Characterization and mass balance of dioxin from a large-scale municipal solid waste incinerator in China

The input and output samples from existing large-scale municipal solid waste incinerator (MSWI) were collected and analyzed for polychlorinated dibenzo-р-dioxins and dibenzofurans (PCDD/Fs) in this study, aiming to evaluate PCDD/F characteristic and the corresponding mass balance through the whole system. The grate-type MSWI is equipped with semi-dry scrubber, activated carbon injection, and bag filter as air pollutant control devices (APCDs). Results showed that on the output side, the stack gas, bottom ash and fly ash presented their mean dioxin levels of 0.078 ng I-TEQ/Nm(3), 12.94 ng I-TEQ/kg and 858 ng I-TEQ/kg, respectively, and showed large similarities in congener profiles. Instead, on the input side, the municipal solid waste (MSW) presented a mean dioxin level of 15.56 ng I-TEQ/kg and a remarkable difference in congener profiles compared with those of the output. The dioxin mass balance demonstrated that the annual dioxin input value was around 5.38 g I-TEQ/yr, lower than the total output value (7.62 g I-TEQ/yr), signifying a positive dioxin balance of about 2.25 g I-TEQ/yr.     

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.     

Persistent organic pollutant emissions from medical waste incinerators in China

The huge amount of medical waste (MW) has caused a tough challenge to environmental protection in China because of its serious infectious potential. At present, incineration is the most common technology for MW disposal. Unfortunately, the medical waste incinerator (MWI) is considered one of the major sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). This study was conducted to investigate the generation and the components of MW; the fingerprint of PCDD/Fs in MWI; and PCDD/F, polychlorinated biphenyl (PCB) and hexachlorobenzene concentrations in residue ash. The estimated annual production of MW was estimated to be 0.97 million tons in China in 2008; in addition, plastic and rubber accounted for 24.5% of MW contents. PCDD/F emissions from MWI could be divided into two main groups according their fingerprints, and the ratio of PCDFs/PCDDs was mostly over 1.5, with a mean value of 3.43. The toxic equivalent of PCDD/Fs was over 30 times that of the value of PCBs in the residue ash, and PCDD/F contents in fly ash accounted for approximately 67% of the total output of PCDD/Fs, which was in line with the UNEP default emission factors for MWI (class 3, 63.7%).     

Sludge as dioxins suppressant in hospital waste incineration

Nitrogen containing compounds such as ammonia, urea and amines can effectively inhibit the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Sewage sludge accumulates both sulfur and nitrogen during wastewater treatment so it could be used to reduce PCDD/Fs formation. Indeed, it is observed in this study that the gas evolving from the sludge drying process can significantly suppress chlorobenzene (CBz) and PCDD/Fs formation from fly ash collected from a hospital waste incinerator. For instance, the reduction of hexachlorobenzene (HxCBz) and PCDD/Fs amount was 92.1% and 78.7%, respectively, when the drying gas evolving from 2g sludge flew through 2g fly ash. These tests were conducted in the frame of projects devoted to hospital waste incineration. The disposal technology for hospital waste (HW), developed in this institute, features rotary kiln pyrolysis combined with post-combustion followed by flue gas cleaning. Hence, some preliminary tests were devoted to investigate dioxins suppression by co-pyrolysis and co-combustion of polyvinyl chloride (PVC) and sludge in lab scale. More experimental research will be conducted to appropriately assess these effects of sludge on PCDD/Fs emissions during co-pyrolysis/combustion of HW and sludge.     

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.     

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.     

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.     

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.     

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.     

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.     

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.     

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.     

An investigation on pollutant emissions from co-firing of RDF and coal

Pollutant emissions from co-firing of refuse derived fuel (RDF) and coal were investigated in a vortexing fluidized bed combustor (VFBC). RDF-5 was made of common municipal solid waste (MSW). CaCO₃ was injected in the combustor to absorb HCl at 850 °C. The results show that NO_x and HCl emissions increase with RDF-5 co-firing ratio. The NO_x concentration in flue gas at the bottom of the combustor is higher than that at the top. However, the trend of HCl released is reverse compared with NO_x emissions. It was found that the HCl concentration decreases with increasing the molar ratio of Ca/Cl. However, the effect of CaCO₃ addition on HCl retention is not significant when the molar ratio of Ca/Cl is higher than 5. The chlorine content in fly ash increases obviously with the molar ratio of Ca/Cl. PCDD/Fs emissions decrease slightly with an addition of CaCO₃. In this study incomplete combustion is regarded as the main cause for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) formation.     

Leaching behaviour of elements and evaluation of pre-treatment methods for municipal solid waste incinerator residues in column leaching tests.

