Effects of combustion and operating conditions on PCDD/PCDF emissions from power boilers burning salt-laden wood waste

This paper discusses the effects of combustion conditions on PCDD/PCDF emissions from pulp and paper power boilers burning salt-laden wood waste. We found no correlation between PCDD/PCDF emissions and carbon monoxide emissions. A good correlation was, however, observed between PCDD/PCDF emissions and the concentration of stack polynuclear aromatic hydrocarbons (PAHs) in the absence of TDF addition. Thus, poor combustion conditions responsible for the formation of products of incomplete combustion (PICs), such as PAHs and PCDD/PCDF precursors, increase PCDD/PCDF emissions. PAH concentrations increased with higher boiler load and/or low oxygen concentrations at the boiler exit, probably because of lower available residence times and insufficient excess air. Our findings are consistent with the current understanding that high ash carbon content generally favours heterogeneous reactions leading to either de novo synthesis of PCDD/PCDFs or their direct formation from precursors. We also found that, in grate-fired boilers, a linear increase in the grate/lower furnace temperature produces an exponential decrease in PCDD/PCDF emissions. Although the extent of this effect appears to be mill-specific, particularly at low temperatures, the results indicate that increasing the combustion temperature may decrease PCDD/PCDF emissions. It must be noted, however, that there are other variables, such as elevated ESP and stack temperatures, a high hog salt content, the presence of large amounts of PICs and a high Cl/S ratio, which contribute to higher PCDD/PCDFs emissions. Therefore, higher combustion temperatures, by themselves, will not necessarily result in low PCDD/PCDFs emissions.     

Analysis of polychlorodibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs) in baked-salt food additives in Korea

Thirty-one samples of baked-salt products used in commercial food additives were analyzed for the presence of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Dioxins were highly detected in 12 samples of baked salts. The amount of dioxins found in the samples ranged from 12.47 pg/g to 406.56 pg/g (0.71 pg TEQ/g to 23.51 pg TEQ/g, respectively). The most abundant congeners, as TEQ values, were 2,3,4,7,8-PeCDF; 1,2,3,7,8-PeCDF; and 1,2,3,4,7,8-HxCDF in PCDF congeners and 1,2,3,7,8-PeCDD; 1,2,3,6,7,8-HxCDD; and 1,2,3,7,8,9-HxCDD in PCDD congeners. Meanwhile, PCDDs/PCDFs were analyzed in high-temperature-treated samples of natural sea salt alone and natural sea salt to which di-(2-ethylhexyl)phthalate (DEHP) had been added. In the former case, PCDD/PCDF formation was most evident at temperatures near 450 degrees C, the total amount of dioxins was 90.07 pg/g (6.07 pg TEQ/g), and PCDD congeners comprised less than 50% of the total PCDDs/PCDFs. However, when the latter samples were heated, the total PCDD/PCDF concentration was 512.30 pg/g (21.53 pg TEQ/g), with PCDD congeners comprising over 87% of the total PCDDs/PCDFs.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from various industrial sources

This study characterized the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the stack flue gases of 17 industrial sources, which were classified into 10 categories. The results show that the mean PCDD/PCDF concentration of secondary zinc smelter (Zn-S) and secondary copper smelter (Cu-S) is 2.44 ng international toxic equivalent (I-TEQ)/Nm3 (N represents normal conditions at 0 degrees C, 760 mmHg), which was found to be significantly greater than that of industrial waste incinerators (mean concentration = 0.15 ng I-TEQ/Nm3). These results imply that the controlling of secondary metallurgical melting processes is more important than industrial waste incineration for the reduction of PCDD/PCDF emissions. The mean emission factors of cement production, Zn-S and Cu-S, are 0.052, 1.99, and 1.73 microg I-TEQ/t product, respectively. For industrial waste incineration, the mean emission factors of waste rubber, waste liquor, waste sludge, industrial waste solid (IWI)-1, IWI-2, IWI-3, and IWI-4 are 0.752, 0.435, 0.760, 6.64, 1.67, 2.38, and 0.094 microg I-TEQ/t feed, respectively. Most of the PCDD/PCDF emission factors established in this study are less than those reported in previous studies, which could be because of the more stringent regulations for PCDD/PCDF emissions in recent years.     

