流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

PCDD/Fs levels in indoor environments and blood of workers of three municipal waste incinerators in Taiwan

This study monitored ambient air concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in three municipal waste incineration plants. Blood PCDD/Fs levels of 133 workers randomly selected from these plants were also measured. The associations between workers' blood PCDD/Fs concentrations and occupational exposures to PCDD/Fs were assessed. Means of air PCDD/Fs levels ranged from 0.08 to 3.01 pg/m3 in international toxic equivalents (I-TEQ). The geometric means of blood PCDD/Fs concentrations were 14.6, 15.8, 19.1 pg/g lipid in World Health Organization (WHO) TEQ, respectively, for workers from three plants. Air levels of total I-TEQ and all congeners, except 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TeCDD) and 1,2,3,4,7,8,9-heptachlorinated dibenzofuran (HpCDF), were significantly higher in plant B. However, blood concentrations of 2,3,7,8-TeCDD, 1,2,3,7,8-PeCDD, 2,3,7,8-TeCDF, 1,2,3,7,8-PeCDF and 1,2,3,4,7,8,9-HpCDF were significantly elevated in plant C workers. Although job contents, duration of employment and time spent in certain location were significantly different among incineration plants, they were not significantly associated with blood concentrations of any congener. Furthermore, results of the multiple regression analysis that assessed important occupational factors simultaneously and adjusted for potential confounders, showed significant associations between four congeners and incineration plant or job contents. However, the results were limited by small R-squares of the regression models. In conclusion, blood concentrations of several PCDD/Fs congeners were significantly different among three incineration plants. The differences were not explained by the discrepancy in job contents, duration of employment, and time activity in these plants.     

PCDD/F and PCB multi-media ambient concentrations, congener patterns and occurrence in a Mediterranean coastal lagoon (Etang de Thau, France)

Ambient concentrations, congener patterns and multi-media distribution of PCDD/Fs and PCBs were determined in air, water, sediment and mussels in a semi-enclosed marine ecosystem (Thau lagoon, France). summation operator2,3,7,8-PCDD/F and summation operator7ICES PCB air concentrations (0.2-1.4 and 31-57pg m(-3), respectively) were typical of rural areas. Concentrations in the water column were very low for PCDD/Fs (163-476fg L(-1)) and low for PCBs (138-708pg L(-1)). PCDD/F and PCB concentrations found in surface sediment (0.15-1.6 and 2.5-33ng g(-1) d.w., respectively) and mussel (13-21pg g(-1) d.w. and 10-39ng g(-1) d.w., respectively) were medium levels. PCDD/F congener patterns observed in air, water particulate phase and sediments were similar suggesting direct coupling among these compartments and atmospheric inputs of PCDD/Fs into the lagoon. Conversely, for the same set of samples, similar patterns were not observed for PCBs in the mentioned compartments.     

Air and soil dioxin levels at three sites in Italy in proximity to MSW incineration plants

Levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in both air and soil samples were measured at three different sites in Italy, in proximity to three municipal solid waste incinerators (MSWIs) to determine baseline contamination and the contributory role of incinerator emissions. At the first site, located in an agricultural, cattle-breeding, typically flattish area of the Po Valley, the dioxin concentrations had already been measured before the start-up of the new MSWI. These dioxin concentrations were then again measured after two years of continual operation of the incinerator. Despite the presence of the plant, the PCDD/Fs concentrations appear not to have been affected and were found to be in a range of 22-125 fg I-TEQ m(-3) in the air samples and 0.7-1.5 pg I-TEQ g(-1) in the soil samples. The second site is located in an industrial district of the Veneto Region, in the surroundings of an old MSWI that is not equipped with Best Available Technology (BAT) dioxin removal system. The PCDD/Fs concentrations in the air samples were between 144 and 337 fg I-TEQ m(-3). This is a typical range of values for industrial areas, while the soil samples showed contamination levels between 1.1 and 1.4 pg I-TEQ g(-1). The third site lies in the Adige Valley, near a MSWI that has been equipped with BAT for flue gas cleaning. The observed values ranged from 10 to 67 fg I-TEQ m(-3) for the air samples and 0.08-1.2 pg I-TEQ g(-1) for the soil samples. The contributory factors of the varying characteristics of the different areas together with the types of technology adopted at each MSWI plant are discussed. The PCDD/Fs levels are subsequently compared with established values from previous studies.     

