A measuring method of chlorobenzenes as a convenient substitute index of dioxins in stack gas from waste incineration facilities

Much labor, high technical skill and extreme cost are required to measure dioxins for obtaining the toxic equivalent quantity (TEQ) values. On one side, it was found that there were high amounts of chlorobenzenes (CBZs) in the flue gas from waste incineration facilities, and they are also thought to be one of the principal precursors for dioxins. The concentrations of CBZs could be used as a convenient substitute index to the TEQ values for controlling and monitoring dioxins in stack gas from waste incineration facilities as shown in another report. In this study, collection efficiencies in the sampling performed by a convenient train which was composed of two bottles containing water and diethylene glycol in a cooling box, recoveries in the evaporation of the extract by an evaporator, proper procedure of the concentration by nitrogen purge were investigated for measuring CBZs. It was found that tetra-, penta-, and hexa-chlorobenzenes (Cl4-6BZs) whose boiling points are higher than ca. 240 degrees C could be sufficiently collected and recovered in the sampling and the evaporation. For sufficient recoveries of Cl4-6BZs in the concentration by the nitrogen purge, the final volume should be larger than 200 microliters with a proper receiver of the K-D concentrator at 35 degrees C. However, Cl1-3BZs were lost in each of the procedures.     

Substance flow analysis of coplanar PCBs released from waste incineration processes

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

Enrichment of PCDDs/PCDFs in the cooling system of municipal solid waste incineration plants

This study measured the levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs), destroyed or formed in combustors and re-synthesized in cooling systems. For the proper control of PCDDs/PCDFs in municipal solid waste (MSW) incinerators, three grate-type MSW incinerators were selected, two of which had boilers, and one of which had a water spray tower (WST) as a cooling system. At the combustor outlets, dusts were in the range of 1640-4270 mg/Sm3 and PCDDs/PCDFs were in the range of 0.103-2.619 ng-TEQ/Sm3, showing the different values according to the grate structure of combustor and the flow direction of flue gas. After the flue gases passed through the cooling system, PCDDs/PCDFs at the waste heat boiler (WHB) outlets were enriched to levels that were 10.8-13.6 times higher than those at the furnace outlets, but PCDDs/PCDFs at the WST outlet was reduced to 5% of the level found at the furnace outlet. The emission patterns, such as the ratio of PCDFs to PCDDs, the ratio of gaseous-phase to particulate-phase PCDDs/PCDFs, and the compositional percentiles of each 2,3,7,8-substituted congener varied according to the types of air pollution control devices (APCDs). Reducing re-synthesis in the cooling system rather than enhancing the removal efficiencies of the APCDs seems to be more effective for lowering the levels of PCDDs/PCDFs in MSW incineration plants.     

Enrichment of PCDDs/PCDFs in peripheral utilities of the municipal solid waste incineration facility

This study was performed to suggest the improvements through measuring the amounts of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), re-synthesized in peripheral utilities (PUs) of a commercial-scale municipal solid waste incineration facility (MSWIF) where a few research results existed. The PUs examined in this study consisted of air pre-heaters (APHs) and gas/gas re-heater (GGRH) and kerosene-fired duct burner for selective catalytic reduction (SCR) process. PCDDs/PCDFs in flue gas were simultaneously measured at the inlet and outlet of PUs.Flue gas was cooled down from 380 °C to 249 °C by exchanging the heat with fresh air in APHs, and then heated up to 383 °C by GGRH and duct burner from 164 °C at the outlet of bag filter. The results showed that PCDDs/PCDFs were 3–4 times higher within this temperature range of PUs. In comparison of PCDDs/PCDFs concentrations at the inlet with those at the outlet of PUs, particulate-phase PCDDs/PCDFs were about 9.5–10 times enriched while gaseous-phase ones were decreased by about 33–41%. The PCDDs/PCDFs re-synthesized in the PUs, where PCDDs were relatively higher than PCDFs, showed somewhat different patterns compared to those formed at incinerators and emitted at stack. Through the investigations for PUs, we conclude that the PUs used in MSWIFs was a potential source for de novo synthesis of PCDDs/PCDFs.     