Mechanism of the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans from chlorophenols in gas phase reactions

The pyrolysis of chlorinated phenates at a temperature of about 280 degrees C results in the formation of definite chlorinated dibenzodioxin (PCDD) congeners [1-3]. It is shown that in gas phase reactions chlorophenols react in the presence of oxygen above 340 degrees C not only to PCDD but also to chlorinated dibenzofurans (PCDF). The mechanism of this reaction of chlorophenols to PCDD and PCDF was elucidated. In a first step phenoxyradicals are formed which are capable of forming PCDDs and PCDFs. This is confirmed by the oxygen dependency of the reaction. In an argon atmosphere no dimerization of chlorophenols could be observed at 420 degrees C. By the identification of intermediates and by analyzing the PCDF isomers formed from individual chlorophenols the reaction pathway is elucidated. As intermediates in the formation of PCDFs polychlorinated dihydroxybiphenyls (DOHB) were identified. These are most likely formed by the dimerization of two phenoxy radicals at the hydrogen substituted carbons in ortho-positions under simultaneous movement of the hydrogen atoms to the phenolic oxygen PCDDs are formed in the gas phase via ortho-phenoxyphenols (POP) analogous to the pyrolysis of phenates, but due to the radical mechanism in the first condensation step to POPs not only a chlorine atom is capable for substitution but also the hydrogen atoms. The formation of the DOHBs and their condensation to PCDFs and hydroxylated PCDFs as well as the ratio of PCDD to PCDF formed show a strong dependency on the reaction temperature, the substitution pattern of the chlorophenols and the oxygen concentration.     

Emissions of Chlorinated Organics from Two Municipal Incinerators in Ontario

In this paper the results of sampling for trace chlorinated organics at two municipal refuse incinerators in Ontario are presented. The information may be of Interest to individuals concerned with the assessment of PCDD/PCDF (polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran) emissions from incineration of refuse and their impact on the energyfrom- waste program. PCDDs, PCDFs, PCBs (polychlorinated biphenyls), CBs (chlorobenzenes) and CPs (chlorophenols) were quantified in all process streams including refuse, ash and stack emissions. Manual sorting of refuse and collection of ash samples were carried out simultaneously with three 24-hour continuous stack sampling tests at each plant. The results suggested that the total output of PCDDs and PCDFs varied proportionately with their input at both incinerators. However, the input of PCDDs/PCDFs could not account for their total output. The chemistry of PCDDs/PCDFs in the input and output streams were different in that only heptachlorinated and octachlorinated species were present in significant quantities in the refuse while lower chlorinated species were predominant in stack emissions and ash streams. There was no correspondence between the Input of PCBs/CBs/CPs and the output of PCDDs/PCDFs. The output of PCDDs/PCDFs, however, varied Inversely with the total output of PCBs/CBs/CPs, suggesting that the latter compounds could have been partially responsible for the formation of PCDDs and PCDFs. The PCDF emissions were also affected by combustion conditions; they were higher in magnitude and consisted of predominantly tetrachlorinated and pentachlorinated species at the plant where the combustion temperatures were lower.     

Evaluation of PCDD/F congener distributions in MWI flue gas treated with SCR catalysts

Partitioning of PCDD/F congeners between gaseous and particulate phases and removal efficiencies of the air pollution control devices (APCDs) for PCDD/Fs at an existing municipal waste incinerator (MWI) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP), wet scrubbers (WS) and selective catalytic reduction system (SCR) as APCDs. The average PCDD/F concentration of stack gas is 1.49 ng/N m³, and the International Toxic Equivalent Quantity (I-TEQ) is 0.043 ng-I-TEQ/N m³. The EP increases PCDD/F concentration by 174.0% while the average removal efficiency of WS + SCR system for PCDD/Fs reaches 99.1%. In addition, the PCDF removal efficiency achieved with WS + SCR system (97.1–99.8%) is higher than that for PCDDs (96.5–99.3%). The results obtained on gas/particulate partitioning in flue gas indicate that the particulate-phase PCDD/Fs accounted for 65% at the inlet of EP, 20% at the outlet of EP and 50% at the stack, respectively, of the total PCDD/F concentrations. This study also indicates that as the chlorination level of PCDD/F congeners increases, the percentage of PCDD/Fs existing in gas phase decreases in all flue gas samples.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from catalytic and thermal oxidizers burning dilute chlorinated vapors

