PCDDs/PCDFs, dl-PCBs and HCB in the flue gas from coal fired CFB boilers

The aim of the project was to measure the actual emissions of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and hexachlorobenzene (HCB) from four selected power plants in Poland in order to update the national inventory of PCDDs/PCDFs emission. Relatively low PCDDs/PCDFs as well as dl-PCBs concentrations in flue gas obtained in measurements in this study for four different circulated fluidized bed (CFB) boilers indicate practical absence of any hazards caused by PCDDs/PCDFs emission from these units. The results of PCDDs/PCDFs determination obtained in this study indicate that hard coal combustion in large CFB in the four central heating plants (CHP) is not a significant source of PCDDs/PCDFs emission to the environment even if operated by co-firing of waste coal. PCDDs/PCDFs concentration in flue gases as well as emission factors were recorded in the range of 0.012-0.060ngI-TEQ/m(n)(3) and 7.51-46.4mugI-TEQ/TJ, respectively. Dl-PCBs concentration was practically below the LOQ=0.006ng WHO-PCB TEQ/m(n)(3) in all experiments. HCB concentration as well as emission factors were recorded in the range of 11.5-42.0ng/m(n)(3) and 6.19-26.7mg/TJ, respectively, where the highest value was obtained for co-firing of waste coal, however. Obtained in this work emission factors will be used for national emission inventory purposes instead of the factors proposed by Toolkit or taken from previous measurements. However, consideration should be given to the fact that the measurements in most cases are related to single installations. Therefore, the need for further development of national factors for the power generation industry in Poland is desired.     

Structure-related distribution of PCDD/Fs, PCBs and HCB in a river-sea system

Water concentrations of PCDD/Fs, HCB, and non-ortho, mono-ortho, and non-dioxin-like PCBs were measured four times during 1 year in a coastal area of the Baltic Sea, to investigate background levels and distribution behaviour. Sampling sites included two rivers, an estuary, and the sea. Particulate and apparently dissolved concentrations were determined using active sampling (filters + PUFs), while freely dissolved concentrations were determined using passive sampling (POM-samplers). The distribution between particulate + colloidal and freely dissolved phases, in the form of TOC-normalized distribution ratios (K_TOC), was found to be near or at equilibrium. The observed K_TOC were not significantly different between sampling sites or seasons. For PCDD/Fs, the concentrations were significantly correlated to suspended particulate matter (SPM), while no correlation to organic carbon (TOC) was observed. In the estuary and the sea, PCB concentrations were correlated to TOC. The sorption of various congeners to SPM and TOC appeared to be related to both hydrophobicity and 3D-structure. The PCDD/F concentration in the sea decreased to one third in May, likely connected to the increased vertical flux of particles during the spring bloom.     

PAHs, PCDD/Fs, PCBs and HCB in leaves from Brisbane, Australia

The concentrations of SOCs in leaves of an evergreen Australian native tree (Melaleuca leucadendra) and grass collected in Brisbane, Australia were determined. The concentrations of PCDD/Fs and PAHs in the leaf tissue were comparable to those reported for urbanised areas in other industrialised countries. A distinct difference in the compound profiles between the leaves of the two species was observed, with higher concentrations of the lower molecular mass PAHs and PCDD/Fs and lower concentrations of the higher molecular mass PAHs and PCDD/Fs in the Melaleuca leaves relative to the grass leaves. The interspecies differences are explained on the basis of the larger size of the lipophilic compartment (for compounds with low K(OA)) and the lower ratio of surface area to volume in the Melaleuca leaves.     

PCDDs and PCDFs in vehicle exhaust particles in Japan.

Vehicle exhaust particles from gasoline and diesel engine cars were analyzed for PCDDs and PCDFs. The congener patterns of PCDDs and PCDFs in exhaust particles were different between gasoline and diesel engine cars. Suspended particulate matter from electrostatic precipitator connected to a highway tunnel was also analyzed for PCDDs and PCDFs. The congener pattern of suspended particular matter was different from both of gasoline and diesel engine cars. Total amounts of PCDDs/PCDFs sum concentrations in gasoline, diesel and suspended particulate matter were 0.21, 0.87 and 26.0 ng/g, respectively. The I-TEQs levels in gasoline, diesel and suspended particulate matter were 4.2, 11 and 242 pg/g, respectively.     

