Monitoring of polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like PCBs and polycyclic aromatic hydrocarbons in food and feed samples from Ismailia city, Egypt

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyl (PCBs) and polycyclic aromatic hydrocarbons (PAHs) have been determined using GC/HRMS in food (butter, seafood and meat) and feed samples (chicken, cattle and fish) purchased from Ismailia city, Egypt. PCDD/F concentrations in food samples ranged between 0.12 and 3.35 pg WHO TEQ/g wet w, while those in feed samples were between 0.08 and 0.2 pg WHO TEQ/g dry w. Levels of PCB TEQ ranged from 0.14 to 3.2 pg/g wet w in the food samples. The feed samples have an average of 0.35 pg PCB TEQ /g dry w. In this study, butter samples showed the highest contamination levels of PCDD/Fs and PCBs. The PCBs contribution to the total TEQ was on average 63% in seafood and on average 49% for meat and butter. The highest contamination levels of PCDD/Fs and PCBs were found in butter samples. The butter TEQ content is several times higher than that reported in all EU countries and exceeded the EU limits, while the PCDD/F levels in seafood and the feed samples is far below the current EU limit. Generally, congener profiles in the food samples reflect the non-industrialized nature of the city and suggest solid waste burning as a significant source of emission. Nevertheless, the profiles for butter suggest an impact from various sources. In the case of the sum of 16 PAH contamination levels in food samples were in the range of 11.7-154.3 ng/g wet w and feed samples had a range of 116-393 ng/g dry w. Benzo(a)pyrene (BaP) has been detected in the range of 0.05-3.29 ng/g wet w in the food samples; butter showed the highest contamination which exceeded the EU standard set for fats and oil. Fingerprints of PAHs suggested both petrogenic and pyrolytic sources of contamination.     

The assimilation of dioxins and PCBs in conventionally reared farm animals: occurrence and biotransfer factors

The assimilation of PCDD/Fs and PCBs in chickens, pigs and sheep was investigated in studies using conventional animal husbandry practices. Closely matched samples of muscle (meat), liver, kidneys, eggs, milk, feed, soil and grass were collected of which 105 were analysed. The data obtained were consistent with the PCB and PCDD/F TEQ concentrations to be expected in rural background locations. A slight decline in TEQ values in meat with increasing age was evident in pigs, sheep and broiler chickens. Higher TEQ values in meat from outdoor pigs compared to those raised indoors, and an increase in TEQs in eggs as a result of free-range conditions might be attributable to additional contaminant intakes from soil. TEQ values in samples of sheep meat were slightly higher than those for pigs and chickens and market ready lowland sheep showed higher meat TEQs than the highland species. PCDD/F TEQs were considerably higher in the liver than meat. Contaminant transfer from dietary sources was investigated using biotransfer factors (BTFs) which tended to be higher in chickens than in sheep or pigs. BTFs for all animals declined in magnitude with age, but on average, BTFs for pigs and chickens showed a sharper initial decline than for sheep. The relative magnitude of the BTFs usually followed the order: (highest first) PCB 153, PCB 169, PCB 126, 1,2,3,7,8-PeCDD/2,3,4,7,8-PeCDF and 2,3,7,8-TCDD. This may suggest that higher chlorinated congeners accumulate more readily in meat tissues. Congener-specific BTF variations were found to be associated with variables such as dietary composition during rearing, differences between feed and animal species.     

Levels and tissue-dependent distribution of dioxin in Japanese domestic leafy vegetables--from the 1999 national investigation

In 1999, Japanese domestic leafy vegetables were successively investigated for levels of dioxins, including 17 dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), four non-ortho co-planar PCBs (co-PCBs) and eight mono-ortho co-PCBs, all of which had been assigned toxic equivalency factors (TEFs) by WHO in 1997. The mean levels of dioxins in the edible portions were 0.07 (0.09) pg TEQ/g in spinach, 0.13 (0.14) pgTEQ/g in garland chrysanthemum, 0.01 (0.04) pg TEQ/g in mitsuba (marsh parsley) and 0.01 (0.03) pg TEQ/g in chingentsuai (Brassica Campestris var. chinesis), when non-detects were set to zero (and set to half the limit of detection). In order to understand the dioxin pollution of leafy vegetables in detail, a further investigation of dioxin levels in the tissues of spinach was conducted. As a result, the dioxin levels in the leaves were found to be higher than those in the stem and red collar, but they were much lower than those found in the primary and secondary roots, which are considerably affected by the soil, which is recognized as a sink of airborne dioxins. The dioxin levels in edible portions (leaves, stem and red collar) were obviously lower than those in non-edible portions (primary and secondary roots). In addition, from the finding that several lower-chlorinated PCDD/Fs and co-PCBs, namely 2,3,7,8-TCDD/F, 1,2,3,7,8-PeCDD, 1,2,3,7,8/2,3,4,7,8-PeCDFs, 1,2,3,7,8,9-HxCDD, 1,2,3,4,7,8-/1,2,3,6,7,8-HxCDFs, 3,3',4,4'-TCB, 2,3,3',4,4'-/2,3',4,4',5-PeCBs, and 2,3',4,4',5,5'-HxCB, were more highly represented in the dioxins in the leaves than in those in the secondary roots, it was suggested that in leafy vegetables the deposition of gaseous, presumably moderately volatile dioxins in leaf wax is another pollution pathway in addition to the adhesion of dioxin-contaminated particles including soil.     

