Catalytic destruction of PCDD/F in a fabric filter: experience at a municipal waste incinerator in Belgium

In order to comply with dioxin and furan (PCDD/F) emission regulations in Belgium, the IVRO municipal waste incinerator adopted catalytic filters for use in the plant's two existing fabric filters. This system replaced the injection of powdered activated carbon (PAC) because of concerns that PAC, used at temperatures above 200 degrees C, would ignite and lead to fires and plant down-time. The performance of the catalytic filter system, since its installation in 1997, is described. PCDD/F emissions are controlled to well below the regulatory limit of 0.1 ng I-TEQ/Nm3. The amount of PCDD/F entering and exiting the fabric filter is quantified. The resulting mass balance shows that greater than 99.5% of the gaseous PCDD/F entering the fabric filter is destroyed by the catalyst within the filter media.     

Characterization of PCDD/Fs and heavy metals from MSW incineration plant in Harbin

The characterization of PCDD/Fs and heavy metals in the flue gas and fly ash of Harbin municipal solid waste (MSW) incineration plant, located in the northeast of China, was investigated in this study. The MSW was treated in a twin internal fluidized (TIF) bed incinerator. The results indicate that the emission of PCDD/Fs into the environment is 0.02 ng I-TEQ/m3 and the level of PCDD/Fs in the fabric filter fly ash is 0.7982 ng I-TEQ/g. The leachability levels of Pb, Cd and Hg in the fly ash are below the limits of environmental protection standard in China. However, the contents of Cu, Zn, and Hg are high in the fly ash. This suggests that the fly ash is a hazardous waste that requires special treatment and disposal. The practice of more than four years of operation shows that the TIF bed incinerator is very suitable and practical for China.     

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.     

SETTING DIOXIN EMISSION LIMITS FOR MSW INCINERATORS: A MULTIMEDIA EXPOSURE ASSESSMENT FRAMEWORK

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are emitted in trace amounts from municipal solid waste (MSW) incinerators. The exposure to PCDD/Fs experienced by an individual is dominated by the food chain pathway, which accounts for over 98% of the total uptake. Defining a target daily intake (the World Health Organization TDI of 10 pg I-TEQ kg.bw⁻¹day⁻¹) exposure assessment algorithms were then applied to arrive at the corresponding PCDD/F levels in air, soil, plants, food products, etc., which would allow the target intake to be met while retaining the balance of intake between the various exposure pathways. These concentrations were converted to an ambient air concentration of PCDD/Fs and ultimately, by defining criteria for acceptability, to a guide value for PCDD/F concentration in emissions from the MSW incinerator. This strategy was applied to PCDD/F emissions from MSW incinerators of various sizes against two illustrative criteria for acceptability: an “insignificant” release and a threshold above which the release may require further assessment for environmental effects and for control. Using the criteria developed in this paper, the current PCDD/F emission limit of 0.1 ng I-TEQ m⁻³results in an emission that is classed as “insignificant” for all plant sizes. However, higher emission concentrations can also be accommodated below the threshold for further assessment and control.     

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.     

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.     

Thiourea leaching of gold from processed municipal solid waste incineration residues

Incineration is one of the key technologies in disposal of municipal waste, which produces municipal solid waste incineration (MSWI) residues with high valuable metal contents. The recycling strategy for the MSWI residues is typically focused on the recovery of scrap metals yielding processed municipal solid waste incineration residues (PIR) as the main byproduct. However, the PIR still contains valuable metals, particularly gold, which cannot be extracted by conventional methods. Here, we evaluated the feasibility of using the 0.5–2.0 mm grain size fraction of PIR containing 28.82 ± 1.62 mg/kg of gold as raw material for a two-stage extraction process. In the first stage the alkalic fine-grained PIR was acidified with a solution of 20% (v/v) of HCl-containing flue gas cleaning liquid that is obtained by the municipal waste incineration plant itself as a waste product. In the second stage we leached the acidified fine-grained PIR by thiourea with Fe³⁺ as an oxidant. Application of the thiourea-Fe³⁺ leaching system resulted in recovery of 16.4 ± 1.56 mg/kg of gold from the fine-grained PIR within 6 h of incubation. Due to high gold market prices, upscaling of the suggested technology can represent a suitable strategy for gold recovery from PIR and other MSWI residues.

