不同垃圾焚烧炉产生的PCDD/Fs和PCBs同类物的分布

要应用高分辨气相色谱一质谱联用技术，测定了3种垃圾焚烧炉产生的飞灰中17种PCDD／Fs和12种共平面PCBs的浓度及毒性当量，比较了PCDD／Fs和PCBs同类物分布的差异．结果表明，流化床焚烧炉和炉排焚烧炉产生的PCDD／Fs多于PCBs，而气化熔融焚烧炉产生的PCBs多于PCDD／Fs；产生的PCBs对总毒性当量的贡献都比较小；3种焚烧炉产生的PCDD／Fs同类物具有相似的浓度分布；流化床焚烧炉和炉排焚烧炉产生的PCBs同类物具有相似的浓度分布，而气化熔融焚烧炉产生的PCBs同类物分布与其他两种焚烧炉差别较大．     

Study on polychlorinated dibenzo‐p‐dioxins and dibenzofurans in rivers and estuaries in Osaka Bay in Japan

In order to search the source of polychlorinated dibenzo‐p‐dioxins (PCDDs) and dibenzofurans (PCDFs) in blue mussel in Osaka bay, sediments from Osaka bay and from rivers running near an urban municipal incinerator were analysed for PCDDs, PCDFs and PCBs. The river and estuary sediments were all found to be contaminated with PCDDs at average levels of 9.8 and 12ppb on the dry basis, PCDFs of 7.8 and 5.1 ppb, and PCBs of 1600 and 1300ppb, respectively. The two sediments contained similar profiles of specific isomers and congeners of PCDDs and PCDFs with each other. In addition, there was observed positive close correlations between PCDD and PCDF levels in the two specimens as well as fly ash from urban municipal incinerators. These allow the conclusion that the main source of the two chemicals in Osaka bay is fly ash from waste incineration.     

The Distribution and Impacts of Dioxins and Polychlorinated Biphenyls in the Taiwan Er-Jen River

The distribution and impacts of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) and polychlorinated biphenyls (PCBs) in the Taiwan Er-Jen River were investigated by monitoring fish distribution and measuring PCDD/DFs and PCBs levels in sediment and fish samples. Most of the fish collected are pollution-resistant species such as Oreochromis spp, Liza macrolepsis, Channa spp and Megalops cyprinoides. the most polluted river sections are in the upstream where large amount of waste effluents from households, livestock rearing and nearby dumping sites were discharged into the river, and the lower reaches of the river where metal recovery activities including open burning of waste electrical wire/scrap occurred. Sediment samples collected near the burning site show 2,3,7,8-TCDD toxicity equivalents (TEQ) ranging from 0.014 to 14.2 ng g^-1 by PCDD/DFs and from 0.015 to 1.03 ng g^-1 by coplanar PCBs (Co-PCBs). the fish samples show TEQ ranging from 0.029 to 0.615 ng g^-1 by PCDD/DFs and from 0.012 to 0.12 ng g^-1 by Co-PCBs. Possible PCDD/DFs sources are discharged PCBs, open burning of waste wire/scrap, and pentachlorophenol. the consumption of these fish will cause an average intake of 54 pg kg^-1 d^-1 TEQ. the prevention of direct discharge of livestock and the dumping of waste effuents into River Er-Jen as well as the control of metal recovery activities appears to be the first step toward the restoration of River Er-Jen.     

The Distribution and Impacts of Dioxins and Polychlorinated Biphenyls in the Taiwan Er-Jen River

