Dioxins and their fingerprint in size-classified fly ash fractions from municipal solid waste incinerators in China—Mechanical grate and fluidized bed units

The distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), in brief dioxins, has seldom been addressed systematically in fly ash from municipal solid waste incinerators (MSWIs). This study shows the amount and fingerprint of PCDD/Fs in fly ash from four different Chinese MSWIs, that is, three mechanical grate units and one circulating fluidized bed unit. In these fly ash samples, dioxins-related parameters (international toxic equivalent quantity, total amount of PCDD/Fs, individual isomer classes, and 17 toxic 2,3,7,8-substituted congeners) all tend to increase with decreasing particle size for mechanical grate incinerators, yet only for the finest fraction for fluidized bed units. Moreover, the fluidized bed incinerator seems superior to grate incineration in controlling dioxins, yet a comparison is hampered by internal differences in the sample, for example, the fluidized bed fly ash has much lower carbon and chlorine contents. In addition, the presence of sulfur from mixing coal as supplemental fuel to the MSW may poison the catalytic steps in dioxins formation and thus suppress the formation of dioxins. With more residual carbon and chlorine in the fly ash, it is easier to form dioxins during cooling. Nevertheless, there is no apparent relation between Fe, Cu, and Zn contents and that of dioxins in fly ash.

Implications This paper is of interest because it presents the amounts and distribution of PCDD/Fs in fly ash samples from some typical waste incineration plants in China, featuring distinct incinerator types, combustion conditions, fuel composition, or residual carbon, chloride, and heavy metal contents in fly ash.     

Dioxins and their fingerprint in size-classified fly ash fractions from municipal solid waste incinerators in China--mechanical grate and fluidized bed units

The distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), in brief dioxins, has seldom been addressed systematically in fly ash from municipal solid waste incinerators (MSWIs). This study shows the amount and fingerprint of PCDD/Fs in fly ash from four different Chinese MSWIs, that is, three mechanical grate units and one circulating fluidized bed unit. In these fly ash samples, dioxins-related parameters (international toxic equivalent quantity, total amount of PCDD/Fs, individual isomer classes, and 17 toxic 2,3,7,8-substituted congeners) all tend to increase with decreasing particle size for mechanical grate incinerators, yet only for the finest fraction for fluidized bed units. Moreover, the fluidized bed incinerator seems superior to grate incineration in controlling dioxins, yet a comparison is hampered by internal differences in the sample, for example, the fluidized bed fly ash has much lower carbon and chlorine contents. In addition, the presence of sulfur from mixing coal as supplemental fuel to the MSW may poison the catalytic steps in dioxins formation and thus suppress the formation of dioxins. With more residual carbon and chlorine in the fly ash, it is easier to form dioxins during cooling. Nevertheless, there is no apparent relation between Fe, Cu, and Zn contents and that of dioxins in fly ash.     

SGA对垃圾焚烧飞灰中重金属的固化性能研究简

根据EPA 1311、HJ/T 299-2007、HJ/T 300-2007和HJ 557-2009等国内外不同标准，研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性，探讨了六硫代胍基甲酸（sixthio guanidine acid，SGA）、二甲基二硫代氨基甲酸盐（sodium dimethyl dithio carbamate，SDD）和Ca（OH）₂浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明，随着浸提液pH的降低，该厂焚烧飞灰中大部分金属元素的浸出量增大，焚烧飞灰浸出液中的Cd、Ni、Pb和Zn浓度分别超过国家危险废物鉴别标准（GB5085.3-2007）规定值的4.75倍、1.47倍、6.72倍和2.20倍，属于危险废弃物，必须进行稳定化处理。当固化剂SGA加入量为0.1 mol/kg时，稳定化后的重金属浸出浓度已经低于危险废物鉴别标准，且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）₂；当固化剂SGA、SDD和Ca（OH）₂加入量为0.5 mol/kg时，稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB 5085.3-2007）中的规定值。与SDD和Ca（OH）₂相比，SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。     

The Relationship between the Quantity of Heavy Metal and PAHs in Fly Ash

ABSTRACT

Heavy metal and polycyclic aromatic hydrocarbons (PAHs) in flue gas have received considerable attention in recent years due to their mutagenic or carcinogenic properties. The present study is carried out to investigate the influence of the quantity of heavy metals on PAHs formation in fly ash.