二(噁)(口英)样品制备与检测技术进展

环境中存在的二噁是一类严重影响食品安全和人类健康的强毒性有机污染物,为了能正确评价这类化合物的来源与环境中分布情况,二噁的分析检测引起了人们强烈的关注。本文介绍了样品检测前处理纯化过程中所用的各种传统的吸附剂(硅酸盐、佛罗里土和活性炭等)和新发展的几种主要吸附剂(2(1芘基)乙基二甲基硅烷化硅胶(PYE)、炭纳米管和多孔石墨炭等)的性能、在样品前处理过程中所起的作用及存在的问题和发展趋势,并在概括样品制备的基础上,阐述了二纯化技术及其检测方法(包括化学分析法和生物分析法)的进展。     

Determination of PCDDs,PCDFs, PCBs and HCB emissions from the metallurgical sector in Poland

Background The aim of the project was to measure the actual emissions of PCDD/F, PCBs and HCB from 20 selected metallurgical installations in Poland, in order to update the national inventory of dioxin emission from metallurgical industry for developing a strategy for dioxins and furans emission abatement from the subject facilities (UNEP 2005). Methods Sampling methodology used in this work was developed at the Cracow University of Technology because of the complexity of simultaneous sampling and determining PCDFs, PCDDs, PCB and HCB. For the determination a GC-MS/MS system was used. Results and Discussion Results from the work indicate that the highest dioxins and PCB concentrations were recorded for iron ore sintering plants at 1.10–1.32 ng total¹ TEQ/Nm³ followed by aluminium scrap melting at 0.03–0.66 ng total TEQ/Nm³. The highest HCB concentrations at 613–1491 ng/Nm³ were also recorded for iron ore sintering plants, whereas at aluminium plants the HCB concentrations were in the range of only 10.1–22.7 ng/Nm³. Conclusions The above investigations indicate that secondary aluminium production is the most significant dioxins source, if calculated as emission factor values. However, iron ore sintering plants are operating at much higher production capacity, causing this process to become the major source of dioxins, PCB and HCB pollution to the atmosphere in Poland. Recommendations and Perspectives Based on the performed tests and the environmental reviews of selected plants several recommendations were formulated for the reduction of generation or of emission of these pollutants from iron ore sintering plants, electric arc furnace steel production processes, hot-blast furnace operations, secondary aluminium smelting and primary zinc production from zinc cathodes.     

PCDDs, PCDFs, PCBs and HCB in marine and estuarine sediments from Queensland, Australia.

Concentrations of 2,3,7,8-chlorine substituted PCDDs, PCDFs, selected PCB congeners and HCB were determined in sediment samples collected from sites along the east coast of Queensland in northern Australia. PCDDs were detectable in all sediment samples while PCDFs, PCBs and HCB were mainly found in sediment samples collected from sites in the Brisbane metropolitan area. The results provide evidence that an unidentified source for higher chlorinated PCDDs exists along the Queensland coast.     

Seasonal and particle size-dependent variations in gas/particle partitioning of PCDD/Fs

This study monitored particle size-dependent variations in atmospheric polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Two gas/particle partitioning models, the subcooled liquid vapor pressure (P(L)(0)) and the octanol-air partition coefficient (K(OA)) model, were applied to each particle sizes. The regression coefficients of each fraction against the gas/particle partition coefficient (K(P)) were similar for separated particles within the same sample set but differed for particles collected during different periods. Gas/particle partitioning calculated from the integral of fractions was similar to that of size-segregated particles and previously measured bulk values. Despite the different behaviors and production mechanisms of atmospheric particles of different sizes, PCDD/F partitioning of each size range was controlled by meteorological conditions such as atmospheric temperature, O(3) and UV, which reflects no source related with certain particle size ranges but mixed urban sources within this city. Our observations emphasize that when assessing environmental and health effects, the movement of PCDD/Fs in air should be considered in conjunction with particle size in addition to the bulk aerosol.     

小型焚烧设施烟气中二噁英类的排放和控制

对中国典型的小型焚烧设施现状和二噁英类排放进行了初步调查研究,未经处理的小型垃圾焚烧设施烟气中二噁英类毒性当量(TEQ)大于6 ng/m3,小型火化机烟气中二噁英类TEQ大于5 ng/m3.设计并检验了布袋除尘器和活性炭滤布的二噁英类去除效果.仅使用布袋除尘器二噁英类去除率不高,布袋除尘器和活性炭滤布联用可以有效去除飞灰和气相中的二噁英类,去除率达到90%左右,可达到《生活垃圾焚烧污染控制标准》(GB 18485-2001)二噁英类排放标准.     

