De-novo formation of dioxins and furans and the memory effect in waste incineration flue gases

The formation of dioxin (polychlorinated-rho-dibenzodioxins - PCDD) and furan (polychlorinated dibenzofurans - PCDF) in waste incineration flyash in relation to temperature has been investigated in a bench scale reactor. The PCDD/PCDF released into the exhaust gases of the reactor and trapped in a condensation and vapour phase adsorption system were also determined. The concentrations of PCDD/PCDF in the flyash were analysed in detail for all congeners and isomers including the mono-, di- and tri-PCDD/PCDF. De-novo synthesis of PCDD/PCDF was clearly seen in the flyash with large changes in concentrations of PCDD/PCDF with only small changes in temperature. Exhaust gas PCDD/PCDF were detected at all temperatures, with the maximum emission occurring at a flyash temperature of 350 degrees C, where the equivalent of over 42 times the total dioxin/furan concentration of the original flyash was lost to the vapour phase per unit mass of initial flyash. Although the desorbed species were mainly the lower mono- to tri-congener group of dioxins and furans, the desorbed dioxin/furans had a considerable toxic equivalent value.     

The toxicity equivalency factor scheme applied to municipal incinerator PCDD/PCDF emissions when specific congener information is lacking

The 2,3,7,8-TODD Toxicity EQuivalents (TEQ) approach provides a useful method for estimating the environmental risk of polychlorodibenzodioxin and polychlorodibenzofuran complex mixtures, thus making it possible to express their toxicological significance with only one number. Generally the conversion of the concentration units into those of TEQ requires an isomer-specific analysis and the appropriate Toxicity Equivalency Factors (TEF). In this paper we propose a “theoretical” model for estimating TEQ values of PCDD + PCDF mixtures which, starting from the experimental value of the PCDD + PCDF concentration (μg Nm⁻³) and the theoretical value of PCDD and PCDF fingerprints in the emissions from municipal incinerators, to make an estimate of the global toxicity in terms of ng TEQ Nm⁻³. The TEQ values estimated for a number of samples are in good agreement with those calculated from the isomer and congener experimental data. Given the investment and running costs plus the time and the analytical complexity in determining the congeners and single isomer concentrations, it seems that the proposed “theoretical” model is a reasonable tool for estimating the exposure hazard related to a complex mixture of PCDD/PCDFs emitted from municipal solid waste (MSW) incinerators. Another objective of this paper is to explore the consistency between scientific knowledge and the authority regulatory guidelines. This work shows that the Italian national emission standard (4 μg Nm⁻³) for the total PCDD+PCDF concentration is higher than the international target of 0.1 ng TEQ Nm⁻³. We suggest a value of 1 μg Nm⁻³ for TCDD + TCDF concentration if Italian regulators want to add a further constraint.     

Verification results of jet resonance-enhanced multiphoton ionization as a real-time PCDD/F emission monitor

A jet resonance-enhanced multiphoton ionization (REMPI) monitor was tested on a hazardous-waste-fired boiler for its ability to determine concentrations of polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs). Jet REMPI is a real-time instrument capable of highly selective and sensitive (from parts per billion to parts per trillion) detection of a broad range of aromatic compounds, including a number of air toxic compounds. The PCDD/F toxic equivalency (TEQ) value was derived from a predetermined correlation (R ² = 0.74) with monochlorobenzene (MClBz). This relationship was applied to nine subsequent jet REMPI on-line measurements of MClBz and parallel, standard extractive sampling for PCDD/F TEQ. For high waste-firing rates, with a range of PCDD/F TEQ values between 3.9 and 6.0 ng TEQ/m³, the TEQ values predicted by jet REMPI had a relative difference of 26% with the standard EPA Method 23 results. At low waste-firing rates (0.9–1.6 ng TEQ/m³), the relative difference increased to 219%. This limited testing shows that jet REMPI has promise as an on-line diagnostic monitor, providing feedback on the effects on PCDD/F emissions of operating parameter changes such as fuel feed interruptions or air pollution control failures.     

