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.     

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.     

Emissions of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Various Industrial Sources

Abstract

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 °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 μg 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 μg 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.     

An assessment of dioxin contamination from the intermittent operation of a municipal waste incinerator in Japan and associated remediation

Significant dioxin (polychlorinated dibenzo-para-dioxins (PCDDs)/polychlorinated dibenzo-furans (PCDFs)) pollution from a municipal solid waste incinerator was discovered in 1997 in Osaka prefecture/Japan. The cause and mechanism of pollution was identified by a detailed assessment of the environment and incinerator plant. The primary sources of PCDD/PCDF pollution were high dioxin releases from an intermittently operated waste incinerator with PCDD/PCDF emissions of 150 ng-TEQ/Nm³. PCDD/PCDF also accumulated in the wet scrubber system (3,000 μg TEQ/L) by adsorption and water recirculation in the incinerator. Scrubber water was air-cooled with a cooling tower located on the roof of the incinerator. High concentrations of dioxins in the cooling water were released as aerosols into the surrounding and caused heavy soil pollution in the area near the plant. These emissions were considered as the major contamination pathway from the plant. Decontamination and soil remediation in and around the incinerator plant were conducted using a variety of destruction technologies (including incineration, photochemical degradation and GeoMelt technology). Although the soil remediation process was successfully finished in December 2006 about 3 % of the waste still remains. The case demonstrates that releases from incinerators which do not use best available technology or which are not operated according to best environmental practices can contaminate their operators and surrounding land. This significant pollution had a large impact on the Japanese government’s approach toward controlling dioxin pollution. Since this incident, a ministerial conference on dioxins has successfully strengthened control measures.     

Long-term automated sampling of PCDD/PCDF flue gas: current status and critical issues

After entry into force of the Stockholm Convention and Aarhus Protocol and in order to implement the upcoming European legal background, the European countries are asked to apply control measures to reduce the release of persistent organic pollutants (POPs) such as dioxins and furans (PCDD/PCDF) and polychlorinated biphenyls as well as to establish POPs release inventories. In this perspective, development of measuring techniques of emissions is a focal issue in acquiring useful information. In this paper, results of various measurement campaigns at different municipal waste incineration (MWI) plants using long-term automated sampling of PCDD/PCDF are presented. The samples collected from both manual and automated campaigns were analyzed following the European Standard EN-1948:2006 by high-resolution gas chromatograph/high-resolution mass spectrometer. Performances of two different commercial systems have been investigated. Anomalous values occurred during one long-term campaign (22.16 pg I-toxic equivalent (TEQ)/Nm(3)), compared to average values (4-5 pg I-TEQ/Nm(3)) of the MWI. At this maximum value, a main occurrence of abnormal and instable operating conditions has been found. Sampling based on long-term basis was found to be more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Nevertheless, the results of long-term campaigns demonstrate that emission levels detected in 15-30 days campaigns, when unsteady operating conditions can occur, as start-up and shut down, are not immediately comparable to the typical levels in a 6-8 h, when operating conditions are generally stable. Moreover, there are often differences observed in the congener profiles between short- and long-term campaigns.     

HCB,PCB, PCDD and PCDF emissions from ships

Since current estimates of hexachlorobenzene (HCB), polychlorinated biphenyls (PCB), dioxins (PCDD) and furans (PCDF) from ships are based on a relatively limited and old data set, an update of these emission factors has been outlined as a target towards improved Swedish emission inventories. Consequently, a comprehensive study was undertaken focusing on these emissions from three different ships during December 2003 to March 2004. Analyses were performed on 12 exhaust samples, three fuel oil samples and three lubricating oil samples from a representative selection of diesel engine models, fuel types and during different “real-world” operating conditions.The determined emissions corresponded reasonably well with previous measurements. The data suggest however that previous PCDD/PCDF emission factors are somewhat higher than those measured here. As expected the greatest emissions were observed during main engine start-up periods and for engines using heavier fuel oils. Total emissions for 2002, using revised emission factors, have been calculated based on Swedish sold marine fuels and also for geographical areas of national importance. In terms of their toxic equivalence (WHO-TEQ), the PCDD/PCDF emissions from ships using Swedish fuels are small (0.37–0.85 g TEQ) in comparison to recent estimates for the national total (ca. 45 g TEQ). Emissions from other land-based diesel engines (road vehicles, off-road machinery, military vehicles and locomotives) are estimated to contribute a further 0.18–0.42 g TEQ. Similarly, HCB and PCB emissions from these sources are small compared to 1995 national emission inventories.     

Dioxin emissions from waste incinerators

Mechanisms that have been proposed to account for the emission of PCDD/PCDF from municipal waste incinerators were evaluated in the light of extensive experimental data obtained from the Quebec City municipal solid waste incinerator by Environment Canada. It was found that PCDD/PCDF emissions were closely related to the quantity of material entrained by the combustion gases.     