Abstract

The distribution and impacts of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) and polychlorinated biphenyls (PCBs) in the Taiwan Er-Jen River were investigated by monitoring fish distribution and measuring PCDD/DFs and PCBs levels in sediment and fish samples. Most of the fish collected are pollution-resistant species such as Oreochromis spp, Liza macrolepsis, Channa spp and Megalops cyprinoides. the most polluted river sections are in the upstream where large amount of waste effluents from households, livestock rearing and nearby dumping sites were discharged into the river, and the lower reaches of the river where metal recovery activities including open burning of waste electrical wire/scrap occurred. Sediment samples collected near the burning site show 2,3,7,8-TCDD toxicity equivalents (TEQ) ranging from 0.014 to 14.2 ng g^?1 by PCDD/DFs and from 0.015 to 1.03 ng g^?1 by coplanar PCBs (Co-PCBs). the fish samples show TEQ ranging from 0.029 to 0.615 ng g^?1 by PCDD/DFs and from 0.012 to 0.12 ng g^?1 by Co-PCBs. Possible PCDD/DFs sources are discharged PCBs, open burning of waste wire/scrap, and pentachlorophenol. the consumption of these fish will cause an average intake of 54 pg kg^?1 d^?1 TEQ. the prevention of direct discharge of livestock and the dumping of waste effuents into River Er-Jen as well as the control of metal recovery activities appears to be the first step toward the restoration of River Er-Jen.     

利用EIA法快速筛查垃圾焚烧飞灰和烟气中的二恶英毒性水平

基于CAPE技术公司的兔子复合克隆抗体的二恶英(PCDD/F)酶免疫分析试剂盒,建立了快速检测垃圾焚烧飞灰和烟气中PCDD/F毒性(TEQ值)的方法.试剂盒的最低检测限为3.3pg·tube-1(即3.3pgTEQ每EIA试管),线性检测范围为10～30pg·tube-1.样品经甲苯索氏抽提后过硅胶柱连接小碳柱净化处理,TCDD/F的回收率大约为50%,与原飞灰PCDD/F分布模式相比净化处理后样品中的TCDD/F含量明显降低.用净化处理后的飞灰溶液作标准溶液,绘制PCDD/F剂量-效应关系曲线,定量分析了2个飞灰样品和2个烟气样品的TEQ浓度,结果表明分析样品的TEQ实测值(HRGC/HRMS分析获得)与预测值(标准曲线计算值)的相对偏差(Rd)均小于15%,说明用该方法定量分析垃圾焚烧飞灰和烟气中PCDD/F毒性是可行的.     

Polychlorinated-dibenzo-p-dioxins, -dibenzofurans and -dioxin-like polychlorinated biphenyls in aquatic organisms from lake Kasumigaura,Japan

Polychlorinated-dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs) and -dioxin-like polychlorinated biphenyls (DLPCBs) were determined in aquatic wildlife of Kasumigaura Lake (KUL), Japan from 1978 to 2001. Two plankton species elucidated several fold greater concentrations (2400–7800) than small tiger fish (310–6500), shrimp (160–1100), and three large fish namely, black bass (120–240), carp (94–120) and mullet (54) on pg/g fat. PCDD homologues were predominant accumulants with >68–<95% contribution and remaining was shared by PCDFs. Accumulation, non-ortho DLPCBs in plankton (3500–9200), shrimp (1600–8600) and small fish (2000–8800) and large fish (1300–3900) on ng/g fat basis were several orders magnitude greater than PCDD/DFs. The mono-ortho DLPCBs in large fish species were 23?000–83?000?ng/g fat and which it is accounted 94.3–95.9% the total dioxin-like PCBs accumulation. Temporal trends of PCDDs, PCDFs, non-ortho PCBs and TEQ in shrimp and small tiger fish were varied. The mullet had minimum toxic equivalency “TEQ” (14?pg?TEQ/g) followed by plankton Neomysis intermedia (25?pg?TEQ/g), small tiger fish (mean: 33, ranges 14–66?pg?TEQ/g), plankton Cyclopus vicinus (34?pg?TEQ/g), carp (mean: 35, ranges 32–38?pg?TEQ/g), shrimp (mean: 38, ranges 11–68?pg?TEQ/g) and black bass (mean: 59, ranges 38–79?pg?TEQ/g) on fat basis. In all the samples, PCDD was predominant TEQ contributor followed by PCDFs and DLPCBs. The contribution of mono-ortho DLPCBs to the total TEQ was 0.52–0.92 in large fish.     