Effects of combustion parameters on polychlorinated dibenzodioxin and dibenzofuran homologue profiles from municipal waste and coal co-combustion

Variation in polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD and PCDF) homologue profiles from a pilot scale (0.6 MW_t, 2×10⁶ Btu/h), co-fired-fuel [densified refuse derived fuel (dRDF) and high-sulfur Illinois coal] combustion system was used to provide insights into effects of combustion parameters on PCDD and PCDF pollutant formation. A 24-run, statistically designed test matrix varied dRDF and/or coal firing rates (at a constant targeted energy release rate) along with a range of process variables including calcium hydroxide injection, hydrogen chloride (HCl) concentration, flue gas temperature, quench, and residence time such that the results would be relatable to a wide variety of combustion conditions. Statistical analysis of the molar homologue profiles enabled interpretation based on non-confounding variables. A multivariate, generalized additive model, based on transformations of the design variables, described 83% of the variation of the profiles characterized by log ratios of the homologue molar concentrations. This method identifies the operating parameters that are most significant in determining the PCDD/F homologue profiles. The model can be exercised to predict homologue profiles through input of these system-specific operating parameters. For example, both higher HCl and sulfur dioxide concentrations favor higher relative formation of the lower chlorinated PCDF homologues.     

Effects of gaseous NH(3) and SO(2) on the concentration profiles of PCDD/F in flyash under post-combustion zone conditions

The influence of gaseous ammonia and sulphur dioxide on the formation of 2378-substituted PCDD/F on a reference flyash from a municipal waste incinerator has been investigated using a laboratory scale fixed-bed reactor. The reference flyash samples (BCR-490) was reacted under a simulated flue gas stream at temperatures of 225 and 375°C for 96h. The experiments were carried out in two series: first with simulated flue gas alone, and then with injection of NH(3) or SO(2) gas into the flue gas just before the reactor inlet. It was found that the injection of gaseous ammonia into the flue gas could decrease the concentration of both PCDD and PCDF by 34-75% from the solid phase and by 21-40% from the gas phase. Converting the results to I-TEQ values, it could reduce the total I-TEQ values of PCDD and PCDF in the sum of the flyash and exhaust flue gas by 42-75% and 24-57% respectively. The application of SO(2) led to 99% and 93% reductions in the PCDD and PCDF average congener concentrations, respectively in the solid phase. In the gas phase, the total reductions were 89% and 76% for PCDD and PCDF, respectively. Moreover, addition of SO(2) reduced the total I-TEQ value of PCDD and PCDF in the flyash and exhaust flue gas together by 60-86% and 72-82% respectively. Sulphur dioxide was more effective than ammonia in suppressing PCDD/F formation in flyash under the conditions investigated.     

Determination of inorganic and organic priority pollutants in biosolids from meat processing industry

The biosolids (BS) generated in the wastewater treatment process of a meat processing plant were monitored and the priority pollutant content was characterized. The trace metal and organic pollutant content – polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) – were determined quantitatively and compared to guideline limits established by the US EPA and EU. PCBs were not detected in the solid samples, while trace metals, PAHs and PCDD/PCDF were detected in concentrations below the limits established by international standards. Toxic equivalent factors were evaluated for the biosolids, and the results proved that these wastes can be safely deposited on land or used in combustion/incineration plants. Since no previous data were found for meat processing waste, comparisons were made using municipal sewage sludge data reported in the literature. Since, this report monitored part of the priority pollutants established by the US EPA for meat and poultry processing wastewater and sludge, the results verified that low pollution loads are generated by the meat processing plant located in the southern part of Brazil. However, the BS generated in the treatment processes are in accordance with the limits established for waste disposal and even for soil fertilizer.     

Catalytic detoxification of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in fly ash

An efficient catalytic detoxification method for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in fly ash produced by municipal waste incinerator has been studied using palladium on carbon (Pd/C) catalyst. As one of the trace components in fly ash, the detoxification of PCDD/Fs is very difficult because of the interferences of other persistent components with higher concentrations. However, the detoxification reaction of PCDD/Fs shows higher activity in water/isopropanol solution using commercial Pd/C catalyst at 40 degrees C under normal pressure. The results indicated that the catalytic degradation of PCDFs has been found to be easier than that of PCDDs. Moreover, the dechlorination ratios were higher for octa- and hepta-chlorinated congeners than those for tetra- and penta-chlorinated ones. The detoxification process worked well in water. The dechlorination efficiencies of almost all of the PCDD/Fs congeners can reach over 99% within a shorter reaction time.     

Formation of chlorinated organics during solid waste combustion

The formation mechanisms of the precursors of polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) were examined in a laboratory reactor. Both homogeneous and heterogeneous reactions were studied between 200 and 800 °C with HCl, Cl₂, and phenol as reactants in a simulated flue gas containing oxygen. Analysis of the reactor effluent showed that homogeneous phase production of chlorophenols and non-chlorinated dioxin and dibenzopdioxin and dibenzofuran, benzofuran potential precursors to PCDD and PCDF, was related to HCl concentration, reaching a maximum formation level around 650 °C. However, Cl₂ produced a greater variety of chlorinated aromatics at levels over three orders of magnitude greater than with HCl, with product concentrations reaching maximum formation levels around 350 °C. Heterogeneous tests at 450 °C using a CuCl catalyst increased formation of chlorinated organics and PCDDs and identified the major chlorinating reactant to be Cl₂.     

