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Emissions of polychlorinated dibenzodioxin and dibenzofuran (PCDD/F) result from inefficiencies of combustion processes, most typically waste combustion. Uncontrolled combustion, such as occurs during so-called "backyard burning" of domestic waste, may th

This paper presents emission factors (EFs) derived for a range of persistent organic pollutants (POPs) when coal and wood were subject to controlled burning experiments, designed to simulate domestic burning for space heating. A wide range of POPs were emitted, with emissions from coal being higher than those from wood. Highest EFs were obtained for particulate matter, PM10, (～ 10 g/kg fuel) and polycyclic aromatic hydrocarbons (～ 100 mg/ kg fuel for ΣPAHs). For chlorinated compounds, EFs were highest for polychlorinated biphenyls (PCBs), with polychlorinated naphthalenes (PCNs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) being less abundant. EFs were on the order of 1000 ng/kg fuel for ΣPCBs, 100s ng/ kg fuel for ΣPCNs and 100 ng/kg fuel for ΣPCDD/Fs. The study confirmed that mono- to trichlorinated dibenzofurans, Cl1,2,3DFs, were strong indicators of low temperature combustion processes, such as the domestic burning of coal and wood. It is concluded that numerous PCB and PCN congeners are routinely formed during the combustion of solid fuels. However, their combined emissions from the domestic burning of coal and wood would contribute only a few percent to annual U.K. emission estimates. Emissions of PAHs and PM 10 were major contributors to U.K. national emission inventories. Major emissions were found from the domestic burning for Cl1,2,3DFs, while the contribution of PCDD/F-ΣTEQ to total U.K. emissions was minor.

The adsorption of polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) by activated carbon (AC) was examined in a fixed-bed AC unit in a hazardous waste incinerator (IZAYDAS) in Turkey. Results showed that the removal efficiencies of PCDD/Fs decrease as the chlorination level increases, which was explained by the difference in gas/particle partitioning of the compounds. Since dioxins are tightly adsorbed by activated carbon, other flue gas constituents showed no clear effect on the dioxin removal. Adsorption kinetics indicated that the adsorption of volatile congeners and homologues fits well with Henry's law, possibly due to the higher gaseous fractions, while the correlation was lower for lowly volatile ones. PCDD/F congeners and homologues had a concentration value up to which no adsorption occurred, which could be attributed to the insufficient contact times at the low concentrations.

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NOx- and CO-emissions are reduced by 90% and 20% to about 50 mg/Nm3 and below 10 mg/Nm3, respectively.

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxins) have been found from 57 field tests on the oxidation of low (a few to a few hundred) parts per million levels of chlorinated and non-chlorinated volatile organic compounds (VOCs). The oxidation occurs in catalytic oxidizers with platinum, platinum/palladium or chromium(IV) oxide combustion catalysts, or in thermal oxidizers (without a catalyst). The catalyst inlet temperatures ranged from 293 to 573°C. The thermal oxidizer operating temperatures (post-flame) were from 773 to 927°C. Data of the toxic dioxin and furan isomers are reported and also weighted and expressed as international toxic equivalents (TEQ) of 2,3,7,8-tetrachlorodibenzo-p-dioxin. The maximum stack emissions, 1.07 ng/m3 TEQ, occurred at 293°C. Salient results of this field study are: (1) TEQ levels in the stack exponentially increase with a decrease in operating temperature, an empirical equation is TEQ (ng/dscm)=8.4 exp(-0.0084T°C); (2) dioxin/furan production occurs at the combustion catalyst; (3) small variations in temperature cause large changes in the congener distribution of the dioxin and furan isomers; (4) molar TEQ yields from the parent compounds fed to the oxidizers are very small (10 -9-10-13); (5) catalytic and thermal oxidizers may destroy dioxins fed from the ambient air; and (6) the oxidation of chlorinated VOCs with non-chlorinated VOCs reduces emissions of dioxins, likely due to the consumption of Cl in producing HCl. Laboratory investigations are needed to understand how dioxins are formed (and emitted) under conditions of this study.