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxins) have been found from 57 field tests on the oxidation of low (a few to a few hundred) parts per million levels of chlorinated and non-chlorinated volatile organic compounds (VOCs). The oxidation occurs in catalytic oxidizers with platinum, platinum/palladium or chromium(IV) oxide combustion catalysts, or in thermal oxidizers (without a catalyst). The catalyst inlet temperatures ranged from 293 to 573 degrees C. The thermal oxidizer operating temperatures (post-flame) were from 773 to 927 degrees C. Data of the toxic dioxin and furan isomers are reported and also weighted and expressed as international toxic equivalents (TEQ) of 2,3,7,8-tetrachlorodibenzo-p-dioxin. The maximum stack emissions, 1.07 ng/m3 TEQ, occurred at 293 degrees C. Salient results of this field study are: (1) TEQ levels in the stack exponentially increase with a decrease in operating temperature, an empirical equation is TEQ (ng/dscm)=8.4 exp(-0.0084T degrees C); (2) dioxin/furan production occurs at the combustion catalyst; (3) small variations in temperature cause large changes in the congener distribution of the dioxin and furan isomers; (4) molar TEQ yields from the parent compounds fed to the oxidizers are very small (10(-9)-10(-13)); (5) catalytic and thermal oxidizers may destroy dioxins fed from the ambient air; and (6) the oxidation of chlorinated VOCs with non-chlorinated VOCs reduces emissions of dioxins, likely due to the consumption of Cl in producing HCl. Laboratory investigations are needed to understand how dioxins are formed (and emitted) under conditions of this study.     

Emissions of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Various Industrial Sources

Abstract

This study characterized the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the stack flue gases of 17 industrial sources, which were classified into 10 categories. The results show that the mean PCDD/PCDF concentration of secondary zinc smelter (Zn-S) and secondary copper smelter (Cu-S) is 2.44 ng international toxic equivalent (I-TEQ)/Nm³ (N represents normal conditions at 0 °C, 760 mmHg), which was found to be significantly greater than that of industrial waste incinerators (mean concentration = 0.15 ng I-TEQ/Nm³). These results imply that the controlling of secondary metallurgical melting processes is more important than industrial waste incineration for the reduction of PCDD/PCDF emissions. The mean emission factors of cement production, Zn-S and Cu-S, are 0.052, 1.99, and 1.73 μg I-TEQ/t product, respectively. For industrial waste incineration, the mean emission factors of waste rubber, waste liquor, waste sludge, industrial waste solid (IWI)-1, IWI-2, IWI-3, and IWI-4 are 0.752, 0.435, 0.760, 6.64, 1.67, 2.38, and 0.094 μg I-TEQ/t feed, respectively. Most of the PCDD/PCDF emission factors established in this study are less than those reported in previous studies, which could be because of the more stringent regulations for PCDD/PCDF emissions in recent years.     

Formation, release and control of dioxins in cement kilns

Co-processing of hazardous wastes in cement kilns have for decades been thought to cause increased emissions of PCDD/PCDFs--a perception that has been evaluated in this study. Hundreds of PCDD/PCDF measurements conducted by the cement industry and others in the last few years, on emissions and solid materials, as well as recent test burns with hazardous wastes in developing countries do not support this perception. Newer data has been compared with older literature data and shows in particular that many emission factors have to be reconsidered. Early emission factors for cement kilns co-processing hazardous waste, which are still used in inventories, are shown to be too high compared with actual measurements. Less than 10 years ago it was believed that the cement industry was the main contributor of PCDD/PCDFs to air; data collected in this study indicates however that the industry contributes with less than 1% of total emissions to air. The Stockholm Convention on POPs presently ratified by 144 parties, classifies cement kilns co-processing hazardous waste as a source category having the potential for comparatively high formation and release of PCDD/PCDFs. This classification is based on early investigations from the 1980s and 1990s where kilns co-processing hazardous waste had higher emissions compared to those that did not burn hazardous waste. However, the testing of these kilns was often done under worst case scenario conditions known to favour PCDD/PCDF formation. More than 2000 PCDD/PCDF cement kiln measurements have been evaluated in this study, representing most production technologies and waste feeding scenarios. They generally indicate that most modern cement kilns co-processing waste today can meet an emission level of 0.1ngI-TEQ/m(3), when well managed and operated. In these cases, proper and responsible use of waste including organic hazardous waste to replace parts of the fossil fuel does not seem to increase formation of PCDD/PCDFs. Modern preheater/precalciner kilns generally seems to have lower emissions than older wet-process cement kilns. It seems that the main factors stimulating formation of PCDD/PCDFs is the availability of organics in the raw material and the temperature of the air pollution control device. Feeding of materials containing elevated concentrations of organics as part of raw-material-mix should therefore be avoided and the exhaust gases should be cooled down quickly in long wet and long dry cement kilns without preheating. PCDD/PCDFs could be detected in all types of solid samples analysed: raw meal, pellets and slurry; alternative raw materials as sand, chalk and different ashes; cement kiln dust, clinker and cement. The concentrations are however generally low, similar to soil and sediment.     