Emissions of organic micropollutants from discontinuously operated municipal waste incinerators

The emission of particles and organic micropollutants (PAH, PCDD and PCDF) was measured from three intermittently operated municipal waste incinerators of medium size. The mutagenicity of the stack gas samples were measured as well. The results show a good agreement between the PAH emitted and the mutagenicity in the stack gases, but none of these parameters correlate with the PCDD/PCDF content.     

Characterization of air emissions and residual ash from open burning of electronic wastes during simulated rudimentary recycling operations

Air emissions and residual ash samples were collected and analyzed during experiments of open, uncontrolled combustion of electronic waste (e-waste), simulating practices associated with rudimentary e-waste recycling operations. Circuit boards and insulated wires were handled separately to simulate processes associated with metal recovery. The average emissions of polychlorinated dibenzodioxins and dibenzofurans (PCDD/PCDFs) were 92 ng toxic equivalency (TEQ)/kg [n = 2, relative standard deviation (RSD) = 98%] and 11 900 ng TEQ/kg (n = 3, RSD = 50%) of the initial mass of the circuit boards and insulated wire, respectively. The value for the insulated wire is about 100 times higher than that for backyard barrel burning of domestic waste. The emission concentrations of polybrominated dibenzodioxins and dibenzofurans (PBDD/PBDFs) from the combustion of circuit boards were 100 times higher than for their polychlorinated counterparts. Particulate matter (PM) sampling of the fly ash emissions indicated PM emission factors of approximately 15 and 17 g/kg of the initial mass for the circuit boards and insulated wire, respectively. Fly ash samples from both types of e-waste contained considerable amounts of several metallic elements and halogens; lead concentrations were more than 200 times the United States regulatory limits for municipal waste combustors and 20 times those for secondary lead smelters. Leaching tests of the residual bottom ash showed that lead concentrations exceeded U.S. Environmental Protection Agency landfill limits, designating this ash as a hazardous waste.     

Environmental Technology Verification (ETV) test of dioxin emission monitors

The performance of four dioxin emission monitors, including two long-term sampling devices, the Dioxin-MonitoringSystem (DMS) and AMESA (the adsorption method for sampling dioxins and furans), and two semireal-time continuous monitors, the resonance ionization with multimirror photon accumulation time-of-flight mass spectrometer (RIMMPA-TOFMS) and the jet resonance-enhanced multiphoton ionization (jet-REMPI) system were tested. A package boiler burning a simulated chlorinated hazardous waste was used for a total of nine tests. Reference samples were collected during each test and analyzed for polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs) using gas chromatography mass spectrometry. The PCDD/F concentrations of the reference samples measured by EPA Method 23 ranged from 0.9 to 6.0 ng toxic equivalence (TEQ)/dry standard cubic meter. The relative accuracies achieved by DMS, AMESA, and jet-REMPI varied from 22.6% to 78.2%, with 100% data completeness. The RIMMPA-TOFMS produced no quantifiable results due to various difficulties associated with the instrument during the testing. The two long-term samplers were easy to install and operate and provided a cumulative, averaged emission for the sampling period. The operations of the two semi-real-time continuous monitors were relatively complex, but one of them provided on-site, real-time data for PCDD/F emissions from measurement of a TEQ correlative indicator compound. This article summarizes results from the individual Environmental Technology Verification reports for the four dioxin monitors. This work was presented, in part, at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

Formation of persistent chlorinated aromatic compounds in simulated and real fly ash from iron ore sintering

Effects of carbon concentration and Cu additive in simulated fly ash (SFA) and real fly ash (RFA) on the formation of polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo-p-dioxins (PCDDs), chlorobenzenes, and polychlorinated biphenyls which were all regarded as persistent chlorinated aromatics in iron ore sintering were investigated. In the annealing process of SFA with various carbon contents, the yield of chlorinated aromatics and the I-TEQ obtained their maximum at 10 wt% carbon content. Active carbon in SFA acted as the carbon source as well as an adsorbent which led to higher production of PCDD/F in solid phase at 10 wt% carbon content. The increase of carbon content will be beneficial on the formation of 2,3,7,8-Chloro-substituted PCDF compared with 2,3,7,8-Chloro-substituted PCDD. In addition, the CuCl₂·2H₂O was a much more powerful catalyst in the formation of chlorinated aromatic compounds compared with elementary Cu, since it served as both a catalyst and a chlorine donor. However, the RFA behaved similarly with SFA with elementary Cu in the formation of chlorinated aromatic compounds. The effect of carbon content and copper additives on formation of 2,3,7,8-chloro-substituted congeners displayed similar characteristics with the tetra- to octa-PCDD/F isomers and even the total PCDD/Fs.     

