Bioremediation of PCDD/Fs-contaminated municipal solid waste incinerator fly ash by a potent microbial biocatalyst

Removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from fly ash poses a serious problem. In the study presented here, we used a microbial biocatalyst which is a mixture of 4 bacterial and 5 fungal dioxin-degrading strains. The ability of this biocatalyst to bioremediate PCDD/Fs from contaminated municipal solid waste incinerator (MSWI) fly ash was examined by solid-state fermentation under laboratory conditions. Treatment of MSWI fly ash with the microbial biocatalyst for 21 days resulted in a 68.7% reduction in total toxic PCDD/Fs. Further analyses revealed that the microbial biocatalyst also removed 66.8% of the 2,3,7,8-substituted congeners from the fly ash. During the treatment period, the presence of the individual strains composing the microbial biocatalyst was monitored by the amplification of strain-specific DNA sequences followed by denaturing gradient gel electrophoresis (DGGE). This analysis showed that all of the bacterial and fungal strains composing this dioxin-degrading microbial mixture maintained under the dioxin treatment conditions. These results demonstrate that this microbial biocatalyst could potentially be used in the bioremediation of PCDD/Fs from contaminated fly ash.     

Characteristic of polychlorinated dibenzo-p-dioxins and dibenzofurans in fly ash from incinerators in china

Fly ash from municipal solid waste (MSW), medical waste (MW) and electrical power plant (EPP) incinerators were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The study showed that the PCDD/F levels in fly ash were EPP < MSW < MW. The homologue profiles of PCDD/Fs in fly ash produced from waste incinerators were similar. However, the homologue profiles of PCDD/Fs in fly ash from electrostatic precipitator (ESP) of electrical power plant were different from that from waste incinerator. The strong correlation was found between the concentration of 2,3,4,7,8-PeCDF and the I-TEQ value of fly ash regardless of the different fly ashes sources.     

二恶英发生源的建立及其性能分析

针对如何在臭氧紫外光-滑动弧系统中建立稳定的二恶英发生源用于降解二恶英的实验系统.该发生源以医疗垃圾飞灰为对象,通过加热飞灰本身和飞灰索提液的方式使其中的二恶英在一段时间内连续挥发.结果表明,290℃时在飞灰发生源系统中,二恶英初始阶段挥发速率极快,后续的挥发速率急剧减小并趋于稳定,总挥发量仅为总量的10%,且难以再提高.相比而言索提液发生源系统挥发出的二恶英更多更稳定,但其挥发量受温度和注射速度的影响较大:当注射速度为1μL.min-1时,在300℃、400℃、500℃三个不同温度段分别为2.78%、7.88%和9.56%;当温度为500℃,注射速度为0.2 mL.min-1时,其挥发率提高到48.7%.研究还发现,注射针头与管壁的残余量是影响挥发效率的两个重要因素,当温度为500℃,载气为1000 mL.min-1,注射速度为0.2 mL.min-1时,连续进样1 h后,两者的残余量分别占注射总量的40.0%和16.7%.     

Evaluation of gas-particle partition of dioxins in flue gas I: evaluation of gasification behavior of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in fly ash by thermal treatment

The gasification behavior of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in fly ash by thermal treatment has been investigated to estimate gas-particle partition in flue gas. The results obtained in thermal experiments under various conditions showed that gasification of PCDD/Fs depends on air flow rate and treatment weight of fly ash as well as treatment temperature. On the other hand, the results obtained in the thermal experiments using dioxin-free fly ash revealed that during thermal treatment, the de novo synthesis, gasification, and decomposition of PCDFs proceeded at different rates. This difference in the reaction rates indicates that thermal treatment time is also a factor in determining the gas-particle partition of PCDD/Fs in fly ash. Therefore, reasonable thermal treatment conditions were established and applied to three ash samples. For all samples, PCDD/Fs started to gasify at 350 degrees C treatment, whereas 53-98% of PCDD/F homologs gasified at 400 degrees C treatment, implying that gaseous PCDD/Fs are dominant in flue gas at temperatures in the range 350-400 degrees C regardless of particle concentration.     

