Optimization of combustion conditions to minimize dioxin emissions

Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) may enter an incinerator with the waste, be created in poor combustion or form in post-combustion zones under certain conditions of temperature and oxygen. Tests of MSW burning plants show a wide range of emissions of PCDD and PCDF. Diagnostic tests show the relationship between combustion conditions and the emission of PCDD/DF before and after emission controls. Mixing effectiveness, tightness of control, moisture, furnace and post-furnace temperatures, and the use of lime and reduced temperatures for acid-gas control all have an effect on emissions of trace organics. Carbon monoxide (CO), oxygen, moisture and furnace temperature have been found to be closely related to PCDD/PCDF emissions. By control of temperature and/or oxygen, and the use of CO as an indicator, it is possible to find and maintain optimum combustion conditions so as to minimize dioxins and furans. Plants having acid-gas controls reduce emissions below those achieved by good combustion alone.     

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.     

Problems associated with the measurement of PCDD and PCDF emissions from waste incineration plants

Fly ash and stack gases from municipal waste and industrial incinerators in the F.R.G. have been analyzed for dioxins (PCDD and PCDF). Most of the currently used procedures of stack gas sampling for PCDD/PCDF have been compared and were found to be equally effective. Differences are found, however, in the recovery of surrogates added to the sampling train before sampling, which makes it difficult to validate the sampling procedure. The analysis for PCDD%PCDF in stack gas or fly ash samples from municipal waste incinerators can no longer be considered an analytical problem. Thirty samples of stack gas from a single (old) municipal waste incinerator showed wide variation in PCDD/PCDF emission, indicating that single measurements are not useful in characterizing a plant for average PCDD/PCDF emission. It will be extremely difficult to correlate plant operating conditions to PCDD/PCDF stack gas emissions or PCDD/PCDF fly ash concentrations, because the effects produced by changing conditions are obscured by the variations which occur in PCDD/PCDF concentrations during steady conditions. The variations found under steady conditions can be explained by the proposed mechanisms of PCDD/PCDF formation and decomposition at low temperatures catalyzed by fly ash. Incineration of hospital waste and pyrolytic reclamation of copper in cables and aluminium produced significant emission of PCDD/PCDF. A major noncombustion source of higher chlorinated PCDD/PCDF (tetra- to octa-isomers) is pentachlorophenol, a widespread preservative which contributes to the PCDD/PCDF concentrations found, for example, in sewage sludge, river sediments and house dust.     

PCDD and PCDF emissions and possible health effects: report on a who working group

An international group of experts, convened by the WHO Regional Office for Europe, discussed the health risks of PCDD and PCDF emissions from the incineration of municipal sewage sludge (MSS) and municipal solid waste (MSW) at a meeting in Naples, Italy, held 17–21 March 1986. A detailed analysis of emission data has shown that old and badly operated incinerators will emit up to many thousand ng Nm⁻³ of PCDD and PCDF, while most modern, highly controlled and carefully operated plants will emit them at a very low level. It is still not known what contribution municipal incinerator emissions make to the overall environmental load and, consequently, human exposure. For modern incineration plants this contribution was estimated to be in the range of about a tenth to a few percent of the total background daily body burden [assumed to be 1–5 pg of 2,3,7,8-TCDD (dioxin) equivalents per kilogram bodyweight and day. The Working Group nevertheless recommended that efforts should be made to reduce further the PCDD and PCDF emissions from municipal incinerators.     

Behavior of PCDD/Fs during open burning of municipal solid waste in open dumping sites