The European dioxin air emission inventory project--final results

Main results of the second stage of the so-called "European Dioxin Emission Inventory" are presented. They cover emission testing data gained from various facilities in the EU (among these the first emission measurements reported from Portugal and Greece) and some central European countries. Further, updated dioxin emission estimates for the most important emission sources in the 17 western European countries and an evaluation of the emission time trend from 1985 to 2005 are presented. The major conclusions are, that at present, iron ore sintering is likely to be the most important emission source type followed by the former "No. 1", municipal waste incineration; measurement data from a considerable number of installations are still missing, in particular from the metal industries in Spain and Italy; there still exist an unknown number of health care waste incinerators with flue gas PCDD/F concentrations above 100 ng I-TEQ/m3 which must be considered as important local sources; in general, considerable emission reduction has been achieved with respect to the industrial emission sources, whereas emissions from non-industrial sources hardly decreased; hence, in the near future the emissions from non-industrial sources are likely to exceed those from industrial installations; the goal of 90% emission reduction set in the 5th EU Action Programme will be achieved for some source types only.     

Open burning of household waste: Effect of experimental condition on combustion quality and emission of PCDD, PCDF and PCB

Open burning for waste disposal is, in many countries, the dominant source of polychlorinated dibenzodioxins, dibenzofurans and biphenyls (PCDD/PCDF/PCB) release to the environment. To generate emission factors for open burning, experimental pile burns of about 100 kg of household waste were conducted with emissions sampling. From these experiments and others conducted by the same authors it is found that less compaction of waste or active mixing during the fire - “stirring” - promotes better combustion (as evidenced by lower CO/CO₂ ratio) and reduces emissions of PCDD/PCDF/PCB; an intuitive but previously undemonstrated result. These experiments also support previous results suggesting PCDD/PCDF/PCB generation in open burning - while still highly variable - tends to be greater in the later (smoldering) phases of burning when the CO/CO₂ ratio increases.     

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.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in the Kanto Region, Japan

The atmospheric bulk (dry and wet) deposition of dioxins was investigated at four locations (Tokyo, Yokohama, Tsukuba, and Tanzawa) in the Kanto region (in Japan) over one year using a stainless-steel pot. Annual average polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) deposition fluxes were estimated to be from 450 to 1300 ng/m2/yr, and the annual average TEQ fluxes from 5.7 to 17 ng-TEQ/m2/yr at the four locations. The PCDD/PCDF deposition flux was higher in winter than in summer. The deposition flux could be related to ambient temperature, particularly for less chlorinated PCDDs/PCDFs, while the deposition flux is not necessarily related to the amount of precipitation. The PCDD/PCDF deposition flux increased as the particle deposition flux increased, for the winter samples. Based on the ratio of the PCDD/PCDF deposition fluxes to the particle deposition fluxes, the contribution of the reentrainment of soil particles to the TEQ of PCDD/PCDF deposition was considered to be negligible in this region. Based on the air concentrations monitored near our deposition sampling points by the municipalities, the ratio of the annual deposition flux to the annual average air concentration was roughly estimated to be 0.082 cm/s. The range of deposition flux in the Kanto region was estimated to be from 1.5 to 31 (median: 9.8) ng-TEQ/m2/yr based on the range of air concentration data measured by the municipalities. The total annual deposition flux in the entire Kanto region was estimated to range from 50 to 900 g-TEQ/yr (median 320 g-TEQ/yr). This estimated flux was of the same order as the sum of estimated emissions from municipal solid waste incinerators and industrial waste incinerators in the Kanto region. The contributions of dioxin-like PCBs in Yokohama, Tsukuba, and Tanzawa depositions were less than 10% of the total TEQ; however, in Tokyo it was almost equal to or more than 50%.     

Concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil in the vicinity of a landfill

Estonia still has no waste incineration facilities, which would act as substantial sources of dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) pollution. As landfill fires may serve as sources of dioxins, we focused on the concentrations of PCDD and PCDF in soil samples taken in the vicinity of the landfill located at south-east Estonia in the course of our inventory. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in five soil samples taken in the vicinity of the Laguja landfill in south-east Estonia. The four soil samples were taken in southern, eastern, western and northern parts not further than 300 m from the landfill, and one sample was taken at the distance of 3 km from the landfill. The PCDD/F concentrations in all soil samples were at background level (0.64-2.33 pg I-TEQ WHO/g dry weight). To maintain this situation, the administrator of the landfill must avoid landfill fires, which are one of the reasons for the generation of dioxins and furans.     