Polychlorinated dibenzo-p-dioxins/dibenzofurans distributions in ash from different units in a municipal solid waste incinerator

This study determined the polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) contents in ash in the super heater (SH), economizer (EC), semi-dryer absorber (SDA), fabric filter (FF), fly ash pit (FAP) and bottom residue (BR) in a municipal solid waste incinerator (MSWI). A high-resolution gas chromatograph/high-resolution mass spectrometer (HRGC/HRMS) was utilized for analyzing 17 PCDD/F species. Experimental results showed that average PCDD/F contents in ash samples from the SH, EC, SDA, FF, FAP and BR were 0.102, 0.788, 0.210, 1.95, 2.04 and 0.0218 ng I-TEQ g(-1), respectively. PCDD/F content was very low in the SH and BR due to high temperatures (around 461 degrees C in the SH and 914 degrees C in combustion chamber). Conversely, total PCDD/F content was significantly high in ash samples from the EC (around 340 degrees C), mainly because the temperature is within the favorable range of 250-400 degrees C for PCDD/F formation due to de nova reformation mechanisms. Although the SDA operated at 245 degrees C, the PCDD/F content decreased very significantly, mainly because the temperature was relatively low and because calcium carbonate was introduced into flue gases to dechlorinate and dilute chlorine-containing species. PCDD/Fs were captured by the active carbon in the FF. Furthermore, the duration that fly ash remained in the FF was longer than that for other incinerator units, and thus causing an increasing trend of PCDD/Fs level downstream (except the SDA). Total PCDD/Fs emission factors (microg tonnes-waste(-1); microg I-TEQ tonnes-waste(-1)) in ash samples from different units were: SH (42.3; 0.846), EC (326; 6.12), SDA (58.1; 1.10), FF (1540; 61.3), FAP (2950; 107) and BR (537; 4.31). Most PCDD/Fs in ash were contributed by the FF (about 56%), and the generation of PCDD/Fs in ash was significant (about 35%) during the transfer process from different units to the FAP. A strong and positive correlation in a logarithmic form existed between PCDD/Fs and chlorine (Cl(-1)) contents in ash. In Taiwan, the government policy for incineration residues advocates their reuse as road sub-bases or secondary building materials provided that total PCDD/Fs content is below the legal limit (1 ng I-TEQ g(-1)). Thus, ash with total PCDD/Fs content below the legal limit, such as that from the SH, EC, SDA and BR, can be collected and transferred to the FAP and reused. Ash with total PCDD/Fs content exceeding the legal limit, such as that from the FF, should be collected separately and be treated properly before being disposal in a landfill.     

Effects of calcium-based sorbents on PCDD/F formation from pentachlorophenol combustion process

Calcium-based sorbents are widely employed to reduce the acidic gases emission from combustion processes, and also have effects on trace organic pollutants formation and emission. Batch experiments were conducted to investigate the effects of calcium-based sorbents on pentachlorophenol (PCP) forming PCDDs/Fs during high temperature combustion processes. The results indicated that highly chlorinated PCDD/F homologues were the predominant dioxin products from PCP thermo decomposition, and only minor increasing of PCDDs happened when Ca/Cl ratio was lower than 1, while a major jump occurred when Ca/Cl ratio increased from 1 to 2. The CaO addition clearly promoted the production of all chlorinated dibenzo-p-dioxins homologue and 4-7DFs homologue. Comparison of total PCDD/F emission and its I-TEQ for three different calcium-based sorbents addition (CaO, CaCO3, basic fly ash) indicated that CaO and fly ash containing CaO had almost the same promotion effects on PCDDs/Fs originated from PCP, while CaCO3 inhibit PCDD/F formation greatly with inhibition efficiency up to 70%. Such effects may be partly proved by the observed clearly different micro-surface structures of their reaction residues. The mechanism of CaO on condensation and dechlorination reactions for PCP forming PCDDs and acid-base interaction were proposed to speculate the promotion effects of CaO, and the reaction precedence was used to speculate the inhibition effects of CaCO3 on PCDDs/Fs originated from PCP. The results of the present paper might be useful for the industrial application of calcium-based sorbents to control PCDD/F emission.     

