Assessment of polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from a hazardous waste incineration plant using long-term sampling equipment

The aim of this work is to evaluate the performance of a continuous monitoring system for the analysis of the mass concentration of PCDD/Fs from stationary sources. Data was acquired from a modern, state of the art, hazardous waste thermal treatment plant for a period of more than 2 years using a commercial available continuous monitoring system. The study consisted of a total of 16 samples, collected in periods from 1 week to 2 months resulting in an average of 360 m³ sampled flue gas per sample. The study showed the system was able to confirm that for a period of more than 2 years the plant was complying with the limit of 0.1 ng I-TEQ/Nm³. In addition, the data showed the typical fingerprint of such installations which is useful for example in impact studies. Long-term samples were compared to five short-term samples (6 h) collected every 6 months during the study period. Principal component analysis was applied to PCDD/Fs obtained data as useful statistical tool to find out trends and similarities between different samples. Improvement in terms of representativeness of data was achieved through continuous assessment since the starts of the project. The obtained data was further used to determine the emission factor for this activity and the total annual PCDD/Fs release to the atmosphere.     

Polycyclic aromatic hydrocarbons in solid residues from waste incineration

Polycyclic aromatic hydrocarbons (PAH) levels in solid residues from clinical waste incineration were measured using HPLC with fluorescence detection. PAH mass emission rates and emission rates as a function of waste burned are also reported. For bottom ash, PAH levels and physical properties were found to be quite consistent. Levels of high molecular mass PAHs were comparable to levels previously reported in the literature when adjusted for differences in sample preparation techniques. However, levels of low molecular mass PAHs were considerably elevated in this study. Possible reasons for this finding include the composition of the waste, combustion conditions and methods of sample preparation. In contrast, no PAHs were found in fly ash, an unexpected finding which is probably attributable to matrix effects resulting from a surfeit of lime in the fly ash. Factors effecting the partitioning of PAHs and their environmental fate are also discussed.     

江苏省城市垃圾焚烧电厂烟气中重金属排放研究

通过对江苏省现有垃圾焚烧电厂进行资料统计,分析了江苏省目前垃圾焚烧电厂规模及分布情况。选择典型垃圾焚烧电厂烟气进行现场采样监测,对垃圾焚烧电厂烟气中重金属铅、汞、镉含量进行分析。根据垃圾焚烧电厂相关信息,结合烟气中重金属含量及相关参数,估算江苏省垃圾焚烧电厂3种重金属年排放量,其中铅为2 010.50kg/a,汞为9.16kg/a,镉为424.63kg/a。根据垃圾焚烧电厂区域分布状况,引入地学模型,对垃圾焚烧电厂重金属区域分布特征进行了分析,结果显示江苏省东部明显高于西部,苏南高于苏北地区,其中苏南地区重金属排放量最大,铅、汞、镉分别占到垃圾焚烧排放总量的48%、51%、60%。通过重金属地学分析和数据统计,确定了江苏省垃圾焚烧重金属排放重点防控区域为苏南地区。     

医疗垃圾焚烧飞灰重金属形态分析

利用原子吸收光谱仪分别对医疗垃圾焚烧飞灰重金属含量和重金属形态及其随颗粒度分布特性进行了分析,结果表明,飞灰中Cd、Zn、Pb等的浸出浓度远超标与这些重金属的可交换态和碳酸盐态含量较高有关;飞灰颗粒度主要在96 μm以下,96～150 μm的颗粒中Cd、Pb含量最高,且Zn、Cd的形态以可交换态为主.     

城市生活垃圾焚烧处理过程中重金属迁移规律研究

通过采集厦门2个垃圾焚烧发电厂进厂垃圾、渗滤液、飞灰、炉渣和烟气样品,分析垃圾组成成分及各组分的重金属含量,结果表明,垃圾中以厨余、橡塑类和纸类为主,共占到垃圾干基的78．08％,重金属含量大小次序为Zn〉Cu〉Pb〉Cr〉Ni〉Cd〉Hg;垃圾渗滤液中除Zn外,其他金属的含量都较低,一厂渗滤液中重金属Ni、Zn迁移量较大,分别达到24．46％和8．52％。二厂渗滤液中重金属的迁移有相同的趋势,但含量相对较高。垃圾焚烧后其重金属主要分布在飞灰和废渣中,烟气中的含量非常少,不同金属的含量均有差别,这与金属的性质有很大关系;通过浸出毒性分析,飞灰中重金属酸溶态含量多,容易浸出,属于危险废物。同时,不同烟气处理工艺产生的飞灰的重金属浸出量有很大差别。     