Changes to the TEF schemes can have significant impacts on regulation and management of PCDD/F and PCB

The changes recommended by the World Health Organisation (WHO) to the toxic equivalency factors (TEFs) for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) and the recommendation to extend both the TEF scheme and the tolerable daily intake (TDI) to include "dioxin-like" PCB congeners have significant implications for regulators who have relied heavily on the International TEF (I-TEF) scheme in setting and monitoring limits and exposure to these compounds. This paper examines example data sets of sources, environmental concentrations, food and exposure to indicate likely changes in calculated toxic equivalent (TEQ) due to the recommended changes to TEFs. Many published data sets available do not provide congener specific data for PCDD/F which limits the ability to recalculate TEQs. There are even fewer congener specific data published to enable calculation of TEQs for the dioxin-like PCBs. In general TEQs calculated using the WHO scheme for emissions to air were found to show small increases (in the order of 1-10%) in comparison to the I-TEQ (for PCDD/F), some sludge samples showed substantial decreases (up to 70%). Levels in food and calculations of exposure showed that the change to TEFs for PCDD/F increased calculated exposure by 10-20% while the change to PCB TEFs decreased calculated TEQ attributable to PCB by 0-10%. The effects of including PCB in the overall TEQ and the changes to TEFs for PCDD/F substantially increase calculated TEQ exposure. Congener specific data should be presented to allow calculation of desired TEQ and the impact of the changes on emission limits, regulations on sludge use and environmental quality standards should all be carefully considered. The absence of data on emissions of dioxin-like PCB means that it is not possible to estimate with any certainty the impact on overall TEQ emissions of including the nominated PCB. Given the potential for confusion with the proliferation of TEFs and the extension to include both PCDD/F and PCB in the calculation of TEQs it is important that great care is taken to clearly express which compounds are included and which TEF scheme has been applied in each case.     

Ambient air monitoring of PCDD/Fs and co-PCBs in Gyeonggi-do, Korea

We started the monitoring for PCDD/Fs in ambient air and soil in August 2001, and co-PCBs in January 2002. Decreasing of PCDD/Fs and co-PCBs levels in ambient air were observed. The higher PCDD/Fs levels were found in winter and lower in autumn. We found that the industrial incinerators influenced the PCDD/Fs levels in ambient air. In the 2,3,7,8-substituted PCDD/Fs concentration profiles, the three major congeners occupied 67% of the total mass. In case of co-PCBs, PCB#118, #105 and #77 were observed as the main congeners. Five cluster groups discriminated by ratio of four components, O(8)CDD, 1,2,3,4,6,7,8-H(7)CDD, 1,2,3,4,6,7,8-H(7)CDF and O(8)CDF, were obtained from HCA (hierarchical cluster analysis).     

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.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from stack flue gases of sinter plants

This study investigated four sinter plants, classified into two categories--with selective catalytic reduction (SCR) (S1, S2 and S3) and without SCR (S4) as its air pollution control device. Polychlorinated dibenzofurans (PCDFs) are dominant in the stack flue gases of sinter plants with and without SCR. The polychlorinated dibenzofurans/polychlorinated dibenzo-p-dioxins (PCDFs/PCDDs) ratio exceeds 1 extremely. The degree of chlorination of the sinter plant without SCR is towards hepta and hexa congeners while that of the sinter plant with SCR is towards penta and hexa congeners. PCDD/Fs are indeed decomposed (75.5% and 69% on ng and ng TEQ bases, respectively) and not only reduced in degree of chlorination. The overall concentration in the stack flue gas of sinter plants with SCR (7.97-14.1 ng/Nm(3); 0.995-2.06 ng TEQ/Nm(3)) is lower than that of the sinter plant without SCR (28.9 ng/Nm(3); 3.10 ng TEQ/Nm(3)). In Taiwan, based on the emission factors of 0.970 microg TEQ/ton-feedstock (sinter plants with SCR) and 3.13 microg TEQ/ton-feedstock (sinter plant without SCR), the annual PCDD/F emission of 44.7 g TEQ/year from sinter plants is 60 and 121 times higher than those from municipal solid waste incinerators (0.750 g TEQ/year) and MWIs (0.369 g TEQ/year). These results show that sinter plants have become the dominating PCDD/F emission source since tighter emission limits have been applied to incinerators.     

