流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

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.     

Dioxins and their fingerprint in size-classified fly ash fractions from municipal solid waste incinerators in China—Mechanical grate and fluidized bed units

The distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), in brief dioxins, has seldom been addressed systematically in fly ash from municipal solid waste incinerators (MSWIs). This study shows the amount and fingerprint of PCDD/Fs in fly ash from four different Chinese MSWIs, that is, three mechanical grate units and one circulating fluidized bed unit. In these fly ash samples, dioxins-related parameters (international toxic equivalent quantity, total amount of PCDD/Fs, individual isomer classes, and 17 toxic 2,3,7,8-substituted congeners) all tend to increase with decreasing particle size for mechanical grate incinerators, yet only for the finest fraction for fluidized bed units. Moreover, the fluidized bed incinerator seems superior to grate incineration in controlling dioxins, yet a comparison is hampered by internal differences in the sample, for example, the fluidized bed fly ash has much lower carbon and chlorine contents. In addition, the presence of sulfur from mixing coal as supplemental fuel to the MSW may poison the catalytic steps in dioxins formation and thus suppress the formation of dioxins. With more residual carbon and chlorine in the fly ash, it is easier to form dioxins during cooling. Nevertheless, there is no apparent relation between Fe, Cu, and Zn contents and that of dioxins in fly ash.

Implications This paper is of interest because it presents the amounts and distribution of PCDD/Fs in fly ash samples from some typical waste incineration plants in China, featuring distinct incinerator types, combustion conditions, fuel composition, or residual carbon, chloride, and heavy metal contents in fly ash.     

Thermal degradation of PCDD/F, PCB and HCB in municipal solid waste ash

A thermal degradation procedure for reducing the concentrations of mono- to octa-chlorinated PCDD/Fs, PCBs and hexa-chlorobenzenes (HCB) in filter ash from incinerated municipal solid waste (MSW) is described. Thermal treatment of filter ash samples at 500 degrees C for 60 min in a closed system providing low oxygen conditions resulted in 97% and 99% reductions in the total and I-TEQ concentrations of PCDD/Fs, to 6.8 microg kg(-1) ash and <0.05 microg I-TEQ kg(-1) ash, respectively. Increasing the thermal treatment time to 480 min, at the same temperature, yielded 99% reductions in both total and I-TEQ concentrations of the mono- to octa-chlorinated PCDD/Fs. Similar effects were observed for HCB and PCBs. The data from this study indicate that PCDD/Fs and other toxic organic compounds in ash from incinerated MSW, can be effectively degraded by this procedure, which combines relatively low-temperatures, short treatment times, and low oxygen conditions.     

Dechlorination of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans on fly ash

Dechlorination of commercial mixtures of polychlorinated biphenyls (PCB) as well as polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) on extracted and non-extracted fly ash obtained from municipal waste incinerator (MWI) was studied in closed systems under nitrogen atmosphere at temperatures of 260°C and 340°C. Decomposition results (given as the difference between PCB or PCDD/F molar amounts before and after the experiment (in %) due predominantly to dechlorination reactions) and detoxification data (expressed similarly but related to toxic PCB and PCDD/F congeners only and given in I-TEQ units) are reported. Detoxification of Delor 105/80T at 260°C and 340°C at a loading of 0.65 wt% was 99.48% and 100%, respectively. The decomposition of Delor 103 at 340°C and for the loading of 0.75 wt% corresponded to 99.99%. The detoxification capability of PCDD/Fs on extracted and non-extracted fly ash for loading of 130 and 264 ng/0.4 g of fly ash at 340°C made 96 and 98%, respectively.     

Emission characteristics for co-combustion of leather wastes,sewage sludge,and coal in a laboratory-scale entrained flow tube furnace

Four different mixed fuels consisted of leather waste, coal, and sewage sludge were combusted in a lab-scale entrained flow fluidized bed furnace. The influence of blending ratio on emission characteristics of SO₂, NO_x, HCl, particulate matter (PM), heavy metals, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was studied. Results showed that the mixing of coal with sewage sludge had a complex effect on the emission characteristics. On the one hand, with more sewage sludge blending in the mixed fuel, the acid gas pollutant (SO₂, NO_x) decreased a lot, and the recovery of volatile heavy metals (Cd, Pb) increased at the same time. Furthermore, the leaching toxicity of Cr in the fly ash and bottom ash went down below the national standard with the adding of sewage sludge. On the other hand, the mixing of sewage sludge which consisted of more ash content resulted in the increase of the PM emission. Moreover, the high content of Cu and chlorine in the sewage sludge can promote the formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) when the fuel 3 and 4 were combusted. Most importantly, the concentration of toxic PCDD/Fs in the flue gas produced from fuel 3 and fuel 4 was successfully controlled down below 0.20 ng I-TEQ/Nm³ by the active carbon.