Assessment of PCDD/F risk after implementation of emission reduction at a MSWI

Municipal solid waste incinerators (MSWIs) have been shown to be important sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The emission of PCDD/Fs by MSWIs is a controversial subject in human health risk assessment. In this study the effect of a MSWI on a residential area was assessed before and after the installation of an additional treatment system for flue gas. This additional treatment system resulted in a dramatic decrease in PCDD/F concentrations in stack flue gas samples by 99.98%, while the concentrations in air decreased by approximately 50% (36,500 and 0.75 pg I-TEQ m(-3) for air in 1999; 3.5 and 0.38 pg I-TEQ m(-3) in 2002; 1.6 and 0.076 pg I-TEQ m(-3) in 2005 for stack gas and air, respectively). Considering the congener distributions of PCDD/Fs between stack flue gas and air samples, the study area seemed to have been contaminated by other urban sources as well as the MSWI. ISC3 model results support the conclusion that this incinerator became only a minor contributor to the study area after installation of the supplementary systems. This resulted from both proper MSWI operation using modern technology and additional sources of contaminants in this region. Finally, PCDD/F uptake by humans through inhalation of contaminated air was estimated. Assuming that inhalation exposure contributes 10% of total exposure, total exposure was lower than WHO guidelines. These results confirm that proper operation and maintenance of the incinerator led to a reduction in emissions and potential health impacts of PCDD/Fs.     

Evaluation of PCDD/F levels in ambient air and soils and estimation of deposition rates in Kocaeli, Turkey

PCDD/F analyses were made in soil and ambient air samples taken from Kocaeli, an industrialized area of Turkey. Results showed that the levels of PCDD/F pollution are comparable to the levels observed in the various urban areas in the world. PCDD/F concentrations in surface soils ranged between 0.4 and 4.27 pg I-TEQ kg(-1) with a geometric mean of 0.76 pg I-TEQ kg(-1), while those in ambient air were between 23 and 563 f gm(-3), with geometric mean of 82.0 f gm(-3). Ambient air PCDD/F concentration in the city center was about 10 times higher than those in the rural area. Combustion activities present in the area were assessed to be the most significant source of the PCDD/F pollution based on the congener and homologue profiles and statistical analysis of the data. The deposition rate modeling of USEPA was applied and the deposition rates were determined in the range between 7.6 and 66.3 ng I-TEQ m(-2)year(-1) with a geometric mean of 15.9 ng I-TEQ m(-2)year(-1). The rates were higher than the recommended deposition rates in relation to the tolerable daily intake (TDI) range of PCDD/Fs for humans. The deposition velocities computed were also found to be high in both low and highly chlorinated PCDD/Fs, and this was attributed to the vapor phase deposition of volatile PCDD/Fs, and the scavenging effect of the precipitation on the particle-bound PCDD/Fs.     