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.     

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.     

Melting and incineration plants of municipal waste. Chemical and biochemical diagnosis of thermal processing samples (emission,residues)

Control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in emissions and thermal residues from incinerators has been a cause of public concern for more than one decade. Recently, several studies showed that other persistent organic pollutants (POPs) such as coplanar polychlorinated biphenyls (co-PCBs) also have dioxin-like activity and are released from incinerators. Therefore, the present study was aimed at making a risk assessment about dioxin-like activity in extracts of thermal waste residues (e.g. combustion gas; fly ash, slag) from incineration and melting processes in Germany and Japan. For this purpose, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (co-PCBs), polychlorinated naphthalenes (PCNs) and polyaromatic hydrocarbons (PAHs) were analyzed by chemical analysis. Additionally, 2, 3, 7, 8-TCDD equivalents (EROD-TEQs) were determined by in vitro Micro-EROD bioassay using rat H4IIE hepatoma cells. EROD-TEQs could be correlated to I-TEQ values (from PCDD/Fs/co-PCBs) analyzed by chemical analysis resulting in a maximal sixfold higher estimate. Our study indicates minor influences of co-PCBs, PAHs and PCNs to the sum of dioxin-like toxicity in the extracts of thermal waste residues as determined here. Furthermore, we showed that the levels of dioxins and co-PCBs contained in slag from melting processes and bottom ashes from incineration processes were lower by 1-2 orders of magnitude than that in fly ash.     

Historical trends of PCDD/Fs and dioxin-like PCBs in sediments buried in a reservoir in Northern Taiwan

Polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF) and polychlorinated biphenyl (PCB) concentrations were analyzed at 1-2cm intervals in a sediment core collected from a reservoir in Northern Taiwan to evaluate the organic pollution history. The highest PCDD/F (14.4ng TEQ/kg d.w.) and PCB (0.261ng TEQ(WHO)/kg d.w.) concentrations were determined at 13-15cm (estimated year: 1992). The ages of the levels of sediment core were estimated from the sedimentation rate. Analysis results demonstrate that the PCDD/F concentration of the sediment core measured in the reservoir reached their peak when the municipal waste incinerators (MWIs) in the area started to operate. Furthermore, the decrease in sediment core PCDD/F concentration is related to the time of enforcement of the PCDD/F emission limit set by the Environmental Protection Administration (EPA) in Taiwan. Significant distribution of OCDD in homologue profiles was noted in archived soil samples in Taiwan in which the major input of PCDD/Fs was thought to be atmospheric. Major PCB congeners found in the sediment core were the major components of the commercial PCB products. Input fluxes of PCDD/Fs (5.75-158ng-I-TEQ/m(2)-yr) and PCBs (0.248-3.71ng TEQ(WHO)/m(2)yr) into the reservoir of interest are also calculated from the concentration and sedimentation rate of the sediment. The results reveal that considerable amounts of PCDD/Fs and PCBs were carried into the reservoir of interest in the flood stage but not during normal stage.     

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).     

Concentration of organic micropollutants in the atmosphere of Trieste, Italy

Purpose

PCDD/Fs, PCBs, and PAHs, ubiquitous environmental pollutants which are part of the POPs, are mainly produced by anthropogenic activities as well as by natural processes. Occurrences of these pollutants in different sites in Trieste are presented. PCDD/Fs distribution and their possible emission sources are discussed.

Methods

Air samples were collected in different sites near the industrial area, in the city center, and in a background area, using a high-volume sampler equipped with a quartz fiber filter and a PUF. Each sampling lasted a week.

Results

The concentrations of the organochlorinated pollutants are consistent with literature data (??PCDD/Fs and ??dl-PCBs were 5?C38?fg TEQ/Nm³ and 4?C31?fg TEQ/Nm³, respectively), and an apparent seasonal trend was found with slightly higher concentrations in the winter and lower levels in both summer campaigns. Moreover, the isomer profile of each sampling campaign was compared to the fingerprint of a sintering plant, a cement plant, and an incinerator, the main industrial activities in Trieste.