Open dumping sites in Surabaya and Palembang, Indonesia, have been studied to investigate emissions of polychlorinated dibenzo-para-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs), as well as the resulting soil contamination that might be caused by open burning of municipal solid waste. The emission factors of the waste residue, accounting for the ratio of waste burned, have also been characterized. The concentrations of PCDD/Fs and DL-PCBs in soil from Palembang were 61–310 pg-TEQ/g (dry weight) and 6.3–32 pg-TEQ/g, respectively. In Surabaya, very low levels of PCDD/Fs and DL-PCBs, ranging from 0.075 to 0.098 and 0.00032 to 0.095 pg-TEQ/g, respectively, were observed in soil for an open dumping site that included a top cover layer of soil above the compacted waste. The large difference in concentrations can be explained by the fact that open burning of waste is the source of PCDD/Fs and DL-PCBs. The emission factors for the residue for PCDD/Fs ranged from 27 to 140 pg-TEQ/g, and a sensitivity analysis found that the maximum emission factor to the residue could be 5600 pg-TEQ/g. Our results indicate that emissions of PCDD/Fs can be controlled by modifying the open dumping process to one that involves depositing soil layers on top of the compacted waste.     

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.     

Dioxin emissions from thermal waste management in Medellín, Colombia: present regulation status and preliminary results

Preliminary results of a study undertaken to characterize dioxin and furan releases from waste incineration plants operating in Medellín-Colombia are presented. Emission and fly ash samples were collected from representative plants burning medical and industrial residues to characterize PCDD/PCDF levels. Analyses were carried out following European standards for stationary gas emissions EN-1948:1996 and US EPA 1613 (fly ashes). Final extracts were analyzed by both high resolution gas chromatography coupled to high resolution mass spectrometry (HRGC-HRMS) and high resolution gas chromatography coupled to ion trap tandem mass spectrometry (HRGC-ITMS/MS). Preliminary results revealed emission levels of 1-30.3 ng I-TEQ/Nm3 depending on whether or not an air pollution control system (APCS) was installed. Fly ashes contained 8.5-68 ng I-TEQ/g. Critical issues that should be addressed in an assessment and in developing waste management plans in Colombia are discussed.     

Correlations between homologue concentrations of PCDD/Fs and toxic equivalency values in laboratory-, package boiler-, and field-scale incinerators

The toxic equivalency (TEQ) values of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) are predicted with a model based on the homologue concentrations measured from a laboratory-scale reactor (124 data points), a package boiler (61 data points), and operating municipal waste incinerators (114 data points). Regardless of the three scales and types of equipment, the different temperature profiles, sampling emissions and/or solids (fly ash), and the various chemical and physical properties of the fuels, all the PCDF plots showed highly linear correlations (R(2)>0.99). The fitting lines of the reactor and the boiler data were almost linear with slope of unity, whereas the slope of the municipal waste incinerator data was 0.86, which is caused by higher predicted values for samples with high measured TEQ. The strong correlation also implies that each of the 10 toxic PCDF congeners has a constant concentration relative to its respective total homologue concentration despite a wide range of facility types and combustion conditions. The PCDD plots showed significant scatter and poor linearity, which implies that the relative concentration of PCDD TEQ congeners is more sensitive to variations in reaction conditions than that of the PCDF congeners.     

Recommended methodology for measurements of PCDD and PCDF in the nordic countries

In April 1986 the Nordic Council of Ministers recommended that the Nordic countries use a specific method for measurements of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in flue gas emissions from waste combustion. The recommended protocol, which will be re-evaluated in a years time, includes the following.A one week registration period during which the plant is studied by continuous registration of a number of operating and emission parameters. The sampling period is included in this time.A sampling procedure based on a heated filter followed by a condenser, a bottle for the condensate and an adsorbent column. Before the sampling, at least two labelled PCDD are added to the filter.No specified analytical procedure. A labelled PCDF is added before the clean-up procedure and an injection standard before the final analysis. The laboratory is free to use any method that gives at least 25% recovery of the sampling standards and 50% recovery of the clean-up standard.Reporting requirements include homologue specific results for PCDD and PCDF containing four to eight chlorine atoms as well as isomer-specific results for the “dirty dozen”. The results should be compensated for incomplete recoveries and the factors used should be reported.     

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.     

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.     

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.     