A fluidized bed incinerator was used in this experiment to obtain fly ash of chemical similarity by incinerating various compositions of waste. The obtained fly ash, both with and without heavy metal, were used to adsorb the PAHs in the flue gas and to investigate the formation of PAHs in fly ash. The results indicate that carbon and heavy metals most greatly influence the formation of PAHs in the fly ash. Carbon is absorptive; heavy metals encourage not only absorption of PAHs but also catalyze PAHs formation.     

油页岩循环流化床锅炉底渣和飞灰中重金属元素浸出毒性研究

为了研究我国桦甸油页岩65 t/h循环流化床锅炉的底渣和飞灰中重金属元素Cr、Cu、Pb和Zn的赋存状态及不同酸度条件下的浸出特性,分别进行了逐级提取实验和分批浸出的淋滤实验。逐级提取实验结果表明,这4种元素在底渣和飞灰中具有基本相当的赋存状态。硫化物结合态和稳定的残渣态是各元素的主要赋存状态,元素的潜在浸出能力大小表现为:PbCrCuZn,飞灰中各元素的潜在浸出能力大于底渣中的。浸出实验结果表明,元素的赋存状态决定了其浸提能力,浸提液的pH值对各元素浸出能力的影响不尽相同,各元素的浸出能力随浸提时间的延长都会趋于平衡,Cr和Pb的浸出浓度都高于地表水和饮用水的国家标准。     

Comparison of 2,4,6-trichlorophenol conversion to PCDD/ PCDF on a MSWI-fly ash and a model fly ash

We performed experiments on two different matrices with 2,4,6-trichlorophenol as precursor to Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD)/F. A municipal solid waste incinerators (MSWI) and a model fly ash were spiked in two different ways. The experiments demonstrated a three times higher formation potential of the trichlorophenol to PCDD on MSWI fly ash compared with the model fly ash used. For both fly ashes the PCDD yield was higher when gaseous trichlorophenol was fed continuously compared to mixing the fly ashes prior to the experiments with the total amount of the precursor. Despite dilution of the fly ashes tenfold with an inactive matrix the conversion of the chlorophenol was very high.     

Analysis of heavy metals in foliage near a modern refuse incinerator

Heavy metals such as cadmium and lead are typically found at high levels in fly ash from refuse incinerators. In two earlier studies it was found that such heavy metals on grass or tree foliage in the vicinity of old refuse incinerators with relatively low stacks and limited or no emission control devices showed a high degree of correlation between diminishing foliar concentration and the logarithm of sampling distance from the incinerator. In the study reported here of the concentration of cadmium and lead on foliage near a modern refuse incinerator with a high stack and efficient emission controls, the foliar concentrations of the metals showed no significant diminution with sampling distance from the incinerator. Factors affecting heavy metal emissions from refuse incinerators and contamination of nearby areas are discussed.     

SGA对垃圾焚烧飞灰中重金属的固化性能研究

根据EPA1311、HJ／T299—2007、HJ／T300—2007和HJ557—2009等国内外不同标准，研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性，探讨了六硫代胍基甲酸（sixthioguanidineacid，SGA）、二甲基二硫代氨基甲酸盐（sodiumdimethyldithiocarbamate，SDD）和Ca（OH）2浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明，随着浸提液pH的降低，该厂焚烧飞灰中大部分金属元素的浸出量增大，焚烧飞灰浸出液中的cd、Ni、Ph和zn浓度分别超过国家危险废物鉴别标准（GB5085．3—2007）规定值的4．75倍、1．47倍、6．72倍和2．20倍，属于危险废弃物，必须进行稳定化处理。当固化剂SGA加入量为0．1mol／kg时，稳定化后的重金属浸出浓度已经低于危险废物鉴别标准，且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）2；当固化剂SGA、SDD和Ca（OH）2加入量为0．5mol／kg时，稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB5085．3-2007）中的规定值。与SDD和Ca（OH）：相比，SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。     