     

The size distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in the bottom ash of municipal solid waste incinerators

In this study, bottom ash was sampled from two Taiwanese municipal solid waste incinerators (MSWIs: A and B) and sieved to size classes of 4.75-9.5 mm, 2.36-4.75 mm, 1.0-2.36 mm, 0.6-1.0 mm, 0.3-0.6 mm, 0.21-0.3 mm, 0.125-0.21 mm, 0.075-0.125 mm and <0.074 mm. For both MSWIs, the major peak in the particle size distribution for the PCDD/F content was found in a particle size <0.21 mm, that is, 16.1 (A) and 4.37 pg I-TEQ/g (B). This is due to the fact that a smaller particle has higher specific surface area thus offering more adsorption sites. The mean cumulative fractions (F%) of PCDD/F I-TEQ in the bottom ash of MSWI A and B in the particle size range below 0.6, 2.36 and 4.75 mm, in sequence, are 40.4%, 77.2% and 95.6%, respectively. We suggest sieving the bottom ash before the subsequent reutilization at the suggested cut size of 0.6 mm. In the view of PCDD/Fs, bottom ash with a particle size larger than 0.6 mm, which is the more non-hazardous part, may be suitable for being the raw material of landfilling soil, road sub-base, and construction blocks. For the minus 0.6 mm fraction, vitrification with fly ash is one of the choices.     

Fate of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans in a Fly Ash Treatment Plant

Abstract

To understand the fate of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a fly ash treatment plant that used the Waelz rotary kiln process (hereafter the Waelz process), the samples of input and output media were collected and analyzed. The most important PCDD/F source in input mass was electric arc furnace (EAF) fly ash, which had a mean PCDD/F content of 18.51 ng/g and contributed more than 99% of PCDD/F input mass, whereas the PCDD/F input mass fractions contributed by the coke, sand, and ambient air were only 0.04%, 0.02%, and 0.000002%, respectively. For the PCDD/F output mass in the Waelz process, the major total PCDD/F contents of 43.73 and 10.78 ng/g were in bag-filter and cyclone ashes, which accounted for approximately 69% and 17%, respectively, whereas those of stack flue gas and slag were 14% and 0.423%, respectively. The Waelz process has a dechlorination mechanism for higher chlorinated congeners, but it is difficult to decompose the aromatic rings of PCDD/Fs. Therefore, this resulted in the accumulation of lower chlorinated congeners. The output/input ratio of total PCDD/F mass and total PCDD/F international toxicity equivalence (I-TEQ) was 0.62 and 1.19, respectively. Thus, the Waelz process for the depletion effect of total PCDD/F mass was positive but minor, whereas the effect for total PCDD/F I-TEQ was adverse overall.     

Dioxins and their fingerprint in size-classified fly ash fractions from municipal solid waste incinerators in China--mechanical grate and fluidized bed units

The distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), in brief dioxins, has seldom been addressed systematically in fly ash from municipal solid waste incinerators (MSWIs). This study shows the amount and fingerprint of PCDD/Fs in fly ash from four different Chinese MSWIs, that is, three mechanical grate units and one circulating fluidized bed unit. In these fly ash samples, dioxins-related parameters (international toxic equivalent quantity, total amount of PCDD/Fs, individual isomer classes, and 17 toxic 2,3,7,8-substituted congeners) all tend to increase with decreasing particle size for mechanical grate incinerators, yet only for the finest fraction for fluidized bed units. Moreover, the fluidized bed incinerator seems superior to grate incineration in controlling dioxins, yet a comparison is hampered by internal differences in the sample, for example, the fluidized bed fly ash has much lower carbon and chlorine contents. In addition, the presence of sulfur from mixing coal as supplemental fuel to the MSW may poison the catalytic steps in dioxins formation and thus suppress the formation of dioxins. With more residual carbon and chlorine in the fly ash, it is easier to form dioxins during cooling. Nevertheless, there is no apparent relation between Fe, Cu, and Zn contents and that of dioxins in fly ash.     