Destruction of PCDD/Fs by SCR from flue gases of municipal waste incinerator and metal smelting plant

Partitioning of PCDD/F congeners between vapor/solid phases and removal and destruction efficiencies achieved with selective catalytic reduction (SCR) system for PCDD/Fs at an existing municipal waste incinerator (MWI) and metal smelting plant (MSP) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP, operating temperature: 230 degrees C), wet scrubbers (WS, operating temperature: 70 degrees C) and SCR (operating temperature: 220 degrees C) as major air pollution control devices (APCDs). PCDD/F concentration measured at stack gas of the MWI investigated is 0.728 ng-TEQ/Nm(3). The removal efficiency of WS+SCR system for PCDD/Fs reaches 93% in the MWI investigated. The MSP investigated is equipped with EP (operating temperature: 240 degrees C) and SCR (operating temperature: 290 degrees C) as APCDs. The flue gas sampling results also indicate that PCDD/F concentration treated with SCR is 1.35 ng-TEQ/Nm(3). The SCR system adopted in MSP can remove 52.3% PCDD/Fs from flue gases (SCR operating temperature: 290 degrees C, Gas flow rate: 660 kN m(3)/h). In addition, the distributions of PCDD/F congeners observed in the flue gases of the MWI and MSP investigated are significantly different. This study also indicates that the PCDD/F congeners measured in the flue gases of those two facilities are mostly distributed in vapor phase prior to the SCR system and shift to solid phase (vapor-phase PCDD/Fs are effectively decomposed) after being treated with catalyst. Besides, the results also indicate that with SCR highly chlorinated PCDD/F congeners can be transformed to lowly chlorinated PCDD/F congeners probably by dechlorination, while the removal efficiencies of vapor-phase PCDD/Fs increase with increasing chlorination.     

Formation of artefacts while sampling emissions of PCDD/PCDF from open burning of biomass

Emission factors for PCDD/PCDF determined from open combustion are used to estimate national emission budgets; therefore, it is important to have confidence in their accuracy. It has been suspected that artefacts may form due to the presence of hot metal surfaces of sampling equipment, thus skewing emission factors. In this study, emissions of PCDD/PCDF from open burning of forest biomass over a brick hearth were sampled. Five experiments were carried out using a portable sampler. Experiments were designed where the key variable, sample hood and inlet temperatures were manipulated. Other variables such as fuel origin, type and density were consistent. The measured concentration of PCDD/PCDF in the smoke samples ranged from 0.01 μg TEQ (t fuel)⁻¹ at the lowest maximum hood temperature (185 °C) to 15 μg TEQ (t fuel)⁻¹ at the highest maximum hood temperature (598 °C). when hood inlet temperatures exceeded 400 °C emission factors were significantly elevated and this is attributed to the formation of artefacts that can cause the over estimation of emission factors. The increase in hood temperature also resulted in a change in the PCDD/PCDF congener and homologue profile of the emissions. For example at the lowest temperature (Fire 1) the PCDD/PCDF ratio measured was 50:1, whereas at the highest temperature (Fire 5) this ratio was about 0.53:1. When the sampler hood and inlet temperatures were kept in the normal operating range of <200 °C, emission factors were comparable to those observed in many previous studies in Australia with emissions dominated by PCDD.     