     

Removal potential of toxic 2378-substituted PCDD/F from incinerator flue gases by waste-derived activated carbons

The application of activated carbons has become a commonly used emission control protocol for the removal or adsorption of persistent organic pollutants from the flue gas streams of waste incinerators. In this study, the 2378-substituted PCDD/F removal efficiency of three types of activated carbons derived from the pyrolysis of refuse derived fuel, textile waste and scrap tyre was investigated and compared with that of a commercial carbon. Experiments were carried out in a laboratory scale fixed-bed reactor under a simulated flue gas at 275 °C with a reaction period of four days. The PCDD/F in the solid matrices and exhaust gas, were analyzed using gas chromatography coupled with a triple quadrupole mass spectrometer. In the absence of activated carbon adsorbent, there was a significant increase in the concentration of toxic PCDD/F produced in the reacted flyash, reaching up to 6.6 times higher than in the raw flyash. In addition, there was a substantial release of PCDD/F into the gas phase, which was found in the flue gas trapping system. By application of the different commercial, refuse derived fuel, textile and tyre activated carbons the total PCDD/F toxic equivalent removal efficiencies in the exhaust gas stream were 58%, 57%, 64% and 52%, respectively. In general, the removal of the PCDDs was much higher with an average of 85% compared to PCDFs at 41%. Analysis of the reacted activated carbons showed that there was some formation of PCDD/F, for instance, a total of 60.6 μg I-TEQ kg⁻¹ toxic PCDD/F was formed in the refuse derived fuel activated carbon compared to 34 μg I-TEQ kg⁻¹ in the commercial activated carbon. The activated carbons derived from the pyrolysis of waste, therefore, showed good potential as a control material for PCDD/F emissions in waste incinerator flue gases.     

Dioxin emissions from municipal solid waste incinerators (MSWIs) in France

The objective of this study was to determine whether the fear of dioxin/furan emissions from waste-to-energy plants was justified by the 2007 status of emissions of French municipal solid waste incinerators (MSWIs). All emissions were examined, plant by plant, but this paper focuses on the incinerator emission that is most frequently mentioned in the French media, toxic dioxins and furans. The study showed that there are 85 large MSWI that generate electricity or heat, i.e., waste-to-energy (WTE) plants, and 39 smaller MSW incinerators. The results showed that all French MSWI are operated well below the EU and French standard of 0.1 ng TEQ Nm^?3 (toxic equivalent nanograms per standard cubic meter) and that their total dioxin/furan emissions decreased from 435 g TEQ in 1997 to only 1.2 g in 2008. All other industrial emissions of dioxins have also decreased and the major source is residential combustion of wood (320 g TEQ). It was extremely difficult to obtain MSWI emission data. This unwarranted lack of transparency has resulted in the public perception that MSWI plants are major contributors to dioxin emissions while in fact they have ceased to be so.     

Application of large volume injection GC-MS to analysis of organic compounds in the extracts and leachates of municipal solid waste incineration fly ash

Organic solvent and water extracts of fly ash from a Milan (Italy) municipal solid waste incinerator (MSWI) were analyzed by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) with programmable temperature vaporizer (PTV). Using injection volumes of 10-100 microl, typically over a hundred compounds were detected in organic solvent extracts and ca. 35% of them could be tentatively identified from their electron impact ionization mass spectra. A protocol for the determination of the maximum amount of a potential environmental pollutant available for leaching (availability test) was developed for four selected target compounds: pentachlorobenzene (PeCB), hexachlorobenzene (HxCB), o-terphenyl (o-TPH) and m-terphenyl (m-TPH). Key parameters, extraction time and liquid-to-solid ratio (L/S), were studied in more detail. Recoveries of PeCB, HxCB and o-TPH spiked into the fly ash samples at two concentration levels ranged from 38% to 53% for freshly spiked and from 14% to 40% for 40-day aged fly ash. Recoveries of m-TPH were 8% to 11% from freshly spiked and less than 3% from aged spiked fly ash. The native amounts in Milan MSWI fly ash, determined in an interlaboratory exercise using the developed protocol, were 31 ng/g PeCB, 34 ng/g HxCB, 72 ng/g o-TPH and 4.4 ng/g m-TPH. A separate methodology was developed for the determination of compounds extracted from fly ash by water (leaching test). Following 8-h sonication at L/S 20, the leached amounts of PeCB, HxCB and o-TPH were 1.1, 3.1 and 6.0 ng/g fly ash, respectively.     

