Flow analysis of PCDD/Fs for Tarragona Province, Spain

The present study was intended to establish an inventory of PCDD/F emissions in Tarragona Province (Catalonia, NE Spain), as a preliminary phase in the development of a flow analysis of PCDD/Fs in this Province. In 1999, global PCDD/F emissions reached a value of 2.24 g I-TEQ/y, which means a density of 3.8 micrograms I-TEQ/inhabitant/y. The low amount of PCDD/Fs emitted to air by the only municipal solid waste incinerator in the Province (approximately 0.04% of the total) has been one of the most notable results. As a reflection of uncertainties in the estimates for individual sources, the 90th percentiles of PCDD/F releases for 1999 ranged up to 4.1 g I-TEQ/y.     

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.     

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.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from stack gases of electric arc furnaces and secondary aluminum smelters

This study investigates the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from four electric arc furnaces (EAFs) and eight secondary aluminum smelters (secondary ALSs) in Taiwan. The mean PCDD/F International-Toxicity Equivalents (I-TEQ) concentrations in the stack gases of these EAFs and secondary ALSs are 0.28 ng I-TEQ/Nm3 (relative standard deviation [RSD]= 100%) and 3.3 ng I-TEQ/Nm3 (RSD = 260%), respectively. The high RSDs, especially for those obtained from secondary ALSs, could be caused by the intrinsic differences in their involved feeding materials, furnace operating conditions, and air pollution control devices. The mean I-TEQ emission factor of PCDD/Fs for EAFs (1.8 microg I-TEQ/tonne-feedstock) is lower than that for secondary ALSs (37 microg I-TEQ/tonne-feedstock). This result might be because the involved furnace temperatures for secondary ALSs (650-750 degrees C) are lower than those for EAFs (1600-1700 degrees C), resulting in the deterioration of the combustion condition, leading to the formation of PCDD/Fs during the industrial process. This study found that the total PCDD/F emissions from EAFs (20 g I-TEQ/yr) and secondary ALSs (18 g I-TEQ/yr) are approximately 27, 53, and approximately 24, 49 times higher than those from municipal solid waste incinerators (MSWIs; 0.74 g I-TEQ/yr) and medical waste incinerators (MWIs; 0.37 g I-TEQ/yr), respectively; while those are 44 and 40% of total PCDD/F emission from sinter plants (45 g I-TEQ/ yr), respectively. Considering a more stringent emission limit has been applied to waste incinerators (0.1 ng I-TEQ/Nm3) in Taiwan lately, the results suggest that the control of the emissions from metallurgical processes has become the most important issue for reducing the total PCDD/F emission from industrial sectors to the ambient environment.     

Human exposure to dioxins and furans: application of the substance flow analysis to health risk assessment

Substance Flow Analysis (SFA) is an important instrument that allows for the undertaking of environmental management for a specific contaminant. 'Control Analysis' is a tool that assesses the effect on a target flow of changes in flows forming part of a control basis set. The purpose of the present study was to perform a modeling of the annual PCDD/F flows in Tarragona Province and to apply the model for human health risk assessment. The validation of the model has been evaluated by comparing estimated fluxes with experimental values. Eleven subsystems, as well as a set of 88 flows of the system in Tarragona Province were considered. The total PCDD/F accumulation in Tarragona Province was between 62.6 and 159.5 g I-TEQ/y. Accumulation in sediments (27.9-74.6 g I-TEQ/y) and soils (35.0-80.8 g I-TEQ/y) are the two principal modes of deposition. Estimated flow in human adipose tissue means a mean intake of PCDD/F (via ingestion and inhalation) of 243 pg I-TEQ/person/day. The food chain pathway accounts for 99% of the total daily intake. As a result of the simulation, a 100% decrease in industrial emissions would cause a 1.7% reduction in the PCDD/F accumulation in humans. In turn, a 100% reduction of PCDD/Fs in the industrial waste waters would cause only an insignificant 0.1% decrease in the accumulation of PCDD/Fs in humans.     