Influence of temperature on PCDD/PCDF desorption from waste incineration flyash under nitrogen

A municipal solid waste incinerator flyash was heated to between 200 and 400 degrees C under nitrogen in a bench-scale, static bed reactor for 4 days soak time. The influence of temperature on the levels of PCDD and PCDF remaining in and desorbed from the ash were investigated using GC-MS/MS. PCDD and especially PCDF formation was seen on the flyash between 225 and 300 degrees C. Large increases in the I-TEQ of the treated ash relative to the increase in its overall PCDD/PCDF content indicated that the formation of 2378-substituted congeners was favoured over that of other substitution patterns. In the absence of a source of gaseous oxygen, formation was mainly attributed to de novo reactions involving solid phase oxygen. Dechlorination of the PCDD/PCDF in flyash became increasingly important above 275 degrees C. Maximum desorption was seen at 325 degrees C, with the equivalent of 35 wt% of the PCDD/F in the original flyash being recovered from the exhaust traps at this temperature. The desorbed species were mainly M(1)CDD/CDDF-T(3)CDD/CDDF resulting from dechlorination of higher chlorinated PCDD/PCDF, with consequently low I-TEQ values.     

Formation of PCDDs and PCDFs during the combustion of polyvinylidene chloride

In laboratory-scale combustion of polyvinylidene chloride (PVDC) with a quartz tubular furnace designed and fabricated to provide the desired combustion temperature and mixing state of combustion gas with air, it was found that at 800 degrees C or higher the level of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans [corrected] (PCDDs/PCDFs) resulting from PVDC combustion was no higher than that from heating air alone, and thus far below the levels which resulted from PVDC combustion at 750 degrees C or lower. The results provide the first laboratory confirmation of the relation between PVDC incineration temperature and PCDD/PCDF formation, and of the primary importance of high temperature, turbulence for mixing between air and combustion gas, and sufficient residence time, as governing factors for the minimization of PCDD/PCDF formation in municipal solid waste incinerators.     

PCDD/PCDF congener profiles in soil and herbage samples collected in the vicinity of a municipal waste incinerator before and after pronounced reductions of PCDD/PCDF emissions from the facility

Congener profiles are the fractional distribution of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) congeners in an environmental release, or in an environmental or biological sample. In 1999, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in an old municipal solid waste incinerator (MSWI) from Montcada (Barcelona, Spain). The main goal of the present study was to determine if the environmental PCDD/F levels in the area under direct influence of the facility were mainly due to PCDD/F emissions from the plant. For this purpose, soil and herbage samples were collected near the MSWI before (1998) and after (2000) the technical improvements were performed. PCDD/F congener profiles were determined and compared with those from samples collected in a suburban area of Constantí (Tarragona, Spain) outside of direct emissions from any MSWI. The results of the present study suggest that the MSWI here assessed is not the main responsible for the environmental PCDD/F concentrations in the area under evaluation. Other PCDD/F emission sources in the same area seem also to have a notable impact on the atmospheric levels of these pollutants.     

Distribution of PCDDs, PCDFs and dioxin-like PCBs in the blood, testis and adipose tissue of suckling beef calves

To determine the distribution of persistent organochlorine compounds in beef cattle, concentrations of 2,3,7,8-substituted PCDDs, PCDFs and dioxin-like PCBs were measured in the blood, testes and adipose tissue of four two-month-old Japanese Black calves. Of 29 congeners analyzed, 19, 20 and 28 were detected in the blood, testes and adipose tissue, respectively, of three or all calves. Total toxic equivalents (TEQs) were similar in the testes and adipose tissue, and approximately two times higher than in the blood on a lipid weight basis (P<0.05). More PCDDs and PCDFs had accumulated in the testes than in adipose tissue (P<0.01), but more dioxin-like PCBs were found in adipose tissue than in the testes (P<0.0001). Accumulation patterns in the testes and adipose tissue varied among the congeners of PCDD and PCDF, whereas the patterns were similar in dioxin-like PCBs. In particular, highly substituted PCDD congeners were detected at high concentrations in the testes but at lower concentrations in adipose tissue compared with other congeners. By contrast, accumulation levels of highly substituted PCDFs were lower in both those tissues than the other congeners. In conclusion, it was demonstrated that PCDDs, PCDFs and dioxin-like PCBs leave the circulation and accumulate in the testes and adipose tissue in bovine calves. It was suggested that congeners of PCDD, especially highly substituted PCDDs, and PCDFs have a tendency to accumulate in the testis and dioxin-like PCB congeners accumulate readily in adipose tissue.     