Impact on health of chlorinated dioxins and other trace organic emissions

The potential health effects of incineration of municipal solid waste (MSW) have been studied by the Swedish National Institute of Environmental Medicine.The greatest concern for health effects relates to the emission of PCDDs and PCDFs (“dioxins”). MSW incineration is presently estimated to be a large source for the emission of these compounds into ambient air. Based upon animal experiments, and by applying safety factors in the range 200–1000, a highest tolerable daily intake (TDI) has been estimated to be 1–5 pg kg⁻¹ of TCDD for humans. This TDI-value has been extended to cover all the congeners of PCDDs and PCDFs by the application of the concept of “TCDD-equivalents” (Eadon et al., 1983). The high concentrations found in human breast milk and fish indicate that the TDI value may be exceeded, especially among breast-milk fed babies. If the emission can be reduced to the proposed Swedish limit value of 0.1 ng m⁻³ n TCDD-equivalents, or less, the contribution from this source will be lowered. MSW incineration can be considered acceptable when the following aspects are taken into account: the risk estimation for TDI is conservative; there is no indication that man belongs to the most sensitive species although infants may be particularly sensitive; available studies indicate that the concept of TCDD-equivalents used overestimates the effect of mixtures of PCDDs and PCDFs; present levels in fish and human milk reflect the cumulative effect of many years of emission. Besides PCDDs and PCDFs, MSW incineration also gives rise to relatively high emissions of PAH, chlorinated PAH, phenols, benzenes and mutagenic substances under less well controlled combustion conditions. The emission of organic compounds is generally dependent on the combustion efficiency. If the combustion process is optimized and advanced flue-gas cleaning is applied so that the emission of TCDD-equivalents does not exceed 0.1 ng m⁻³, emission of other organics probably will not cause significant health hazards.     

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.     

Behavior of PAHs from sewage sludge incinerators in Korea

Although production of sewage sludge increases every year, its proper treatment has only been recently raised as a new issue, as current landfill and ocean dumping arrangements are expected to become increasingly difficult to manage in the future. The Korean Ministry of Environment plans to diversify its processing facilities and expand its processing systems by 2011, with the purpose of processing all sludge produced in Korea. According to this plan, incineration (including incineration of municipal wastes) will process 30% of the entire sewage sludge throughout the country in 2011. This study reviews the characteristics of PAH, which is one of the organic substances found in sewage sludge during the incinerating process. The total amount of PAH produced from sewage sludge incineration was found to be 6.103 mg/kg on average, and investigation performed on 16 PAHs of inlets and outlets of the air control devices at five full-scale incineration facilities showed that concentrations of the PAHs on the inlet and on the outlet ranged from 3.926 to 925.748 microg/m(3) and from 1.153 to 189.449 microg/m(3), respectively. In the case of the incineration facility fed with municipal waste (95%) and sewage sludge (5%), the total of the PAH emissions concentration was higher than that found at the incineration facilities used exclusively to treat sewage. The combustion of waste vinyl and plastics contained in municipal waste fed into the facility might contribute to the high levels of PAHs in the stack gas. However more investigation is needed on the production mechanism of PAHs at different operating conditions of the incineration facilities, such as the types of waste, and other relevant factors.     

Parallel sampling for dioxins using various sampling techniques at a swedish municipal solid waste incinerator

Parallel sampling was carried out in a Swedish municipal solid waste (MSW) incinerator, on two consecutive days, with five different sampling techniques. The samples were analysed for chlorinated dioxins (PCDDs) and chiorodibenzofurans (PCDFs) at two laboratories, one in Sweden and the other in Germany. Two different spiking protocols were used, both including pre-sampling or clean-up spikes from each homolog group of the tetra to octa CDDs and CDFs. Comparable results were obtained for all five sampling methods for the emission data and the recoveries for all pre-sampling spikes were above 50%. The agreement between the two laboratories was good. The different sampling methods resulted in very similar congener distributions (congener profiles) or isomer distributions (isomer patterns). However, the sampling techniques differ considerably in the distribution of PCDDs/PCDFs in various sampling compartments. The sampling techniques where large contribution of PCDDs and PCDFs could be found in the wash solvent may suffer from losses and/or cross-contamination problems unless the washing is carried out properly. The use of a cooled probe in combination with an adsorption (polyurethane foam plug) or absorption (ethoxyethanol) trap, where the main portion of the PCDDs and PCDFs were found in the condensate, is considered as a convenient and efficient sampling technique.     

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%).     

