fish 2378-substituted PCDDs accounted for 100% of the total concentrations of PCDDs, and 2378-substituted PCDFs accounted from 59% to 73% of the total PCDFs. The 2378-substituted isomers accounted for only 3% of the total PCDDs/DFs in shellfish. Ambient air collected from two sites contained a wide range of isomers of tetra- through heptachlorinated PCDDs/DFs. Even though the total concentration of PCDDs/DFs in ambient air (12.8 pgm(-3)) collected from an industrial area was 2-fold greater than that in air samples (6.3 pgm(-3)) collected from an urban/rural area, total TEQs (0.07 and 0.08 pgm(-3)) there was no statistical difference between the two samples.     

Specific biomagnification of polychlorinated dibenzo-p-dioxins and dibenzofurans in tufted ducks (Aythya fuligula), common cormorants (Phalacrocorax carbo) and their prey from Lake Shinji, Japan

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) were detected in waterfowl such as common cormorants, tufted ducks, and their prey, namely fish and bivalves from Lake Shinji, Japan. The concentration of total PCDDs/DFs-TEQ was found to be higher in the muscle tissues of common cormorants than in those of tufted ducks. The results of hierarchical cluster analysis implied that the residue distribution pattern of PCDD/DF homologues was considerably different between these two species. Furthermore, biomagnification factors (BMFs) were estimated from bivalves as prey to tufted duck muscles as target organs. Despite the highest concentrations of 1,3,6,8- and 1,3,7,9-TeCDD in tufted ducks and their prey, however, the BMFs of these isomers were calculated to be lower than those of the toxic 2,3,7,8-substituted PCDDs/DFs. On the other hand, log BMF of toxic 2,3,7,8-substituted PCDDs/DFs were significantly higher for lower chlorinated isomers than those of the higher chlorinated isomers. The biota-sediment accumulation factors (BSAFs) of PCDDs/DFs were also estimated using shijimi clam and fish samples against sediment from Lake Shinji. The average BSAFs were estimated and ranged from 4.0×10⁻³ to 2.2×10⁻¹ and 2.0×10⁻⁴ to 2.0×10⁻¹ for bivalve and fish samples, respectively. Based on calculated BMFs and BSAFs, the total PCDD/DF-TEQ levels in the tufted duck were estimated to have been lowest (2.0 pg TEQ/g dry weight basis) in 1947 and highest (9.8 pg TEQ/g) in 1971.     

Multi-component behavior of fixed-bed adsorption of dioxins by activated carbon fiber

The multi-component behavior of fixed-bed adsorption of dioxins (DXNs) was examined through detailed analyses of the concentration profiles of isomers in fixed-bed activated carbon fiber (ACF). Regularities in both adsorption rates and strengths were clarified. (1) The rate of transfer in the adsorption of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCCDs/DFs) tends to increase with decreasing number of chlorine substituents. Axial dispersion also tends to increase with a decreasing number of chlorine substituents under our experimental conditions. (2) Homologues with the same number of chlorine substituents in PCDDs/DFs have similar adsorption strengths. The adsorption strength of PCDD/DF isomers is probably greater than that of co-planar polychlorinated biphenyls (co-PCB) isomers when the number of chlorine substituents is identical. (3) The adsorption strength of isomers depends on their molecular structure. In PCDDs/DFs the toxic isomers, all of which have vicinal chlorine substituents at the 2, 3, 7 and 8 positions, are relatively strong. It is clear, especially in TeCDDs, that isomers with vicinal chlorine substituents are stronger than isomers without. In co-PCBs, isomers without chlorine substituents at ortho positions are stronger than those with, and (4) A close analogy exists between the adsorption strength order for ACF and the elution order in gas chromatography (GC).     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.     