Removal characteristics of PCDD/Fs by the dual bag filter system of a fly ash treatment plant

In this study, a dual bag filter system was established to decrease the concentration of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in the stack flue gases of a fly ash treatment plant, which retained zinc from the fly ash of electric arc furnaces. Compared to the original single bag filter system with activated carbon injection (ACI) of 40 kg h(-1), the PCDD/F concentrations in the stack flue gas after the plant was equipped with the dual bag filter system dropped enormously from 3.38-7.73 ng I-TEQNm(-3) to 0.03 ng I-TEQNm(-3), and the total PCDD/F I-TEQ removal efficiency increased from 97.6% to 99.3% with ACI of 16 kg h(-1), that is, about 40% of the original AC usage. The AC utilization efficiency (0.560 mg I-TEQ absorbed kg ACI(-1)) of the dual bag filter system (AC: 16 kg h(-1)) was estimated about three times higher than that (0.192 mg I-TEQ absorbed kg ACI(-1)) of single bag filter system with ACI (40 kg h(-1)). The reason is that the particulate phase PCDD/Fs and some gas phase PCDD/Fs (captured by the recycled AC/ash mixture) were removed first by the first bag filter, and the rest of the gas phase PCDD/Fs were able to be adsorbed more completely by the AC/ash mixture due to a lower fly ash load, and then were removed by the second bag filter.     

Evaluation of PCDD/Fs emission from fluidized bed incinerators co-firing MSW with coal in China

The levels and homologue profile of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from stack gas of three typical fluidized bed incinerators co-firing municipal solid waste (MSW) with Chinese coal were measured. The PCDD/Fs emission was in the range of 0.0054-0.1961 ng I-TEQ/N m(3). Comparison of PCDD/Fs detection results by HRGC/HRMS and HRGC/LRMS suggested that it was feasible to detect fly ash with high PCDD/Fs concentration by HRGC/LRMS. Several factors on PCDD/Fs emission were discussed. The primary reason for the lower PCDD/Fs emission was the inhibition mechanism of relatively high sulfur in feeding coal on PCDD/Fs formation. The emission results also showed that there was no directly correlation between PCDD/Fs levels and CO, O(2) and HCl concentration in flue gas. It was estimated that about 0.1034 g I-TEQ was annually emitted to atmosphere from the tested three MSW incinerators (total daily treatment capacity is 800 tonnes MSW).     

Polychlorinated dibenzo-p-dioxins/dibenzofuran mass distribution in both start-up and normal condition in the whole municipal solid waste incinerator

Although many researches focused on the polychlorinated dibenzo-p-dioxins/dibenzofuran (PCDD/F) emissions from stack, in the bottom ash and in the surrounding environment, researches focused on PCDD/F mass distributions in the whole incineration plant have seldom been addressed. This study determined PCDD/F emissions in the whole plant. A high-resolution gas chromatograph/high-resolution mass spectrometer was utilized for analyzing 17 PCDD/F species. Experimental results displayed that PCDD/Fs were formed during fly ash from super heater (SH), economizer (EC), semi-dryer absorber (SDA) and fabric filter (FF) was transferred to fly ash pit. Mass distribution ratios of PCDD/Fs in g I-TEQ (Toxicity Equivalency Quantity) per week from stack, SH, EC, SDA, FF, generation and bottom residue (BR) in start-up operations were 14.6%, 0.1%, 8.3%, 1.0%, 41.7%, 33.4% and 0.9%, respectively. Above results indicated that main PCDD/F source in the MSWI was from fly ash. However, the fly ash is easily controlled and PCDD/F emitted from stack flue gases will be difficult to be handled. Therefore, we should pay more attention on PCDD/F emission from flue gases especially from start-up procedure. Besides, fly ash should be controlled by sodium hypophosphite before being landfilled. MSWI did require further detoxification treatments for the solid residues and flue gases.     

