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.     

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.     

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.     

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.     

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%).     

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.     

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.     

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.     

The estimation of N2O emissions from municipal solid waste incineration facilities: The Korea case

The greenhouse gases (GHGs) generated in municipal solid waste (MSW) incineration are carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). In South Korea case, the total of GHGs from the waste incineration facilities has been increasing at an annual rate 10%. In these view, waste incineration facilities should consider to reduce GHG emissions.This study is designed to estimate the N₂O emission factors from MSW incineration plants, and calculate the N₂O emissions based on these factors. The three MSW incinerators examined in this study were either stoker or both stoker and rotary kiln facilities. The N₂O concentrations from the MSW incinerators were measured using gas chromatography-electron capture detection (GC-ECD) equipment.The average of the N₂O emission factors for the M01 plant, M02 plant, and M03 plant are 71, 75, and 153 g-N₂O/ton-waste, respectively. These results showed a significant difference from the default values of the intergovernmental panel on climate change (IPCC), while approaching those values derived in Japan and Germany. Furthermore, comparing the results of this study to the Korea Energy Economics Institute (KEEI) (2007) data on waste incineration, N₂O emissions from MSW incineration comprised 19% of the total N₂O emissions.     

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.     

Statistical modelling for the prediction and control of PCDDs and PCDFs emissions from municipal solid waste incinerators

The emissions of a full range of polychlorinated dibenzo-p-dioxins and furans (PCDDs/PCDFs) have become one of the most controversial issues in siting and building new municipal incinerators. The lack of comprehensive evaluation of the PCDDs/PCDFs formation and emission control technologies in earlier times resulted in ambiguity in the decision-making of incineration projects. Until the last decade, several emission tests of municipal solid waste incineration regarding to new combustion criteria, public regulations, and risk assessments were conducted and reported in the literature. However, only a few analyses of statistical prediction and control have been established. This paper presents a series of multiple linear regression models for PCDDs/PCDFs emission prediction and control corresponding to different types of incinerators. The data used in the regression analysis were integrated from several testing programmes held in North America. By applying these regression results, evaluation of various combustion criteria, public regulations, and environmental and health risk assessment can then be achieved. Such evaluation is valuable for some developing countries which do not have sufficient finance or engineering experience to pursue large scale emission tests, but need rapid promulgation of emissions control for municipal solid waste incinerators.     

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.     

PCDD/F EMISSION CONTROL BY INTERMEDIATE DUST REMOVAL AT MEDICAL WASTE INCINERATORS

A 1 tonne day⁻¹medical incinerator that meets the new national emission standards for PCDD/F of less than 0.1 ng TEQm⁻³was installed in Eger, Hungary in January 1994. The unit is batch operated and is charged once or twice a day. It has an intermediate dust control filter between a pyrolysis chamber and an afterburner. Dry lime is inserted before this filter. Two polishing filters using zeolite and coke, respectively, follow a waste heat boiler.     

PCBs,PBDEs and dioxin-related compounds in floor dust from an informal end-of-life vehicle recycling site in northern Vietnam: contamination levels and implications for human exposure

Floor dusts from Vietnamese end-of-life vehicle (ELV)-processing households were investigated to elucidate the contamination levels and exposure risk of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and dioxin-related compounds (DRCs). The concentrations were in order of PBDEs (260–11,000, median 280 ng/g overall) > PCBs (19–2200, median 140 ng/g) > dioxin-like PCBs (8.8–450, median 22 ng/g) ? polybrominated dibenzo-p-dioxin/dibenzofurans (PBDD/Fs, 2000–28,000, median 8500 pg/g) > polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs, 440–4100, median 1800 pg/g) > MoBPCDD/Fs (1.9–1200, median 250 pg/g). Concentrations of PCBs and DRCs were higher than those reported for Vietnamese urban houses, indicating ELV processing as a significant source of these contaminants. Higher concentrations of PCBs relative to PBDEs suggest the abundance of old electrical capacitors/transformers in ELVs. The PBDD/F and PCDD/F profiles were indicative of DecaBDE-containing materials and combustion sources, respectively. PBDFs, PCDFs and DL-PCBs were the most important dioxin-like toxic equivalent (TEQ) contributors. The estimated PCB and TEQ intake doses from dust ingestion approached or exceeded the reference doses for children living in some ELV-processing households, indicating potential health risk. More comprehensive risk assessment of the exposure to PCBs and DRCs is required for residents of informal ELV recycling sites.     

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.     

Sources and behaviour of polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in Spanish sewage sludge

Presence, sources and behaviour of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were evaluated in Spanish sewage sludge. A total of 120 samples were seasonally collected from October 2005 to September 2006 at 31 urban wastewater treatment plants (WWTPs). Concentrations of PBDEs (ranging between 57.5 and 2606 ng/g dry weight) were two to three orders of magnitude higher than those obtained for PCDDs (0.17-5.03 ng/g d.w.) and PCDFs (0.05-3.07 ng/g d.w.). All the samples presented International Toxicity Equivalents (I-TEQ) levels (ranging between 2.06 and 44.4 ng/kg d.w.) below the limit values proposed by European Union for land application. Congener patterns evaluation revealed that the use of Deca-BDE commercial mixture seems to be the major source of PBDEs in the sludge. Nevertheless, origin of PCDD/Fs should be related to atmospheric deposition, faeces and presence of PCDD/Fs precursors such as pentachlorophenol in the sludge. No correlations (p > 0.05) were found between pollutant concentrations (PBDEs and PCDD/Fs) and wastewater treatment plant (WWTP) characteristics (capacity nor sludge rate). Lower levels of PBDEs and PCDFs were found in WWTPs using biological nitrogen and phosphorous elimination, suggesting that these compounds are susceptible of microbial elimination. According to our knowledge, this is the first work comparing together both PBDEs and PCDD/Fs sludge patterns.     

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.     

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.     

Mercury emission from sewage sludge incineration in Japan

Sewage sludge contains trace amounts of mercury, and sewage sludge incineration is a major source of mercury emissions. However, relatively few studies have reported on mercury emissions from sewage sludge incineration. Consequently, data on emissions from sewage sludge incinerators must be updated to estimate current emissions of mercury. In this study, we examined mercury emissions and speciation using continuous mercury analyzers in two incinerators. The mercury concentrations in stack gas from facilities A and B were 36.6 and 21.1???g/Nm³, respectively. As a result, the emission rate was calculated to be 0.282?C0.750?g/ton-dry sludge. Considering the total amount of sewage sludge incinerated in Japan, the mercury emissions from sewage sludge incinerators were estimated to be 0.49?C1.31?tons/year.     

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.