Sampling and analysis of ambient dioxins in northern Taiwan

In this study, ambient air samples were taken concurrently in the vicinity area of a large-scale municipal waste incinerator (MWI) and the background area for measuring polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) concentrations from November 1999 through July 2000 in northern Taiwan. The results obtained from eighteen ambient air samples indicate that the mean PCDD/F concentration of seventeen 2,3,7,8-substituted congeners in wintertime (188–348 fg-I-TEQ/m³) is significantly higher than that measured in summertime (56–166 fg-I-TEQ/m³). In addition, the seasonal PCDD/F concentrations are compared with the ambient air quality data including CO, NO₂, PM₁₀ and TSP sampled from Taipei area to gain better insights. It indicates that the variation of ambient air PCDD/F concentrations is closely correlated with that of PM₁₀ concentrations. Besides, the results indicate that the I-TEQ concentration of ambient air in sampling site B (directly downwind of the MWI) is of the highest while the sampling site A (upwind of MWI) is of the lowest among all sampling sites. This implies that existing MWI can be a significant emitter of PCDD/Fs in this area. Furthermore, the patterns of the PCDD/F congener distribution at all sampling sites (including the background site in Taoyuan) are quite similar. OCDD concentration is of the highest among seventeen PCDD/F congeners investigated and accounts for about 35% of the total concentration. As for the I-TEQ concentrations, 2,3,4,7,8-PeCDF is the most significant contributor, generally being responsible for 30–45% of the total I-TEQ values depending on the sampling sites and seasons.     

PBDD/F impurities in some commercial deca-BDE

The study presented the concentrations and distributions of polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans (PBDD/Fs) as impurities in some commercial decabromodiphenyl ether (DBDE) mixtures that were produced by several manufacturers. The total concentrations of 12 2,3,7,8-substituted tetra- to octa-BDD/F congeners were found to be in the range of 3.4-13.6 (mean 7.8) μg/g, averagely accounting for 99% of total PBDD/Fs. OBDF was the prevailing congener, followed by 1,2,3,4,6,7,8-HpBDF. In addition, OBDD and 1,2,3,4,7,8-HxBDF were also obviously detectable. The total concentrations of PBDD/Fs varied both between the manufacturers and between the lots. On the basis of the global demand for the commercial DBDE in 2001, the annual potential emissions of PBDD/Fs were calculated coarsely to be 0.43 (range: 0.21-0.78) tons. The major dioxin congeners, OBDF and 1,2,3,4,6,7,8-HpBDF, presenting in DBDE, were estimated to be formed from BDE-209, BDE-206, and/or BDE-207 via an intra-molecular elimination of Br₂/HBr.     

Influence of a municipal solid waste incinerator on ambient air and soil PCDD/Fs levels

To examine the influence of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) emissions from a municipal solid waste incinerator (MSWI) on the environment, we measured the levels of PCDD/Fs in ambient air and soil samples collected near a MSWI in Bucheon, Korea. The PCDD/Fs concentrations in the ambient air samples ranged from 0.22 to 1.16 pg I-TEQm(-3) (13.39-75.16 pg m(-3)), with an average of 0.66 pg I-TEQ m(-3) (35.62 pg m(-3)). The soil samples contained between 1.25 and 74.98 pg I-TEQ g(-1) (38.15-3,303.33 pg g(-1)), with an average of 19.06 pg I-TEQ g(-1) (1,077.11 pg g(-1)). These levels were higher than those previously reported by other investigators in a number of surveys. The furan homologues predominated in the air samples and some soil samples, and the soil PCDD/Fs levels decreased with increasing distance from the MSWI. Comparison of the homologue patterns and a multivariate statistical analysis showed that PCDD/Fs emission from the MSWI directly affected the pattern of PCDD/Fs in air, while the PCDD/Fs patterns in soil differed according to the location relative to the MSWI, roads, and construction sites. These results collectively indicate that the MSWI was the major PCDD/Fs emission source in this area, but that unidentified combustion sources and vehicles might influence the environment to some extent.     

Improvements to the UK PCDD/F and PCB atmospheric emission inventory following an emissions measurement programme

