Removal efficiencies of PCDDs/PCDFs by air pollution control devices in municipal solid waste incinerators

Removal efficiencies of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) by air pollution control devices (APCDs) in the commercial-scale municipal solid waste (MSW) incinerators with a capacity of above 200 ton/day were evaluated. The removal efficiencies of PCDDs/PCDFs were up to 95% when the activated carbon (AC) was injected in front of electrostatic precipitator (EP). Spray dryer absorber/bag filter (SDA/BF) had high removal efficiency (99%)) of PCDDs/PCDFs when a mixture of lime and AC was sprayed into the SDA. When the AC was not added in scrubbing solution, the whole congeners of PCDDs/PCDFs were enriched in the wet scrubber (WS) with negative removal efficiencies of -25% to -5731%. Discharge of PCDDs/PCDFs was decreased with increasing the proportions of AC added in scrubbing solution. Selective catalytic reduction (SCR) system had the removal efficiencies of up to 93% during the test operation.     

Dechlorination and destruction of PCDDs/PCDFs in fly ashes from municipal solid waste incinerators by low temperature thermal treatment

Dechlorination and destruction characteristics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in fly ashes from commercial-scale municipal solid waste incinerators by low temperature thermal treatment using a laboratory-scale heating system were investigated. Experiments were carried out in reducing atmosphere at temperatures of 300 degrees C, 450 degrees C and 600 degrees C respectively, for the treatment time of 1h and 3h. Concentrations of PCDDs/PCDFs in raw fly ashes ranged from 35.5 to 107.3 microg kg(-1) (1.5-3.4 microg TEQ kg(-1)) and treated fly ashes ranged from 0.34 to 45.3 microg kg(-1) (0.012-1.63 microg TEQ kg(-1)). Concentrations of PCDDs/PCDFs in fly ashes treated at the different temperatures and times were observed to decrease with increase of treatment temperature and time by dechlorination or destruction. The distribution of octa- and hepta-chlorinated congeners were decreased and tetra-, penta- and hexa-chlorinated congeners were increased at 300 degrees C and 450 degrees C, but the distribution of octa- and hepta-chlorinated congeners were increased and tetra-, penta- and hexa-chlorinated congeners were again decreased at 600 degrees C. Total destruction efficiencies of PCDDs/PCDFs in fly ashes showed above 95% at the treatment temperature of 450 degrees C for 3h. However, removal efficiency of each congener in fly ashes varied, especially, 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDD in fly ash A increased. And the dechlorination and destruction characteristics of PCDDs/PCDFs in fly ash A and B was different due to difference in contents of Ca-compounds and metal oxides such as CuO and PbO in fly ashes.     

A pilot and field investigation on mobility of PCDDs/PCDFs in landfill site with municipal solid waste incineration residue

A field investigation by boring was carried out in a landfill site primarily with municipal solid waste incineration residue. From the collected core samples, vertical profiles of homologous content of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in the landfill layer were traced and the behavior of PCDDs/PCDFs was examined. In addition, a pilot-scale study was conducted on the PCDDs/PCDFs leached from incineration fly ash and the treated one using large landfill simulation columns (lysimeters) and the leaching behavior of PCDDs/PCDFs was examined. As a result, it was found that the coexistence of dissolved coloring constituents (DCCs), which might be composed of constituents like dissolved humic matters having strong affinity for hydrophobic organic pollutants, could enhance the leachability of PCDDs/PCDFs, thus contributing to the vertical movement and leaching behavior of PCDDs/PCDFs in the landfill layers of the incineration residue. Moreover, it is highly probable that DCCs derive from the unburned carbon in the bottom ash mixed and buried with the fly ash containing a high content of PCDDs/PCDFs.     

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.     

Application of multivariate data analysis to evaluate total PCDDs and PCDFs in municipal incinerator emission

Total concentrations of PCDDs and PCDFs were predicted from the concentrations of specifically identified dioxin and furan isomers of each congener group by partial least-squares (PLS). The accuracy of this prediction can be used to evaluate results from different data sets or different sources which were calculated by an automatic identification and quantification program-TASQ^R.     

Sampling,occurrence and evaluation of PCDDs and PCDFs from incinerated solid urban waste

The sampling procedure of solid and gaseous pollutants, contained in flue gas emitted into the atmosphere by solid waste incinerating furnaces were investigated. Because of their extraordinary toxicological properties, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are taken into particular consideration. The analytical work is based on the use of high-resolution gas chromatography in combination with low-resolution mass spectrometry. Details of the extensive sample clean-up will follow the GC-MS separation and identification of the isomers detected for each group of PCDDs and PCDFs. Quantitative data of these pollutants distribution levels deriving from different investigated incinerators are also reported.     