Contaminated land clean-up using composted wastes and impacts of VOCs on land

This paper describes experiments that demonstrate the effects and potential for remediation of a former steelworks site in Wales polluted with polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Under field conditions, PAH-contaminated soil was composted in-vessel, with or without organic feedstocks, receiving forced aeration for 80 days followed by 4 months maturation. Treatments compared PAH removal in contaminated soil to contaminated soil mixed with three different organic waste mixes after composting and after composts were spread to land. After composting, PAH concentrations declined in all treatments, by up to 38%. Sixteen months after the composts were landspread and vegetation was established, only those containing contaminated soil with organic additions exhibited further PAH removal, by up to 29%. Composting resulted in a decline in the relative concentration of small PAHs, whereas the landspreading-vegetation phase saw a decline in the relative concentration of medium PAHs in two of the three composts exhibiting PAH removal. Under controlled glasshouse conditions, vegetated soil columns of differing depths were exposed to VOCs from beneath. VOC vapour affected both shoot and root growth and soil microbial activity; effects varied with distance from the VOC source. This work demonstrated that on-site remediation of aged PAH-contaminated land can be successfully initiated by in-vessel co-composting followed by land spreading and vegetation, within a practical timeframe.     

Treatment of Sydney N.S. tar pond sludge in a pilot‐scale rotary kiln

Tar pond wastes from Sydney, Nova Scotia, containing 50 ppm or more of polychlorinated biphenyls (PCBs) were treated in a pilot‐scale rotary kiln. In order to use the existing feed system attached to the rotary kiln, the wastes were first oven‐dried. Stack gas sampling was conducted during the test, which included measurement of volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), semi‐volatile organic compounds (SVOCs), HCl, and metals. The purpose of this study was to determine emissions from treatment of the tar pond waste using rotary kiln technology. It was found that the dried sludge could sustain combustion in the kiln without any supporting fuel. The emissions of polychlorinated dibenzodioxins/furans (PCDD/Fs) were higher than the Canadian Council of Ministers of the Environment (CCME) air emissions guidelines, and the reasons for this are discussed. © 2008 Wiley Periodicals, Inc.     

Air Quality Management in Izmir Region of Turkey as Required by Clean Air Plans

As a first step to work out an abatement plan against air pollution, a local emission inventory with 1 hr temporal and 1 km spatial resolution in the city of Izmir and its surroundings was prepared. The study area consisted of a 200 × 170 km² rectangle having the city of Izmir at the centre. The studied pollutants were total particulate matter (PM), sulfur oxides (SO_x), nitrogen oxides (NO_x), volatile organic compounds (VOC) and carbon monoxide (CO). Emissions of these pollutants were determined by estimation methods making use of suitable emission factors. Emission sources were evaluated in three categories; point, area and line sources. For year 2000 total emissions in the study area on an average day were estimated as 173 tons PM, 299 tons SOx, 136 tons NOx, 68 tons VOC and 320 tons CO. At the second part of the study, calculated emissions were transformed into air quality predictions in the area by using the Industrial Source Complex – Short Term (ISCST3) dispersion model. Model results were tested with monitoring data from urban air quality stations obtained during the year 2000. Results of the past, present and future air quality estimates in the region were discussed. In order to do so, future scenarios including various control technology applications were formulated and tested to see their effect on the future air quality.     

Generation and distribution of PAHs in the process of medical waste incineration

After the deadly earthquake on May 12, 2008 in Wenchuan county of China, several different incineration approaches were used for medical waste disposal. This paper investigates the generation properties of polycyclic aromatic hydrocarbons (PAHs) during the incineration. Samples were collected from the bottom ash in an open burning slash site, surface soil at the open burning site, bottom ash from a simple incinerator, bottom ash generated from the municipal solid waste (MSW) incinerator used for medical waste disposal, and bottom ash and fly ash from an incinerator exclusively used for medical waste. The species of PAHs were analyzed, and the toxicity equivalency quantities (TEQs) of samples calculated. Analysis results indicate that the content of total PAHs in fly ash was 1.8 × 10³ times higher than that in bottom ash, and that the strongly carcinogenic PAHs with four or more rings accumulated sensitively in fly ash. The test results of samples gathered from open burning site demonstrate that Acenaphthylene (ACY), Acenaphthene (ACE), Fluorene (FLU), Phenanthrene (PHE), Anthracene (ANT) and other PAHs were inclined to migrate into surrounding environment along air and surface watershed corridors, while 4- to 6-ring PAHs accumulated more likely in soil. Being consistent with other studies, it has also been confirmed that increases in both free oxygen molecules and combustion temperatures could promote the decomposition of polycyclic PAHs. In addition, without the influence of combustion conditions, there is a positive correlation between total PCDD/Fs and total PAHs, although no such relationship has been found for TEQ.     

