Dechlorination/hydrogenation and destruction reactions of PCDDs in OCDD-added fly ash heated under vacuum

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.     

Adsorption of PCDD/F on MWI fly ash

The removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) from waste incinerator off-gas is a costly task, because a considerable part of the PCDD/F may exist in the gas phase (often 50-100% around 200 degrees C). The volatile fraction passes the particle filter and the subsequent gas cleaning equipment, so that an additional unit is needed to remove the gaseous PCDD/F from the flue gas. Moreover, dioxins and furans can accumulate in some parts of the equipment in a way that they can act as a latent source. In this work, we investigate the possibility to adsorb the PCDD/F at the fly ash particles and to remove them during the filtration. The gas/particle partitioning of the PCDD/F depends on the temperature, the vapor pressure, the particle size, the particle number density and on the physical and chemical properties of the particle surface. These relationships are investigated by model calculations and by pilot scale experiments (500 Nm3/h) which employ one selected hexachlorinated dioxin congener. At room temperature, approx. 90% of the HxCDD are found in the particulate phase, while at 135 degrees C that portion is only 10%. This means that at ambient temperatures, the gas/particle partitioning of the dioxin corresponds well to the sublimation equilibrium. At higher temperatures, it is much different from the sublimation equilibrium and the apparent adsorption enthalpy is smaller than the enthalpy of sublimation. This observation is in agreement with literature data. From the above experiments and from similar literature data, the efficiency of fly ash particles as a sink for PCDD/F can be evaluated. The data suggest that the adsorption rate is not the limiting factor for the transfer into the particulate phase. The important factors appear to be the chemical composition of the fly ash and the temperature.     

PCDDs/DFs emissions from crematories in Japan

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.     

Congener-specific intake fractions for PCDDs/DFs and Co-PCBs: modeling and validation

Intake fractions (iFs) for emissions to air, water, and soil for 17 PCDDs/DFs and 12 Co-PCBs were calculated with a level III multimedia model and a food-chain exposure model in succession. The two integrated models were tested by comparing the predicted and measured concentrations in the environment and by comparing intakes through food. Measurement-based iFs were also calculated and compared with the model-based iFs. The air concentrations predicted by the fate model were close to the median of the observed concentrations, whereas the predicted soil and water concentrations were one-third to one-tenth the observed concentrations. This difference was large in case of PCDDs and Co-PCBs, which was explained by the past pollution such as commercial PCB products and PCDD impurities in chloronitrofen (CNP) and pentachlorophenol (PCP). For fish, the predicted and observed exposures agreed well each other. For meat and milk, the predicted exposures were about 10 times the observed exposures for PCDDs/DFs, whereas the predicted and observed values agreed well for Co-PCBs. When the model was modified to consider feeding of fish meal to livestock and geographic bias in feed-grass production, the predicted congener profile was comparable to the measured profile. The comparison also suggested that chickens should be modeled separately from other terrestrial livestock. The model-based iFs for air emission of OCDD and 2378-TCDD were 0.001% and 0.1%, respectively. The iFs of most Co-PCBs were higher than those of PCDDs/DFs. These iF differences suggest the importance of the fate factor in assessing emissions of the 29 congeners.     

粉煤灰对焦化废水总铬去除的影响

以1 mg/L模拟焦化废水为研究对象,采用高锰酸钾氧化-二苯基碳酰二肼分光光度法测定焦化废水中总铬,研究不同条件下粉煤灰对总铬去除率的影响.结果表明:(1)粉煤灰粒径、粉煤灰用量、搅拌时间、pH对总铬去除率都有一定的影响.最佳条件:粉煤灰粒径为150μm,粉煤灰用量为4.00 g/L,搅拌时间为40 min,pH为3.在最佳条件下,总铬去除率可达98.82%.(2)在粉煤灰处理模拟焦化废水的最佳条件下,粉煤灰处理实际焦化废水的总铬去除率达90.00%.(3)粉煤灰处理焦化废水,可以以废治废,而且处理效果好、处理费用低、原料获取方便,在实践中具有可操作性.     