Correlation of PCDD/F emissions with operating parameters of municipal solid waste incinerators

Municipal solid waste incinerator (MSWI) operators frequently have expressed the need for an indirect indication of the expected production of PCDD/F and associated abatement procedures through a possible correlation with other real-time data, through using marker pollutants (e.g., penta/hexachlorinated aromatics), or through other indications. Since real-time measurement of PCDD/F is impossible, a correlation of PCDD/F emissions with other operating parameters could help in achieving these goals. Literature data of large-scale MSWIs concerning these correlations are scarce and seldom conclusive. Extensive data of Flemish MSWIs are used to statistically assess possible correlations of PCDD/F and other operating parameters. The effect of temperature in the electrostatic precipitator (ESP) is of major importance. When converting values measured between 180 and 270 degrees C to a reference temperature of, for example, 230 degrees C, PCDD/F concentrations achieve nearly constant values, stressing that the major correlating parameter is the temperature of the ESP. High temperatures that enhance de novo synthesis should be avoided.     

Formation of PCDDs and PCDFs by the chlorination of water

Two samples of tab water and double distilled water were chlorinated using chlorine gas. A series of PCDFs could be identified from these experiments, however no PCDDs could be found. The two water samples gave very similar isomeric patterns ( . . tetra-CDFs), however the congener profile (Cl₄ --- Cl₈) was different. These experiments indicate that all products formed by chlorination reactions are potentially contaminated by PCDFs by a specific “chlorine pattern”.     

Studies on sampling methods for PCDDs and PCDFs in stack emission

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in stack emission exist both as vapor and sorbed onto the surface of particles. The partition between the two phases is of a dynamic nature and changes rapidly with temperature. When monitoring stack emissions, a sampling method must be used that efficiently collects both phases as well as any condensation aerosol formed in the sampling train. In this study, the two sampling methods used in Sweden, the cooled probe polyurethane foam plug (PUFP) sampling train and the sampling train recommended by the Swedish Environmental Protection Board has been tested for particle collection ability. The results show that an aerosol filter has to be introduced after the condensor in order to collect particle bound PCDDs and PCDFs efficiently.     

Leaching characteristics of PCDDs/DFs and dioxin-like PCBs from landfills containing municipal solid waste and incineration residues

To investigate the leaching characteristic of persistent organic pollutants (POPs), such as non-ortho and mono-ortho substituted chlorobiphebyls (dioxin-like PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), in leachate from municipal solid waste (MSW) landfill sites containing incineration residues, raw leachate samples were collected twice from 12 selected MSW landfill sites. The samples were divided into their liquid and solid phases using GF/B (pore size 1.0 microm), and the concentrations of POPs then determined. The concentrations of PCDDs/DFs ranged from 0.65 to 5.88 pg-TEQ/l (average 2.86 pg-TEQ/l), and those of dioxin-like PCBs from 0.05 to 0.32 pg-TEQ/l (average 0.18 pg-TEQ/l). The major congeners of leached PCDDs/DFs and dioxin-like PCBs in liquid and solid phases were OCDD (about 60%), 2,3',4,4',5-PeCBs (about 30%), and 2,3,4,4',5-PeCBs (about 54%). The relationship between landfill age and the leaching concentration of PCDDs/DFs, and effects of dissolved organic carbon (DOC) on the leaching of PCDDs/DFs are also discussed. Finally, a leaching prediction model of PCDDs/DFs from MSW landfills has been suggested using parameters, such as hydrophobic neutral organic carbons, total dissolved solid, and the ratio of non-biodegradable wastes in landfill sites.     

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.     

Levels of PCDDs and PCDFs in two kinds of fast foods in Korea

We initiated an attempt to gather preliminary Korean fast food data on the concentrations, whole weight and international toxic equivalent (TEQ), in two kinds of fast foods, hamburger and fried chicken. The levels of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) in hamburgers are detected to be lower than in fried chickens. Total TEQ level of PCDDs in fried chicken is 47.45 times higher than in hamburger. In case of PCDFs, it is 48.61 times. Even though these are compared to the only one brand and three samples each, we think that these high levels of PCDDs/PCDFs in fried chicken are very important data because of the potentially increasing daily intake. If we continue to survey for PCDDs/PCDFs in fast foods more even, especially fried chicken, these data will be useful to calculate the estimated daily intake of TEQ levels of PCDDs/PCDFs in Korea.     