Conclusions

The organic micropollutants were detected in levels consistent with literature data. The results show that the pollutants are uniformally distributed in the atmosphere of Trieste. PCDD/F fingerprints in each site remained almost identical during summer and winter, confirming the yearly prevalence of the emissions from the nearby sintering plant.     

Formation characteristics of PCDD and PCDF during pyrolysis processes

In recent years, pyrolysis processes have become technologies developed to industrial scale and discussed as alternatives to the existing waste combustion technology. However, little information is published regarding PCDD/F formation characteristics during pyrolysis processes. Two common shredder fractions – industrial light shredder (ILS) and refrigerators (REF) – both with high chlorine and copper content were pyrolysed for this pyrolysis study using a pilot plant with a capacity of 100 kg/h. At oxygen concentrations below 2% and temperatures between 430°C and 470°C, considerable amounts of PCDD/F were formed during the pyrolysis. More than 90% of total TEQ was found in the oil fraction (gas phase). The PCDD/PCDF ratio and the homologue pattern differed significantly from those formed during waste incineration. Considering mono- to octachlorinated congeners, up to 400 times more PCDF were formed compared to PCDD. For the investigated pyrolysis conditions, the formation of low chlorinated congeners was highly favoured. The distribution of TEQ within the individual congeners were very similar in all investigated runs. More than 80% of total TEQ stem from 2,3,7,8-substituted T₄CDF and P₅CDF. The isomer pattern, however, did not show significant differences compared to the common waste incineration pattern suggesting that the basic formation routes are similar.     

Quantification of PCDD/F concentrations in animal manure and comparison of the effects of the application of cattle manure and sewage sludge to agricultural land on human exposure to PCDD/Fs

PCDD/Fs were quantified in samples of cattle, pig, sheep and chicken manure. TEQs ranged from 0.19 ng TEQ/kg dw for the pig manure to 20 ng TEQ/kg dw for one cattle manure sample. Exposure assessments were carried out to compare the effect of various sewage sludge and cattle manure land application scenarios on human PCDD/F exposure. Background exposure was estimated at 4.9 pg TEQ/kg bw/day and it was found that land application of sewage sludge and cattle manure at contemporary rates did not increase PCDD/F TEQ background exposure. It was concluded that the application of sewage sludge, under the new UK guidelines, and cattle manure to agricultural land, do not make a significant contribution to human exposure to PCDD/Fs.     

Survey of commercial pasteurised cows' milk in Wallonia (Belgium) for the occurrence of polychlorinated dibenzo-p-dioxins,dibenzofurans and coplanar polychlorinated biphenyls

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 35 samples of commercial long-life pasteurised cows' milk issued from eight different brands available in Walloon supermarkets (Belgium). The observed congener profile was characteristic of milk samples issued from industrialised countries with good inter and intra-brand reproducibility's. The PCDDs to PCDFs ratio was equal to 1.8 in concentration. The toxic equivalent (TEQ based on WHO-TEF) value for PCDD/Fs in all analysed milks was 1.09+/-0.30 pg TEQ/g fat (range 0.86-1.59), which is below the recommended EU non-commercialisation threshold value of 3 pg TEQ PCDD/Fs/g of milk fat. The mean TEQ value including cPCBs was 2.23+/-0.55 pg TEQ/g fat. These PCBs actually contributed for 49+/-8.6% of the total TEQ. Among PCDD/Fs and cPCBs, tetrachloro dibenzo-p-dioxin (TCDD), pentachloro dibenzo-p-dioxin (PeCDD), pentachloro dibenzofurans (PeCDFs) and 3,3',4,4',5-pentachloro biphenyl (PCB-126) were the most important contributors to the TEQ. Estimated daily intake (EDI) due to consumption of such milks was 0.34 pg TEQ/kg of body weight/day for PCDD/Fs and 0.69 pg TEQ/kg of body weight/day when cPCBs were included.     