PCDDs/DFs emissions from crematories in Japan

Concentrations of PCDDs and PCDFs in emission gases from 10 crematories were measured. The relationship between PCDDs/DFs and several factors such as structure, equipment and operational state of the crematory is discussed. Furthermore, emission of PCDDs/DFs from all crematories in Japan is estimated. The following results are obtained: (1) total concentration of PCDDs/DFs was 2.2-290 ng/N m3, whose TEQ concentration was 0.0099-6.5 ng TEQ/N m3; (2) total concentration of PCDFs was higher than that of PCDDs; (3) T4CDFs was the highest in the homologue pattern and 2,3,7,8-T4CDF was the highest in the isomer pattern; (4) emission of PCDDs/DFs was the largest in the first 20 min of cremation; (5) concentration of PCDDs/DFs was related to the existence of a secondary combustion chamber and a dust collector, and the ratio of the numbers of main and secondary combustion chambers; (6) total emission of PCDDs/DFs from crematories in Japan was estimated to be 8.9 g TEQ/yr.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in urban and suburban areas of Korea

Bulk atmospheric samples (wet and dry) were collected monthly throughout a year at urban and suburban areas of Korea to assess the deposition flux and seasonal variations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The PCDDs/DFs deposition fluxes ranged from 1.0 to 3.7 ng TEQ/m²/year in the urban area and from 0.5 to 4.6 ng TEQ/m²/year in the suburban area. The deposition fluxes of PCDDs/DFs in this study were comparable to or lower than those previously reported at different locations. The atmospheric deposition fluxes of particles and PCDDs/DFs in winter tended to be higher than those in summer. However, monthly variations between particle and PCDDs/DFs deposition fluxes were small, and the correlation coefficients between the deposition fluxes of air particles and each homologue group of PCDDs/DFs varied according to the degree of chlorination of the homologue group. The deposition velocity of PCDDs/DFs in the urban area was estimated at 0.04 cm/s, which is a lower value than those found in other studies. The two most likely factors affecting the monthly variation of deposition fluxes are the ambient temperature and the amount of precipitation. In particular, the ambient temperature had an influence on the lower chlorinated homologues of PCDDs/DFs while precipitation had an influence on the higher chlorinated PCDDs/DFs. The PCDDs/DFs profiles in atmospheric deposition bulk samples showed a similar pattern at the urban and suburban sites. The possibility of the loading of PCDDs/DFs by Asian dust events could be partly confirmed by investigation of homologue profiles.     

Measures to prevent emissions of PCDDS/DFs and co-planar PCBs from crematories in Japan

In this study, PCDDs/DFs and co-planar PCBs concentrations in flue gases from 17 crematories and in fly ashes and bottom ashes (mainly bone) from several crematories were measured to grasp the present state of PCDDs/DFs emissions from crematories. The effects of several factors were discussed to prevent PCDDs/DFs emissions from crematories. Total concentration (normalized by 12% O2) of PCDDs/DFs was ranged from 4.9 to 1200 ng/m3 N, and toxic equivalent concentration was ranged from 0.064 to 24 ng TEQ/m3 N. As the results obtained in this research, the following measures to reduce PCDDs/DFs emission are recommended for existing crematories: (1) keeping the temperature at 800 degrees C in main/secondary chambers during a whole cremation, and (2) lowering the temperature in the dust collector. For newly installed crematories, following measures to prevent PCDDs/DFs emission including the measures for existing ones are recommended: (1) connecting one secondary chamber to one main chamber, (2) installing the high efficiency dust collector and reducing dust concentration to less than 0.01 g/m3 N, and (3) installing the sampling point for monitoring of PCDDs/DFs.     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.     