PCDD/F data are presented from 75 samples of primary emissions sampled between 1995-97 as part of the compliance monitoring survey undertaken by the UK Environment Agency. Municipal solid waste (MSW), chemical waste and clinical waste incinerators, cement kilns, sinter plants and sewage sludge incinerators were the source categories monitored and reported here. Based on this monitoring programme, the previous national UK emission estimates by Eduljee and Dyke (1) of 560-1100 g I-TEQ a(-1) for 1993 have been revised downwards to 220-660 g I-TEQ a(-1). Despite source reduction measures, MSW incinerators remain a significant source of PCDD/Fs to the atmosphere, contributing between 30-50% of the EPCDD/F I-TEQ emission, rather than the approximately 80% they were estimated to contribute in 1993. 2,3,7,8-substituted PCDD/F congener profile data are presented for some of the source categories and generally support the view that differences in the mixtures ('fingerprints') of PCDD/Fs emitted from different sources are observed. New data on the dioxin-like PCB emissions are presented for cement kilns and sinter plants. These show that TEQ-rated PCBs can make an important contribution to the I-TEQ emitted from certain combustion sources. High concentrations of a full range of PCB congeners/homologues have been measured in the atmosphere close to sintering strands, although the precise source of PCBs from this process remains unclear.     

Ten years measuring PCDDs/PCDFs in ambient air in Catalonia (Spain)

This work summarizes the results of a ten year surveillance programme on PCDD/F in ambient air carried out in Catalonia (Spain). The study has been conducted by the Dioxin Laboratory of Spanish Council for Scientific Research (CSIC) in collaboration with the Environment Department of the Catalonian Government. 175 samples have been collected throughout Catalonia from 1994 to 2004. Different sampling locations classified as industrial, traffic, urban, suburban and rural sites have been monitored in order to find the most contaminated zones as well as the ones with expected background concentrations. The highest concentrations found in this study were determined at the industrial locations. Concentrations ranging from 5 to 1196 fg I-TEQ/m3, with a mean value of 140 fg I-TEQ/m3 and from 10 to 357 fg I-TEQ/m3, with a mean value of 72 fg I-TEQ/m3 were determined in industrial and traffic sampling points, respectively. In contrast, the lowest concentrations were found in rural stations, ranging from 5 to 45 fg I-TEQ/m3, with a mean value of 28 fg I-TEQ/m3. The PCDD/F concentration trend in Catalonian ambient air shown a clear drop of the median values occurred during the study sampling period. A decline of about 70% was observed from 1997-1998 to 2003-2004.     

Post-combustion syntheses of PCDD/F and PBDD/F from halogen-rich fuel is suppressed by a pebble heater technology

GOAL, SCOPE AND BACKGROUND: Changes in German and European legislation shifted processing of polymer-rich shredding residues (SR) from landfill to thermal treatment. However, when waste of electric and electronic equipment (WEEE) is the source of SR, thermal treatment is complicated by halogens as well as the presence of polybrominated dioxins and furans (PBDD/F) and brominated flame retardants (BFR). Hence, WEEE requires high temperature incineration with sufficient residence times. Post-combustion synthesis of polyhalogenated dioxins and furans (PXDD/F) is dominant in the temperature range between 250-450 degrees C. Thus, a very rapid gas cooling from 450 degrees to 250 degrees C is important for proper raw gas treatment. The pebble heater technology developed by ATZ Entwicklungszentrum (Sulzbach-Rosenberg, Germany) might serve as an alternative to the state-of-the-art quench cooling. It is based on the application of a pebble bed of natural bulk material, which the exhaust gases flows through radially. It provides an excellent heat transfer and a temperature gradient in the range of 1,500-2,000 K/m. The paper presents data of a pilot application of the pebble heater technology for the treatment of raw gas derived from the incineration of polymeric materials from WEEE. METHODS: A liquid fuel was chosen in order to minimise technical modifications of the plant. It was analysed for halogens by x-ray fluorescence, for brominated flame retardants by HPLC-UV/MS and for PXDD/F by GC-HRMS. Combustion gases were rapidly cooled down to temperatures below 200 degrees C and emissions of PBDD/F and PCDD/ F were estimated without further off-gas treatment. PBDD/F emissions were computed as PCDD/F toxicity equivalents applying two different calculation approaches. RESULTS AND DISCUSSION: PCDD/F emissions accounted for 0.04 ng I-TEQ/Nm3 and are in compliance with European emission limits. Calculated PBDD/F toxicity equivalents exceeded the emission limit of 0.1 ng I-TEQ/Nm3 by factors of 75 and 208 depending on the calculation approach. A mass balance of PBDD/F and PCDD/F congeners revealed an efficient elimination of more than 95% in most cases. Lower reduction rates (76% for 2,3,7,8-TeBDF and 82% for 1,2,3,7,8-PeBDF) were attributed to incomplete combustion. An intended recovery of halogens by one-stage scrubbing downstream of the pebble heater was ineffective, recovering 28% of the applied chlorine and 9% of the bromine, only. CONCLUSIONS: Our pilot incineration test indicates that the pebble heater technology can effectively suppress a post-combustion synthesis of PCDD/F and PBDD/F, resulting in low PCDD/F emission levels without further off-gas treatment. The presented data state that WEEE is sensible to incomplete combustion, which will lead to increased PBDD/F emissions without increasing PCDD/F emission limits. This finding is especially relevant for small and low-technical incineration appliances, which have been reported to treat WEEE in developing countries and are considered to serve as a significant source of PXDD/F these days. RECOMMENDATIONS AND PERSPECTIVES: Monitoring of PCDD/F emissions only might considerably underestimate the total emission of dioxins and dioxin-like compounds. It is therefore an ineffective means for assessing resulting health risks, at least for those waste treatment plants which are considered to handle the increasing amounts of PBDD/ F-containing polymers from WEEE in future. Consequently, it is recommended to initiate a screening programme for PXDD/F emissions in large scale incineration facilities which are capable of treating WEEE shredder residues.     