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.     

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.     

Effect of leachate recirculation on the migration of copper and zinc in municipal solid waste and municipal solid waste incineration bottom ash co-disposed landfill

Municipal solid waste incinerator (MSWI) bottom ash was allowed to be disposed of with municipal solid waste (MSW) in landfill sites in the recently enacted standard of China. In this study, three sets of simulated landfill reactors, namely, conventional MSW landfill (CL), conventional MSWI bottom ash and MSW co-disposed landfill (CCL), and leachate recirculated MSWI bottom ash and MSW co-disposed landfill (RCL), were operated to investigate the environmental impact of the co-disposal. The effect of leachate recirculation on the migration of Cu and Zn in the co-disposed landfill was also presented. The results showed that the co-disposal of MSWI bottom ash with MSW would not enhance the leaching of Cu and Zn from landfill. However, the co-disposal increased the Cu and Zn contents of the refuse in the bottom layer of the landfill from 56.7 to 65.3 mg/kg and from 210 to 236 mg/kg, respectively. The recirculation of the leachate could further increase the Cu and Zn contents of the refuse in the bottom layer of the landfill to 72.9 and 441 mg/kg, respectively. Besides these observations, the results also showed that the co-disposed landfill with leachate recirculation could facilitate the stabilization of the landfill.     

Mass and element balance in food waste composting facilities

The mass and element balance in municipal solid waste composting facilities that handle food waste was studied. Material samples from the facilities were analyzed for moisture, ash, carbon, nitrogen, and the oxygen consumption of compost and bulking material was determined.Three different processes were used in the food waste composting facilities: standard in-vessel composting, drying, and stand-alone composting machine. Satisfactory results were obtained for the input/output ash balance despite several assumptions made concerning the quantities involved. The carbon/nitrogen ratio and oxygen consumption values for compost derived only from food waste were estimated by excluding the contribution of the bulking material remaining in the compost product. These estimates seemed to be suitable indices for the biological stability of compost because there was a good correlation between them, and because the values seemed logical given the operating conditions at the facilities.     

PCDD/F in source-sorted waste fractions and emissions from their co-combustion with reed canary-grass

The dry combustible fraction of source-sorted household waste, including material that would otherwise be recycled, was mixed with the energy crop reed canary-grass (Phalaris arundinacea L.), and combusted as briquettes in 150 and 600 kW biofuel-boilers without advanced cleaning systems. The source-sorted waste was further sorted and characterized according to its material and chemical contents. The bulk of the waste's chlorine content came from the non-package plastic fraction, whereas 90-95% of summation operator PCDD/F (74-90% of WHO-TEQ) originated from the textile fraction. The sources of the dioxins in the waste fractions are discussed. The balance of dioxin levels was negative, i.e., the amounts of dioxins output in the flue gas were lower than those input in the fuel, except when there were operational disturbances in the combustion. In one of the combustion trials the total levels of dioxins in the flue-gas and ashes were also lower than the input levels. The use of additional cleaning equipment will be needed to ensure that emissions of dioxins and hydrochloric acid will be below legal limits.     

Strength, leachability and microstructure characterisation of Na2SiO3-activated ground granulated blast-furnace slag solidified MSWI fly ash.

The chemical composition and the leachability of heavy metals in municipal solid waste incinerator (MSWI) fly ash were measured and analysed. For the leachability of unstabilized MSWI fly ash it was found that the concentrations of Pb and Cr exceeded the leaching toxicity standard. Cementitious solidification of the MSWI fly ash by Na2SiO3-activated ground granulated blast-furnace slag (NS) was investigated. Results show that all solidified MSWI fly ash can meet the landfill standards after 28 days of curing. The heavy metals were immobilized within the hydration products such as C-S-H gel and ettringite through physical encapsulation, substitution, precipitation or adsorption mechanisms.     

