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The dioxin removing capacity of the shell dedioxin system (SDDS a - Ti/V oxidative type catalyst) has been tested using the Umefa lab-scale incinerator over the temperature range 100 -230°C and at space velocities of 8000 and 40,000 h-1. Other analogous organic compounds, such as PCBs, PAHs, chlorobenzenes and chlorophenols have also been investigated. Results show a high degree of dioxin removal already at 100°C (82%), which occurs mainly by adsorption. When the temperature is raised a transition towards destruction is seen and at 150°C, gas hour space velocity (GHSV) 8000 and at 230°C, GHSV 40,000 virtually all removal is by destruction. High PCDD/F destruction efficiencies are reported (> 99.9%, based on I-TEQ); the other dioxin-related species and PAHs are also removed and destroyed to a significant extent. The SDDS has proved to be an effective means of destroying organic compounds in the gas phase, particularly dioxins, at temperatures as low as 150°C.

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.

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

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°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.

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 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 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 chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C2 through C8 organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene. (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. (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)).

The potential to form polychlorinated dibenzo-p-dioxins/furans (PCDD/F) was investigated in carbon model systems containing ferrous chloride tetrahydrate and a matrix representative of that found in particle emission from the catalytic extraction process (CEP) for wastes. Various types of carbons were used resulting in different PCDD/F yields but, with one exception, similar homologue distributions. Due to the similarity between the turbostratic structure of the carbon in the representative CEP dusts and the carbon blacks used in the model system, experiments were performed using two carbon blacks (termed CBA and CBB). On a mass basis, CBB was more reactive over the temperature range of 275-325°C and reaction times of 20-60 min in the formation of PCDD/F; as well as more adsorptive in terms of the desorption of PCDD/F. On a volume basis, the reactivities and adsorptivities were similar. A maximum in PCDD/F formation occurred at an oxygen concentration of 2% in nitrogen. (C) 2000 Elsevier Science Ltd.

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.

Total homologue concentrations and select congener concentrations from amongst the mono- to tri-chlorinated dibenzodioxins (CDDs) and dibenzofurans (CDFs) are used to model both Total (mono- to octa-) CDD + CDF emissions and the toxicity equivalent (TEQ) of the 2,3,7,8-chlorine-substituted emissions. Analysis of emission data from two facilities indicates that use of total homologue concentrations shows limited, facility-specific correlations with Total CDDs/CDFs and TEQ. Concentrations of select mono- to tri-CDD/CDF congeners show promising correlation with CDD/CDF TEQ across facilities, suggesting that these compounds can act as TEQ indicators. (C) 2000 Elsevier Science Ltd.

Chlorophenols (CP) are transformed in vitro to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) by a peroxidase-catalyzed oxidation. This is shown for 2,4,5-tri-, 2,3,4,6-tetra- and pentachlorophenol with plant horseradish peroxidase and with myeloperoxidase recovered from human leukocytes, each in the presence of hydrogen peroxide. The yield, the reaction and the PCDD/F-pattern found are dependent on the CP. The amounts of PCDD/F formed within 4 or 24 h are in the μmol/mol-range for all substrates and both peroxidases. The experiments suggest that biochemical formation of PCDD/F from precursors such as CPs can take place in the human body and that this metabolic pathway may lead to a higher inner exposure to PCDD/F than up to now assumed based on intake data for PCDD/F. Copyright (C) 1999 Elsevier Science Ireland Ltd.

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.

Pentachlorophenol, 1, its sodium salt and the sodium salts of 2,3,4,5-tetrachlorophenol, 2, and 2,4,6-trichlorophenol, 3, have been submitted to pyrolysis-gas chromatography-mass spectrometry for 20 s at 990 deg C and at 500 deg C.Polychlorophenols (PCPs) and polychlorodibenzodioxins (PCDDs) were formed at the lower temperature.PCPs, PCCDs and polychlorobenzenes (PCBzs) were formed at the higher temperature.Compounds derived from loss of one or two carbon atoms were also formed from the sodium salt of 1 at the higher temperature.A mechanism based on the formation of ketocarbenes and arynes is suggested.

An efficient microscale chlorination procedure termed "surface chlorination" is described.By use of this technique with a silica supporting matrix, 7.4 μg of -2,3,7,8-tetrachlorodibenzo-p-dioxin is converted to -octachlorodibenzo-p-dioxin in cca 60 min at 100 deg C.Following liquid chromatography product purification and identification and confirmation of component identity using instrumental techniques, an 80percent yield is achieved.The unique advantages and other possible applications of this reaction matrix are also discussed.