Effect of MSW source-classified collection on the emission of PCDDs/Fs and heavy metals from incineration in China

Municipal solid waste (MSW) source-classified collection represents a change in MSW management in China and other developing countries. Comparative experiments were performed to evaluate the effect of a newly established MSW source-classified collection system on the emission of PCDDs/Fs (polychlorinated dibenzo-p-dioxins and dibenzofurans) and heavy metals (HMs) from a full-scale incinerator in China. As a result of presorting and dewatering, the chlorine level, heavy metal and water content were lower, but heat value was higher in the source-classified MSW (classified MSW) as compared with the conventionally mixed collected MSW (mixed MSW). The generation of PCDDs/Fs in flue gas from the classified MSW incineration was 9.28 ng I-TEQ/Nm(3), only 69.4% of that from the mixed MSW incineration, and the final emission of PCDDs/Fs was only 0.12 ng I-TEQ/Nm(3), although activated carbon injection was reduced by 20%. The level of PCDDs/Fs in fly ash from the bag filter was 0.27 ng I-TEQ/g. These results indicated that the source-classified collection with pretreatment could improve the characteristics of MSW for incineration, and significantly decrease formation of PCDDs/Fs in MSW incineration. Furthermore, distributions of HMs such as Cd, Pb, Cu, Zn, Cr, As, Ni, Hg in bottom ash and fly ash were investigated to assess the need for treatment of residual ash.     

Characterization of dibromopolychlorodibenzo-p-dioxins and dibromopolychlorodibenzofurans in municipal waste incinerator fly ash using gas chromatography/mass spectrometry.

Several fly ash samples from different countries were analyzed for dibromopolychlorodibenzo-p-dioxins and -dibenzofurans (DBPCDD/Fs) using capillary column gas chromatography/high-resolution mass spectrometry. Concentrations of these compounds ranged from low to high parts-per-trillion (pptr) depending on the location where the samples were collected. The mass spectrometer, operated at greater than 10,000 mass resolution in combination with the high resolving power of capillary column GC, permitted characterization of DBPCDD/Fs in municipal waste incinerator fly ash for the first time. The isomer patterns of tetra- through octa-congener groups of DBPCDD/Fs are remarkably similar regardless of where the fly ash originated, indicating common mechanisms of formation of these compounds in the incinerators.     

Evaluation of PCDD/F partitioning between vapor and solid phases in MWI flue gases with temperature variation

Partitioning of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofuran) between vapor and solid phases in flue gas is affected by several factors including temperature variation. In this study, PCDD/F removal efficiencies achieved with activated carbon injection (ACI) and partitioning of vapor/solid phase PCDD/Fs in flue gases with temperature variation in a municipal waste incinerator (MWI) are evaluated via intensive flue gas sampling. Results indicate that most PCDD/Fs in flue gas downstream of the ACI+bag filter (BF) exist in vapor phase (over 90%) while the removal efficiencies of vapor and solid phase PCDD/Fs are 98.5-99.6% and 99.8-99.9%, respectively. The results of flue gas samplings also indicate that there is optimal operating temperature for PCDD/F removal achieved with ACI. Additionally, a pilot-scale adsorption system (PAS) is constructed in this study to evaluate the PCDD/F partitioning affected by temperature. The results of the PAS experimentation indicate that about 55% and 25% vapor phase PCDD/Fs passing through the filter cake (adsorbent) are transferred to solid phase at 150 and 200 degrees C, respectively. As the temperature is increased to 250 degrees C, filter cake (adsorbent) cannot effectively adsorb vapor phase PCDD/Fs and significant PCDD/Fs are formed via de novo synthesis.     

Distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in the landfill site for solidified monoliths of fly ash

One landfill site, which co-treated solidified monoliths of fly ash and bottom ash, was investigated comprehensively to characterize its PCDD/F distribution. The solidified monoliths, soil, banyan leaves, groundwater in the monitoring wells and the treated landfill leachates in this landfill site for solidified monoliths of fly ash were all sampled to clarify their PCDD/F characteristics. Although the PCDD/F leaching concentrations were extremely lower than the Taiwan PCDD/F TCLP regulation of solidified monoliths, the PCDD/F contents in the surface soils of the landfill site are 460 times higher than that of urban soils and the highest value is 2.8 times higher than the Taiwan soil regulation (1000 ngI-TEQkg(-1)). The elevated PCDD/F contents in the soil reveal their potential for causing adverse health risk for humans, including the pathway of resuspension of soil particles and volatilization of PCDD/Fs from soil. The PCDD/F concentrations in the groundwater and the treated landfill leachates of the landfill site for solidified monoliths were both higher than that in the control samples, suggesting its potential to be a PCDD/F source of nearby water environment. Without proper control and management, landfill sites for solidified monoliths of fly ash can seriously hazard the surrounding environment, therefore, are important to consider.     

A novel method to enhance polychlorinated dibenzo-p-dioxins and dibenzofurans removal by adding bio-solution in EAF dust treatment plant

In order to understand the effect of different amounts of powder-activated carbon (PAC) injection and bio-solution (NOE-7F) addition on the removal efficiencies of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a fly ash treatment plant with Waelz rotary kiln process, the PCDD/F concentrations in the stack flue gasses were measured and discussed. In the amount of 20, 40 and 50 kg/h PAC injection, the removal efficiencies of PCDD/Fs in the stack flue gas were 86, 96 and 97%, respectively. While adding more amounts of PAC did enhance the removal efficiencies, the reduction fractions of low chlorinated PCDD/F congeners were much higher than those of highly chlorinated PCDD/F congeners. Particularly, a lower amount of PAC injection (20 kg/h), not only cannot remove highly chlorinated PCDD/Fs, but also the carbon surface of the PAC can act as a precursor for the formation promotion of highly chlorinated PCDD/F congeners. The addition of NOE-7F in the raw materials had the dechlorination effect on the PCDD/F removal and mainly inhibited highly chlorinated PCDD/F formation. The combination of both PAC injection and NOE-7F addition has a high potential for practical application.     

Characteristics and heavy metal leaching of ash generated from incineration of automobile shredder residue

Bottom and fly ash collected from automobile shredder residue (ASR) incinerator have been characterized in terms of particle size, compositions, and heavy metal leaching by the standard TCLP method. Two alternative methods were also examined for the treatment of heavy metals in ASR incinerator ash from the aspect of recycling into construction or lightweight aggregate material. It was remarkable that the concentration of Cu was very high compared to common MSWI bottom and fly ash, which was probably originated from copper wires contained in ASR. As a whole, the results of characterization of ASR fly ash were in good agreement with common MSWI fly ash in terms of particle size, pH, and water-soluble compounds. It was clearly found that heavy metals could be removed thoroughly or partly from ASR fly ash through acid washing with dilute HCl solution so that the remaining fly ash could be landfilled or used as construction material. It was also found that the amount of heavy metal leachability of lightweight aggregate pellet prepared with ASR incineration ash could be significantly decreased so that the application of it to lightweight aggregate would be possible without pre-treatment for the removal of heavy metals.     

Biotoxicity evaluation of fly ash and bottom ash from different municipal solid waste incinerators

Different types of municipal solid waste incinerator (MSWI) fly and bottom ash were extracted by TCLP and PBET procedures. The biotoxicity of the leachate of fly ash and bottom ash was evaluated by Vibrio fischeri light inhibition test. The results indicate the following: (1) The optimal solid/liquid ratio was 1:100 for PBET extraction because it had the highest Pb and Cu extractable mass from MSWI fly ash. (2) The extractable metal mass from both fly ash and bottom ash by PBET procedure was significantly higher than that by TCLP procedure. (3) The metal concentrations of fly ash leachate from a fluidized bed incinerator was lower than that from mass-burning and mass-burning combined with rotary kiln incinerator. (4) The TCLP and PBET leachate from all MSWI fly ash samples showed biotoxicity. Even though bottom ash is regarded as a non-hazardous material, its TCLP and PBET leachate also showed biotoxicity. The pH significantly influenced the biotoxicity of leachate.     