销毁含多氯联苯废弃物焚烧炉的二噁、类二噁和多氯联苯排放

我国正在研制专用于销毁高浓度多氯联苯（ＰＣＢｓ）的焚烧炉,主要处理废旧的含（ＰＣＢｓ）的电力电容器和变压器,应用可靠准确的监测方法测定了试验性焚烧炉渣、烟灰排气和废水中的二口恶口英（ｄｉｏｘｉｎｓ）,类二口恶口英多氯联苯（ｄｉｏｘｉｎｌｉｋｅＰＣＢｓ）和ＰＣＢｓ含量,结果表明该炉试烧高浓度ＰＣＢｓ时,焚毁率可以达到９９．９９９９％,炉渣中的２,３,７,８ＴＣＤＤ毒性当量为８７．８６ｐｇＴＥＱ／ｇ,烟灰中残留二口恶口英和类二口恶口英的总２,３,７,８ＴＣＤＤ毒性当量为４７．２３ｎｇＴＥＱ／ｇ．     

Fate of polychlorinated dibenzo-p-dioxins and dibenzofurans in a fly ash treatment plant

To understand the fate of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a fly ash treatment plant that used the Waelz rotary kiln process (hereafter the Waelz process), the samples of input and output media were collected and analyzed. The most important PCDD/F source in input mass was electric arc furnace (EAF) fly ash, which had a mean PCDD/F content of 18.51 ng/g and contributed more than 99% of PCDD/F input mass, whereas the PCDD/F input mass fractions contributed by the coke, sand, and ambient air were only 0.04%, 0.02%, and 0.000002%, respectively. For the PCDD/F output mass in the Waelz process, the major total PCDD/F contents of 43.73 and 10.78 ng/g were in bag-filter and cyclone ashes, which accounted for approximately 69% and 17%, respectively, whereas those of stack flue gas and slag were 14% and 0.423%, respectively. The Waelz process has a dechlorination mechanism for higher chlorinated congeners, but it is difficult to decompose the aromatic rings of PCDD/Fs. Therefore, this resulted in the accumulation of lower chlorinated congeners. The output/input ratio of total PCDD/F mass and total PCDD/F international toxicity equivalence (I-TEQ) was 0.62 and 1.19, respectively. Thus, the Waelz process for the depletion effect of total PCDD/F mass was positive but minor, whereas the effect for total PCDD/F I-TEQ was adverse overall.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in eggs of eight avian species from Dongting Lake, China

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in eggs of eight avian species collected from Dongting Lake of China to assess residue levels, accumulation patterns, and toxic potential in different avian species. Concentrations of total 2,3,7,8-substituted PCDD/Fs were in the range of 10.8-182pgg(-1) lipid weight. Eggs of great egret and lesser pied kingfisher contained higher levels of PCDD/Fs than eggs of other species, indicating the specific exposure and accumulation of PCDD/Fs relating to feeding habits and the life span. PCDD/Fs congener patterns varied among species. The patterns of PCDD/Fs in the eggs may be influenced by feeding habits, specific elimination, and metabolism. In general, concentrations of PCDDs were higher than those of PCDFs in avian eggs. On basis of lipid weight, total 2,3,7,8-TCDD toxic equivalents (TEQs) calculated based on the WHO TEFs for birds ranged from 2.04 to 42.0pgg(-1); and on basis of wet weight, total WHO-TEQs ranged from 0.19 to 1.59pgg(-1). 2,3,7,8-TCDF, 2,3,4,7,8-PeCDF, 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD were the major contributors to TEQ concentration in most avian eggs, whereas 1,2,3,4,7,8-HxCDD also accounted for a major portion of TEQs in eggs of azure-winged magpie. Values of TEQs in avian eggs were lower than toxic threshold values, implying risk reduction and natural restoration of PCDD/Fs contamination in Dongting Lake region.     

Distribution patterns of PCDD/Fs in chlorinated chemicals

The purpose of this research was to determine polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in five chlorinated chemicals (phthalocyanine copper, phthalocyanine green, chloranil-1 and 2, and triclosan), and to compare their 2,3,7,8-tetrachlordibenzo-IpI-dioxin equivalents (TEQ). The distribution patterns of total PCDD/Fs and 2,3,7,8-substituted PCDD/Fs were elucidated in detail. The TEQ values of toxic PCDD/Fs in all chemicals were in the range of 5.03-1379.55 ng I-TEQ/kg. The contribution of OCDD and OCDF in phthalocyanine green was 75% of the total TEQ. For chloranils, the maximum contribution of toxic PCDD/Fs was from 2,3,7,8-substituted HxCDF and 2,3,7,8-substituted HpCDF. The TEQ of HxCDF and HpCDF in chloranil-1 was 90% and in chloranil-2 was 71%. And the toxic contribution increased with the degree of chlorination for PCDFs.     