Removal of PCDDs/DFs and dl-PCBs in MWI fly ash by heating under vacuum

Temperature dependence of PCDD/DF and dioxin-like polychlorinated biphenyl (dl-PCB) concentrations in fly ash from a municipal waste incinerator (MWI) heated under vacuum has been investigated as a function of sample temperature ranging from T(s)=425 to 800 K to find out if PCDDs/DFs in fly ash evaporate and are trapped in a liquid nitrogen-cooled trap. The results show that more than 99.98% of PCDDs/DFs in TEQ is removed from fly ash by vacuum heat treatment at T(s)>650 K for 4 h. Almost no PCDDs/DFs were detected in the liquid nitrogen-cooled trap. Homologue distributions indicate that dechlorination/hydrogenation (DCH) reactions proceed in fly ash at T(s)>450 K. Arrhenius rate parameters for the DCH reactions have been determined for each homologue assuming that only DCH reactions occur. The fly ash heated under vacuum at 650 or 800 K was reheated at 573 K (300 degrees C) in a stream of dry or humid air to see how much PCDDs/DFs and dl-PCBs are regenerated. We have found that (1) PCDDs/DFs are regenerated in both 650 K and 800 K treated fly ash, whereas dl-PCBs are regenerated in 650 K treated fly ash, (2) formation of PCDFs predominates over that of PCDDs or dl-PCBs, and (3) less chlorinated homologues are abundant for PCDDs/DFs and dl-PCBs.     

Leaching characteristics of PCDDs/DFs and dioxin-like PCBs from landfills containing municipal solid waste and incineration residues

To investigate the leaching characteristic of persistent organic pollutants (POPs), such as non-ortho and mono-ortho substituted chlorobiphebyls (dioxin-like PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), in leachate from municipal solid waste (MSW) landfill sites containing incineration residues, raw leachate samples were collected twice from 12 selected MSW landfill sites. The samples were divided into their liquid and solid phases using GF/B (pore size 1.0 microm), and the concentrations of POPs then determined. The concentrations of PCDDs/DFs ranged from 0.65 to 5.88 pg-TEQ/l (average 2.86 pg-TEQ/l), and those of dioxin-like PCBs from 0.05 to 0.32 pg-TEQ/l (average 0.18 pg-TEQ/l). The major congeners of leached PCDDs/DFs and dioxin-like PCBs in liquid and solid phases were OCDD (about 60%), 2,3',4,4',5-PeCBs (about 30%), and 2,3,4,4',5-PeCBs (about 54%). The relationship between landfill age and the leaching concentration of PCDDs/DFs, and effects of dissolved organic carbon (DOC) on the leaching of PCDDs/DFs are also discussed. Finally, a leaching prediction model of PCDDs/DFs from MSW landfills has been suggested using parameters, such as hydrophobic neutral organic carbons, total dissolved solid, and the ratio of non-biodegradable wastes in landfill sites.     

Prediction of physico-chemical properties for PCs/DFs using the UNIFAC model with an alternative approximation for group assignment

The original-type UNIFAC model was used to predict the environmentally important physico-chemical properties of PCDDs/DFs, such as aqueous solubility, Henry's law constant, and 1-octanol/water partition coefficient, through the UNIFAC-derived infinite dilution activity coefficient. In this application, we suggest an alternative approximation that the aromatic ether group AC-O in PCDD/DF molecules is replaced with the aliphatic ether group CH-O, because the AC-O group is not available in the conventional UNIFAC model. With this approximation, the ability of the UNIFAC model to predict those properties was examined by comparing with experimental data. The UNIFAC model provided comparatively good estimation results. From these results, it is shown that the alternative approximation is useful for the UNIFAC estimation of physico-chemical properties for PCDDs/DFs. Furthermore, the predicted solubilities of 2,3,7,8-T4CDD and O8CDD in organic solvents and the co-solvency effect on solubility of PCDDs in methanol/water mixture indicate that the UNIFAC calculation presented here could well predict the physico-chemical properties of PCDDs/DFs in various solution conditions.     