Fate of antimony in municipal solid waste incineration

The average antimony concentration in municipal solid waste is estimated to be about 10-60 ppm. Thermodynamical models predict a volatile behavior for antimony compounds, yet literature mass balances show that about 50% of the antimony input remains in the grate ashes. This fact can be explained by the formation of thermally stable antimonates in the fuel bed due to interactions with alkali or earth-alkali metals. Thermogravimetric experiments revealed an increased thermal stability for antimony oxide in presence of oxygen and calcium oxide. Spiking experiments on the test incinerator TAMARA showed that chlorination processes have a strong effect on antimony volatilization whereas high fuel-bed temperatures and addition of antimony oxide only have a moderate effect. In the grate ashes, antimony shows a pH-depending leaching property, which is typical for anionic species. This fact supports the thesis that antimony is present in the grate ashes in an anionic speciation.     

垃圾焚烧飞灰磷酸洗涤对重金属的固定效应研究

重金属的固定是垃圾焚烧飞灰资源化技术的核心问题.通过系统试验,研究了垃圾焚烧飞灰磷酸洗涤对重金属溶出、后续烧结过程中重金属挥发,以及重金属化学形态变迁的影响.试验结果表明,磷酸洗涤在有效洗脱飞灰中氯盐的情况下,能够显著减少洗涤过程中重金属的溶出,抑制烧结过程中重金属的挥发,从而避免了飞灰处理过程的二次污染;同时,磷酸洗涤使飞灰中的重金属在烧结前后均向更为稳定的化学形态转化,烧结产物中重金属主要以残留态存在,从而提高了烧结产物资源化利用的长期环境安全性.     

Extraction of heavy metals from MSW incinerator fly ash using saponins

An extraction process with saponins was evaluated for removing heavy metals from MSW (municipal solid waste) incinerator fly ashes. Two different fly ashes, A and B, were treated on a laboratory scale with three triterpene-glycoside type of saponins, M, Q, and T, in the pH range 4-9. The results were compared with those of the HCI and EDTA treatment. The treatment with saponins extracted 20-45% of Cr from the fly ashes. Saponins were also effective in extracting Cu from fly ash A attaining 50-60% extraction. Saponin T extracted 100% of Pb from fly ash A at pH around 4. The extraction of Zn with the saponin treatment was similar to that of the HCl treatment. Further, Cr, Cu, Pb, and Zn were fractionated by sequential extraction to investigate the effect of saponins on each fraction. Extraction behavior of other elements during the saponin treatment was also studied. The leaching test on the residues received after the saponin treatment showed that the fly ashes were successfully detoxified to meet the landfilling guideline.     

Screening of heavy metal containing waste types for use as raw material in Arctic clay-based bricks

In the vulnerable Arctic environment, the impact of especially hazardous wastes can have severe consequences and the reduction and safe handling of these waste types are therefore an important issue. In this study, two groups of heavy metal containing particulate waste materials, municipal solid waste incineration (MSWI) fly and bottom ashes and mine tailings (i.e., residues from the mineral resource industry) from Greenland were screened in order to determine their suitability as secondary resources in clay-based brick production. Small clay discs, containing 20 or 40% of the different particulate waste materials, were fired and material properties and heavy metal leaching tests were conducted before and after firing. Remediation techniques (washing in distilled water and electrodialytical treatment) applied to the fly ash reduced leaching before firing. The mine tailings and bottom ash brick discs obtained satisfactory densities (1669–2007 kg/m³) and open porosities (27.9–39.9%). In contrast, the fly ash brick discs had low densities (1313–1578 kg/m³) and high open porosities (42.1–51. %). However, leaching tests on crushed brick discs revealed that heavy metals generally became more available after firing for all the investigated materials and that further optimisation is therefore necessary prior to incorporation in bricks.     