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

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

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPXDD/Fs) in the atmosphere and bulk deposition in Kyoto, Japan

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPXDD/Fs) in atmosphere, bulk atmospheric deposition and soil in Kyoto, which is an urban city in Japan, were measured. Decabromodiphenyl ether (D(10)BDE, BDE-209) was detected in relatively high concentrations compared to other PBDE congeners in most samples. Similar results, in which D(10)BDE was predominantly detected, were reported in other studies in Japan. However, these homologue profiles differ from those of studies conducted in North America. The partitioning of semivolatile organic compounds between atmospheric gas phase and particulate-associated phase is an important factor in their environmental behavior. In this study, atmospheric particulate phase fraction (f(P)) of the brominated compounds increased with increasing bromine number, and f(P) was higher in samples collected in winter than in those collected in summer. Moreover, f(P) of PBDFs and MoBPXDFs was higher than that of PCDFs with the same halogen number. These results agree well with expectations from the vapor pressure of the brominated compounds and PCDD/Fs. Among the brominated compounds in the atmosphere, the level of MoBPXDD/Fs correlates positively with that of PCDD/Fs. This relationship has been previously observed in waste incineration samples. These results suggest that one of the sources of MoBPXDD/Fs in the atmosphere is incineration byproduct. The level of PBDD/Fs seems to correlate positively with that of PBDEs. This relationship suggest that the PBDD/Fs in the atmosphere relate to PBDEs, which is an impurity of PBDE products, or formed by the manufacture or combustion of plastics containing PBDEs.     

Evaluation of PCDD/F congener distributions in MWI flue gas treated with SCR catalysts

Partitioning of PCDD/F congeners between gaseous and particulate phases and removal efficiencies of the air pollution control devices (APCDs) for PCDD/Fs at an existing municipal waste incinerator (MWI) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP), wet scrubbers (WS) and selective catalytic reduction system (SCR) as APCDs. The average PCDD/F concentration of stack gas is 1.49 ng/N m³, and the International Toxic Equivalent Quantity (I-TEQ) is 0.043 ng-I-TEQ/N m³. The EP increases PCDD/F concentration by 174.0% while the average removal efficiency of WS + SCR system for PCDD/Fs reaches 99.1%. In addition, the PCDF removal efficiency achieved with WS + SCR system (97.1–99.8%) is higher than that for PCDDs (96.5–99.3%). The results obtained on gas/particulate partitioning in flue gas indicate that the particulate-phase PCDD/Fs accounted for 65% at the inlet of EP, 20% at the outlet of EP and 50% at the stack, respectively, of the total PCDD/F concentrations. This study also indicates that as the chlorination level of PCDD/F congeners increases, the percentage of PCDD/Fs existing in gas phase decreases in all flue gas samples.     