Catalytic combustion over a 2 wt % Pt/γ-Al2O3 catalyst of chlorobenzene (PhCl) and of a micropollutant-like mixture representative for a primary combustion offgas has been investigated. Typical conditions were 1000-1500 ppm of organics in the inflow, contact times ～0.3 s, 16% O2 in nitrogen at ～1 bar, and temperature range 200-550 °C. PhCl reacts considerably slower than when processing Cl-free compounds such as heptane. At intermediate temperatures-and incomplete conversion-byproducts are formed, especially polychlorobenzenes (PhCl x). These are accompanied by polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) at levels of about 10-6 relative to PhClx. Additional HCl-made by co-reacting PhCl with tert-butylchloride-leads to much higher levels of PhClx and PCDD/Fs. Using the micropollutant-like mixture, the total chlorine input is reduced almost 20-fold, but it nevertheless leads to a 30-fold higher PCDD/F output. This is ascribed to reaction of the small amounts of (chloro)phenols in the mixture. The congener/isomer patterns of the PCDD/Fs for the mixture and with PhCl per se are quite comparable with those found in emissions from incinerators. As carbon is not present nor formed on the catalyst surface, de-novo formation therefrom cannot be involved. Rather condensation of phenolic entities or like precursors must have occurred. Consequences and options to ensure safe application are briefly discussed as well.

The aim of this study was to evaluate the influence of using waste materials, such as tires or meat meal, as a secondary fuel during clinker production on the polychlorinated dibenzo-p-dioxin (PCDD)/polychlorinated dibenzofuran (PCDF) emission levels to the atmosphere. For this purpose, three different cement plants in Spain were chosen to conduct the project in different sampling episodes. Different materials were separately evaluated in each plant: the first plant included the addition of meat meal in the kiln, the second plant used rejected tires, and the third plant used a mixture of both. In all cases, PCDD/F emission values remained below the limit established by the European Union Directive of 0.1 ng I-TEQ/Nm3, with values ranging from 0.001 to 0.042 ng I-TEQ/Nm3. The major contribution to total TEQ in the majority of cases came from 2,3,7,8-tetrachlorodibenzofuran owing to its relatively higher levels and 2,3,4,7,8-pentachlorodibenzofuran because of its TEF of 0.5. The remaining 15 toxic congeners collectively provided only a minor contribution to TEQ. Furthermore, no marked differences were found compared with reported data obtained from Spanish cement kiln plants using conventional fuel. This fact indicates that the addition of used tires or meat meals had no effect on PCDD/ PCDF emission levels.

Iron ore sintering is an important source of dioxins , polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/ Fs). This paper reports on attempts to identify materials, conditions, and mechanisms responsible for PCDD/F formation (i) by investigating salient properties of ores (viz., with respect to oxidation, condensation, and chlorination of model organics) and (ii) by mimicking the industrial process on a microscale with real-life materials. Principles of Design of Experiments (DOE) are employed. The reactivities of iron ores differ greatly. Limonite/goethite soft ore is a very active oxidation catalyst (e.g., for benzene and phenol), a property that may be useful in cleaning up crude sintering process offgases, whereas hematite/magnetite hard ore is not. The latter, however strongly promotes condensation of phenol to dibenzofuran. A newly built labmicroscale sintering facility could satisfactorily imitate the large-scale process, in part or as a whole. Results obtained with realistic feed mixtures point at dioxin formation in the sinter bed at levels significant enough to explain a major part of the outputs observed in the real-life process. With ～8 ppm (wt) of chloride added as NaCl, the PCDD/F output doubled, but with the same proportion of chlorine administered as C2Cl4, the dioxin output was over 2 orders of magnitude larger. The use of process reverts, etc. containing chlorinated organics should therefore be avoided. PCDD/F congener patterns are also reported and compared with those observed in practice.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) formation by the thermal reactions of phenols with CuCl2 under oxygen flux were carried out in relation to their formation mechanisms: To evaluate the effect of photocatalytic degra

The effect of oxygen-nitrogen atmosphere (N2 + 10%O2, N2 + 1%O2 and 99.999% N2) on the formation of PCB, PCDD and PCDF by the de novo synthetic reactions in the system consisting of extracted fly ash

This study was carried out to examine the formation and the emission status of polychlorinated dibenzo-p-dioxins/ polychlorinated dibenzofurans (PCDDs/PCDFs) in the flue gases of commercial-scale municipal solid waste (MSW) incinerators, and thus to provi