垃圾焚烧飞灰浸出特性及固化试验的研究

垃圾焚烧飞灰残留有重金属元素和二恶英等物质而被认为是危险废物,必须对之进行稳定化处理.通过试验研究分析了国内首家自主开发成功的广东省东莞市某回转窑垃圾焚烧发电厂垃圾焚烧飞灰的化学成分及矿物组成,研究了飞灰的浸出毒性,考察了水泥固化焚烧飞灰的效果,并与熔融/玻璃固化进行了比较.研究表明,该焚烧飞灰中重金属Cd的浸出毒性严重超标,并且随pH值的减小而增大,水泥固化效果随龄期的增大而更加显著.熔融/玻璃固化的效果优于水泥固化,但其经济性有待提高.     

水泥对垃圾焚烧飞灰的固化处理试验研究

对垃圾焚烧飞灰的化学成分、重金属物质的含量及浸出浓度进行测试分析.结果表明,飞灰中Pb和Cr等重金属物质浸出量超过浸出毒性标准,因而被认为是危险废物,必须进行固化处理.还考察了水泥对焚烧飞灰中重金属物质固化的效果,研究表明当飞灰掺量适当时,重金属物质的固化效果良好.重金属物质通过物理固封、替代,沉淀反应和吸附等形式可固化进水泥水化产物结构中.     

Dechlorination and destruction of PCDDs/PCDFs in fly ashes from municipal solid waste incinerators by low temperature thermal treatment

Dechlorination and destruction characteristics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in fly ashes from commercial-scale municipal solid waste incinerators by low temperature thermal treatment using a laboratory-scale heating system were investigated. Experiments were carried out in reducing atmosphere at temperatures of 300 degrees C, 450 degrees C and 600 degrees C respectively, for the treatment time of 1h and 3h. Concentrations of PCDDs/PCDFs in raw fly ashes ranged from 35.5 to 107.3 microg kg(-1) (1.5-3.4 microg TEQ kg(-1)) and treated fly ashes ranged from 0.34 to 45.3 microg kg(-1) (0.012-1.63 microg TEQ kg(-1)). Concentrations of PCDDs/PCDFs in fly ashes treated at the different temperatures and times were observed to decrease with increase of treatment temperature and time by dechlorination or destruction. The distribution of octa- and hepta-chlorinated congeners were decreased and tetra-, penta- and hexa-chlorinated congeners were increased at 300 degrees C and 450 degrees C, but the distribution of octa- and hepta-chlorinated congeners were increased and tetra-, penta- and hexa-chlorinated congeners were again decreased at 600 degrees C. Total destruction efficiencies of PCDDs/PCDFs in fly ashes showed above 95% at the treatment temperature of 450 degrees C for 3h. However, removal efficiency of each congener in fly ashes varied, especially, 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDD in fly ash A increased. And the dechlorination and destruction characteristics of PCDDs/PCDFs in fly ash A and B was different due to difference in contents of Ca-compounds and metal oxides such as CuO and PbO in fly ashes.     

Immobilization and volume reduction of heavy metals in municipal solid waste fly ash using nano-size calcium and iron-dispersed reagent

This study was conducted to examine the synthesis and application of novel nano-size calcium/iron-based composite material as an immobilizing and separation treatment of the heavy metals in fly ash from municipal solid waste incineration. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash). Heavy metals in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized, respectively. Additionally, scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDS) observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO₄-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO₄] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. These results appear to be extremely promising. The addition of a nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals.

Implications: After grinding with nano-Fe/Ca/CaO and nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash), whereas heavy metals either in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized. These results appear to be very promising, and the addition of nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique may be considered potentially applicable for the remediation and volume reduction of contaminated fly ash by heavy metals.     