Hydrothermal treatment of MSWI fly ash for simultaneous dioxins decomposition and heavy metal stabilization

Researches on the hydrothermal treatment of municipal solid waste incineration (MSWI) fly ash were conducted to eliminate dioxins and stabilize heavy metals. In order to enhance decomposing polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) during hydrothermal process, a strong reductant carbohydrazide (CHZ) is introduced. A hydrothermal reactor was set up by mixing raw MSWI fly ash or the pre-treated fly ash with water and then heated to a pre-set temperature; CHZ was spiked into solution according to specially defined dosage. Experimental results showed that under the temperatures of 518 K and 533 K, the decomposition rates of PCDDs/PCDFs were over 80% and 90%, respectively, by total concentration. However, their toxic equivalent (TEQ) decreased only slightly or even increased due to the rising in concentration of congeners 2, 3, 7, 8-TCDD/TCDF, which might be resulted from the highly chlorinated congeners losing their chlorine atoms and being degraded during the hydrothermal process. Better results of TEQ reduction were also obtained under the higher tested temperature of 533 K and reactor with addition of 0.1%wt CHZ was corresponded to the best results. Good stabilization of heavy metals was also obtained in the same hydrothermal process especially when ferrous sulphate was added as auxiliary agent.     

Research on low emission MSW gasification and melting system

In order to eliminate secondary pollution caused by municipal solid waste (MSW) incineration, a MSW gasification and melting process is proposed. The process is expected to reduce the emission of pollutants, especially heavy-metals and dioxins. In this paper, the combustible components of MSW and simulated MSW were gasified in a lab-scale fluidized bed at 400°C–700°C when the excess air ratio (ER) was between 0.2 and 0.8. The experimental results indicated that the MSW could be gasified effectively in a fluidized bed at approximately 600°C–700°C when excess air ratio was 0.2–0.4. The melting characteristics of two typical fly ash samples from MSW incinerators were investigated. The results indicated that fly ash of pure MSW incineration could be melted at approximately 1,300°C and that of MSW and coal co-combustion could be melted at approximately 1,400°C. When temperature was over 1,100°C, more than 99.9% of the dioxins could be decomposed and most of the heavy-metals could be solidified in the slag. Based on the above experiments, two feasible MSW gasification and melting processes were proposed for low calorific value MSW: (1) sieved MSW gasification and melting system, which was based on an idea of multi-recycle; (2) gasification and melting scheme of MSW adding coal as assistant fuel.     

Polychlorobenzenes and polychlorinated biphenyls in ash and soil from several industrial areas in North Vietnam: residue concentrations,profiles and risk assessment

Polychlorinated benzenes (PCBzs) including penta- and hexachlorobenzene can be unintentionally formed from thermal processes in different industrial activities, and very little information is available on the contamination and emission characteristics of these new persistent organic pollutants from industries in Vietnam. In this study, contamination of PCBzs (including penta- and hexachlorobenzene, named PeCBz and HCB, respectively) and PCBs (including CB-28, 52, 101, 153, 138, 180) in fly ash, bottom ash and soil from combustion processes of waste incineration, metallurgy (steel making and zinc production) and cement production from several provinces in the Northern Vietnam, including Hai Duong, Hanoi, Bac Ninh, Hai Phong and Thai Nguyen, was preliminary investigated. The PCBzs concentrations in fly ash, bottom ash and soil ranged from 2.7 to 100 ng g^?1, from 2.7 to 159 ng g^?1 and from 0.28 to 33.9 ng g^?1, respectively. Relatively high residues of PeCBz in fly ash and bottom ash from municipal waste incinerators in some provinces from the Northern Vietnam were encountered. Total PCBs concentrations ranged from 18.0 to 8260 ng g^?1, from 1.0 to 10600 ng g^?1 and from 14.5 to 130 ng g^?1 for the fly ash, bottom ash and soil, respectively. Daily intakes of PeCBz, HCB and PCBs through soil ingestion and dermal exposure estimated for children ranged 0.33–9.93 (mean 3.14), 0.39–21.1 (mean 4.9) and 6.09–1530 ng/kg bw/day (mean 346), respectively; and these intakes were about 4.7–5.4 times higher than those estimated for adult. The intakes of PeCBz and HCB were relatively low, while those for PCBs exceeded WHO TDI for some samples.     