Polycyclic aromatic hydrocarbons in weathered bottom ash from incineration of municipal solid waste

Polycyclic aromatic hydrocarbons (PAHs) were analysed in weathered bottom ash from different municipal solid waste incinerators. The sum of the 16 "USEPA" PAHs was found to vary from 480 to 3590 microg/kg. The amounts of carcinogenic PAHs were between 89 and 438 microg/kg ash. The maximum levels of carcinogenic PAHs exceed the Swedish generic guidelines for sensitive land use. The results showed that the amount of PAHs in fresh and weathered bottom ash are similar, indicating that the PAHs are strongly bound to the ash and only limited amounts are released to the surroundings.     

Thermal removal of PCDD/Fs from medical waste incineration fly ash--effect of temperature and nitrogen flow rate

The fly ash used in this study was collected from a bag filter in a medical waste rotary kiln incineration system, using lime and activated carbon injection followed by their collection as mixed fly ash. Experiments were conducted on fly ash in a quartz tube, heated in a laboratory-scale horizontal tube furnace, in order to study the effect of temperature and nitrogen flow rate on the removal of PCDD/Fs. Results indicated that in this study PCDD/Fs in the fly ash mostly were removed and desorbed very little into the flue gas under thermal treatment especially when the heating temperature was higher than 350 °C, and dechlorination and destruction reactions took important part in the removal of PCDD/Fs. However, in terms of flow rate, when flow rate was higher than 4 cm s⁻¹, destruction efficiency of PCDD/Fs decreased dramatically and the main contributors were P₅CDF, H₆CDF and H₇CDF desorbed to flue gas, the PCDD/Fs in the fly ash decreased with enhanced flow rate.     

Polycyclic aromatic hydrocarbon exhaust emissions from different reformulated diesel fuels and engine operating conditions

The study of light-duty diesel engine exhaust emissions is important due to their impact on atmospheric chemistry and air pollution. In this study, both the gas and the particulate phase of fuel exhaust were analyzed to investigate the effects of diesel reformulation and engine operating parameters. The research was focused on polycyclic aromatic hydrocarbon (PAH) compounds on particulate phase due to their high toxicity. These were analyzed using a gas chromatography–mass spectrometry (GC–MS) methodology.Although PAH profiles changed for diesel fuels with low-sulfur content and different percentages of aromatic hydrocarbons (5–25%), no significant differences for total PAH concentrations were detected. However, rape oil methyl ester biodiesel showed a greater number of PAH compounds, but in lower concentrations (close to 50%) than the reformulated diesel fuels. In addition, four engine operating conditions were evaluated, and the results showed that, during cold start, higher concentrations were observed for high molecular weight PAHs than during idling cycle and that the acceleration cycles provided higher concentrations than the steady-state conditions. Correlations between particulate PAHs and gas phase products were also observed.The emission of PAH compounds from the incomplete combustion of diesel fuel depended greatly on the source of the fuel and the driving patterns.     

湿解焚烧综合处理垃圾技术的原理及应用

详细介绍了湿解焚烧处理生活垃圾技术的原理和其在武汉经济技术开发区的具体应用，并简述了其在一段时间的调试和运行后表现出的优点。为国内未来垃圾气化熔融焚烧技术的推广提供了参考。     

不同城市生活垃圾焚烧技术的综合评价

通过工程的经济性分析、工艺过程的能流分析以及工程的环境影响分析,综合分析了流化床、炉排炉、气化熔融和等离子体气化等不同城市生活垃圾焚烧技术。结果表明:(1)在零补贴的情况下,流化床焚烧技术的工程效益最佳,但从项目投产年算起,其投资回收期也需9年;炉排炉、气化熔融与等离子体气化焚烧技术要达到流化床焚烧技术零补贴情况下的经济效益,分别需补贴约70、140、500元/t。(2)各城市生活垃圾焚烧技术下区域的水体富营养化和全球变暖影响最显著,而人体毒性影响最小。气化熔融焚烧技术和等离子体气化焚烧技术的环境影响比其他两种焚烧技术小一个数量级。(3)考虑污染物排放的环境效益,在现行中国排放标准下,流化床、炉排炉与气化熔融焚烧技术的工程效益都将得到较大提升。随着排放标准的更加严格,流化床焚烧技术的年收益率下降最显著;气化熔融焚烧技术的工程效益相较最优。     