Emissions of unintentional persistent organic pollutants from open burning of municipal solid waste from developing countries

Open burning of waste is the most significant source of polychlorinated dibenzo-para-dioxins and dibenzofurans (PCDD/PCDF) in many national inventories prepared pursuant to the Stockholm Convention on Persistent Organic Pollutants. This is particularly true for developing countries. Emission factors for POPs such as PCDD/PCDF, dioxin-like polychlorinated biphenyls (dl-PCB) and penta- and hexachlorobenzenes (PeCBz/HCB) from open burning of municipal solid waste in China and Mexico are reported herein. Six different waste sources were studied varying from urban-industrial to semi-urban to rural. For PCDD/PCDF, the emission factors to air ranged from 3.0 to 650 ng TEQ kg⁻¹ waste and for dl-PCB from 0.092 to 54 ng TEQ kg⁻¹ waste. Emission factors for PeCBz (17-1200 ng kg⁻¹ waste) and HCB (24-1300 ng kg⁻¹ waste) spanned a wide but similar range. Within the datasets there is no indication of significant waste composition effect on emission factor with the exception of significantly higher Mexico rural samples.     

Effects of combustion and operating conditions on PCDD/PCDF emissions from power boilers burning salt-laden wood waste

This paper discusses the effects of combustion conditions on PCDD/PCDF emissions from pulp and paper power boilers burning salt-laden wood waste. We found no correlation between PCDD/PCDF emissions and carbon monoxide emissions. A good correlation was, however, observed between PCDD/PCDF emissions and the concentration of stack polynuclear aromatic hydrocarbons (PAHs) in the absence of TDF addition. Thus, poor combustion conditions responsible for the formation of products of incomplete combustion (PICs), such as PAHs and PCDD/PCDF precursors, increase PCDD/PCDF emissions. PAH concentrations increased with higher boiler load and/or low oxygen concentrations at the boiler exit, probably because of lower available residence times and insufficient excess air. Our findings are consistent with the current understanding that high ash carbon content generally favours heterogeneous reactions leading to either de novo synthesis of PCDD/PCDFs or their direct formation from precursors. We also found that, in grate-fired boilers, a linear increase in the grate/lower furnace temperature produces an exponential decrease in PCDD/PCDF emissions. Although the extent of this effect appears to be mill-specific, particularly at low temperatures, the results indicate that increasing the combustion temperature may decrease PCDD/PCDF emissions. It must be noted, however, that there are other variables, such as elevated ESP and stack temperatures, a high hog salt content, the presence of large amounts of PICs and a high Cl/S ratio, which contribute to higher PCDD/PCDFs emissions. Therefore, higher combustion temperatures, by themselves, will not necessarily result in low PCDD/PCDFs emissions.     

Evaluation of the measurement uncertainty in automated long-term sampling of PCDD/PCDFs

Since the publication of the first version of European standard EN-1948 in 1996, long-term sampling equipment has been improved to a high standard for the sampling and analysis of polychlorodibenzo-p-dioxin (PCDD)/polychlorodibenzofuran (PCDF) emissions from industrial sources. The current automated PCDD/PCDF sampling systems enable to extend the measurement time from 6–8 h to 15–30 days in order to have data values better representative of the real pollutant emission of the plant in the long period. EN-1948:2006 is still the European technical reference standard for the determination of PCDD/PCDF from stationary source emissions. In this paper, a methodology to estimate the measurement uncertainty of long-term automated sampling is presented. The methodology has been tested on a set of high concentration sampling data resulting from a specific experience; it is proposed with the intent that it is to be applied on further similar studies and generalized. A comparison between short-term sampling data resulting from manual and automated parallel measurements has been considered also in order to verify the feasibility and usefulness of automated systems and to establish correlations between results of the two methods to use a manual method for calibration of automatic long-term one. The uncertainty components of the manual method are analyzed, following the requirements of EN-1948-3:2006, allowing to have a preliminary evaluation of the corresponding uncertainty components of the automated system. Then, a comparison between experimental data coming from parallel sampling campaigns carried out in short- and long-term sampling periods is realized. Long-term sampling is more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Automated sampling systems can assure very useful emission data both in short and long sampling periods. Despite this, due to the different application of the long-term sampling systems, the automated results could not be directly compared with manual results, not even in terms of measurement uncertainty. This investigation focuses on both uncertainty and repeatability of the automated sampling method. The standard 20988, developed by Internarional Organization of Standardization (ISO) can be used to estimate the measurement uncertainty. The results confirm that the uncertainties of manual and automated methods are comparable. At the same time, it is not appropriate to consider the manual method as a reference for the evaluation of the uncertainty of the automated sampling system, due to the high variability of both systems.     