Polycyclic aromatic hydrocarbon (PAH) emission from co-firing municipal solid waste (MSW) and coal in a fluidized bed incinerator

Polycyclic aromatic hydrocarbons (PAH) emissions from a commercial municipal solid waste incinerator (MSWI) were studied. A MSW–coal mixture and coal only were used as fuel for the fluidized bed incinerator. Seven sampling points were chosen according to the classified four PAH emission pathways: flue gas, residue, ash and water. The mixture of MSW and coal resulted in PAH emission more than that of coal only, and PAH emission increased with increasing MSW mass percentage. Calcium oxide (CaO) or calcium carbonate (CaCO₃) was added as a desulfurizer. PAH emission also changed with different desulfurizers because of their different influences on heat balance. The PAH toxic equivalent (TEQ) of all operating conditions was also examined, showing that total daily PAH emission from MSWI can be determined.     

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.     

Biostabilization of municipal solid waste

A mechanical-biological process for municipal solid waste (MSW) treatment was monitored for one year. Mechanical pre-treatment provided two fractions. The oversize fraction (diameter > 50 mm) (yield of 600 g kg(-1) ww) (46 Mg day(-1)) was used for refuse derived fuel production, after undergoing a mechanical refining processes, because of low moisture content (200-250 g kg(-1)) and high calorific value (2500-2800 kcal kg ww(-1)). The undersize fraction (diameter < 50 mm) (yield 400 g kg(-1) ww) (30 Mg day(-1)) contained about 800 g kg(-1) of the MSW organic matter. This fraction was biologically treated using an aerobic process with an organic waste fraction from separate collection (77 Mg day(-1)) and recycled stabilized material (62 Mg day(-1)) obtained from end-product sieve (diameter < 20 mm) used as bulking agent. A retention time of three weeks was sufficient to obtain stabilized products in agreement with up-dated rules of the Lombardy Region (North Italy) regarding biostabilization and composting processes. Dynamic Respiration Index (DRI), such as required by both Lombardy Region rules and suggested by the European Community, was chosen in preference to other indices in order to assess the degree of biological stability of the end products. A mean DRI value of 1164 mg O2 kg SV(-1) h(-1) was obtained and is in agreement with the proposed limit of 1000+/-200 mg O2 kg SV(-1) h(-1). Self-heating test, potential biogas production and fermentable volatile solids were also used as parameters to describe the potential impact of treated waste, providing further useful information. Nevertheless, all of these methods revealed analytical or interpretative limits. A complete mass balance of the biological treatment section showed that, from a net input of 107 Mg day(-1), only 250 g kg(-1) (27 Mg day(-1)) of the waste needed to be landfilled, with 750 g kg(-1) (80 Mg day(-1)) being lost as CO2 and H2O.     

Recovery of MSWI and soil washing residues as concrete aggregates

The aim of the present work was to study if municipal solid waste incinerator (MSWI) residues and aggregates derived from contaminated soil washing could be used as alternative aggregates for concrete production.Initially, chemical, physical and geometric characteristics (according to UNI EN 12620) of municipal solid waste incineration bottom ashes and some contaminated soils were evaluated; moreover, the pollutants release was evaluated by means of leaching tests. The results showed that the reuse of pre-treated MSWI bottom ash and washed soil is possible, either from technical or environmental point of view, while it is not possible for the raw wastes.Then, the natural aggregate was partially and totally replaced with these recycled aggregates for the production of concrete mixtures that were characterized by conventional mechanical and leaching tests. Good results were obtained using the same dosage of a high resistance cement (42.5R calcareous Portland cement instead of 32.5R); the concrete mixture containing 400 kg/m³ of washed bottom ash and high resistance cement was classified as structural concrete (C25/30 class). Regarding the pollutants leaching, all concrete mixtures respected the limit values according to the Italian regulation.