In thermal metallurgical processes such as iron ore sintering and metal smelting operations, large flows of off-gases are generated. Mainly due to residue recycling in such processes, chlorine and volatile organics are always present in the feed. As a consequence of de novo formation, the off-gases from such processes typically contain dioxins in the range 0.3-30 ng I-TEQ/Nm3. So far there are only very few studies about the mechanisms of dioxin formation and destruction in these metallurgical processes. In an European Union (EU) research project Minimization of dioxins in thermal industrial processes: mechanisms, monitoring and abatement (MINIDIP) , integrated iron and steel plant has been selected as one of the industrial sectors for further investigation. A large number of particulate samples (feed, belt siftings, electrofilter) were collected from the iron ore sintering installations from various steel plants and analyzed for their organochlorocompound contents. Measurable amounts of PCDD/F, PCBz, PCB were found for all samples. The various parameters influencing their de novo synthesis activity were also evaluated in laboratory experiments, and such activity was found to be moderate for samples from the ore sinter belt, but extremely high for some ESP dusts. Fine dust is active in a wide range of temperatures starting at 200°C and declining above 450°C; the optimal temperature for de novo synthesis was found to be around 350°C; some inhibitors, such as triethanolamine, may reduce de novo activity by 50%, and lowering the O2 concentration in the gas stream leads to a much lower amount of PCDD/F formation. On the basis of their relative mass, typical operating conditions and specific activity of the different samples, the regions in the sintering plant where de novo synthesis may take place were tentatively established.

The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10 000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 μg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.

The formation of the 17 toxic 2,3,7,8-substituted-PCDDs and PCDFs during combustion of selected chemicals were measured by high-resolution GC/MS. The 16 chemicals studied were commonly used chlorinated pesticides, industrial chemicals, and PVC. In a series of experiments carried out in a DIN 53,436 furnace, 2.5 g of these compounds were burned at 500°C and 900°C, respectively. The resultant yields ranged from 740 ng ITEQ/g for pentachlorophenol, to below 0.01 ng ITEQ/g for PVC and dichlobenil. The results show that some chemicals generate PCDD/F in very high - possibly dangerous - amounts during burning, whereas others generate insignificant amounts. The influence of scale were studied for chlorobenzene and 4-chloro- 3-nitro-benzoic acid in additional experiments, carried out in a cone calorimeter burning 20 g substance, and in ISO 9705 room test burning about 50 kg. A good agreement between the results for large and small scale indicated that formation of PCCD/F during a fire may be estimated from laboratory experiments. This suggest laboratory test may be used to screen for chemicals posing a hazard for release of PCDD/F during fires.

The evolution of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in sewage sludge-amended soils used in the restoration of degraded lands, like quarries, has been studied. Two experiments were performed: one in the lab, under controlled conditions, and another in a quarry. Two different doses of sewage sludge were applied in both experiments (with two types of application in the quarry experiment) and the evolution of the amended soils were compared with that of the respective control soils (without addition of sewage sludge). The samples were analyzed with a previously validated method by HRGC-HRMS after the extraction and the necessary clean-up steps. The results reveal that polluted sewage sludge increases PCDD/F concentration in soils and that these compounds are persistent in the matrix after long periods of time. (C) 2000 Elsevier Science Ltd. The evolution of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in sewage sludge-amended soils used in the restoration of degraded lands, like quarries, has been studied. Two experiments were performed: one in the lab, under controlled conditions, and another in a quarry. Two different doses of sewage sludge were applied in both experiments (with two types of application in the quarry experiment) and the evolution of the amended soils were compared with that of the respective control soils (without addition of sewage sludge). The samples were analyzed with a previously validated method by HRGC-HRMS after the extraction and the necessary clean-up steps. The results reveal that polluted sewage sludge increases PCDD/F concentration in soils and that these compounds are persistent in the matrix after long periods of time. Laboratory and field experiments were conducted in Spain to examine the evolution of PCDDs and PCDFs in sewage-sludge-amended soils. The PCDD/F concentrations were measured in the original sewage sludge and in soil samples over time. Results from the laboratory showed that the PCDD/F concentration in amended soils was related directly to the sewage-sludge dose applied. After 1 yr, however, no evolution of PCDD/Fs was observed in any sample. In the field, high dispersion was observed, which did not allow establishment of a concentration trend over time. (from Eighteenth Symp on Halogenated Environ Organic Pollutants-Dioxin '98, Stockholm, Sweden (Aug 17-21, 98)).