Environmental Technology Verification (ETV) test of dioxin emission monitors

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

Pilot-scale studies on the effect of bromine addition on the emissions of chlorinated organic combustion by-products

The addition of brominated organic compounds to the feed of a pilot-scale incinerator burning chlorinated waste has been found previously, under some circumstances, to enhance emissions of volatile and semivolatile organic chlorinated products of incomplete combustion (PICs) including polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs). This phenomenon appears to be sensitive to temperature and combustion conditions. This paper reports on a study to evaluate the emissions of organic combustion by-products while varying amounts of bromine (Br) and chlorine (Cl) are being fed into a pilot-scale incinerator burning surrogate waste materials. The surrogate waste was fed at a constant molar halogen input rate, with varying Br/Cl molar ratios. In these tests, an approximately 30% decrease in the total PCDD/F concentrations due to the addition of Br was observed. This decrease appears to be a decrease only in the chlorinated dioxin and furan species; other halogenated dioxins and furans were formed instead. PCDD/F homologue distribution shifted towards the higher chlorinated species. Perhalogenated or nearly perhalogenated mixed bromo-chloro furans were also observed in quantities that could potentially account for the observed decrease in PCDDs/Fs. This research illustrates the need for careful trial burn planning if Br will be present in the facility's feed-stock during normal operation.     

Bioremediation treatability studies of contaminated soils at wood preserving sites

Bioremediation has been used frequently at sites contaminated with organic hazardous chemicals where releases from processing vessels and the mismanagement of reagents and generated waste have contributed to significant impairment of the environment. At wood treater sites, process reagents such as pentachlorophenol (PCP), and creosote have adversely impacted the surrounding soil and groundwater. When PCP has been used at these sites, polychlorinated dibenzo‐p‐dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are typically found. Where creosote has been used as the wood preservative of choice, polynuclear aromatic hydrocarbons (PAHs) are commonly found. Many of these compounds are considered to be persistent, bioaccumulative, and toxic (PBT) and are particularly recalcitrant.     

Sources and relative importance of PCDD and PCDF emissions

Polychlorinated dioxins (PCDD) and dibenzofurans (PCDF) have been identified in technical products and pesticides, most of which are not very widely used today. Other sources are incinerators of various types like MSW incinerators, hazardous waste incinerators and industrial incinerators. PCDDs and PCDFs have also been identified in exhausts from cars running on leaded gasoline with halogenated additives. Background levels of PCDDs and PCDFs have been identified in fish and other aquatic organisms from the Great Lakes and the Baltic Sea, and also in human adipose tissue samples from U.S.A., Canada, Sweden, Japan and Vietnam as well as in samples of breast milk from Sweden, Denmark, West Germany, the Netherlands, Yugoslavia and Vietnam. The isomeric pattern in all these biological samples is very similar. The relative importance of different sources to the general background is difficult to estimate although the contribution of direct inhalation from point sources like MSW incinerators is small.     

Japan’s waste management policies for dioxins and polychlorinated biphenyls

We summarize the measures taken by the Japanese government to prevent the emission of dioxins and polychlorinated biphenyls (PCBs) into the environment. Because incineration is the main method of waste management in Japan, reducing the amount of dioxins emitted from waste incinerators is an essential aspect of proper waste treatment. Intensive measures to prevent the formation of dioxins at the source have been implemented, with a focus on waste treatment methods and improving comprehensive management. The efforts have been very successful, with a 95% reduction in the amount of dioxins emitted between 1997 and 2003. The toxicity of PCBs has been monitored with keen interest since the Yusho incident. Unfortunately, treatment facilities for PCB wastes were not built until long after PCBs had been removed from use, and PCB wastes remained in storage in an untreated state. The Japanese government has promoted the construction of facilities for treating PCB wastes, and five such facilities have commenced operations. To more completely eradicate dioxins, a future challenge will be to reduce the amount of PCB-derived dioxins, which are persistent in the environment and have a long exposure pathway from the environment media to the organism and the human body.     

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.     

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.     

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.     

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.     

生活垃圾焚烧发电厂二恶英对人体健康的风险评价

介绍了生活垃圾焚烧过程中二恶英的产生机理、对人体的危害及控制措施,以某生活垃圾焚烧发电厂环境影响评价为例,提出了二恶英对人体健康风险评价方法,同类项目环境影响评价提供借鉴。     

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.