Characterisation of polycyclic aromatic hydrocarbons in flue gas and residues of a full scale fluidized bed combustor combusting non-hazardous industrial waste

This paper studies the fate of PAHs in full scale incinerators by analysing the concentration of the 16 EPA-PAHs in both the input waste and all the outputs of a full scale Fluidized Bed Combustor (FBC). Of the analysed waste inputs i.e. Waste Water Treatment (WWT) sludge, Refuse Derived Fuel (RDF) and Automotive Shredder Residue (ASR), RDF and ASR were the main PAH sources, with phenanthrene, fluoranthene and pyrene being the most important PAHs. In the flue gas sampled at the stack, naphthalene was the only predominant PAH, indicating that the PAHs in FBC’s combustion gas were newly formed and did not remain from the input waste. Of the other outputs, the boiler and fly ash contained no detectable levels of PAHs, whereas the flue gas cleaning residue contained only low concentrations of naphthalene, probably adsorbed from the flue gas. The PAH fingerprint of the bottom ash corresponded rather well to the PAH fingerprint of the RDF and ASR, indicating that the PAHs in this output, in contrast to the other outputs, were mainly remainders from the PAHs in the waste inputs. A PAH mass balance showed that the total PAH input/output ratio of the FBC ranged from about 100 to about 2600 depending on the waste input composition and the obtained combustion conditions. In all cases, the FBC was clearly a net PAH sink.     

Adapting the Speciation of the VOCs Emission Inventory in the Greater Athens Area

An adaptation procedure of a new emission inventory of theGreater Athens Area is attempted, based on a sensitivityanalysis on the treatment of the VOC emissions. Throughthis procedure the impact that a more detailed treatment ofthe VOCs emissions might have on the atmospheric chemistrysimulations, is examined. For this analysis three differentchemical mechanisms were applied for two differentlocations (urban and city plume) with different VOC andNO_x mixture characteristics. Finally, this studyrecommends new carbon fractions, reflecting the localconditions in Athens basin.     

Study of the VOC emissions from a municipal solid waste storage pilot-scale cell: comparison with biogases from municipal waste landfill site

The emission of volatile organic compounds (VOCs) from municipal solid waste stored in a pilot-scale cell containing 6.4 tonnes of waste (storage facility which is left open during the first period (40 days) and then closed with recirculation of leachates during a second period (100 days)) was followed by dynamic sampling on activated carbon and analysed by GC–MS after solvent extraction. This was done in order to know the VOC emissions before the installation of a methanogenesis process for the entire waste mass. The results, expressed in reference to toluene, were exploited during the whole study on all the analyzable VOCs: alcohols, ketones and esters, alkanes, benzenic and cyclic compounds, chlorinated compounds, terpene, and organic sulphides.The results of this study on the pilot-scale cell are then compared with those concerning three biogases from a municipal waste landfill: biogas (1) coming from waste cells being filled or recently closed, biogas (2) from all the waste storage cells on site, and biogas (3) which is a residual gas from old storage cells without aspiration of the gas. The analysis of the results obtained revealed: (i) a high emission of VOCs, principally alcohols, ketones and esters during the acidogenesis; (ii) a decrease in the alkane content and an increase in the terpene content were observed in the VOCs emitted during the production of methane; (iii) the production of heavier alkanes and an increase in the average number of carbon atoms per molecule of alkane with the progression of the stabilisation/maturation process were also observed.Previous studies have concentrated almost on the analysis of biogases from landfills. Our research aimed at gaining a more complete understanding of the decomposition/degradation of municipal solid waste by measuring the VOCs emitted from the very start of the landfill process i.e. during the acidogenesis and acetogenesis phases.