Bromine in waste incineration partitioning and influence on metal volatilisation

INTENTION, GOAL, SCOPE, BACKGROUND: The halogen bromine is far less abundant than chlorine, but it can be found at high concentrations in special materials like flame retarded plastics. The fate and effects of Br in waste incineration are not well understood. It may have similar implications like Cl for the volatilisation of heavy metals and the formation of low volatile organic compounds. Due to its lower oxidation potential, there is a risk of formation of elementary Br2 in the offgas. OBJECTIVE: Co-combustion tests of different types of Br containing plastic waste materials (up to 22%) and MSW in the TAMARA pilot plant for waste incineration were conducted to investigate the Br partitioning and the influence of Br on metal volatilisation. METHODS: The Br inventory of the fuel mix was elevated to approx. 1 wt-%. All input and output mass flows of the furnace have been sampled and the partitioning of Cl, Br, S, and a number of heavy metals, has been calculated on the basis of closed mass balances. RESULTS AND DISCUSSION: Organically-bound Br was typically released to more than 90% into the raw gas. Elementary Br2 was detected at high Br levels. Its presence was always analysed when all SO2 in the raw gas was oxidised to SO3. Br enhances the volatilisation of metals like K, Zn, Cd, Sn, Sb, and Pb out of the fuel bed principally in the same way as Cl. The tests gave strong indication that the promoting influence of the halogens on metal volatilisation is more pronounced than that of the fuel bed temperature. The volatilised metals are condensated on the fly ashes and are discharged along with the filter ashes. CONCLUSIONS: As long as a surplus of SO2 is present in the raw gas no Br2 is formed. Although the halogen induced transfer out of the fuel bed causes high concentrations of volatile metals in the filter ashes, a recovery is not economically feasible for the time being. The volatilisation gives no rise to metal emission problems as long as efficient dedusting is achieved. RECOMMENDATION AND OUTLOOK: If there is a risk of Br2 formation, in wet scrubbing a reducing agent has to be added to the neutral scrubber for efficient abatement. Filter ashes should be disposed of in a way that enables access for recovery in the future. The exact volatilisation characteristics of the various metals have to be studied in future using specifically tailored experiments.     

Dehalogenation potential of municipal waste incineration fly ash

BACKGROUND, AIMS AND SCOPE: It is well known that the fly ash from filters of municipal waste incinerators (MWI-FA) shows dehalogenation properties after heating it to 240-450 degrees C. However, this property is not general, and fly ash samples do not possess dehalogenation ability at all in many cases. Fly ash has a very variable composition, and the state of the fly ash matter therefore plays the decisive role. In the present paper, the function of important components responsible for the dehalogenation activity of MWI-FA is analysed and compared with the model fly ash. METHODS: With the aim of accounting for the dehalogenation activity of MWI-FA, the following studies of hexachlorobenzene (HCB) dechlorination were performed: The role of copper in dehalogenation experiments was evaluated for five types of metallic copper. The gasification of carbon in MWI-FA was studied in the 250-350 degrees C temperature range. Five different kinds of carbon were used, combined with conventional Cu(o) and activated nanosize copper powder. The dechlorination experiments were also carried out with Cu(II) compounds such as CuO, Cu(OH)2, CuCl2 and CuSO4. The results were discussed from the standpoint of thermodynamics of potential reactions. Based on these results, the model of fly ash was proposed, containing silica gel, metallic copper and carbon. The dechlorination ability of MWI-FA and the model fly ash are compared under oxygen-deficient atmosphere. CONCLUSIONS: The results show that, under given experimental conditions, copper acts in the dechlorination as a stoichiometric agent rather than as a catalyst. The increased surface activity of copper enhances its dechlorination activity. It was found further that the presence of copper leads to a decrease in the temperature of carbon gasification. The cyclic valence change from Cu(o) to Cu+ or Cu2+ is a prerequisite for the dehalogenation to take place. RECOMMENDATION AND OUTLOOK: Thermodynamic analysis of the dechlorination effect, as well as the comparison of dechlorination pathways on MWI-FA and model fly ash, can provide a deeper understanding of the studied reaction.     