Dioxin-/Furan-“Verbrennungsprofile” in Abgasen aus Hochtemperaturprozessen

Different mechanisms downstream from high temperature processes lead to the formation of polychlorinated dibenzo(p) dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Independent from any concentrations, these mechanisms cause comparable PCDD/F patterns, the percentage proportion of single congeners or homologous groups related to the total of 17 2,3,7,8-Cl-substituted congeners or with respect to the sum of the homologous groups tetra to octa CDD/F. The characteristics of these so-called “combustion profiles” can help to interpret corresponding data from burning and melting facilities, such as municipal waste incinerators, coal power plants, sintering plants, metal finishing facilities, cement kilns, crematoria, hazardous waste incinerators and landfill gas burners     

Abstracts to forthcoming papers

Soil and sediments collected at a former chlor‐alkali plant in coastal Georgia (United States), revealed the presence of PCDF concentrations as great as 82.3 ng/g, dry wt. PCDF congener profile in soil was typical of “chlorine pattern”; with elevated proportions of OCDF and HpCDF. Concentrations of PCDFs declined gradually by 44‐fold at a distance of about 500 m along the contamination gradient. Of PCDDs/DFs, 2,3,7,8‐substituted PCDFs accounted for 94–98% of the TCDD‐like activity, which declined by 25‐fold, corresponding with the reduction of total PCDF concentrations. Concentrations of PCDDs in sediments were as great as 17 ng/g, with an elevated contribution from OCDD. The magnitude of decline in PCDD concentrations with distance from the source was less pronounced than that for PCDFs. PBDDs and PBDFs were not detected. Polybrominated biphenyl ether (PBBE) and monobromo‐heptachloro dibenzo‐p‐dioxins and dibenzofurans (PXDDs/DFs) were found, though, at low concentrations. Their spatial distribution was similar to those of PCDDs.     

我国垃圾焚烧二噁(口英)类排放源的初步调查

1　IntroductionIncinerationisnotthedominantwaytodisposalofmunicipalsolidwaste (MSW)atpresentinChina[1 ].However,moreandmorecitieswithrapiddevelopmentofeconomyareplanningtobuildMSWincinerationfacilities.AccordingtothelatestresultofinvestigationonMSWtreatme…     

Levels and patterns of polychlorinated biphenyls in residues from incineration of established source-classified MSW in China

Municipal solid waste (MSW) source-classified collection represents an advancement in resource cycling and secondary pollution control in China. Comparative experiments were performed to assess the levels and patterns of polychlorinated biphenyls in bottom ash, fly ash from boiler, and fly ash from bag filter from an MSW incineration plant with source-classified collection of MSW. Polychlorinated biphenyls were concentrated in the bag filter fly ash and in the bottom ash. The total amount of polychlorinated biphenyls was much lower than in fly ashes and bottom ash from traditional mixed waste incineration. Total concentration of coplanar polychlorinated biphenyls and toxic equivalent quantities were also reduced. Due to variations of feed waste, complete combustion, including continuously high incineration temperature, low CO concentrations and high air excess ratio were observed. Incineration temperature showed a negative correlation, while CO concentration showed a positive correlation with total and coplanar polychlorinated biphenyls, indicating that the latter can be reduced by controlling combustion conditions related to properties of feed waste.     