Two new pre-treatment methods (water-washing/carbonation and carbonation/phosphate stabilization) of municipal solid waste (MSW) incinerator residues were evaluated by column leaching tests under aerobic conditions and anaerobic conditions (which were changed to aerobic conditions after 10 months). A mixture of bottom ash and fly ash (5:1 ratio) was pre-treated using each method. Shredded incombustible residues (SIR) were added to each ash preparation in proportions similar to the ratios present in landfills. For comparison, landfill wastes typical of Japan, namely, a mixture of bottom ash, chelating-pre-treated fly ash, and SIR, were also examined. Leachate samples were collected periodically and analysed over a 15-month period. When compared with chelating pretreatment, both water-washing/carbonation and carbonation/ phosphate stabilization reduced the leaching of Pb, Al, and Cu by about one to two orders of magnitude. Moreover, the initial concentrations of Ca and Pb in leachates from column of water-washing/carbonation were 56-57% and 84-96% less than those from the column of carbonation/phosphate stabilization. Therefore, water-washing/carbonation was considered to be a promising approach to obtain early waste stabilization and to reduce the release of heavy metals to near-negligible levels. The leaching behaviour of elements was also discussed.     

Paper fibers as a carbon source for the de novo formation of polychlorinated dioxins and furans

The formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from carbon that was produced by the pyrolysis of paper fibers and from wood charcoal was investigated experimentally. Fibers obtained from filter paper were pyrolyzed at 300° and 800°C to produce low- and high-temperature carbon samples. The two types of carbon and wood charcoal were mixed with silica (SiO₂) and trace copper oxide to produce three synthetic fly ash samples. Experiments to measure the formation of PCCDs/Fs from the three ash samples were conducted using a bench-scale reactor. The two carbon samples derived from paper fibers generated more PCDDs/Fs than was generated by the wood charcoal. The PCDDs/Fs generated by the low-temperature carbon and by the wood charcoal were dominated by the lower-chlorinated PCDFs. Such unique homologue distribution patterns are very similar to those generated by the open burning of household waste. The high-temperature carbon generated more highly chlorinated PCDDs/Fs. The effect of pyrolysis temperature on the de novo formation of PCDDs/Fs from residual carbon is discussed. Paper and paper products contained in household waste are likely to be the source of unburned carbon that contributes to high PCDD/F emissions in the open burning of household waste.     

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.     

Corrosion behavior of glass and glass-ceramics made of municipal solid waste incinerator fly ash

Glasses and glass-ceramics were prepared by melting municipal solid waste (MSW) incinerator fly ash and their corrosion properties were evaluated. Corrosion of both materials proceeded in two different steps. At the initial stage, the corrosion process is a diffusion-controlled process. After approximately 10 h at the initial stage, weight losses increased linearly with time due to the total dissolution of glasses or glass-ceramics. Leaching of heavy metals from glasses and glass-ceramics were well within international environmental regulations. Corrosion proceeded uniformly in fly ash glass while Na2CaSiO4 crystalline phase was preferentially dissolved in the glass-ceramics.     

Mercury leaching characteristics of waste treatment residues generated from various sources in Korea

In this study, mercury (Hg) leaching characteristics of the waste treatment residues (fly ash, bottom ash, sludge, and phosphor powder) generated from various sources (municipal, industrial, medical waste incinerators, sewage sludge incinerator, oil refinery, coal-fired power plant, steel manufacturing plant, fluorescent lamp recycler, and cement kiln) in Korea were investigated. First, both Hg content analysis and toxicity characteristic leaching procedure (TCLP) testing was conducted for 31 collected residue samples. The Hg content analysis showed that fly ash from waste incinerators contained more Hg than the other residue samples. However, the TCLP values of fly ash samples with similar Hg content varied widely based on the residue type. Fly ash samples with low and high Hg leaching ratios (R_L) were further analyzed to identify the major factors that influence the Hg leaching potential. Buffering capacity of the low-R_L fly ash was higher than that of the high-R_L fly ash. The Hg speciation results suggest that the low-R_L fly ashes consisted primarily of low-solubility Hg compounds (Hg₂Cl₂, Hg⁰ or HgS), whereas the high-R_L fly ashes contain more than 20% high-solubility Hg compounds (HgCl₂ or HgSO₄).     

Effects of the type of sintering atmosphere on the chromium leachability of thermal-treated municipal solid waste incinerator fly ash

The sintering process offers an opportunity to combine detoxification and resource recovery for the treatment of municipal solid waste (MSW) incinerator fly ash. However, the chromium (Cr) in the sintered fly ash becomes more readily leachable with increasing sintering time and temperature, thus posing severe threats to the environment and human health when the sintered ash is recycled or reused. This study investigated the enhanced leachability of fly ash containing Cr, by heating the chromium (III) oxide (Cr2O3)-spiked fly ash to 800 degrees C in atmospheres containing air, nitrogen gas (N2), and 5% H2 + 95% N2, respectively. The results indicated that trivalent chromium was converted to its soluble hexavalent form during sintering in the air atmosphere; whereas sintering in a nitrogen atmosphere significantly reduced the leachability of Cr due to lack of oxygen (O2) to oxidize. The effects of the sintering temperature on the total chromium content and the leaching concentration in the toxicity characteristic leaching procedure (TCLP) extract are also discussed.