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1.
Octachlorodibenzo-p-dioxin (OCDD)-added, pretreated fly ash was heated under vacuum at sample temperatures ranging from T(s)=450 to 650 K. The fly ash and liquid nitrogen-cooled trap samples were analyzed for DD/DF through OCDD/DF. The total amounts of DD through OCDD decrease with increasing T(s), which indicates that dechlorination/hydrogenation (DCH) reactions are not the only reaction channels. Reduction of toxic equivalent (TEQ) for PCDDs by more than 99% was achieved in the fly ash by the vacuum heat treatment at T(s)=650 K for 4 h. The total amount of PCDDs and DD detected in the liquid nitrogen-cooled trap relative to that of added OCDD was about 17%, i.e., PCDDs and DD which were adsorbed to the fly ash surfaces can evaporate into the gaseous phase. The difference between the evaporation behavior of PCDDs in the present and the previous studies is discussed in the light of their states of existence.  相似文献   

2.
In this study, PCDDs/DFs and co-planar PCBs concentrations in flue gases from 17 crematories and in fly ashes and bottom ashes (mainly bone) from several crematories were measured to grasp the present state of PCDDs/DFs emissions from crematories. The effects of several factors were discussed to prevent PCDDs/DFs emissions from crematories. Total concentration (normalized by 12% O2) of PCDDs/DFs was ranged from 4.9 to 1200 ng/m3 N, and toxic equivalent concentration was ranged from 0.064 to 24 ng TEQ/m3 N. As the results obtained in this research, the following measures to reduce PCDDs/DFs emission are recommended for existing crematories: (1) keeping the temperature at 800 degrees C in main/secondary chambers during a whole cremation, and (2) lowering the temperature in the dust collector. For newly installed crematories, following measures to prevent PCDDs/DFs emission including the measures for existing ones are recommended: (1) connecting one secondary chamber to one main chamber, (2) installing the high efficiency dust collector and reducing dust concentration to less than 0.01 g/m3 N, and (3) installing the sampling point for monitoring of PCDDs/DFs.  相似文献   

3.
Noma Y  Yamamoto T  Giraud R  Sakai S 《Chemosphere》2006,62(7):1183-1195
In the first known study to characterize the emissions of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) from the thermal treatment of wastes containing PCNs, the formation and decomposition behavior of these pollutants was investigated both at laboratory scale and at plant scale. Exhaust gas measurements from laboratory-scale combustion of rubber belts containing PCNs (FB belts) were used as the basis for calculations predicting that the incremental dioxin toxic equivalency (TEQ) emissions from municipal solid waste (MSW) incinerators would be less than 0.1 ng/m3 N. In order to directly examine co-incineration of FB belts with MSW and to address potential differences between the laboratory experiment and full-scale MSW incinerators, experiments were conducted using a larger scale thermal treatment test facility with sampling and analysis at several points in the thermal treatment process. Congener specific analysis of PCNs clearly showed that both destruction and synthesis simultaneously occurred during combustion in the kiln. Most of the PCNs were destroyed by secondary combustion, and almost all PCNs were removed after flue gas treatment. Almost all PCDDs/DFs were synthesized as by-products of kiln combustion, most of them were destroyed by the secondary combustion, and almost all dioxins (PCDDs/DFs and dl-PCBs) were removed after flue gas treatment. The TEQ emission levels were less than 0.1 ng/m3 N for all plant-scale tests, and differences in TEQ emission levels were very small. Adding wastes containing PCNs to MSW will not influence thermal treatment emissions to the environment from modern solid waste incinerators.  相似文献   

4.
PCDDs/DFs emissions from crematories in Japan   总被引:1,自引:0,他引:1  
Concentrations of PCDDs and PCDFs in emission gases from 10 crematories were measured. The relationship between PCDDs/DFs and several factors such as structure, equipment and operational state of the crematory is discussed. Furthermore, emission of PCDDs/DFs from all crematories in Japan is estimated. The following results are obtained: (1) total concentration of PCDDs/DFs was 2.2-290 ng/N m3, whose TEQ concentration was 0.0099-6.5 ng TEQ/N m3; (2) total concentration of PCDFs was higher than that of PCDDs; (3) T4CDFs was the highest in the homologue pattern and 2,3,7,8-T4CDF was the highest in the isomer pattern; (4) emission of PCDDs/DFs was the largest in the first 20 min of cremation; (5) concentration of PCDDs/DFs was related to the existence of a secondary combustion chamber and a dust collector, and the ratio of the numbers of main and secondary combustion chambers; (6) total emission of PCDDs/DFs from crematories in Japan was estimated to be 8.9 g TEQ/yr.  相似文献   