Dioxin levels in fly ash coming from the combustion of bagasse

Levels of dioxins (PCDD/Fs) were determined in fly ash samples collected from a power plant burning bagasse for production of electricity. The concentrations ranged from 2.2 pgWHO-TEQ/g to 190 pg WHO-TEQ/g with samples collected after ESP containing significantly much higher (more than 12 times on average) levels than samples collected before ESP. Our results seem to indicate that both the de novo and the precursor mechanisms are significantly involved in the formation of dioxins the fly ash during combustion of bagasse.     

The behaviour of Al in MSW incinerator fly ash during thermal treatment

Fly ash from municipal solid waste (MSW) incinerators contains leachable metals, including potentially hazardous heavy metals. The metal content of the fly ash can be reduced by thermal treatment, which vaporizes the volatile metal compounds. After heat treatment of fly ash at 1000 degrees C for 3 h, less metal was able to be leached from the thermally treated ash than from the ash without thermal treatment. Al and Cr were the exceptions. These metals were more soluble in the ash that had been thermally treated. This paper focuses on the leaching behaviour of Al only. Both simple and sequential extraction leaching tests showed that the leachable Al for the heat-treated fly ash is about twice that of the untreated fly ash. The sequential test further revealed that (i) the majority of the leachable Al is associated with Fe-Mn oxides in the fly ash, and (ii) most of the unleachable Al resides in the silicate matrices of the heat-treated and untreated fly ash. Pure chemicals, Al(2)O(3), CaO and CaCl(2), simulating the relevant ingredients in the fly ash, were used for studying their reactions at 1000 degrees C. The aluminum compounds were identified by X-ray Diffraction (XRD). Two new chemical phases produced by the thermal treatment were identified; Ca(AlO(2))(2) and 12CaO.7Al(2)O(3). Their formation suggests a mechanism whereby thermal treatment of fly ash would produce more soluble Al.     

Performance Characteristics of Centrifugal Slurry Pump with Multi-Sized Particulate Bottom and Fly Ash Mixtures

The present study reports on the performance characteristics of the centrifugal slurry pump with multi-sized particulate slurry of bottom ash and fly ash mixtures. The performance characteristic of the pump was experimentally evaluated at rotational speed 1450 rpm for bottom ash slurries with and without the addition of fly ash in the concentration range of 10% to 50% (by weight). Addition of fly ash in the bottom ash was varied from 10% to 30% (by weight). The pump total head, overall efficiency, and pump input power at different flow rates were evaluated. The performance characteristics results show that the value of head and the efficiency of the pump depend on the solid concentration. It was also observed that the performance parameter of the pump strongly depends on slurry properties. The addition of fine particles fly ash in the coarser particles of bottom ash slurry, leads to reduce the additional head losses in the pump. The pump performance in terms of head and efficiency improved with addition of fly ash in bottom ash slurry.     

Influence of memory effect caused by aged bag filters on the stack PCDD/F emissions

To our best knowledge, this study is the first research which investigates whether the PCDD/F memory effect could also be caused by bag filters. In this study, the PCDD/F characteristics of the flue gases in front of and behind the bag filters of one municipal solid waste incinerator (MSWI) and two electric arc furnaces (EAFs) were investigated to clarify the memory effect of PCDD/Fs and their influence on emissions. After the bag filters were operated for over four years, the PCDD/F concentrations in the stack flue gases were all higher than those prior to the aged bag filter, rendering a negative PCDD/F removal. This memory effect is because gaseous phase PCDD/Fs are released from the contaminated filters of the aged bag filters. The release of 2,3,7,8-TeCDF, 1,2,3,7,8-PeCDF and 2,3,4,7,8-PeCDF from the contaminated filters of the EAFs increased the PCDD/F concentration and their fractions in the stack flue gases. In contrast, the MSWI exhibited increasing fractions of 1,2,3,4,6,7,8-HpCDD, OCDD after flue gases passed through its aged bag filter. The activated carbon of the MSWI adsorbed more lower chlorinated-substituted PCDD/Fs in the raw flue gases, and the remaining higher chlorinated congeners gradually accumulated on the aged filters, and were released in lower PCDD/F concentration conditions.