Combustion of brominated flame retardants and behavior of its byproducts

The substance flow rate of PBDDs/DFs into flue gas and incineration residues from incineration of three types of waste samples containing brominated flame retardants were examined. The samples used consisted of PBDEs (a typical retardant), used TV casing materials (actual waste materials), and waste printed circuit boards. PBDDs/DFs concentrations in the experimental samples of PBDEs/PE, waste TV casing materials and printed circuit boards ranged between 3000 and 130,000 ng/g. These values are very high when compared to other investigations. The increase of chlorine concentration in input sample reduced the ratio of PBDDs/DFs in flue gas and raised the ratio of PCDDs/DFs. With adequate combustion control and flue gas treatment, the amount of PBDDs/DFs released from the incineration of resin containing brominated flame retardants was lower than the input amount. The presence of PBDDs/DFs in incineration residues dominated the total amount of dioxins released. When PBDDs/DFs, PCDDs/DFs and PXDDs/DFs were considered as a total, the total amount released was lower than the total amount input.     

PCDD/DF formations by the heterogeneous thermal reactions of phenols and their TiO2 photocatalytic degradation by batch-recycle system

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) formation by the thermal reactions of phenols with CuCl2 under oxygen flux were carried out in relation to their formation mechanisms. To evaluate the effect of photocatalytic degradation of titanium dioxide (TiO2) thin film prepared by the sol-gel method, the photocatalysis of PCDD/DFs in acetonitrile/water solution by batch-recycle system was conducted. For the thermal reaction system of powder mixtures of 2,4,5-trichlorophenol (2,4,5-TCP) and CuCl2, the formation rates were 8.1 microg/g-2,4,5-TCP/min for total PCDD/DFs and 6.9 microg/g-2,4,5-TCP/min for PCDDs, and total PCDD/DF rate was higher by approximately 40 fold compared to phenol vapor/oxygen/CuCl2 powder system. For the system of 2,4,5-TCP, PCDDs were mainly formed via ortho-phenoxyphenols (POP) intermediate by the condensation of 2,4,5-trichlorophenate. For PCDD/DF photocatalytic degradations, most PCDD congeners photodecomposed rapidly and the rates presented more than 70% (as dechlorination rates of 76% for PCDDs) at 24 h after irradiation, using PCDD/DFs formed with 2,4,5-TCP. The rate constants were in the order of 4.8-6.1 x 10(-3) min(-1), assuming the pseudo-first-order reactions for their low levels.     

Study on PCDDs/PCDFs and co-PCBs content in food samples from Catalonia (Spain)

The results of a surveillance programme on polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (co-PCBs) determination in 70 foodstuffs samples produced all over the four provinces of Catalonia is presented. The study included the analyses of raw milk, pure virgin olive oil, butter, chicken, pork and mussel samples collected between November 1999 and January 2000. Milk, virgin oil, pork or butter presented a variable dioxin and co-PCBs content, even though the limits proposed in the draft of the EC Regulation for its commercialization in the European countries were not reached. The levels of PCDDs/PCDFs and co-PCBs determined in chicken samples varied between 0.36–3.59 pg I-TEQ/g fat chicken (0.4–3.8 WHO-TEQ/g fat). Just one case presented remarkable content of dioxins (about 30 pg I-TEQ/g fat) with a complex congener-specific profile which indicates the presence of an external contamination. On the other hand, a congener-specific profile dominated by 2,3,7,8-TCDF and OCDD was observed in mussel samples from Catalonia. This fact was also observed in mussel samples from other sites in Spain.     

An intercalibration study on organobromine compounds: Results on polybrominated diphenylethers and related dioxin-like compounds