水热条件下碳酰肼分解二噁英的研究

研究了保温温度为245、260℃水热条件下使用碳酰肼分解垃圾焚烧飞灰中二噁英的分解效果.结果表明,在高温水热条件下使用碳酰肼作为添加剂有利于二噁英的分解;在245、260℃下保温1 h,二噁英的分解率分别达到80%和90%以上,但二噁英毒性当量因2,3,7,8-TCDD的再生成减小很少,甚至增大;同时,在水热条件下,垃圾焚烧飞灰中的重金属取得了良好的稳定效果.     

Bio-availability of PCDDs and PCDFs on fly ash after semi-chronic oral ingestion by the rat

Groups of rats (n = 5) were fed a diet containing 2.5% RCl pre-treated fly ash from the electrostatic precipator of a municipal incinerator during 34, 59 and 99 days. Livers were analysed for 2,3,4,7,8-pentachlorodibensofuran and higher chlorinated dibenso(p)dioxins (PCDDs) and dibensofurans (PCDFs). All isomers retained in the liver had a 2,3,7,8-chlorine substitution pattern. Total group dose varied between 0.2 and is μg for each individual retained compound. Retention in the liver was highest for 2,3,4,7,8-PnCDF, being 14% of the dose for the group killod on day 99. The other isomers detected in the livers had a retention generally below 10%. The 2,3,7,8-substituted hexa- and hepta- chlorinated PCDDs and PCDFs were retained in the liver in constant relative concentrations throughout the experiment, which closely approached a linear relationship to the administered dose.     

Dynamics of PCDDs/DFs and coplanar-PCBs in an aquatic food chain of Tokyo Bay

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.     

Formation of dioxins (PCDDs/PCDFs) by dioxin-free fly ash as a catalyst and relation with several chlorine-sources

Simplified thermal formation experiments have been conducted using dioxin-free fly ash as a catalyst with many kinds of combustible samples such as newspaper, kerosene, paraffin, PE (polyethylene), PP (polypropylene) and PVC. Chlorine sources were PVC, NaCl and HCl. The combustion of samples containing chlorine in the absence of dioxin-free fly ash produced dioxins at a low level although HCl was present in the gas stream. On the other hand, the combustion of samples without chlorine with dioxin-free fly ash increased dioxins formation to a level around 10 times higher than that upon heating dioxin-free fly ash alone. This result is considered to be due to the presence of metal chloride in the fly ash and hydrocarbons in the gas stream. The combustion of samples containing either an organic or inorganic chlorine source or using a HCl stream with dioxin-free fly ash increased dioxin level dramatically.     

Removal of PCBs from wastewater using fly ash

Liquids and sludges containing polychlorinated biphenyls (PCBs) can be treated to concentrate the PCBs in a solid residue. The latter can then be handled to destroy the PCBs. A study on sorption kinetics of PCBs on fly ash was conducted in controlled batch systems. TCB and HeCB are removed at 25 degrees C by adsorption on fly ash up to 97% at pH 7, with an adsorbent dose of 5 g/l. An examination of the thermodynamic parameters shows that the adsorption of TCB and HeCB by fly ash is a process occurring spontaneously at ambient conditions. Activation energies for the sorption process ranged between 5.6 and 49.1 kJ/mol. It was observed that the rate at which TCB and HeCB are adsorbed onto fly ash showed a diffusion limitation. The uptake rate of TCB and HeCB increases with increasing initial concentration and gradually tends to a constant value. A decrease in the adsorption of TCB and HeCB was observed when interfering ions and other PCB congeners were present. Changing the pH in the aqueous solution from 2 to 10 had no effect on the adsorption process. Overall, fly ash can be used for an efficient removal of PCBs from several aqueous solutions.     