垃圾焚烧飞灰中不同粒径的毒性特性

对广州市某垃圾焚烧发电厂的焚烧飞灰进行粒径分级毒性分析研究。主要研究了粒径在35～1 000μm范围内的飞灰的腐蚀性和短期浸出毒性,包括Cr、Cd、Mg、Pb、Mn、Fe、Cu、Zn、Ni、Co等重金属,SO24-,Cl-,NO3--N和NO2--N,同时也研究了飞灰的物质组成和矿物特性。研究结果表明,所有粒径飞灰的浸出液pH值在12.3～12.5之间,属于有腐蚀性的危险废物,重金属Mg、Pb、Zn的浸出浓度最高,分别为168.78、53.94和86.40 mg/L。飞灰浸出液和含量最高分别达到8.87g/L和1.38 g/L,同时浸出液中测出一定量的硝态氮和亚硝态氮,证明飞灰吸附了垃圾焚烧过程中产生的氮氧化物气体。另外,研究得出飞灰的基本组成元素为Ca、Si、Cl、K、Na、S、Al、Mg和Fe,而重金属则以Zn、Pb、Mn、Cu、Cr等为主。矿物相主要为含硅和钙的化合物及NaCl和KCl等氯化物。     

水泥窑处置生活垃圾过程中的TOC排放

随着水泥窑协同处置生活垃圾、污泥和危废等技术的推广应用,相关环保控制要求也不断提高,处置过程烟道气中总有机碳(total organic carbon,TOC)含量高低,也逐渐成为人们关注和控制的目标。为了消除人们的疑虑,将未经发酵的筛下(厨余)物直接加入低温烘干粉磨的水泥生料磨系统中,经实验检测分析和工程现场测试实践证明,在控制一定添加量的情况下,该过程中各环节TOC含量非但不会增加,反而有所降低,其降幅高达40%。     

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.     

Modeling the formation of PCDD/F in solid waste incinerators

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) appear in unacceptable amounts in the gaseous emissions during the incineration of wastes containing significant quantities of chlorine and metals, such as MSW and medical waste. They are formed both in the gas phase at temperatures above 600 degrees C and on the surface of the solid phase (flyash) in the temperature range 400-225 degrees C. Both the precursor (from existing smaller chlorinated molecules) and de novo (from elemental carbon) routes are involved. An empirically derived global model for their de novo formation on flyash in MSW and medical waste incinerators has now been extended to include the precursor mechanism, and a gas phase formation component, with separate rate expressions for PCDD and PCDF. Homogeneous PCDD formation is governed by the concentration of chlorophenols and PCDF by that of chlorophenols and chlorobenzenes. The result is more complete system which distinguishes between the gas and solid phase contributions to the I-TEQ. An additional step for the adsorption of gaseous PCDD/F back onto the solid phase during cooling suggests this should be minimal in the gas ducts of an incinerator. The extended model has been tested against experimental data collected from a well-controlled pilot incinerator and commercial incinerators, and found to adequately describe the measured outputs. With the model it should be possible to predict the PCDD/F emissions from commercial incinerators, provided that the ash properties and the overall temperature-time profiles are known.     

Baseline soil levels of PCDD/Fs established prior to the construction of municipal solid waste incinerators in China

In order to determine the baseline contamination by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in different areas in China, prior to the construction of municipal solid waste incinerators (MSWIs), a total of 32 representative soil samples was collected near 16 incinerators and analyzed for their PCDD/F concentrations. The PCDD/F baseline concentrations in the soil samples ranged from 0.32 to 11.4 ng I-TEQ kg⁻¹ (dry matter), with average and median value of 2.73 and 2.24 ng I-TEQ kg⁻¹ (dry matter), respectively, and a span between maximum and minimum recorded value of 36. The PCDD homologues predominated in 26 out of 32 soil samples, with the ratio (PCDDs)/(PCDFs) ranging from 1.1 to 164; however in the other 6 samples, PCDF homologues were larger, with the same ratio varying from 0.04 to 0.8. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were used to examine PCDD/F amount and profile in these soil samples, and their possible associations with known emission sources: in this process 6 really distinct isomer fingerprints were identified. Background PCDD/F levels and profiles were comparable to those found in soils from China and other countries and indicate a rather low baseline PCDD/F contamination of soils. The present data provide the tools for future assessment of a possible impact of these MSWIs.     

Determination of PCDDs and PCDFs in PCB oil from a hazardous waste site

This paper describes the analysis of hazardous waste oil samples with procedures that were developed primarily to clean up and analyze biological samples. Details of the cleanup procedure and the results from the analysis of several waste PCB oil samples are presented.