Assessment of the PCDD/F fate from MSWI residue used in road construction in France

MSWI fly ash is susceptible to contain high amount of polychlorinated dibenzo-dioxins and polychlorinated dibenzo-furans. However, the use of MSWI residue for road construction started in France at a period when MSWI Bottom Ash and MSWI fly ash were not separated. From four old road sites, MSWI residue, road soils, reference soils and geo-textiles were sampled and their PCDD/F contents were analyzed. MSWI residue show a great heterogeneity but also high amounts of PCDD/F (14-2960 ng I-TEQ kg(-1)dm). Soils underlying the road show less heterogeneity and PCDD/F contents between 0.57 and 7.23 ng I-TEQ kg(-1)dm, lower than ordinary soils. Moreover, the specific analysis of the 17 toxic PCDD/F congeners (notably the 2,3,7,8-TetraCDD) indicates the very low harmfulness of road soils. The study also allows to assert the relation between the MSWI residue particle size and the PCDD/F content.     

Determination of polychlorinated dibenzo-p-dioxins and dibenzo-furans in solid residues from wood combustion by HRGC/HRMS

PCDD/PCDF were determined in solid samples from wood combustion. The samples included grate ashes, bottom ashes, furnace ashes as well as fly and cyclone ashes. The solid waste samples were classified into bottom and fly ash from native wood and bottom and fly ash from waste wood. For each of the four classes concentration distribution patterns from individual congeners, the sums of PCDD/PCDF and the international toxicity equivalents (I-TEQ) values are given. The I-TEQ levels of fly ash from waste wood burning can be approximately up to two thousand times higher than the values from fly ashes of natural wood. The I-TEQ levels in bottom ashes from waste wood combustion systems are as low as the corresponding ashes from the combustion of native wood. Grate ash samples from waste wood combustion systems with low carbon burnout show high levels of PCDD/PCDF.     

PCDD/Fs levels in indoor environments and blood of workers of three municipal waste incinerators in Taiwan

This study monitored ambient air concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in three municipal waste incineration plants. Blood PCDD/Fs levels of 133 workers randomly selected from these plants were also measured. The associations between workers' blood PCDD/Fs concentrations and occupational exposures to PCDD/Fs were assessed. Means of air PCDD/Fs levels ranged from 0.08 to 3.01 pg/m3 in international toxic equivalents (I-TEQ). The geometric means of blood PCDD/Fs concentrations were 14.6, 15.8, 19.1 pg/g lipid in World Health Organization (WHO) TEQ, respectively, for workers from three plants. Air levels of total I-TEQ and all congeners, except 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TeCDD) and 1,2,3,4,7,8,9-heptachlorinated dibenzofuran (HpCDF), were significantly higher in plant B. However, blood concentrations of 2,3,7,8-TeCDD, 1,2,3,7,8-PeCDD, 2,3,7,8-TeCDF, 1,2,3,7,8-PeCDF and 1,2,3,4,7,8,9-HpCDF were significantly elevated in plant C workers. Although job contents, duration of employment and time spent in certain location were significantly different among incineration plants, they were not significantly associated with blood concentrations of any congener. Furthermore, results of the multiple regression analysis that assessed important occupational factors simultaneously and adjusted for potential confounders, showed significant associations between four congeners and incineration plant or job contents. However, the results were limited by small R-squares of the regression models. In conclusion, blood concentrations of several PCDD/Fs congeners were significantly different among three incineration plants. The differences were not explained by the discrepancy in job contents, duration of employment, and time activity in these plants.     