垃圾焚烧飞灰去除硫化氢气体

生活垃圾焚烧飞灰由于含有铅镉等重金属,是一种危险废物,若处理不当,会造成重金属迁移和污染地下水等环境生态问题.近年来,垃圾焚烧飞灰的污染控制及资源化利用得到国内人广泛的关注.以垃圾焚烧飞灰为吸附材料,对比研究了2种不同性质的垃圾焚烧飞灰、热电厂粉煤灰以及砂土在相同条件下对硫化氢(H2S)的吸附性能.结果表明,垃圾焚烧飞灰的H2S吸附能力优于其他吸附材料.通过分析吸附前后垃圾焚烧飞灰的浸出液毒性,发现吸附前Cd、Pb 2种金属离子浓度超标,H2S吸附后的飞灰浸出液中金属离子浓度均有一定程度的降低.     

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.     

机械力活化固硫灰固化处理生活垃圾焚烧飞灰

为实现城市生活垃圾焚烧飞灰的安全处理,通过机械力化学法活化循环流化床燃煤固硫灰,探讨了球磨样品制备固化体的参数。并采用X射线衍射仪（XRD）和傅里叶变换红外光谱仪（FTIR）手段对垃圾焚烧飞灰中重金属的固化机制进行了研究。结果表明,当垃圾焚烧飞灰掺加比为60%,球磨转速为600 r·min-1,球磨时间为5 h,养护温度60 ℃时的固化体28 d和56 d抗压强度分别达到15.6 MPa和17.9 MPa,采用原子吸收光谱仪（AAS）测得固化体中Zn、Pb、Cu、Cd和Cr重金属浸出量均低于GB 5085.3-2007规定限值。XRD和FTIR表征结果表明,在水化过程中,该混合体系生成了水化硅酸钙（C—S—H）、斜方钙沸石和钙矾石（AFt）等水化产物,并且C—S—H凝胶可通过物理包裹的形式固化垃圾焚烧飞灰中重金属;斜方钙沸石和钙矾石以化学吸附的方式使垃圾焚烧飞灰中的重金属离子达到固化/稳定化效果,实现了垃圾焚烧飞灰中重金属的安全处理。     

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.     

Bioavailability of PCDDs and PCDFs on fly ash after semi-chronic oral ingestion by guinea pig and syrian golden hamster

Groups of guinea pigs and syrian golden hamster (n = 5) were fed 2.5% HCL pre-treated fly ash from the electrostatic precipitator of a municipal incinerator during one, two and three months, respectively, in the diet. The livers were analyzed for tetra-, penta- and hexa-chlorinated dibenzo(p)dioxins (PCDDs) and dibenzofurans (PCDFs).In the livers of the hamsters 2,3,7,8-substituted PCDDs and PCDFs were the major isomers retained. In the livers of the guinea pigs 2,3,7,8 substituted PCDDs and PCDF congeners were retained, but also a number of otherwise substituted PCDFs. These other PCDF congeners included some having a 2,3,6,7 or alternate chlorine substitution pattern. Those congeners retained in the livers were generally below 5% of the group dose. The PCDF congener which had the highest retention in the livers of guinea pig was 1,2,3,7,8-PnCDF, 11.3% after 95 days. In the livers of the hamsters highest retention was found for 2,3,4,7,8-PnCDF, 8.4% after 95 days. For most 2,3,7,8-substituted PCDDs and PCDFs the retention in the livers of the guinea pigs and hamsters was not significantly different during the whole period, which could indicate a bioconcentration approaching a linear relationship to the administered dose. Constant relative concentrations in the livers were found for the 2,3,7,8- substituted penta- and hexa-chlorinated PCDDs and PCDFs in both species during the three time periods.     

Removal of arsenic species from water by batch and column operations on bagasse fly ash