Sources of dioxins in the United Kingdom: the steel industry and other sources

Several countries have compiled national inventories of dioxin (polychlorinated dibenzo-p-dioxin [PCDD] and polychlorinated dibenzofuran [PCDF]) releases that detail annual mass emission estimates for regulated sources. High temperature processes, such as commercial waste incineration and iron ore sintering used in the production of iron and steel, have been identified as point sources of dioxins. Other important releases of dioxins are from various diffuse sources such as bonfire burning and domestic heating. The PCDD/F inventory for emissions to air in the UK has decreased significantly from 1995 to 1998 because of reduced emissions from waste incinerators which now generally operate at waste gas stack emissions of 1 ng I-TEQ/Nm3 or below. The iron ore sintering process is the only noteworthy source of PCDD/Fs at integrated iron and steelworks operated by Corus (formerly British Steel plc) in the UK. The mean waste gas stack PCDD/F concentration for this process is 1,2 ng I-TEQ/Nm3 based on 94 measurements and it has been estimated that this results in an annual mass release of approximately 38 g I-TEQ per annum. Diffuse sources now form a major contribution to the UK inventory as PCDD/Fs from regulated sources have decreased, for example, the annual celebration of Bonfire Night on 5th November in the UK causes an estimated release of 30 g I-TEQ, similar to that emitted by five sinter plants in the UK.     

The Spanish dioxin inventory part I: Incineration as municipal waste management system

The main objectives of the Spanish dioxin inventory and the incidence of municipal waste incinerators in the PCDD/Fs releases in the period from January 1997-November 1999 are presented. Preliminary data about the stack emission levels, fly ashes and slags as solid residues and the PCDD/Fs input in the USW are also presented to elaborate an initial balance for the incineration sector. A great decrease, from 20 to 1.2 g I-TEQ/y, from incineration gas emissions has been observed since 1996. The preliminary balance in the MWI sector suggests an overall PCDD/Fs destruction. The calculated emission factor, 1.06 microg I-TEQ/Mg, indicates a high quality of the air pollution control systems. The assumption of PCDD/Fs in the USW permits an initial evaluation of other waste management systems.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans emissions from open burning of crop residues in China between 1997 and 2004

Annual emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from open burning of crop residues in each province of China mainland between 1997 and 2004 were estimated to be ranged from 1.38x10(3) to 1.52x10(3) g I-TEQ/yr, with the average of 1.50+/-0.08x10(3) g I-TEQ/yr, which contributed to approximately 10% approximately 20% of the total emissions in China. The PCDD/F emissions mainly occurred in the largest crop-producing provinces, especially in those of higher economic levels. The major sources of PCDD/F emissions from open burning in China were found to be cereal residues (i.e. rice, wheat, and corn), which accounted about 70% of the total emissions. Moreover, the first-order one-variable grey differential equation model (GM (1,1) model) for annual emissions of PCDD/Fs was established based on grey system theory. The GM (1,1) model was proved to be robust to predict the annual PCDD/F emissions from crop residue field burning in forthcoming years.     

Environmental impact of a new hazardous waste incinerator in Catalonia,Spain: PCDD/PCDF levels in herbage samples

In April 1996 and 1998, the concentrations of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were determined in 40 herbage samples collected in the neighborhood of a hazardous waste incinerator (HWI) under construction in Constanti (Catalonia, Spain). In April 2000, 20 months after the HWI began operating, herbage samples were again collected at the same sampling points in which samples had been taken in the previous surveys. PCDD/F concentrations ranged between 0.13 and 0.65 ng I-TEQ/kg (dry matter), with a median and mean values of 0.29 and 0.32 ng I-TEQ/kg (dry matter), respectively. The results were compared with those obtained in the 1996 (median, 0.53 ng I-TEQ/kg; mean, 0.61 ng I-TEQ/kg) and the 1998 (median, 0.23 ng I-TEQ/kg; mean, 0.31 ng I-TEQ/kg) surveys. While in the period 1996-1998 a significant decrease (49%, P < 0.001) in the mean PCDD/F levels was noted, in the period 1998-2000 an increase of 3% (P > 0.05) was found in the concentrations of PCDD/Fs. The analysis of the results suggests two potential hypotheses: either the emissions of PCDD/Fs from the HWI are not negligible, or the current PCDD/F emissions from other sources near the HWI remained at similar levels to those reached in 1998. Anyhow, an exhaustive evaluation of the present data shows an absence of notable PCDD/F contamination by the HWI in the area under its direct influence. It seems also probable that the decline in the atmospheric levels of PCDD/Fs due other emission sources of PCDD/Fs in this area is currently stopped.     