PCBs,PCDDs and PCDFs in soil samples from uncontrolled burning of waste electrical material for metal reclamation

PCDDs, PCDFs and PCBs have been analysed in soil samples where waste electrical equipment has been burned directly on the ground in three locations of Burgos (Spain). High levels of PCDDs, PCDFs and PCBs were detected in the centre of combustion sites. The results show PCB levels between 0.824 and 1.240 μg/g, and PCDDs and PCDFs levels between 8.73–36.37 ng/g and 12.79–50.95 ng/g. The I‐TEF values between 2.96–9.15 for dioxins and furans indicate that these soils are heavily polluted and may represent a risk for human and animal health.     

Residues of PCDD,PCDF, and PCBs in some marine organisms in Lake Temsah,Ismailia, Egypt

Residues of PCDDs/F, non-ortho, mono-ortho PCBs, and other PCBs were monitored in the tissues of mullet fish, bolti fish, bivalves and crab taken from Lake Temsah, at Ismailia, Egypt.

Results showed that 2,3,7,8 Tetra CDD and 1,2,3,7,8 Penta CDD were the most frequently detected PCDD congeners. Similarly, 2,3,7,8 Tetra CDF, 1,2,3,7,8 Penta CDF and 2,3,4,7,8 Penta CDF were the most frequently detected PCDF congeners. No relationship was apparent between the concentrations of detected PCDDs congeners and the degree of chlorination, except with crab samples in which an increase in the chlorination coincided with a decrease in the concentrations of the congeners.

In PCDF congeners, detected residues have had a reversed relationship with chlorination increase. In PCDD congeners, Octa CDD had the highest detected concentrations in the two fish species, while in the bivalves and crab, 2,3,7,8 Tetra CDD had the highest concentrations. The mullet fish had the highest total PCDDs concentration, at 0.398?pg/g fresh weight, followed by crab at 0.395?pg/g fresh weight, then bivalves and bolti fish at 0.187 and 0.062?pg/g fresh weight, respectively. In all the examined organisms, the total concentrations of PCDFs were much higher than the total concentrations of the PCDD congeners. The WHO–TEQ values were 11.92, 39.12, 25, and 3.6?pg/g fresh weight, for mullet fish, bolti fish, bivlaves and crab, respectively. The concentration of the mono-ortho congeners CB 118 was the highest detected of all non-ortho and mono-ortho PCBs congeners, with values of 0.382, 0.022, 0.231 and 0.357?ng/g fresh weight, in mullet fish, bolti fish, bivalves and crab, respectively. The WHO–TEQ concentrations were 0.799, 0.003?pg/g fw, 0.05?pg/g fresh weight, 0.676?pg/g, and 0.799?pg/g fresh weight, for the same species, respectively. The total concentration of PCBs 28, 52, 95, 99, 101, 105, 110, 118, 138, 146, 149, 151, 153, 170, 177, 180, 187 were 6.86?ng/g fresh weight for mullet fish, 0.2?ng/g fresh weight, for bolti fish, 2.72?ng/g fresh weight for bivalves and 2.8?ng/g fresh weight for crab, respectively.     

城市固体废弃物的预处理系统研究

对城市生活垃圾处置前进行有效的预处理，不仅可以减少处理量，提高处理的效果，而且可以回收部分资源性物质。由于垃圾的特性多变及处理方式的不同，统一的处理系统不仅难以达到处理垃圾的要求，而且可能造成不必要的浪费。文章针对垃圾焚的需求以及垃圾的特点，分析了垃圾焚烧炉预处理系统的设计和设计设备参数的确定，并介绍了与循环流化床垃圾焚烧炉配套的预处理系统。     

Detailed analysis of PCBs and PCDD/Fs impurities in a dielectric oil sample （ASKAREL Nr 1740） from an imported transformer in China