Correlation of PCDD/PCDF and CO values in a MSW incinerator--indication of memory effects in the high temperature/cooling section

The correlation of PCDD/PCDF levels with the CO emissions in a full-scale municipal waste incinerator was assessed during a four-week measurement effort. PCDD/PCDF concentrations in fly ashes-containing more than 99% of the total PCDD/PCDF burden of the fluidized bed incinerator (FBI)-were measured and compared with the emitted CO concentrations. The CO concentration during the sampling time showed no significant correlation to the PCDD/ PCDF amount in fly ash (R2 = 0.078). However, a comparison of the time integrated CO concentration several hours before sampling lead to a correlation with the PCDD/PCDF burden. Maximum correlation was found for the time integrated CO values of 3 and 4 h before sampling (R2 = 0.467 and R2 = 0.457 respectively). This indicates a memory effect in the high temperature cooling section of several hours. Possible mechanisms leading to the memory effect are discussed. The correlation of PCDD/PCDF with CO concentration demonstrate that the combustion conditions play an important role for PCDD/PCDF formation in FBIs. However the variability in the correlation of CO to PCDD/PCDF levels show that other factors have a significant influence on PCDD/PCDF formation.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.     

Formation, release and control of dioxins in cement kilns

Co-processing of hazardous wastes in cement kilns have for decades been thought to cause increased emissions of PCDD/PCDFs--a perception that has been evaluated in this study. Hundreds of PCDD/PCDF measurements conducted by the cement industry and others in the last few years, on emissions and solid materials, as well as recent test burns with hazardous wastes in developing countries do not support this perception. Newer data has been compared with older literature data and shows in particular that many emission factors have to be reconsidered. Early emission factors for cement kilns co-processing hazardous waste, which are still used in inventories, are shown to be too high compared with actual measurements. Less than 10 years ago it was believed that the cement industry was the main contributor of PCDD/PCDFs to air; data collected in this study indicates however that the industry contributes with less than 1% of total emissions to air. The Stockholm Convention on POPs presently ratified by 144 parties, classifies cement kilns co-processing hazardous waste as a source category having the potential for comparatively high formation and release of PCDD/PCDFs. This classification is based on early investigations from the 1980s and 1990s where kilns co-processing hazardous waste had higher emissions compared to those that did not burn hazardous waste. However, the testing of these kilns was often done under worst case scenario conditions known to favour PCDD/PCDF formation. More than 2000 PCDD/PCDF cement kiln measurements have been evaluated in this study, representing most production technologies and waste feeding scenarios. They generally indicate that most modern cement kilns co-processing waste today can meet an emission level of 0.1ngI-TEQ/m(3), when well managed and operated. In these cases, proper and responsible use of waste including organic hazardous waste to replace parts of the fossil fuel does not seem to increase formation of PCDD/PCDFs. Modern preheater/precalciner kilns generally seems to have lower emissions than older wet-process cement kilns. It seems that the main factors stimulating formation of PCDD/PCDFs is the availability of organics in the raw material and the temperature of the air pollution control device. Feeding of materials containing elevated concentrations of organics as part of raw-material-mix should therefore be avoided and the exhaust gases should be cooled down quickly in long wet and long dry cement kilns without preheating. PCDD/PCDFs could be detected in all types of solid samples analysed: raw meal, pellets and slurry; alternative raw materials as sand, chalk and different ashes; cement kiln dust, clinker and cement. The concentrations are however generally low, similar to soil and sediment.     

Occurrence of dioxins in cow's milk in the vicinity of municipal waste incinerators and a metal reclamation plant in the Netherlands

Over 200 samples of cow's milk have been analysed for dioxins in a survey on the occurrence of dioxins in milk from the vicinity of municipal waste incinerators (MSWs) and other potential dioxin sources in The Netherlands. Levels in milk were found to vary considerably with time, depending on emission rates, the direction and distance to the source and the feeding and housing of cows. Highest levels of up to 13.5 pg TEQ/g of milk fat were found in the Lickebaert area and Zaandam near two incinerators with highest emission rates. The background level ranged between 0.7 and 2.5 pg TEQ/g of milk fat. Levels in winter were comparable to those found in summer and, in some areas, even higher, when cows were fed with hay and silage harvested on the same farm. After the closure of the MSW in Zaandam, cow's milk from neighbouring farms showed a significant decrease in dioxin levels to below the critical limit of 6 pg TEQ/g of milk fat. Dioxin levels in the vicinity of a metal reclamation plant were comparable to those in milk from the vicinity of a MSW with moderate emissions. Differences were observed in the ratio PCDF/PCDD, which was higher in milk near the metal reclamation plant. Principal component analysis has been applied on a large data set of patterns of the 2,3,7,8-chlorine substituted PCDDs and PCDFs in cow's milk. This technique has proved to be useful for distinguishing and identification of sources on the basis of the isomer pattern in milk.     

Response surface models for the formation of PCDD and PCDF in a pilot plant combustion of MSW

Experimental data on PCDD and PCDF emissions in raw gases from municipal solid waste combustion in a pilot plant were processed by Response Surface models to gain information on process parameter values which minimize both the total PCDD/PCDF concentrations and those of a selected congener group.