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.     

Study of PCDD/Fs distribution in fly ash,ash deposits,and bottom ash from a medical waste incinerator in China

Over the past decades in China, the number of medical waste incinerators (MWIs) has been rising rapidly, causing emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, samples of fly ash, ash deposits, and bottom ash from typical MWIs were analyzed for PCDD/Fs and their distribution characteristics. Results showed international toxic equivalent (I-TEQ) values in the range of 6.9–67 ng I-TEQ/g in fly ash and ash deposits, whereas the concentration in bottom ash was extremely low (only 1.33 pg I-TEQ/g), yet the generation of PCDD/Fs was mostly de novo synthesis in fly ash and ash deposits according to the ratio of PCDFs to PCDDs; the major distribution differences of PCDD/Fs in fly ash was manifested by the content of toxic furan 2,3,7,8-TCDF, but other toxic PCDD/Fs showed similar distribution. Other findings are that 2,3,4,7,8-PeCDF had the most contribution to TEQ concentration, and that the most abundant toxic furan congener is 1,2,3,4,6,7,8-HpCDF. Correlation analysis showed that there was no significant correlation between PCDD/Fs concentration and several other physical and chemical parameters.

Implications: This paper is of interest because it presents the emission performances of PCDD/Fs in ash from medical waste incineration in China. PCDD/F contents in fly ash and ash deposits vary between 6.9 and 67.3 ng I-TEQ/g. However, the concentration in bottom ash was extremely low (only 1.33?×?10^?3 ng I-TEQ/g). The fingerprints of PCDD/Fs in fly ash are almost similar, except for 2,3,7,8-TCDF. There is no marked correlation between PCDD/Fs and other physicochemical properties.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

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.     

PCDD/F inhibition by prior addition of urea to the solid fuel in laboratory experiments and results statistical evaluation

The objectives of this work were to study the effect of urea addition to the fuel before the combustion on the suppression of PCDD/F emissions, to examine the influence of urea to PCDD/F isomer patterns by employing statistical analysis techniques and to determine the most effective method of urea addition. Urea in the form of powder and as an aqueous solution was mixed with RDF and the fuel mixtures were incinerated in a lab-scale reactor at 1000 degrees C. PCDD/F emitted during combustion experiments were collected in a quartz wool filter downstream the reactor unit. Analysis and quantification of PCDD/F showed that urea significantly affected PCDD/F emissions. Combustion of RDF containing 10% w/w urea resulted in PCDD/F emissions lower than 8 I-TEQ ng/g RDF, while the corresponding average value from single RDF combustion was 17 I-TEQ ng/g RDF. The PCDD/F prevention capacity of urea was independent from the method of urea addition to the fuel, as similar results were obtained after the addition of urea in the solid and in the aqueous phases. Results assessment by statistical methods showed that isomer patterns remained almost stable and were not affected by the method of urea addition.     

Comparison of emission of dioxins and furans from gasohol- and ethanol-powered vehicles

