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.     

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.     

A performance history of the base catalyzed decomposition (BCD) process

Remediation of halogenated organic compounds—such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs)—poses a challenge because these compounds are resistant to microbial attack and to degradation by many common chemicals. Since the mid-1980s, the Environmental Protection Agency's (EPA's) Office of Research and Development in Cincinnati, Ohio—the National Risk Management Research Laboratory (NRMRL)—has funded research and development efforts to develop specialized, chemical dehalogenation processes for detoxifying PCBs and related compounds. NRMRL owns domestic rights for “basic process” patents on a chemical dehalogenation process commonly known as Base Catalyzed Decomposition (BCD). EPA has licensed the process to two firms for use in the United States. This article summarizes laboratory-scale, pilot-scale, and field performance data on BCD technology collected to date by various governmental, academic, and private organizations.     

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.     

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     

Comparative evaluation of demonstration testing of two PCB detoxification technologies

This paper presents a summary of the comparative analysis of two polychlorinated biphenyl (PCB) detoxification technologies that were evaluated in pilot scale equipment. Two treatment technologies, base catalyzed decomposition (BCD) and gas phase chemical reduction, treated materials removed from the PCB landfill in Warren County, North Carolina. There has been a remarkable amount of public opposition to this landfill. Very stringent performance criteria for soil cleanup of PCBs and dioxins and for air emissions from the treatment equipment were used, along with a number of other factors to evaluate the two technologies. The BCD technology was selected as the best performing one for this project.     

Convenient substitute indices to toxic equivalent quantity for controlling and monitoring dioxins in stack gas from waste incineration facilities

It is necessary to develop technical systems for controlling and monitoring dioxins in stack gas from waste incineration facilities. However, it required much labor, high technical skill and extreme cost to measure dioxins for obtaining the toxic equivalent quantity (TEQ) values. In this study, the positive correlations of the WHO-TEQ values of PCDDs/PCDFs/Co-PCBs or PCDDs/PCDFs with the conventional I-TEQ values of PCDDs/PCDFs were confirmed beforehand for a large number of incineration facilities in a wide concentration range of a hundred thousand times. The relationships between the TEQ values and the concentrations of total PCDDs/PCDFs, each toxic isomer of PCDDs/PCDFs, total Cl4-6BZs, or each homologue of Cl4-6BZs were investigated for various incineration facilities. And it was found that positive correlations of the TEQ values with the concentrations of total PCDDs/PCDFs, 2,3,4,7,8-P5CDF, or Cl5BZ for a large number of different incineration facilities and in a wide concentration range. Consequently, the concentrations of total PCDDs/PCDFs, 2,3,4,7,8-P5CDF and Cl5BZ, whose measuring methods are much easier than that of obtaining the TEQ values, could be used as convenient substitute indices to the TEQ values for controlling and monitoring dioxins in stack gas from various waste incineration facilities.     

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.     

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%).     

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.     

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.     

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.     

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.     

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.     

Analytical,Risk Assessment,and Remedial Implications Due to the Co‐Presence of Polychlorinated Biphenyls and Terphenyls at Inactive Hazardous Waste Sites

Investigations conducted at three inactive hazardous waste sites in New York State have confirmed the co‐presence of polychlorinated hiphenyls (PCBs) and polychlorinated terphenyls (PCTs) in soils, sediments, and biota. The PCTs at all three sites were positively identified as Aroclor 5432, with the most probable source being the hydraulic fluid Pydraul 312A utilized for high‐temperature applications. The identification of the lower‐chlorinated PCT formulations in environmental samples is problematical, since PCT Aroclors 5432 and 5442 are not chromatographically distinct from the higher‐chlorinated (PCB) Aroclors 1254, 1260, 1262, and 1268 using conventional gas chromatography–electron capture detection. Results from this study indicate that U.S. Environmental Protection Agency (USEPA) approved PCB methods routinely utilized by most commercial laboratories based on Florisil adsorption column chromatography cleanup are inadequate to produce valid chromatographic separation and quantitative results with soils, sediment, and biota samples containing both PCBs and PCTs. The presence of co‐eluting PCBs and PCTs precludes accurate quantitation due to significant differences in PCB/PCT electron capture detector response factors, and the potential for misidentification of PCT Aroclors as higher chlorinated PCB Aroclors. A method based on alumina column adsorption chromatography was used, allowing for the accurate identification and quantitation of PCB and PCT Aroclors. The results of this study suggest that the utilization of alumina adsorption column separation may have applicability and regulatory significance to other industrially contaminated sites which historically used Pydraul 312A. Inferences.     

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.     

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.     

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.