Identifying source regions for the atmospheric input of PCDD/Fs to the Baltic Sea

PCDD/F contamination of the Baltic Sea has resulted in the European Union imposing restrictions on the marketing of several fish species. Atmospheric deposition is the major source of PCDD/Fs to the Baltic Sea, and hence there is a need to identify the source regions of the PCDD/Fs in ambient air over the Baltic Sea. A novel monitoring strategy was employed to address this question. During the winter of 2006–2007 air samples were collected in Aspvreten (southern Sweden) and Pallas (northern Finland). Short sampling times (24 h) were employed and only samples with stable air mass back trajectories were selected for analysis of the 2,3,7,8-substituted PCDD/F congeners. The range in the PCDD/F concentrations from 40 samples collected at Aspvreten was a factor of almost 50 (range 0.6–29 fg TEQ/m³). When the samples were grouped according to air mass origin into seven compass sectors, the variability was much lower (typically less than a factor of 3). This indicates that air mass origin was the primary source of the variability. The contribution of each sector to the PCDD/F contamination over the Baltic Sea during the winter half year of 2006/2007 was calculated from the average PCDD/F concentration for each sector and the frequency with which the air over the Baltic Sea came from that sector. Air masses originating from the south–southwest, south–southeast and east segments contributed 65% of the PCDDs and 75% of the PCDFs. Strong correlations were obtained between the concentrations of most of the PCDD/F congeners and the concentration of soot. These correlations can be used to predict the PCDD/F concentrations during the winter half year from inexpensive soot measurements.     

PCDD/F and "Dioxin-like" PCB emissions from iron ore sintering plants in the UK

Investigations have been carried out at the three Corus UK sinter plants over the period 2002-2004 to characterise the emissions of both 2,3,7,8-PCDD/Fs and WHO-12 PCBs, to estimate annual mass releases of these organic micro-pollutants using the I-TEF and WHO-TEF schemes, and to investigate the formation of PCBs in the iron ore sintering process. Results showed that the sintering of iron ore produces a characteristic WHO-12 PCB and PCDD/F congener pattern that is substantially the same for all UK sinter plants. With regard to WHO-12 PCBs, the most abundant congeners were typically PCBs 118 (6-9 ngNm(-3)), 105 (2-4 ngNm(-3)) and 77 (2-3 ngNm(-3)). All other WHO-12 PCBs were also detected at concentrations around 1 ngNm(-3). All sinter plants investigated exhibited very similar TEQ concentrations. WHO-12 PCB emissions were in the range 0.042-0.111 ngWHO-TEQNm(-3), whereas PCDD/F emissions ranged from 0.39 to 1.62 ngWHO-TEQNm(-3). PCDF congeners were the main contributors to the overall TEQ in sintering emissions (ca. 85%). Amongst WHO-12 PCBs, PCB 126 was the only noteworthy contributor to total TEQ (ca. 5-7%), a similar contribution to that from PCDDs. Based on the measurements that Corus UK has undertaken at these three sinter plants, annual mass releases of WHO-12 PCBs and PCDD/Fs have been calculated. For UK sinter plants, a total mass release of 29.5 g WHO-TEQ per annum [WHO-12 PCBs+PCDD/Fs] has been estimated, representing 9% of the total PCDD/F emissions to the UK atmosphere. Measurements were also carried out at a UK sinter plant to determine the windleg emission profile of WHO-12 PCBs. Results showed that WHO-12 PCBs were formed in the same regions of the sinter strand as 2,3,7,8-PCDD/Fs, indicating that there was a strong correlation between the formation of WHO-12 PCBs and PCDD/Fs in the iron ore sintering process.     