Decreased PCDD/F formation when co-firing a waste fuel and biomass in a CFB boiler by addition of sulphates or municipal sewage sludge

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed during waste incineration and in waste-to-energy boilers. Incomplete combustion, too short residence times at low combustion temperatures (<700 °C), incineration of electronic waste and plastic waste containing chlorine are all factors influencing the formation of PCDD/Fs in boilers. The impact of chlorine and catalysing metals (such as copper and iron) in the fuel on PCDD/F formation was studied in a 12 MW_th circulating fluidised bed (CFB) boiler. The PCDD/F concentrations in the raw gas after the convection pass of the boiler and in the fly ashes were compared. The fuel types were a so-called clean biomass with low content of chlorine, biomass with enhanced content of chlorine from supply of PVC, and solid recovered fuel (SRF) which is a waste fuel containing higher concentrations of both chlorine, and catalysing metals. The PCDD/F formation increased for the biomass with enhanced chlorine content and it was significantly reduced in the raw gas as well as in the fly ashes by injection of ammonium sulphate. A link, the alkali chloride track, is demonstrated between the level of alkali chlorides in the gas phase, the chlorine content in the deposits in the convection pass and finally the PCDD/F formation. The formation of PCDD/Fs was also significantly reduced during co-combustion of SRF with municipal sewage sludge (MSS) compared to when SRF was fired without MSS as additional fuel.     

Substance flow analysis of coplanar PCBs released from waste incineration processes

Previous reports have focused on the emission of coplanar polychlorinated biphenyls (Co-PCBs) which have a toxic mechanism similar to that of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/DFs) released from municipal solid waste (MSW) incineration. Such emissions accounted for a small percentage of all the dioxins (PCDDs/DFs and Co-PCBs) recorded at the toxicity equivalent (TEQ) level. There is, however, very little information about Co-PCBs, such as the quantities being released and their effect on overall environmental pollution. The aim of this research has been to clarify the substance flow of Co-PCBs from MSW incineration processes. The results reveal that whereas the input of Co-PCBs into the MSW incineration facilities in Kyoto City was 0.13–0.29 μg-TEQ per ton waste, the total output of Co-PCBs (the sum of Co-PCBs released from emission gas, fly ash, and bottom ash) was 4.9 μg-TEQ per ton waste. The total output was therefore found to be higher than the total input. Over 90% of the total PCBs were decomposed in the incineration process. In comparing the profiles of congeners and homologues, those in the MSW were found to be similar to those detected in the atmosphere and products containing PCBs, but different from those in the MSW incineration gas. Received: August 26, 1998 / Accepted: March 2, 1999     

Repartition of PCDD and PCDF in the emissions of municipal solid waste incinerators between the particulate and volatile phases

The present paper refers to the results of a research project on the polychlorinated dibenzyil-p-dioxin (PCDD) and polychlorinated dibenzofurans repartition in particulate and volatile phase in emissions from municipal solid waste incinerators. The distribution of such micropollutants between the different phases is analyzed in terms of absolute weights and in terms of 2, 3, 7, 8 TCDD Equivalents. This paper shows that more than half of the total content of PCDD/Fs emitted are adsorbed in the fly ash, with the remaining part in the volatile phase. Such repartition is inverted if the PCDD/Fs are expressed in terms of 2, 3, 7, 8 TCDD Equivalent.     

Hydrodechlorination/detoxification of PCDDs,PCDFs, and co-PCBs in fly ash by using calcium polysulfide