5.
Moon HB  Lee SJ  Choi HG  Ok G 《Chemosphere》2005,58(11):1525-1534
Bulk atmospheric samples (wet and dry) were collected monthly throughout a year at urban and suburban areas of Korea to assess the deposition flux and seasonal variations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The PCDDs/DFs deposition fluxes ranged from 1.0 to 3.7 ng TEQ/m2/year in the urban area and from 0.5 to 4.6 ng TEQ/m2/year in the suburban area. The deposition fluxes of PCDDs/DFs in this study were comparable to or lower than those previously reported at different locations. The atmospheric deposition fluxes of particles and PCDDs/DFs in winter tended to be higher than those in summer. However, monthly variations between particle and PCDDs/DFs deposition fluxes were small, and the correlation coefficients between the deposition fluxes of air particles and each homologue group of PCDDs/DFs varied according to the degree of chlorination of the homologue group. The deposition velocity of PCDDs/DFs in the urban area was estimated at 0.04 cm/s, which is a lower value than those found in other studies. The two most likely factors affecting the monthly variation of deposition fluxes are the ambient temperature and the amount of precipitation. In particular, the ambient temperature had an influence on the lower chlorinated homologues of PCDDs/DFs while precipitation had an influence on the higher chlorinated PCDDs/DFs. The PCDDs/DFs profiles in atmospheric deposition bulk samples showed a similar pattern at the urban and suburban sites. The possibility of the loading of PCDDs/DFs by Asian dust events could be partly confirmed by investigation of homologue profiles.  相似文献   

6.
Concentrations and accumulation profiles of PCDDs/DFs and coplanar-PCBs (co-PCBs) in aquatic biota (e.g., plankton, shellfish, benthic invertebrate, and fish) and sediment from Tokyo Bay were examined to elucidate the relationship between bioaccumulation and trophic level in the food web as determined by the stable nitrogen isotope analysis. Bioaccumulation patterns of PCDDs/DFs and co-PCBs varied greatly among congeners. Accumulation patterns of PCDDs/DFs and co-PCBs are not solely explained by their physicochemical properties. Biota-sediment accumulation factors (BSAFs) for co-PCBs in biota from Tokyo Bay were significantly greater than those of PCDDs/DFs. Furthermore, the slopes of the plots of delta15N and BSAF values and water solubility of 2,3,7,8-substituted PCDDs/DFs and co-PCBs were highly correlated. The results of our study would provide the valuable information to understand the accumulation properties of PCDDs/DFs and co-PCBs that can be used as a scientific basis to determine the sediment quality criteria of PCDDs/DFs and co-PCBs.  相似文献   

7.
Ok G  Ji SH  Kim SJ  Kim YK  Park JH  Kim YS  Han YH 《Chemosphere》2002,46(9-10):1351-1357
The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.  相似文献   

8.
The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.  相似文献   

9.
Song GJ  Kim SH  Seo YC  Kim SC 《Chemosphere》2008,71(2):248-257
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.  相似文献   

10.
Muto H  Saitoh K  Funayama H 《Chemosphere》2001,45(2):129-136
Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) formation by the thermal reactions of phenols with CuCl2 under oxygen flux were carried out in relation to their formation mechanisms. To evaluate the effect of photocatalytic degradation of titanium dioxide (TiO2) thin film prepared by the sol-gel method, the photocatalysis of PCDD/DFs in acetonitrile/water solution by batch-recycle system was conducted. For the thermal reaction system of powder mixtures of 2,4,5-trichlorophenol (2,4,5-TCP) and CuCl2, the formation rates were 8.1 microg/g-2,4,5-TCP/min for total PCDD/DFs and 6.9 microg/g-2,4,5-TCP/min for PCDDs, and total PCDD/DF rate was higher by approximately 40 fold compared to phenol vapor/oxygen/CuCl2 powder system. For the system of 2,4,5-TCP, PCDDs were mainly formed via ortho-phenoxyphenols (POP) intermediate by the condensation of 2,4,5-trichlorophenate. For PCDD/DF photocatalytic degradations, most PCDD congeners photodecomposed rapidly and the rates presented more than 70% (as dechlorination rates of 76% for PCDDs) at 24 h after irradiation, using PCDD/DFs formed with 2,4,5-TCP. The rate constants were in the order of 4.8-6.1 x 10(-3) min(-1), assuming the pseudo-first-order reactions for their low levels.  相似文献   