The exhaust emissions of 17 polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were investigated in two spark-ignition light-duty vehicles, one gasohol-fueled and a flexible-fuel one fueled with hydrated ethanol. Gasohol is a mixture of gasoline and 22% ethanol. The influence of fuel type and quality, lubricant oil type, and use of fuel additives on the formation of these compounds was tested using standardized U.S. Federal Test Procedure (FTP)-75 cycle tests. The sampling of the PCDD/Fs followed the recommendations of a modified U.S. Environmental Protection Agency (EPA) Method 23 (www.epa.gov/ttn/ emc/promgate/m-23.pdf) and the analysis basically followed the U.S. EPA Method 8290 (http://www.epa.gov/osw/ hazard/testmethods/sw846/pdfs/8290a.pdf). Results showed that emission factors of PCDD/Fs for the.gasohol vehicle varied from undetected to 0.068 pg international toxic equivalency (I-TEQ) km(-1) (average of 0.0294 pg I-TEQ km(-1)), whereas in the ethanol vehicle they varied from 0.004 to 0.157 pg (I-TEQ) km(-1) (average of 0.031 pg I-TEQ km(-1)). In the gasohol-powered vehicle, the use of fuel additive diminished the emission of Octachlorodibenzo-p-dioxin (OCDD) significantly, whereas in the ethanol vehicle no significant associations were observed between the investigated variables and the emissions.     

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.     

First assessment of dioxin emissions from coal-fired power stations in Spain

In this work, the findings of the first assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in emissions releases to the atmosphere from coal-fired power plants are given. A total of five plants were selected for the study located at different provinces in Spain. In all the cases, the results revealed very low levels, in the range of 0.41 pg I-TEQ/Nm(3). The profile indicated in the majority of the cases predominance of highly chlorinated congeners being OCDD the most important contributor. The findings were also used to estimate contribution of PCDDs/PCDFs emitted from coal-fired power plants in Spain. Individual plant results revealed values below 0.02 g I-TEQ per year and plant. Nevertheless, considering the total coal consumption in Spain in 1997, the values are comparable to those reported in other countries in the range of 0.6-0.7 g I-TEQ per year. Moreover, emission factors were determined considering operating conditions of evaluated plants. In general, large variability was observed and values below 1-5 pg I-TEQ/kg coal were early reached.     

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.     

PCDD/F emissions from heavy duty vehicle diesel engines

The currently available information on PCDD/F emissions from diesel vehicles is briefly surveyed. Considerable uncertainty is identified concerning the emissions from heavy duty diesel trucks which have been measured only twice so far. These measurements led to emission factors differing by a factor of 200; similar discrepancy was also revealed by measurements of ambient air in traffic tunnels. New PCDD/F emission measurement results are presented which have been carried out at the exhaust systems of a stationary engine and of a modern heavy duty vehicle engine at transient operation conditions simulated on a test bench. PCDD/F concentrations in the exhaust gases were found to be in the range of control blank samples. Based on the highest concentration observed in the truck engine exhaust (9.7 pg I-TEQ/dry standard m3) a worst case estimate of the annual PCDD/F emission freight from diesel fuel combustion in the European countries of about 30 g I-TEQ/year is calculated. This emission appears to be irrelevant compared to the overall emission rate of more than 6,000 g I-TEQ/year being inventoried recently. Finally the possibilities to link congener/homologue profiles of diesel emission to profiles found in food or human samples are discussed.     

Evaluation of the Spanish hot dip galvanising sector as a source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans

A survey to estimate the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) emissions of Spanish hot dip galvanising sector was carried out during 2002. This investigation is the first presenting Spanish experimental data related to this industrial sector. Three different matrices: flue gas, ash and filter dust were tested to quantify the PCDD/Fs generated during the galvanising process. The organic source of PCDD/F formation could be from the insufficient degreasing o from inhibitors or additives used in the pickling steps such as quinoline, isoquinoline, 8-methylquinoline or polyether phosphoric acid. Low levels PCDD/Fs were achieved in air emissions when air control devices are used. On the contrary, filter dusts are highly contaminated; indicating that the absence of air control devices would increase the risk of fugitive emissions. Homologue profiles and Principal Component Analysis demonstrate there are differences in the formation mechanisms in the bath zone (ashes) compared to the stack location (filter dusts and air emissions), related to the de novo synthesis and reaction time. The annual PCDD/F emission to the atmosphere for this sector during 2002 has been estimated in 0.023g I-TEQ. The emission factor of plants with air control devices has been calculated at 0.030microg I-TEQ/ton of galvanised steel.