下排气旋风分离器结构优化研究

下排气旋风分离器是一种新型的气固分离装置,但存在对细颗粒夹带严重,导致细颗粒分离效率稍低的现象.采用RNG k-ε湍流模型和拉格朗日坐标系下的离散相模型,对75 t/h循环流化床锅炉的下排气旋风分离器的气固两相流动进行数值研究并提出结构优化措施.结果表明,下排气旋风分离器进口改为减缩型、排气管位置下移并采用圆台入口,对...     

A modified clean-up procedure for the determination of PCDDs in soil samples

PCDDs can be determined in soil samples in the presence of high amounts of hexachlorocyclohexanes with a modified method, including a clean-up procedure with a column containing carbon. To reach low detection limits use is made of a column switching system in the GC-MS analysis.     

Emission profiles of polychlorinated dibenzodioxins, polychlorinated dibenzofurans (PCDD/Fs), dioxin-like PCBs and hexachlorobenzene (HCB) from secondary metallurgy industries in Portugal

This paper reports, for the first time, a study of dioxin emissions from 10 siderurgies and metallurgies, secondary copper, aluminum and lead metallurgies, in Portugal. The study reports the emission factors and total emission amounts of PCDD/Fs, dioxin-like PCBs and hexachlorobenzene (HCB). The congener patterns were characterized and are discussed. The results showed that the total amount of PCDFs is higher than PCDDs in flue gas of each industrial unit. The toxic equivalent emission factors of pollutants emitted are 3098-3338 ngI-TEQt(-1) for PCDD/Fs and 597-659 ng I-TEQt(-1) for dioxin-like PCBs in siderurgies production (total estimated emission amounts released to atmosphere of 3.9-4.5 g I-TEQyr(-1)), 50-152 ng I-TEQt(-1) for PCDD/Fs and 24-121 ng I-TEQt(-1) for dioxin-like PCBs in ferrous foundries production (total estimated emission amounts released to atmosphere of 0.0010-0.0016 g I-TEQyr(-1)) and 5.8-5715 ng I-TEQt(-1) for PCDD/Fs and 0.49-259 ng I-TEQt(-1) for dioxin-like PCBs in non-ferrous foundries production (total estimated emission amounts released to atmosphere of 0.00014-0.12 g I-TEQyr(-1)). The HCB emission from siderurgies production is 0.94-3.2 mg t(-1) (total estimated emission amounts released 0.94-3.8 g yr(-1)), being much smaller, residual, in the emissions of the other types of plants (0.0012-0.026 mg t(-1) production and total estimated emission amounts released to atmosphere of 0.013-1.7 mg yr(-1)).     

Comparison of various sampling methods for PCDDs and PCDFs in stack gas

There have been discussions about how complete PCDDs and PCDFs are sampled from stack gas of waste combustion plants by various sampling methods. In Germany, at present, a sampling method is used, which was first proposed by Nottrodt et al.¹, consisting of a filter device, condenser, and an absorption train. Since this sampling procedure complicates sampling and analysis, we compared this “standard procedure” with a “dilution method”, where only a filter, impregnated with paraffin, is used as trapping device, and also tested the effectiveness of XAD-2 as an adsorption trap.

As standard procedure the standard train was always used in parallel to other sampling methods. The results of four parallel sampling periods confirmed, that comparable results are obtained, when parallel sampling is carried out with the standard train.

The result of our investigation can be summarized as follows: The total emission of PCDDs and PCDFs determined by different sampling procedures varies only insignificantly. This means that sampling and analysis for PCDDs and PCDFs in stack gas could be simplified considerably.     

Study on PCDDs/PCDFs and co-PCBs content in food samples from Catalonia (Spain)

The results of a surveillance programme on polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (co-PCBs) determination in 70 foodstuffs samples produced all over the four provinces of Catalonia is presented. The study included the analyses of raw milk, pure virgin olive oil, butter, chicken, pork and mussel samples collected between November 1999 and January 2000. Milk, virgin oil, pork or butter presented a variable dioxin and co-PCBs content, even though the limits proposed in the draft of the EC Regulation for its commercialization in the European countries were not reached. The levels of PCDDs/PCDFs and co-PCBs determined in chicken samples varied between 0.36–3.59 pg I-TEQ/g fat chicken (0.4–3.8 WHO-TEQ/g fat). Just one case presented remarkable content of dioxins (about 30 pg I-TEQ/g fat) with a complex congener-specific profile which indicates the presence of an external contamination. On the other hand, a congener-specific profile dominated by 2,3,7,8-TCDF and OCDD was observed in mussel samples from Catalonia. This fact was also observed in mussel samples from other sites in Spain.     