Homolog and congener profiles of polychlori- nated biphenyls （PCBs）, polychlorinated dibenzo-p- dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） in commercial PCBs formulations are useful information for the source appointment of PCBs contam- ination as well as the risk assessment caused by potential exposure. Dielectric oil （ASKAREL Nr 1740） in an imported transformer found in China was sampled and analyzed by isotope dilution technology using high resolution gas chromatography-high resolution mass spectrometry （HRGC/HRMS）. The detailed homolog and congener profiles of PCBs obtained were compared with those of known Aroclor formulations. High similarity in the homolog profile between the oil sample and Aroclor 1260was found, with the hexachlorinated and hepta- chlorinated biphenyls accounting for more than 80.2% of the total PCBs concentration. Severn indicator PCBs contribute about 30%, while 12 PCB congeners （i.e., # 153, #143, #168, #180, #149, #165, #138, #170, #190, #187, #174, #181） account for more than 50% of the total PCB concentrations. Total concentration ofPCDDs, PCDFs and dioxin-like PCBs （DL-PCBs） was found to be 740 ng TEQ/g, of which 620 ng TEQ/g came from DL-PCBs. The contribution of PCDDs to the total TEQ was neglectable. The concentration of PCDFs homologs follows the order of OCDF 〉 HxCDFs 〉 HpCDFs 〉 PeCDFs 〉 TeCDFs, which is in consistence with the previous study on Aroclor 1260. Three DL-PCBs congeners （i.e., #118, #156, #157） accounted for 77% of the total concentration of DL-PCBs, also they contribute 72% in the TEQ caused by DL-PCBs.     

Prevention of dioxins de novo formation by ethanolamines

Two inhibitors, triethanolamine (TEA) and monoethanolamine (MEA), were tested for their ability to prevent the de novo formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) on sinter plant fly ash. The amounts of both PCDDs and PCDFs, formed by thermal treatment of the fly ash, decreased when inhibitors were added. Up to 90% reduction of the PCDD/Fs formation was reached when 2 wt % monoethanolamine was mixed with fly ash. The temperatures tested, 325 and 400 °C, did not affect the inhibition activity. However, a longer reaction time, 4 h instead of 2 h, gave higher percentages of PCDD/Fs reduction. The laboratory results show that ethanolamines reduce the dioxins formation on sinter plant fly ash under various conditions of temperature and reaction time. Moreover, factory tests performed in parallel at a sinter plant are in good agreement with the laboratory experiments, thus confirming that the use of ethanolamine inhibitors is an appropriate technique for the prevention of dioxins emissions from sintering processes. Electronic Publication     

Polychlorinated dibenzo p-dioxins and dibenzofurans emissions in a primary copper smelter in China

Metallurgical production is the largest polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) emission source in China. However, PCDD/F monitoring and research are rarely conducted on primary metallurgical production. In this study, a demonstration primary copper smelter in China was selected to investigate PCDD/F characteristics and control. Samples were collected from major PCDD/F release points in the smelter process (fly ashes and waste water sludge). Specific analysis of PCDD/F congeners was carried out using a high resolution gas chromatography/high resolution mass spectrometry method. The results showed that PCDD/Fs might be unintentionally produced in the primary copper smelter processes, with sample concentrations of 180–6110 pg/g dry wt; highly chlorinated PCDD/F homologues were predominant. The toxicity of all the samples was calculated to be 120 pg WHO TEQ/g, fly ashes from the refining process furnaces air pollution control device and sludge were hazardous waste with higher PCDD/F toxicity. Both precursor formation and de novo synthesis were found to contribute to PCDD/F formation in the smelter process. PCDD/F characteristics and formation were compared with reported secondary copper smelters. Life-cycle control of PCDD/F was proposed for retrofitting of this smelter and for similar plants in China's primary copper production sector, including control at the PCDD/F formation, removal and disposal stages.     

Fates and partitioning of heavy metals in municipal solid waste incineration process

The fate and partitioning of heavy metals (including Hg, Cd, Pb, Zn, As, Cr, Ni, and Cu) from MSW incinerators located in Taiwan were determined. Results of stack sampling indicate that most Hg and As (more than 80%) exists in the gas phase while other metals partition differently among bottom ash, fly ash, and flue gases. Removal efficiencies of existing air pollution control devices for Hg and As are lower (about 70%) than other metals. Bottom ash contains higher concentration of Cd compared with European incinerators. In addition, strong enrichment of Cd on fly ash particles is observed.