Dioxin contents in fly ash from large-scale MSW incinerators in Taiwan

In this study, fly ash samples were collected from three municipal waste incinerators (MWI) in Taiwan. These MWIs investigated are equipped with different air pollution control devices (APCDs). Preliminary results indicated that 2,3,7,8-PCDD/Fs homologue patterns of various types of fly ash were quite similar for all three MWIs. Concentrations of higher-chlorinated congeners of PCDDs and PCDFs were remarkably higher than those of lower-chlorinated congeners. In the case of MSW-A, the PCDD/PCDF ratios of ashes were found in the decreasing order for cyclone, boiler and baghouse. The PCDD/PCDF ratios in various types of fly ash of MWI-B was boiler-A < boiler-B < ESP < boiler-C. As for MSW-C, no obvious trend has been observed for PCDD/PCDF ratio. However, the ratio in boiler ash was higher than that in baghouse ash of MWI-A. The dioxin contents in fly ash would increase as the fly ash passed through APCD zones. In other words, the environmental conditions of APCD may actually cause the increase of the dioxin contents in fly ash. The trend for dioxin contents in fly ash collected from three MSW incinerators investigated was MSW-C < MSW-A < MSW-B.     

Monitoring dioxins and furans in a population living near a hazardous waste incinerator: levels in breast milk

In this study, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs) in breast milk from mothers living in the vicinity of a new hazardous waste incinerator (HWI) were determined. Monitoring was performed after three years of regular operations in the facility and the present results were compared with baseline concentrations obtained in a pre-operational program. PCDD/PCDF levels were determined by HRGC/HRMS in 15 samples. In the present study, PCDD/PCDF concentrations ranged from 4.9 to 39.9 pg I-TEQ/g fat (5.1-46.8 pg WHO-TEQ/g fat), with a median value of 7.7 pg I-TEQ/g fat (9.1 pg WHO-TEQ/g fat). In the baseline survey, PCDD/PCDF concentrations ranged between 5.9 and 17.1 pg I-TEQ/g fat, with a median value of 11.7 pg I-TEQ/g fat. In relation to this, a percentage of reduction of 34.2% was noted. This decrease is in agreement with the relevant reduction found in the dietary intake of PCDD/PCDFs between both surveys. The results of the present study, as well as other recent environmental and biological data, indicate that living in the vicinity of this HWI should not mean additional health risks due to PCDD/PCDFs for the general population.     

Desorption of PCDD/PCDF from municipal solid waste incinerator flyash under post-combustion plant conditions

The influence of temperature on the levels of PCDD and PCDF remaining in, and desorbed from, a municipal solid waste incinerator flyash was investigated by heating the ash to between 200 and 400 degrees C under a simulated flue gas for four days reaction time. Considerable desorption of PCDD/PCDF from the flyash was seen at 275 degrees C and above. Maximum desorption occurred at 350 degrees C, with the equivalent of nearly eight times the total PCDD/PCDF concentration of the original flyash being lost to the vapour phase per unit mass of initial flyash. The I-TEQ value of the desorbed PCDD/PCDF was considerable, being over fourteen times that of the original flyash at 325 degrees C. The results indicate that formation of PCDD/PCDF on flyash deposits in the post-combustion plant of incinerators can result in the release of significant amounts of PCDD/PCDF to the flue gas stream.     