Models for gas/particle partitioning,transformation and air/water surface exchange of PCBs and PCDD/Fs in CMAQ

We have added the capability to simulate polychlorinated biphenyls (PCBs) and polychlorinated dibenzo [p] dioxins and polychlorinated dibenzo-furans (PCDD/Fs) to the Community Multiscale Air Quality (CMAQ) modeling system, thus taking advantage of the latter's capability to simulate atmospheric advection, diffusion, gas-phase chemistry, cloud/precipitation, and aerosol processes. The modifications reported here include the addition to the CMAQ system of two gas/particle partitioning models options: the Junge–Pankow adsorption model and the K_OA absorption model, as well as chemical transformations and atmosphere/water surface exchange processes for these semi-volatile organics. Simulations for the purpose of model testing and validation were conducted for the years 2000 and 2002 on a domain covering most of North America. Both partitioning models give reasonable results when compared with available measurements. The model predictions of deposition and air concentrations also agree well with measurements. The modeling results also indicate that the long-range transport is important and anthropogenic emissions of PCBs and PCDD/Fs are dominant although surface exchange of PCBs may be important for some clean locations.     

TiO_2/AC复合催化剂的制备及其对六氯苯的光催化降解性能研究

以颗粒活性炭（AC）和钛酸丁酯为原料,采用微波辐射法制备TiO2/AC复合光催化剂,并对制备的催化剂进行了表征;采用该催化剂对六氯苯进行光催化降解,确定了六氯苯降解的最佳工艺条件,并就几种外加试剂对TiO2/AC光催化降解六氯苯的强化作用进行了探讨。结果表明,制备的催化剂中TiO2均匀分布在活性炭表面、呈单一的锐钛矿晶型,晶粒生长完善。该催化剂催化降解六氯苯的最佳工艺条件为：pH值为5、TiO2负载量为18.2%、TiO2/AC投加量为0.4 g/L、反应时间为60 min。在此条件下,六氯苯降解效率达90.3%。添加适量的H2O2、AgNO3、K2S2O8、KIO4和KMnO4均能提高TiO2/活性炭对六氯苯的光催化降解效率。5种外加试剂的适宜添加量分别为0.3%、1.0、1.0、0.1和0.1 mmol/L,对TiO2/AC光催化效率的强化作用大小顺序为：H2O2〉AgNO3〉K2S2O8〉KMnO4〉KIO4。     

等离子体炉尾气处理系统的研制

等离子体炉裂解有机砷化物后的尾气经二次炉有氧燃烧,排出的高温废气主要污染物为三氧化二砷、二氧化硫、氮氧化物、氯化氢及粉尘等。研制的尾气处理系统需将高温气体冷却、洗涤净化,分离含砷废渣并返回等离子炉内熔融玻璃体固化处置。通过研制和实验,该系统实现了负压运行、有效急冷尾气、控制污染物,玻璃体浸出液砷的浓度小于0.03 mg·L-1,经处理后的废物均可达标排放。     

TiO2/AC复合催化剂的制备及其对六氯苯的光催化降解性能研究

以颗粒活性炭（AC）和钛酸丁酯为原料,采用微波辐射法制备TiO₂/AC复合光催化剂,并对制备的催化剂进行了表征;采用该催化剂对六氯苯进行光催化降解,确定了六氯苯降解的最佳工艺条件,并就几种外加试剂对TiO₂/AC光催化降解六氯苯的强化作用进行了探讨。结果表明,制备的催化剂中TiO₂均匀分布在活性炭表面、呈单一的锐钛矿晶型,晶粒生长完善。该催化剂催化降解六氯苯的最佳工艺条件为：pH值为5、TiO₂负载量为18.2%、TiO₂/AC投加量为0.4 g/L、反应时间为60 min。在此条件下,六氯苯降解效率达90.3%。添加适量的H₂O₂、AgNO₃、K₂S₂O₈、KIO₄和KMnO₄均能提高TiO₂/活性炭对六氯苯的光催化降解效率。5种外加试剂的适宜添加量分别为0.3%、1.0、1.0、0.1和0.1 mmol/L,对TiO₂/AC光催化效率的强化作用大小顺序为：H₂O₂＞AgNO₃＞K₂S₂O₈＞KMnO₄＞KIO₄。     

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。