Emission of PCDD/Fs and dioxin-like PCBs from metallurgy industries in S. Korea

The metallurgy industry and municipal waste incinerators are considered the main sources of polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs) in many countries. This study investigated the emission factors and total emissions of PCDD/Fs and dioxin-like polychlorinated biphenyls (PCBs) emitted from metallurgy industries (including ferrous and nonferrous foundries) in Korea. The toxic equivalency (TEQ) emission factor of PCDD/Fs was the highest for secondary copper production, at 24451 ng I-TEQ/ton. The total estimated emissions of PCDD/Fs from these sources were 35.259 g I-TEQ/yr, comprising 0.088 g I-TEQ/yr from ferrous foundries, 31.713 g I-TEQ/yr from copper production, 1.716 g I-TEQ/yr from lead production, 0.111 g I-TEQ/yr from zinc production, and 1.631 g I-TEQ/yr from aluminum production. The total estimated annual amounts of dioxin-like PCBs emitted from these sources were 13.260 g WHO-TEQ/yr, comprising 0.014 g WHO-TEQ/yr from ferrous foundries, 12.675 g WHO-TEQ/yr from copper production, 0.170 g WHO-TEQ/yr from lead production, 0.017 g WHO-TEQ/yr from zinc production, and 0.384 g WHO-TEQ/yr from aluminum production. The highest emission factor was found for secondary copper smelting, at 9770 ng WHO-TEQ/ton.     

Monitoring PCDD/Fs, PCBs and metals in the ambient air of an industrial area of Catalonia, Spain

In 2005 and 2006, the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and metals (As, Be, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sn, Tl and V) were measured in air samples collected in an industrial area of Sant Adrià del Besòs (Barcelona, Catalonia, Spain) where a municipal solid waste incinerator (MSWI) is placed, and in a background/control area. In general terms, concentrations of all environmental pollutants were higher at the industrial site. No significant seasonal/temporal variations were observed in any of the areas. No Pearson correlation was found between the PCDD/F concentrations and the environmental conditions of the two sampling periods considered. Principal component analyses (PCA) were performed to get information on the relationship among samples, pollutants, and emission sources. The results indicate that the MSWI of S. Adrià de Besòs is not a significant emission source of the above compounds for the area under its direct influence. Moreover, a notable difference in the PCDD/F congener profiles was found between ambient air and stack gas emissions, indicating that the current levels of PCDD/Fs are more related to other potential emissions sources rather than to those from the MSWI.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from various industrial sources

This study characterized the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the stack flue gases of 17 industrial sources, which were classified into 10 categories. The results show that the mean PCDD/PCDF concentration of secondary zinc smelter (Zn-S) and secondary copper smelter (Cu-S) is 2.44 ng international toxic equivalent (I-TEQ)/Nm3 (N represents normal conditions at 0 degrees C, 760 mmHg), which was found to be significantly greater than that of industrial waste incinerators (mean concentration = 0.15 ng I-TEQ/Nm3). These results imply that the controlling of secondary metallurgical melting processes is more important than industrial waste incineration for the reduction of PCDD/PCDF emissions. The mean emission factors of cement production, Zn-S and Cu-S, are 0.052, 1.99, and 1.73 microg I-TEQ/t product, respectively. For industrial waste incineration, the mean emission factors of waste rubber, waste liquor, waste sludge, industrial waste solid (IWI)-1, IWI-2, IWI-3, and IWI-4 are 0.752, 0.435, 0.760, 6.64, 1.67, 2.38, and 0.094 microg I-TEQ/t feed, respectively. Most of the PCDD/PCDF emission factors established in this study are less than those reported in previous studies, which could be because of the more stringent regulations for PCDD/PCDF emissions in recent years.     

Trends of PCDD/F and PCB concentrations and depositions in ambient air in Northwestern Germany

Time series of polychlorinated dioxins and furans (PCDD/F) and polychlorinated biphenyls (PCB) in ambient air of a large conurbation in North-Western Germany are presented and analyzed. The trend of PCDD/F concentrations, starting from as early as 1988, shows a pronounced decrease by at least one order of magnitude, demonstrating that the emission reductions were effective. The PCDD/F depositions also have decreased by a factor of 5 since 1992. However, both trends have leveled out since 2005. Time series of PCB concentrations and depositions starting in 1994 show only slight decreases for the concentrations and almost no decrease for the depositions. From the decay rates following first order kinetics, half-lives in the order of 5-15 years for the PCDD/F and 15-31 years for the sum of the six indicator PCB could be calculated, which are much longer than the half-lives estimated from their reactivity towards the OH radical. Apparently, small fresh emissions (PCDD/F), considerable secondary emissions and evaporation from contaminated soils slow down their decay in the atmosphere of big conurbations. Analyzing the decay rates of individual PCB congeners shows that the lower chlorinated and more volatile ones are removed faster than the higher chlorinated congeners, probably via gas phase reactions with the OH radical. It can be concluded from the present study that the input of PCDD/F and PCB into the food chain via the air path will continue for another one or two decades in big conurbations.