11.
Ham SY  Kim YJ  Lee DH 《Chemosphere》2008,70(9):1685-1693
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.  相似文献   

12.
Osako M  Kim YJ  Lee DH 《Chemosphere》2002,48(8):849-856
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.  相似文献   

13.
Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), including 2378-substituted isomers were present in samples of shellfish and fish, and ambient air collected from Masan Bay, and Masan City, South Korea. Total concentrations of PCDDs/DFs in mussel and clam were 750 pg g(-1), lipid weight (lw), and 3418 pg g(-1), lw, respectively. Total concentrations of PCDDs/DFs in mullet, gizzard and flounder were 52, 82, and 122 pg g(-1), lw, respectively. Shellfish tissues contained a greater number of PCDD/DF isomers, contributing greater total concentrations of PCDDs/DFs compared to fish collected from the same locations. The predominance of 2378-substituted PCDDs/DFs in fish is represented in greater total concentrations of 2378-TeCDD equivalents (TEQs), whereas there was very limited occurrence of 2378-substituted isomers in shellfish. TEQ concentrations in samples of mussel and clam were 0.97 and 12 pg g(-1), lw, respectively. Total TEQs in mullet, gizzard and flounder were 12, 22 and 18 pg g(-1), lw, respectively. In fish 2378-substituted PCDDs accounted for 100% of the total concentrations of PCDDs, and 2378-substituted PCDFs accounted from 59% to 73% of the total PCDFs. The 2378-substituted isomers accounted for only 3% of the total PCDDs/DFs in shellfish. Ambient air collected from two sites contained a wide range of isomers of tetra- through heptachlorinated PCDDs/DFs. Even though the total concentration of PCDDs/DFs in ambient air (12.8 pgm(-3)) collected from an industrial area was 2-fold greater than that in air samples (6.3 pgm(-3)) collected from an urban/rural area, total TEQs (0.07 and 0.08 pgm(-3)) there was no statistical difference between the two samples.  相似文献   

14.
Very limited information is available on body burdens and environmental levels of dioxins and dioxin-like PCBs (dl-PCBs) in mainland China. In the current studies, human milk samples were collected from 30 breastfeeding mothers in Shijiazhuang city (industrialized) and 11 in the Tanshan countryside (agricultural) of Hebei Province in northern China. An additional 20 samples were obtained from mothers in Tokyo, Japan. PCDDs, PCDFs, and dl-PCBs in human milk were analyzed by high-resolution gas chromatography/high-resolution mass spectrometry. Our results show that arithmetic means for body burdens of PCDDs/Fs and dl-PCBs in Hebei were 3.6 and 1.9 pg TEQ g−1 fat, respectively, which were only about one fourth of the levels in Japan. In addition, no difference was found in the chemical levels except dl-PCBs between the urban and rural areas. Based on the results of an in-person interview of the Chinese mothers using a 59-item questionnaire, freshwater fish consumption was found to correlate with the body burden of dioxins. Principal component analysis of dioxin congeners revealed that the patterns of dioxins in the Hebei urban and rural areas are quite similar; however, they are clearly different from those in Japan. Collectively, our results suggest that the lower body burdens of dioxin in Hebei may be due in part to the relatively slow industrialization and a lower consumption of marine foods. Finally, the results indicate that comprehensive monitoring of dioxins and dl-PCBs in humans as well as in the environment and foods is necessary in China.  相似文献   