An intercalibration study on organobromine compounds has been conducted to evaluate the accuracy and reliability in the analysis of brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and their related compounds like polybrominated and monobromo-polychlorinated dibenzodioxins and -furans (PBDDs/DFs, MoBPCDDs/DFs). This paper reports the results for these compounds in 'Mixed Standard Solutions' and 'Air-Dried Sediment'. The relative standard deviations (RSDs) for PBDEs, PBDDs/DFs and MoBPCDDs/DFs in mixed standard solutions ranged from 9% to 24%, 4% to 20% and 8% to 27%, respectively. The results of this study are better than those reported in earlier international interlaboratory studies due to general improvement in analytical methods and an increasing number of available authentic standards, particularly for PBDEs. In the analysis for higher brominated compounds such as octabromodibenzodioxin, the participants were advised to optimize the calibration curves befitting the range of concentrations found in samples because variation of relative response factors was noted. The results for 'Air-Dried Sediment' were also reasonable with RSDs from 10% to 38% for PBDEs, 8% to 38% for PBDDs/DFs and 17% to 36% for MoBPCDDs/DFs. In the sediment sample, possible errors in the sample pretreatment and/or interference by other compounds/impurities were indicated. The concentrations of pentabromodiphenylether, BDE100, varied more than the other PBDE isomers due to its poor separation in some chromatographic conditions. In addition, interference by PBDEs was observed in the analysis for PBDFs. Potential degradation/secondary formulation of PBDEs and PBDFs during the Soxhlet extraction were suggested when copper powder was added into the sediment samples. Inspite of these observations, the results in this study are better than those reported in other interlaboratory studies due to the advice given to participants for improving the results. Compared with the results for PCDDs/DFs (5-23% RSDs) and Co-PCBs (6-24% RSDs), the RSDs for most of the organobromine compounds were high, indicating an immature QA/QC approach for the analysis of PBDEs and related compounds in comparison to common chlorinated dioxins.     

Congener-specific intake fractions for PCDDs/DFs and Co-PCBs: modeling and validation

Intake fractions (iFs) for emissions to air, water, and soil for 17 PCDDs/DFs and 12 Co-PCBs were calculated with a level III multimedia model and a food-chain exposure model in succession. The two integrated models were tested by comparing the predicted and measured concentrations in the environment and by comparing intakes through food. Measurement-based iFs were also calculated and compared with the model-based iFs. The air concentrations predicted by the fate model were close to the median of the observed concentrations, whereas the predicted soil and water concentrations were one-third to one-tenth the observed concentrations. This difference was large in case of PCDDs and Co-PCBs, which was explained by the past pollution such as commercial PCB products and PCDD impurities in chloronitrofen (CNP) and pentachlorophenol (PCP). For fish, the predicted and observed exposures agreed well each other. For meat and milk, the predicted exposures were about 10 times the observed exposures for PCDDs/DFs, whereas the predicted and observed values agreed well for Co-PCBs. When the model was modified to consider feeding of fish meal to livestock and geographic bias in feed-grass production, the predicted congener profile was comparable to the measured profile. The comparison also suggested that chickens should be modeled separately from other terrestrial livestock. The model-based iFs for air emission of OCDD and 2378-TCDD were 0.001% and 0.1%, respectively. The iFs of most Co-PCBs were higher than those of PCDDs/DFs. These iF differences suggest the importance of the fate factor in assessing emissions of the 29 congeners.     

Polychlorinated-naphthalenes, -biphenyls, -dibenzo-p-dioxins, -dibenzofurans and p,p'-DDE in bluefin tuna,swordfish, cormorants and barn swallows from Italy

Concentrations of p,p'-DDE, polychlorinated biphenyl congeners (PCBs), polychlorinated-dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs) and -naphthalenes (PCNs) were measured in bluefin tuna, swordfish, common cormorants, and barn swallows collected from Italy. Average concentrations of PCBs in livers of tuna, swordfish, cormorant, and swallows were 930, 745, 1420 and 1230 ng PCBs g-1, w.w. respectively. p,p'-DDE was found in tuna, swordfish, cormorant, and swallow livers at mean concentrations of 82, 135, 166 and 95 ng DDE g-1, w.w. respectively. PCNs were found in all the samples analyzed, although at concentrations less than those reported for biota from the Baltic Sea. PCBs, particularly, non-ortho coplanar PCBs accounted for 80-90% of the total TEQs in tuna and swordfish. Relative contribution of PCDDs/DFs to TEQs was greater in cormorants and swallows compared to that in fishes. PCDD/DF congeners accounted for up to 80 and 45% of the total TEQs in cormorants and swallows, respectively.