Backyard burning of household waste in barrels is a common waste disposal practice for which pollutant emissions have not been well characterized. This study measured the emissions of several pollutants, including polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs), from burning mixtures designed to simulate waste generated by a 'recycling' and a 'nonrecycling' family in a 208-L (55-gal) burn barrel at the EPA's Open Burning Test Facility. This paper focuses on the PCDD/PCDF emissions and discusses the factors influencing PCDD/PCDF formation for different test burns. Four test burns were made in which the amount of waste placed in the barrel varied from 6.4 to 13.6 kg and the amount actually burned varied from 46.6% to 68.1%. Emissions of total PCDDs/PCDFs ranged between 0.0046 and 0.48 mg/kg of waste burned. Emissions are also presented in terms of 2,3,7,8-TCDD toxic equivalents. Emissions of PCDDs/PCDFs appear to correlate with both copper and hydrochloric acid emissions. The results of this study indicate that backyard burning emits more PCDDs/PCDFs on a mass of refuse burned basis than various types of municipal waste combustors (MWCs). Comparison of burn barrel emissions to emissions from a hypothetical modern MWC equipped with high-efficiency flue gas cleaning technology indicates that about 2-40 households burning their trash daily in barrels can produce average PCDD/PCDF emissions comparable to a 182 000 kg/day (200 ton/day) MWC facility. This study provides important data on a potentially significant source of emissions of PCDDs/PCDFs. Backyard burning of household waste in barrels is a common waste disposal practice for which pollutant emissions have not been well characterized. This study measured the emissions of several pollutants, including polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs), from burning mixtures designed to simulate waste generated by a 'recycling' and a 'nonrecycling' family in a 208-L (55-gal) burn barrel at the EPA's Open Burning Test Facility. This paper focuses on the PCDD/PCDF emissions and discusses the factors influencing PCDD/PCDF formation for different test burns. Four test burns were made in which the amount of waste placed in the barrel varied from 6.4 to 13.6 kg and the amount actually burned varied from 46.6% to 68.1%. Emissions of total PCDDs/PCDFs ranged between 0.0046 and 0.48 mg/kg of waste burned. Emissions are also presented in terms of 2,3,7,8-TCDD toxic equivalents. Emissions of PCDDs/PCDFs appear to correlate with both copper and hydrochloric acid emissions. The results of this study indicate that backyard burning emits more PCDDs/PCDFs on a mass of refuse burned basis than various types of municipal waste combustors (MWCs). Comparison of burn barrel emissions to emissions from a hypothetical modern MWC equipped with high-efficiency flue gas cleaning technology indicates that about 2-40 households burning their trash daily in barrels can produce average PCDD/PCDF emissions comparable to a 182 000 kg/day (200 ton/day) MWC facility. This study provides important data on a potentially significant source of emissions of PCDDs/PCDFs.

We performed experiments on two different matrices with 2,4,6- trichlorophenol as precursor to Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD)/F. A municipal solid waste incinerators (MSWI) and a model fly ash were spiked in two different ways. The experiments demonstrated a three times higher formation potential of the trichlorophenol to PCDD on MSWI fly ash compared with the model fly ash used. For both fly ashes the PCDD yield was higher when gaseous trichlorophenol was fed continuously compared to mixing the fly ashes prior to the experiments with the total amount of the precursor. Despite dilution of the fly ashes tenfold with an inactive matrix the conversion of the chlorophenol was very high. (C) 2000 Elsevier Science Ltd.

PCDD/PCDF were determined in solid samples from wood combustion. The samples included grate ashes, bottom ashes, furnace ashes as well as fly and cyclone ashes. The solid waste samples were classified into bottom and fly ash from native wood and bottom and fly ash from waste wood. For each of the four classes concentration distribution patterns from individual congeners, the sums of PCDD/PCDF and the international toxicity equivalents (I-TEQ) values are given. The I-TEQ levels of fly ash from waste wood burning can be approximately up to two thousand times higher than the values from fly ashes of natural wood. The I-TEQ levels in bottom ashes from waste wood combustion systems are as low as the corresponding ashes from the combustion of native wood. Grate ash samples from waste wood combustion systems with low carbon burnout show high levels of PCDD/PCDF.

The aim of this study was to investigate the influence of variation in combustion conditions on the primary formation of organic micropollutants (OMPs). The flue gas samples were taken at a relatively high flue gas temperature (650°C), to enable mechanistic studies on the high temperature formation (primary formation). Eleven experiments were performed in a laboratory scale fluidized bed reactor fed with an artificial municipal solid waste (MSW). The samples were analyzed for mono- to octachlorinated dibenzo- p-dioxins and dibenzofurans (CDDs/Fs), tri- to decachlorinated biphenyls (CBs), di- to hexachlorinated benzenes (CBzs), and di- to pentachlorinated phenols (CPhs). In addition to chlorinated OMPs, nonchlorinated dibenzo-p- dioxin (DD), dibenzofuran (DF), and biphenyl (BP) were analyzed. The experiments show that variations in the CE influence the degree of chlorination of the organic micropollutants. A correlation between low CE and formation of non- and low-chlorinated DMPs was seen and a distinct relationship of higher chlorinated homologues and efficient combustion condition. Thus, the DiCDFs and DiCBzs are formed during low combustion efficiency (CE), while the PeCDF and PeCBzs formation take place at higher CE. The distribution between primary and secondary air is important for the formation of higher CDD/Fs and CBzs. The primary formation of CDDs and CDFs is through different mechanisms. The CDDs are mainly formed by condensation of CPhs, while the CDFs are formed through a non- or a low-chlorinated precursor followed by further chlorination reactions.

Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) emitted from municipal waste incinerators appear to have a chlorination pattern that is quite constant across various samples and conditions. This suggested that these patterns may be controlled by thermodynamic properties of the individual PCDD/F congeners, such as the free Gibbs energy of formation (Δg°(f,T)). This would make prediction of the isomer composition of a particular sample (and hence its TEQ value) possible, based on values of ΔG°(f,T). A laboratory scale study was carried out with activated carbon on fly ash as the source of PCDD/F formation. Although it was found that the isomer distributions within homologues were independent of the reaction time (proof of thermodynamic control), other observations (lack of equilibrium/isomerization between isomers and lack of similarity between isomer distributions measured and predicted by ΔG°(f,T)) contradicted the possibility of thermodynamic control. Hence, this study could not confirm that de novo formation of PCDD/F could explain thermodynamically controlled isomer distributions in incinerators. Some recommendations for further work- time-based studies with precursors, isomerization studies with single congeners, and more data on ΔG°(f,T) values of PCDD/F-were made. Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) emitted from municipal waste incinerators appear to have a chlorination pattern that is quite constant across various samples and conditions. This suggested that these patterns may be controlled by thermodynamic properties of the individual PCDD/F congeners, such as the free Gibbs energy of formation (ΔG°f,T). This would make prediction of the isomer composition of a particular sample (and hence its TEQ value) possible, based on values of ΔG°f,T. A laboratory scale study was carried out with activated carbon on fly ash as the source of PCDD/F formation. Although it was found that the isomer distributions within homologues were independent of the reaction time (proof of thermodynamic control), other observations (lack of equilibrium/isomerization between isomers and lack of similarity between isomer distributions measured and predicted by ΔG°f,T) contradicted the possibility of thermodynamic control. Hence, this study could not confirm that de novo formation of PCDD/F could explain thermodynamically controlled isomer distributions in incinerators. Some recommendations for further work - time-based studies with precursors, isomerization studies with single congeners, and more data on ΔG°f,T values of PCDD/F - were made.

Dibenzofuran (DF) on fly ash can be converted to polychlorinated dibenzofurans (PCDF)in a N2/O2/HCl atmosphere, yielding especially 2,3,7,8- substituted congeners. This is consistent with an electrophilic aromatic substitution mechanism. 1,2,3,4,7,8-Hexa-chlorodibenzo-p-dioxin (1,2,3,4,7,8- H6CDD) on fly ash can be chlorinated by HCl both in N2 and O2 atmospheres. Dechlorination and decomposition reactions are not important under these conditions, and isomerization reactions do not take place either. 1,2,3,4,7,8-H6CDD dechlorinates or decomposes on fly ash when no HCl is present. Only a limited number of dechlorination products are formed. Chlorination and dechlorination are separate processes, not occurring simultaneously.

Photolysis at 290 nm and higher wavelengths of octachlorodibenzofuran (OCDF) and octachlorodibenzp-p-dioxin (OCDD) was studied in three organic solvents hexane, 1,4-dioxane and methanol. It appeared that the degradation kinetics strongly depended on the type of solvent. OCDD degraded fastest in hexane, whereas OCDF degraded fastest in methanol. Less than 5 percent of the total loss of OCDD degraded by reductive dechlorination, with preferential loss of chlorine atoms at the 1 or 9 positions. 25 to 50 percent of the total loss of OCDF degraded via reductive dechlorination, with preferential loss of lateral chlorine. OCDF degraded faster than OCDD in all studied solvents. Photolysis at 290 nm and higher wavelengths of OCDD and OCDF adsorbed onto alumina impregnated with copper (alumina/Cu) in the presence of natural and distilled water was also investigated. Under these more relevant environmental aquatic conditions, photolysis of OCDD and OCDF was much slower than photolysis in the studied organic solvents. Significant loss was only found for OCDF. A part of the loss OCDF could be explained by reductive dechlorination; the results suggested that other mechanisms of degradation occurred in addition to reductive dechlorination. All photolysis experiments showed that OCDF was photochemically less stable than OCDD.

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