Cluster Analysis for Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans Concentrations in Southern Taiwan

Abstract

This study investigates the characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the ambient air of two municipal solid waste incinerators (MSWIs: GS and RW) and a coal-fired power plant (PW) in the Kaohsiung County (KC) area in Taiwan. The results show that the toxic equivalency (TEQ) concentration in the flue gas of GS and RW averaged 0.090 and 0.044 ng international toxic equivalents (I-TEQ)/N·m³, respectively. The TEQ concentration in the flue gas of PW averaged 0.050 ng I-TEQ/N·m³. All PCDD/Fs concentrations from the stack flue gas are lower than the Taiwan Environmental Protection Administration emission standard. Furthermore, the mean I-TEQ concentration in the ambient atmosphere ranged from approximately 0.019 to 0.165 pg I-TEQ/N·m³, much lower than the environmental quality standards for dioxins in Japan (0.6 pg TEQ/N·m³). This work classified all sampling sites into three clusters according to k-means cluster analysis. The result shows a probable direct correlation between the GS incinerator and site C. Although the concentration from the PW plant did not exceed the emission standard, it was much higher than that in Fernández-Martínez’s study. For proper environmental management of dioxins, establishing a complete emission inventory of PCDD/Fs is necessary. The government of Taiwan should particularly pay more attention to power plants to address the information shortage.     

The PCDD/F and PBDD/F pollution in the ambient atmosphere of Shanghai, China

Rapid economic growth in the last two decades in Shanghai has had a great adverse influence on its air quality. Therefore, the atmospheric pollutants of Shanghai have received much concern. In this study, concentrations of 2,3,7,8-substituted PCDD/Fs and PBDD/Fs congeners were measured in the ambient air of four districts in Shanghai. The mean atmospheric concentrations (TEQs) of total 2,3,7,8-PCDD/Fs and 2,3,7,8-PBDD/Fs were 8031 fg m(-3) (497.1 fg I-TEQ m(-3)) and 1358 fg m(-3) (304.1 fg I-TEQ m(-3)) for Jiading District, 5308 fg m(-3) (289.0 fg I-TEQ m(-3)) and 709 fg m(-3) (146.9 fg I-TEQ m(-3)) for Zhabei District, 4014 fg m(-3) (144.4 fg I-TEQ m(-3)) and 1239 fg m(-3) (256.9 fg I-TEQ m(-3)) for Pudong District, 3348 fg m(-3) (143.2 fg I-TEQ m(-3)) and 699 fg m(-3) (148.4 fg I-TEQ m(-3)) for Huangpu District, respectively. Our results showed that almost all the PCDD/Fs and PBDD/Fs congeners were partitioned into the particulate phase except the lower chlorinated or brominated ones. The logarithm of the gas/particle partitioning coefficient K(p) has good linear correlation with that of the sub-cooled vapor pressure p(L). Concentrations of PCDD/Fs and PBDD/Fs were both positively correlated to elemental carbon in all districts except Pudong District, suggesting elemental carbon could be a good indicator for dioxins' air pollution. It is intensively suggested that more detailed and deeper studies about PBDD/Fs should be carried out due to their relatively high atmospheric concentrations in Shanghai.     

PCDD/F concentrations in milk of nonoccupationally exposed women living in southern Catalonia, Spain

Concentrations of 17 toxic 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) have been determined in pooled samples of breast milk from 15 mothers living in two residential areas (Tarragona downtown and an industrial area) in the vicinity of a new hazardous waste incinerator (HWI), now under construction in Tarragona (southern Catalonia, Spain). PCDD/Fs in human milk samples ranged between 5.9 and 17.1 pg I-TEQ/g fat (162-498 pg I-TEQ/l), with a mean value of 11.8 pg I-TEQ/g fat (310.8 pg I-TEQ/l). The percentages of fat ranged between 1.53 and 3.52. Although PCDD/F levels in milk from mothers living in the industrial area were found to be slightly higher than those observed in women living Tarragona downtown, most differences did not reach the level of statistical significance. In general terms, PCDD/F concentrations in human milk (pooled) samples of mothers living in the area of Tarragona are similar or lower than those previously reported for most industrialized countries.     

Generation of PCDD/F in fly ash from municipal solid waste incinerators

Fly ash from municipal solid waste incinerators (MSWIs) has been characterized in terms of polychlorinated dibenzyl-p-dioxin and polychlorinated dibenzofuran (PCDD/F) content. Increasing values of PCDD/Fs have been found to correlate with decreasing temperatures of sampling points in flue gas treatment lines of the plants, confirming other researchers' findings about temperature as the major controlling parameter for the PCDD/F formation. Measured PCDD/F ratios show that de novo synthesis is the dominant formation mechanism. The increasing trends of particulate-bound PCDD/Fs can be explained not only through the dominant de novo synthesis process but also considering the adsorption of gaseous PCDD/Fs on fly ash deposits, even outside the typical de novo synthesis temperature ranges. The effective role of a post-combustor unit, imposed by Italian law to destroy PCDD/ Fs, also needs to be carefully reconsidered.