城市垃圾焚烧渗沥液中Ca2＋对厌氧EGSB处理效果的影响

研究了城市生活垃圾焚烧厂渗沥液中Ca2＋对厌氧颗粒污泥膨胀床反应器（EGSB）处理效果的影响,并采用静态实验方法考察了Ca2＋对厌氧颗粒污泥产甲烷活性的影响。实验结果表明,进水COD为17000mg／L的条件下,当Ca2＋浓度低于6000mg／L时,EGSB对COD去除率达93％以上;当Ca2＋浓度高于6000mg／L时,COD去除率随运行时间明显下降,并在污泥中形成大量沉淀。静态实验结果表明,废水中低浓度Ca2＋促进了厌氧颗粒污泥的产甲烷活性,但高浓度Ca2＋明显抑制了其产甲烷活性,这是导致高Ca2＋浓度条件下EGSB对COD去除率降低的主要原因。研究表明,颗粒污泥产甲烷活性恢复程度随Ca2＋浓度增加而减弱。     

Curbing dioxin emissions from municipal solid waste incineration in China: Re-thinking about management policies and practices

As one of the countries with large amounts of dioxin releases, the control of dioxins is a major challenge for China. Municipal solid waste (MSW) incineration should be considered a high priority source of dioxin emissions because it is playing an increasingly more important role in waste management. MSW incineration in China has much higher emission rates of dioxins than in the developed countries, partially resulting from the gaps in the technologies of incineration and flue gas cleaning. Moreover, the current management policies and practices also contribute significantly to the problem. We recommend lowering dioxin emission standard, strengthening fly ash management, and improving regulation enforcement to reduce dioxin releases into the environment from MSW incineration. We also propose that alternative strategies should be considered on dioxin control and call for an expansion of economic instruments in waste management to reduce waste generation and thus the need for incineration.     

Polycyclic aromatic hydrocarbons in cigarette sidestream smoke particulates from a Taiwanese brand and their carcinogenic relevance

Polycyclic aromatic hydrocarbons (PAHs) adsorbed on cigarette sidestream smoke particulates (CSSPs) have been regarded as important contributors to lung carcinogenesis in never smokers. However, limited information is available on PAH levels in cigarette sidestream smoke. Here we determine the concentrations of 22 PAHs, including 16 US EPA priority PAHs, in CSSPs generated from a high market-share domestic brand in Taiwan. Five of the 22 PAHs are undetectable. The remaining 17 PAHs constitute about 0.022% of the total mass of CSSPs. Near one fifth of the PAH mass come from IARC group 1 and group 2 carcinogens. Carcinogenic potency is equivalent to 144 ng benzo[a]pyrene per cigarette converted according to potency equivalency factors (PEFs). The CSSP condensate could activate AhR activity and induce AhR target gene expression. High concentrations of CSSPs also exhibited AhR-independent cytotoxicity. However, mixing the 17 PAHs as the composition in the CSSP condensate could not reconstitute either capacity. Since AhR activation and cytotoxicity are important mechanisms underlying carcinogenic potency, the results suggest that other component compounds play a more active role in carcinogenesis. The approach of individual PAH profiling plus PEF conversion commonly used in risk assessment is likely to underestimate the risk caused by environmental cigarette smoke exposure.     