Seasonal variation of PCDD/Fs in the metropolis of Istanbul,Turkey

Atmospheric concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) compounds were investigated at three different regions of Istanbul which reflect urban, urban/industrial, and sub-urban characteristics. Air samples were collected simultaneously for both gaseous and particulate phases using high volume samplers on monthly time intervals from May 2011 to October 2012. The highest concentrations (3,056 fg/m³ and 156 fg I-TEQ/m³) were observed at the sampling site that reflects traffic, residential, and industrial emission source characteristics, while the lowest concentrations (829 fg/m³ and 38 fg I-TEQ/m³) were observed at the sampling point which is far away from centrum and reflects sub-urban characteristics. Concentrations of PCDD congeners were, in general, found to be higher than PCDF congeners, and OCDD, 1,2,3,4,6,7,8-HpCDD/F, and OCDF congeners were recorded to be the most abundant congeners. Winter season concentrations were also found to be higher especially in particulate phase. As a result, combustion processes such as motor vehicles and residential heating equipment were thought to be the principal sources of emissions of PCDD/F compounds when both congener profiles and seasonal variations are considered. Basic statistical evaluation of the data resembled high degree of inverse correlations between PCDD/F concentrations and UV and solar radiation.     

Occurrence of PCDD/Fs in urban air before and after the ban of leaded gasoline

The source of PCDDs and PCDFs in automotive exhaust is not yet fully explained. The chlorinated hydrocarbons used in the formulation of lead-alkyl additives were suspected as a possible major source. Based on this, the decreasing use of leaded gasoline followed by its final ban (occurred on 1/1/2002, in Italy) should have resulted in a decreasing presence of PCDD/Fs in urban air and possibly some differences in their profile. To investigate these aspects, we monitored PCDD/Fs for one year starting in September 2001, at a medium-traffic road site in Rome, with weekly frequency. Results were then compared with those obtained in a previous study performed before the ban (from February 2000 to January 2001) at the same site. As compared with the previous study, the yearly-averaged overall PCDD/F concentration, as toxic equivalent of 2,3,7,8-TCDD, decreased from 60 to 50 fg m(-3) I-TEQ; it remained unchanged, however, if one sample with a particularly high PCDD/F content was excluded from each data set. The monthly trend confirmed the one found in the former study. On an annual basis, the two mean congener profiles were almost identical. The concentration levels and the constancy of profiles, as calculated for the two periods, do not support the hypothesis of a major role of leaded gasoline, substantially different from unleaded one, in contributing to PCDD/F air pollution.     

Nationwide monitoring of atmospheric PCDD/Fs and dioxin-like PCBs in South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured in ambient air samples collected from different parts of South Korea in 2008, and the measured levels were used for assessing the spatial and temporal distribution of atmospheric PCDDFs and DL-PCBs in South Korea. The average concentrations of atmospheric PCDD/Fs and DL-PCBs among the 37 sites were 28 fg I-TEQ m⁻³ (ND ∼ 617) and 1 fg WHO-TEQ m⁻³ (ND ∼ 0.016). Elevated atmospheric levels of PCDD/Fs and DL-PCBs observed at residential/industrial sites and in the north-west of Korea, indicated a potential contribution and impacts of anthropogenic sources of PCDD/Fs and DL-PCBs. These levels were similar or lower than those previously reported in other ambient air surveys. Average concentrations of PCDD/Fs showed small seasonal variations (ANOVA analysis, p = 0.144). The highest concentrations of PCDD/Fs were observed during winter, followed by spring, autumn and summer. Atmospheric PCDD/Fs and DL-PCBs in South Korea rapidly decreased during the last 10 years (1998-2008), demonstrating the efficiency of stricter regulations and the application of best available technologies/best environmental practices at emission sources. Comparison of the congener profiles and principal component analysis showed that current atmospheric PCDD/Fs are mostly influenced by industrial sources and PCBs from old commercial PCB uses. Nationwide POPs monitoring will continue and allows an effective evaluation of the implementation of the Stockholm Convention on POPs.