15.
A method involving supercritical fluid extraction (SFE) with a solid phase trap containing activated alumina was investigated for the rapid analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin like polychlorinated biphenyls (DL-PCBs) in soils and sediments. The samples were extracted by using supercritical carbon dioxide with water (2% versus CO(2) flow velocity) being used as an entrainer at a pressure of 30 MPa and a temperature of 130 degrees C for 50 min. The extracts were adsorbed on an activated alumina trap that was maintained at a temperature of 150 degrees C, and then, PCDD/DFs and DL-PCBs were eluted with 20 ml of hexane at 60 degrees C. After concentration, they were measured with a high-resolution gas chromatograph interfaced to a high-resolution mass spectrometric detector. The average concentrations of PCDD/DFs and DL-PCBs corresponded to the results obtained by the conventional method, and the reproducibility of this SFE method was below 21% of the relative standard deviations for all samples. The total time required for the analysis of the pretreatment of this method was only 2 h.  相似文献   

16.
Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and certain dioxin-like polychlorinated biphenyls (dl-PCBs) are a family of chemically-related lipophilic compounds characterized by similar toxicity. Due to their properties they are universally distributed in the environment and classified as persistent organic pollutants (POPs). From most of studies carried out to evaluate human dietary intake, milk and dairy products result as a major contributors of PCDD/Fs uptake. Of course the main source of milk contamination is animal feeds. Lactating ruminants, cows included, transfer these compounds to the food chain by ingestion of contaminated vegetables or soil. Their resistance to degradation and a high lipophilicity means that PCDD/Fs and dl-PCBs may be accumulated into fat tissues from which they are transferred to milk during lactation period.Seventy-nine cows milk samples, collected in the monitoring plan 2008, were analyzed for PCDD/Fs and dl-PCBs. Eleven milk samples were non-compliant corresponding to five breeding livestock located in Caserta province. The distribution of PCDD/Fs and dl-PCBs congeners in these samples was examined in order to determine the likely sources of dioxins. The results show that the congener profile is characterized by a prevalence of PCDFs in respect of PCDDs, that represents the typical pattern of thermal origin contamination.  相似文献   

17.
The catalytic effects of copper and iron compounds were examined for their behavior in promoting formation of chlorine (Cl2), the major chlorinating agent of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in an environment simulating that of municipal waste fly ash. Formation of Cl2 occurred as a result of a metal-catalyzed reaction of HCl with O2. Catalytic activity was greatest at a temperature of approximately 400 °C, supporting a theory of de novo synthesis of PCDDs and PCDFs on fly ash particles downstream of waste combustion.  相似文献   

18.
Combustion of brominated flame retardants and behavior of its byproducts   总被引:13,自引:0,他引:13  
The substance flow rate of PBDDs/DFs into flue gas and incineration residues from incineration of three types of waste samples containing brominated flame retardants were examined. The samples used consisted of PBDEs (a typical retardant), used TV casing materials (actual waste materials), and waste printed circuit boards. PBDDs/DFs concentrations in the experimental samples of PBDEs/PE, waste TV casing materials and printed circuit boards ranged between 3000 and 130,000 ng/g. These values are very high when compared to other investigations. The increase of chlorine concentration in input sample reduced the ratio of PBDDs/DFs in flue gas and raised the ratio of PCDDs/DFs. With adequate combustion control and flue gas treatment, the amount of PBDDs/DFs released from the incineration of resin containing brominated flame retardants was lower than the input amount. The presence of PBDDs/DFs in incineration residues dominated the total amount of dioxins released. When PBDDs/DFs, PCDDs/DFs and PXDDs/DFs were considered as a total, the total amount released was lower than the total amount input.  相似文献   

19.
This report presents our results in a low-temperature mechanochemical hydrodechlorination process applied to fly ash coming from a municipal waste incinerator in order to efficiently remove all traces of PCDDs, PCDFs and PCBs. We found that the most suitable degradation agent is a mixture of metallic calcium and calcium oxide. A sample of fly ash presenting a TEQ of 5200 pg g−1 was completely detoxified (no traces of PCDDs, PCDFs and PCBs detected) after ball-milling at 400 rpm over night.  相似文献   

20.
Dioxin contents in fly ash from large-scale MSW incinerators in Taiwan   总被引:6,自引:0,他引:6  
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.  相似文献   

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