PCDD/F formation from oxy-PAH precursors in waste incinerator flyash

The yield of PCDD/F in relation to the presence of oxygenated PAH in model waste incinerator flyash has been investigated in a fixed bed laboratory scale reactor. Experiments were undertaken by thermal treatment of the model flyash at 250 and 350 °C under a simulated flue gas stream for 2 h. After reaction, the PCDD/F content of the reacted flyash and the PCDD/F released into the exhaust gas, and subsequently trapped by XAD-II resin in a down-stream condensation system were analyzed. The PAHs investigated were, dibenzofuran and benzo[b]naphtho[2,3-d]furan and were spiked onto the model flyash as reactant precursors for PCDD/F formation. The results showed significant formation of furans from both of the PAH investigated, however except from some highly chlorinated dioxin congeners, the formation of dioxins was not so common. Benzonaphthofuran was significantly more reactive than dibenzofuran in PCDD/F formation, in spite of the fact that dibenzofuran is structurally more similar to that of PCDD/F. Thus, there was no clear attribution between the chemical structure of PAH used and the formation of PCDD/F. There were considerable differences between the yields of PCDD/F congeners in the gaseous species and those in the reacted flyash under the same operational conditions. The concentration of PCDD/Fs was reduced at the higher reaction temperature of 350 °C; however, the higher temperature resulted in the majority of the PCDD/F formed on the flyash being released into the gas phase.     

Polycyclic aromatic hydrocarbons and their hydroxylated metabolites in fish bile and sediments from coastal waters of Colombia

Sediments and fish bile collected from the Atlantic coastal waters of Colombia were analyzed for 16 parent polycyclic aromatic hydrocarbons (PAHs), and 23 hydroxylated PAHs (OH-PAHs), respectively. Sediments contained overall mean SigmaPAH concentrations of 2090, 234 and 170 ng/g, dry wt, for Cartagena Bay, Caimanera Marsh, and Totumo Marsh, respectively. The mean concentration of the summed OH-PAHs in fish bile was 1250, 180 and 64.1 ng/g bile wt for Cartagena Bay, Caimanera Marsh, and Totumo Marsh, respectively. The results suggest that Cartagena Bay is heavily polluted by PAHs, and that exposure to high concentrations of PAHs together with other factors could contribute to the decreased health of fish living in this ecosystem. This is one of the first studies to describe the analysis of 23 individual OH-PAHs in fish bile, using authentic standards.     

Memory effect on the dioxin emissions from municipal waste incinerator in Taiwan

Evaluation of the dioxin removal efficiency of the air pollution control device (APCD) at an existing municipal waste incinerator (MWI) located in Taiwan is conducted via stack sampling and analysis. The MWI investigated is equipped with cyclones, dry lime scrubbing systems and fabric filters as APCDs. Results indicate that the patterns of dioxin isomers at APCDs' inlet and stack are similar. During the first year of carbon injection, the concentrations of emitted dioxin decreased greatly. The dioxin removal efficiency increased from 26.9% to 96.6% after injecting 115 kg/day activated carbon (AC). At the second year, the dioxin removal efficiency reaches 98.7% after injecting the same rate of AC continuously. The lower efficiency achieved with activated carbon injection (ACI) during the first year can be attributed to the memory effect, i.e. the dioxin or precursor desorbs slowly to the flue gas and increases the dioxin concentration at stack, resulting in a lower dioxin removal efficiency than expected.     

电子垃圾焚烧排放的二噁英对周围大气环境的影响

为了研究电子垃圾焚烧产生的二噁英对周围环境的影响,同时在E1和E2采样点分别采集9个大气样品.E1周围分布大量的电子垃圾焚烧点,E2则位于E1南9 km处,周围无其他明显的二噁英排放源.所采样品用同位素稀释法进行分析测定,结果表明,E1和E2大气样品中二噁英的平均质量浓度分别为127.37、22.37 pg/m3,平均毒性当量浓度分别为8.777、1.305 pg I-TEQ/m3.八氯代二苯并呋喃(OCDF)、八氯代二苯并二噁英(OCDD)、七氯代二苯并呋喃(1,2,3,4,6,7,8-HpCDF)和七氯代二苯并二噁英(1,2,3,4,6,7,8-HpCDD)对2,3,7,8位氯代的二噁英的总浓度贡献较大,而五氯代二苯并呋喃(2,3,4,7,8-PeCDF)则对总毒性当量浓度贡献最大,其贡献率超过40%.在E1和E2两个采样点,二噁英在气相中的比例均随着氯原子取代数的增加而降低.两采样点相似的二噁英分布模式和气固分配,说明E2大气中二噁英主要来自于E1电子垃圾焚烧产生的二噁英.     

The effect of oils on PAH, PCDD, PCDF, and PCB emissions from a spark engine fueled with leaded gasoline

The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 microg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.