Bagasse fly ash (BFA, a sugar industrial waste) was used as low-cost adsorbent for the uptake of arsenate and arsenite species from water. The optimum conditions for the removal of both species of arsenic were as follows: pH 7.0, concentration 50.0 μg/L, contact time 50.0 min, adsorbent dose 3.0 g/L, and temperature 20.0 °C, with 95.0 and 89.5 % removal of arsenate and arsenite, respectively. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to analyze the results. The results of these models indicated single-layer uniform adsorption on heterogeneous surface. Thermodynamic parameters, i.e., ΔG°, ΔH°, and ΔS°, were also calculated. At 20.0 to 30.0 °C, the values of ΔG° lie in the range of ?4,722.75 to ?4,878.82 and ?4,308.80 to ?4,451.73 while the values of ΔH° and ΔS° were ?149.90 and ?121.07, and 15.61 and 14.29 for arsenate and arsenite, respectively, indicating that adsorption is spontaneous and exothermic. Pseudo-first-order kinetics was followed. In column experiments, the adsorption decreased as the flow rate increased with the maximum removal of 98.9 and 95.6 % for arsenate and arsenite, respectively. The bed depth service time and Yoon and Nelson models were used to analyze the experimental data. The adsorption capacity (N _o) of BFA on column was 3.65 and 2.98 mg/cm³ for arsenate and arsenite, respectively. The developed system for the removal of arsenate and arsenite species is economic, rapid, and capable of working under natural conditions. It may be used for the removal of arsenic species from any contaminated water resources.     

粉煤灰复合氧化钙去除铬渣渗滤液中的总铬

粉煤灰虽然具有较大的比表面积,但单独做为处理剂处理含铬废水,效果并不理想,具有吸附容量小、溶解损失大、且有毒性浸出等特点.为了解决粉煤灰以上缺陷,提出氧化钙复合粉煤灰去除铬渣渗滤液中总铬的技术,研究表明,在室温25℃条件下,总铬初始浓度在0.30~80.00 mg/L范围内,选择粉煤灰与CaO配比为1:1时,以150 r/min转速充分振荡24 h,总铬去除率均能达到90%以上.通过空白对照实验研究表明,粉煤灰复合CaO使用,对总铬的去除远优于单独使用粉煤灰或CaO做为吸附剂的处理效果.利用SEM,XRD,红外光谱分析3种材料表征方法,对粉煤灰原料、CaO-粉煤灰处理后残渣等进行分析,结果表明,在水介质条件下,粉煤灰与CaO能生成晶体矿物.当溶液中有铬存在时,晶体矿物在形成的过程中能将铬裹入其结构中.通过浸出实验表明,此晶体矿物对铬具有很好的固定作用.     

Some pharmacokinetic aspects of PCDDs and PCDFs in mammals after administration of a fly ash extract from a municipal incinerator

Fly ash extracts were fed to male hamster (single dose), male rat (single dose and multiple dose), pregnant and lactating female rat (multiple dose). The retention of four isomers, 2,3,7,8-TCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PnCDD and 2,3,4,7,8-PnCDF, was studied in the liver of the adults, foetuses and liver of the sucklings.

Liver retention was structure dependent and different for both species. Transportation of the isomers via the mother milk was 50–100 times more effective than via the placenta.

After a single intravenous dose of fly ash extract to male rats the elimination of these four isomers was studied in the liver, during a period of 10 days. Elimination rates for 2,3,7,8-TCDD, 1,2,3,7,8-PnCDD and 2,3,4,7,8-PnCDF were in the same range. Pharmacokinetic calculations were done on both tetra congeners, to obtain information about the validity of the published K_e values in the multiple dose experiments with male rats.

For 2,3,7,8-TCDF the K_e value was applicable, but for 2,3,7,8-TCDD the validity of the K_e could not be determined.     

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.     

氧化镁烟气脱硫废渣-硫酸镁废水-高钙粉煤灰脱氮除磷

在分析高钙粉煤灰（HCFA）对模拟废水脱氮除磷特性的基础上,先后采用氧化镁烟气脱硫废渣（MFGDR）、烟气脱硫（硫酸镁）废水和HCFA综合处理酸洗磷化废水和垃圾渗滤液。当酸洗磷化废水和垃圾渗滤液混合废水的NH3-N浓度为1 135 mg·L-1、PO43--P浓度为2 766 mg·L-1时,通过调整氮磷比,经过吸附、化学沉淀反应等,将污染物吸附、转化为磷酸铵镁等,并进行固液分离,NH3-N和PO43-P的去除率分别可达到98%和99%,废水经处理可达到排放标准。不仅同步解决了热电固废、硫酸镁废水、酸洗磷化废水以及垃圾渗滤液的处理处置问题,还以废治废,降低了药剂成本,具有良好的应用前景。