The formation and emission of dioxins in large scale thermal processes

The paper assesses extensive data of PCDD/F measurements on flue gas emissions from thermal processes, including, e.g. municipal solid waste incinerators (MSWIs), combustors of wood and industrial waste, coal fired powerplants and boilers, ferro and non-ferro processes. Numerous investigators have conducted laboratory experiments to assess the formation mechanisms of PCDD/F. The results, obtained from fixed-bed experiments, have been critically evaluated and indicate that de novo synthesis is the dominant mechanism in actual thermal processes where conditions that favour the precursor formation are not experienced. The analysis of PCDD/F profiles from the large scale thermal processes in general, and MSWIs in particular, supports the dominant role of the de novo synthesis, irrespective of the type of thermal process considered. The PCDF/PCDD ratio exceeds 1 and the degree of chlorination points towards the dominant presence of HpCDD and OCDD within the dioxin group, and of PeCDF, HxCDF and HpCDF within the furan group. Since real-time measurement of PCDD/F is impossible, the correlation of PCDD/F emissions with operating parameters and/or emission levels of other more easily measured pollutants could be a tool in predicting the PCDD/F formation levels. Data of Flemish MSWIs were used to statistically assess such correlations. From an evaluation of the data at a given operating temperature, misleading conclusions can be drawn. Only the effect of temperature is evident. After converting all data at a reference temperature of, e.g. 230 degrees C, PCDD/F concentrations achieve nearly constant values, irrespective of the values of other parameters, thus stressing that the major controlling parameter for the PCDD/F emission is the temperature of the ESP. The PCDD/F concentrations increase with temperature in the range up to 280 degrees C. The ESP temperature should be kept preferably between 180 degrees C and 200 degrees C, where de novo synthesis is reduced and where PCDD/Fs are increasingly adsorbed on the fly ash, in line with the standard temperature dependence of adsorption isotherms.     

Distribution of PCDDs and PCDFs in Soils Collected from the Denver Front Range - Principal Components Analysis of Diffuse Dioxin Sources (10 pp)

Background, Aims and Scope The Rocky Mountain Arsenal (RMA) is a US Army facility located northeast of Denver, Colorado that has been listed on the National Priorities List (NPL). It is currently being re-mediated under the authority of the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) and the Superfund Amendments and Reauthorization Act of 1986 (SARA). As part of the remediation activities at RMA, indications were found that a source of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) had existed on the RMA. As a result, investigations were undertaken to assess the possible nature and extent of any potential sources of PCDDs and PCDFs on the RMA site. In addition, other studies were conducted that examined PCDD/PCDF contamination in the Denver area. The goal of these studies was to examine nature and extent of PCDD/PCDF contamination both on the RMA as well as in the surrounding Denver area. The intent of this study was to characterize sources of dioxins (PCDDs) and dibenzofurans (PCDFs) at low environmental concentrations which might have originated from diffuse sources in the Denver Colorado area and in particular, the Rocky Mountain Arsenal (RMA) using Principal Component Analysis (PCA). Methods Over 200 soil samples were collected from the RMA and the Denver area. From the RMA, soil was collected as part of three studies that included a (1) random site-wide sampling of the RMA, (2) soils from the Western Tier Parcel (WTP), and (3) soils from Historic Use areas. Denver area soil samples were collected from five different land use categories: Residential, Agricultural, Open Space, Commercial, and Industrial. PCA was conducted on concentrations of 17 2,3,7,8-substuituted PCDD and PCDF congeners in 220 soil samples collected from the RMA and the Denver Front Range region. Results and Discussion PCA demonstrated the presence of possible minor sources of dioxins on the RMA. Current remediation efforts on RMA will result in the removal of these sources. Samples from the RMA were identified by the presence of a congener profile containing higher chlorinated PCDFs while the Denver Front Range areas were characterized by the presence of higher chlorinated PCDD congeners. The presence of a PCDF signature for the RMA samples does not necessarily indicate a major source of these contaminants on-site. Indeed, the relatively diffuse nature of the sample clusters would argue strongly against the presence of a single large source. Instead, the predominance of the PCDF congeners probably indicates the mixed industrial activities that took place on and near the site. Conclusion PCA results indicate that PCDD/PCDF profiles in soils collected from the RMA differed from those collected from the outlying Denver areas but that a major source of these contaminants was not present. Rather, the diffuse nature of sample clusters from the PCA indicated that the congener profile of RMA samples was most likely a result of the mixed industrial activities that historically have taken place on and near the site. PCA also indicated that many of the 'open area' (peripheral site-wide) RMA soils samples did not differ from Denver are reference congener profiles. This finding was also true for samples collected from the WTP that were essentially indistinguishable from Off-RMA reference samples. In addition, total TEQ concentrations in soils collected from WTP were similar to those measured in soils collected from the Denver Front Range areas indicating that lack of a major source of PCDD/PCDF within the WTP zones of the RMA. Recommendation and Outlook Analytical as well as statistical results of the soil congener data indicate that the WTP soils are indistinguishable from soils collected from non-industrial areas in the Denver area. This finding would support the recent 'de-listing' of the WTP from the other RMA areas and its' transfer to other authorities in the Denver area.