Dioxins like polychlorinated dibenzo-p-dioxins (PCSDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are mainly emitted from waste incinerators (WIs) and have become an international research focus because of its serious concerns over the adverse health effects. The detoxification of PCCDs/Fs and PCBs is very difficult because of their stable chemical structure. A significant hydrodechlorination/detoxification of polychlorinated 1-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were achieved in fly ash by using an aqueous mixture of calcium hydroxide and sulfur. Two different fly ashes were studied: originating from municipal waste incinerator (FA1) and industrial waste incinerator (FA2). They were heated with the aqueous mixture at 150 °C for 30 or 60 min with agitation. Higher decomposition (87%) and detoxification (87.7%) of PCDD/Fs and PCBs were achieved at 150 °C with two runs; every run was for 30 min, compared to one run for 60 min. FA2 gave higher decomposition and detoxification as compared to FA1, which might be due to higher metal content that played a catalytic role to decompose and detoxify the PCDDs, PCDFs and PCBs. The decomposition and detoxification of PCDFs in fly ash was higher than PCDDs and was augmented with increasing number of chlorides on aromatic compounds. As the highly significant decomposition and detoxification of higher concentration of PCDD/Fs and PCBs were achieved in 1 hour without additive catalyst and at low temperature of 150 °C, therefore, the developed method is cost effective and most suitable to apply on commercial/industrial level. The detail results of hydrodechlorination/detoxification of PCDD, PCDFs at different conditions are described and its mechanism is discussed.     

Indication of PCDD/F formation through precursor condensation in a full-scale hazardous waste incinerator

This paper gives the PCDD/F fingerprint of boiler and fly ash of a full scale hazardous waste incinerator and demonstrates that, when the waste to be incinerated contains high concentrations of PCBs and chlorinated pesticides, heterogeneous precursor condensation is the dominant PCDD/F formation mechanism rather than de novo synthesis. This is in contrast to full-scale municipal solid waste incinerators, where de novo synthesis has been shown to be the dominant PCDD/F formation mechanism. This paper agrees with earlier predictions based on numerous lab scale experiments.     

Characterizing emissions from open burning of military food waste and ration packaging compositions

Emissions from open burning of military food waste and ration packaging compositions were characterized in response to health concerns from open burning disposal of waste, such as at military forward operating bases. Emissions from current and prototype Meals, Ready-to-Eat (MREs), and material options for their associated fiberboard packaging were quantified to assess contributions of the individual components. MREs account for 67–100% of the particulate matter (PM), volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated dibenzo-p-dioxins and -furans (PCDDs/PCDFs) emissions when burned in unison with the current fiberboard container and liner. The majority of the particles emitted from these burns are of median diameter 2.5 µm (PM_2.5). Metal emission factors were similar regardless of waste composition. Measurements of VOCs and PAHs indicate that targeted replacement of MRE components may be more effective in reducing emissions than variation of fiberboard-packaging types. Despite MRE composition variation, equivalent emission factors for PM, PAH, VOC, and PCDD/PCDF were seen. Similarly, for fiberboard packaging, composition variations exhibited essentially equivalent PM, PAH, VOC, and PCDD/PCDF emission factors amongst themselves. This study demonstrated a composition-specific analysis of waste burn emissions, assessing the impact of waste component substitution using military rations.     

Environmental contamination from electronic waste recycling at Guiyu, southeast China

The disposal, recycling, and part salvaging of discarded electronic devices such as computers, printers, televisions, and toys are now creating a new set of waste problems. This study is aimed at identifying the sources and quantifying the pollution levels generated from electronic waste (e-waste) activities at Guiyu, Guangdong Province, China, and their potential impacts on the environment and human health. The preliminary results indicate that total polycyclic aromatic hydrocarbons (PAHs) in soil obtained from a printer roller dump site was 593 μg/kg dry weight (dry wt.) and in sediment from a duck pond, the PAH concentration was 514 μg/kg (dry wt.). Sediment from the Lianjiang River was found to be contaminated by polychlorinated biphenyls (743 μg/kg) at a level approaching three times the Canadian Environmental Quality Guidelines probable effect level of 277 μg/kg. Total mono- to hepta-brominated diphenyl ether homologue concentrations (1140 and 1169 μg/kg dry wt.) in soils near dumping sites were approximately 10–60 times those reported for other polybrominated diphenyl ether-contaminated locations in the world. In-house study on the open burning of cable wires showed extremely high levels of polychlorinated dibenzo-p-dioxins and dibenzofurans resulting in 12419 ng toxic equivalents (TEQ)/kg of waste input and 15 610 ng TEQ/kg for two separate tests, respectively, which were about three orders of magnitude higher than those for the open burning of household waste. High levels of Cu (712, 528, and 496 mg/kg), exceeding the new Dutch list action value, were determined for soil near the printer roller dumping area, sediment from Lianjiang River, and soil from a plastic burn site, respectively. A more thorough study is underway to elucidate the extent of contamination of toxic pollutants in different ecological compartments to establish whether these pollutants are bioaccumulated and biomagnified through food chains. Assessments of human health impacts from oral intake, inhalation, and dermal contact will be subsequently investigated. An erratum to this article is available at.