Dechlorination and destruction of PCDD,PCDF and PCB on selected fly ash from municipal waste incineration

The potential of fly ash to dechlorinate and destroy PCDD, PCDF and PCB was tested under oxygen deficient conditions in the laboratory. Specifically, two types of fly ash were compared, originating either from a fluidized bed incinerator using Ca(OH)₂ spray (FA1), or a stoker incinerator without Ca(OH)₂ impact (FA2).

Results from the present study indicate that on FA2 type fly ash, the degradation processes of OCDD, OCDF and D₁₀CB occurred primarily via dechlorination/hydrogenation up to temperature settings of 340 °C. In contrast, FA1 type fly ash was found to effect both dechlorination and destruction of these compounds already at temperature settings of 260 °C.

The dechlorination velocity of PCDD and PCDF did not differ significantly. However, the first dechlorination step of OCDF in the 1,9-position occurred faster compared to the first dechlorination step of OCDD.

The isomer pattern resulting from the dechlorination processes was quite similar on both FA1 and FA2, indicating that differences in alkalinity or elemental composition of the two types of fly ashes do not have a significant influence on the position of dechlorination. PCDD and PCDF dechlorination of the 2,3,7,8-positions was not favoured over dechlorination of the 1,4,6,9-positions on either type of fly ash. In contrast, dechlorination of PCB occurred predominantly on the toxicological relevant 3- and 4-positions.

The dechlorination/destruction processes were completed on both types of fly ash at 380 °C within one hour, which correlates well with results obtained from actual plant operation practices.     

Cytotoxicity of municipal solid waste incinerator ash wastes toward mammalian kidney cell lines

In this study, three municipal solid waste incinerator (MSWI) ash wastes-bottom ash, scrubber residue, and baghouse ash-were extracted using a toxicity characteristic leaching procedure (TCLP) extractant. These so-called final TCLP extracts were applied to African green monkey kidney cells (Vero), baby hamster kidney cells (BHK-21), and pig kidney cells (PK-15), multi-well absorption reader analysis was performed to test how the cytotoxicity of the incineration ashes would affect the digestive systems of animals. Ion-coupled plasma analyses indicated that the baghouse ash extract possessed the highest pH and heavy metal concentration, its cytotoxicity was also the highest. In contrast, the bottom ash and the scrubber residue exhibited very low cytotoxicities. The cytotoxicities of mixtures of baghouse ash and scrubber residue toward the three tested cell lines increased as the relative ratio of the baghouse ash increased, especially for the Vero cells. The slight cytotoxicity of the scrubber residue arose mainly from the presence of Cr species, whereas the high cytotoxicity of the baghouse ash resulted from its high content of heavy metals and alkali ions. In addition, it appears that the dissolved total organic carbon content of these ash wastes can reduce the cytotoxicity of ash wastes that collect in animal cells.     

Arrested municipal solid waste incinerator fly ash as a source of heavy metals to the UK environment

Arrested fly ash samples from most currently operating municipal solid waste (MSW) incinerators in the UK have been analysed for a range of elements. Some of the more important heavy metals ranged in concentration as follows: Cd, 21-4646 (median = 271) mg kg(-1); Cu, 296-1307 (642) mg kg(-1); Cr, 44-1328 (574) mg kg(-1); Ni, 45-2204 (74) mg kg(-1); Pb, 447-9704 (4337) mg kg(-1); and Zn, 2285-13,500 (9232) mg kg(-1). These concentrations represent considerable enrichments relative to median UK soil concentrations. Enrichment ratios (defined as median fly ash: median UK soil) were as follows: Mn 1.6; Co 2.6; Ni 3.3; Ba 11; Sr 11; Cr 15; Cu 35; Pb 108; Zn 113; Cd 387. It is estimated that MSW incinerator ash contributes c. 15 t Cd and 241 t Pb to UK landfill sites per annum. These figures compare with previous studies by Hutton & Symon (Hutton, M. & Symon, C. (1986). The quantities of cadmium, lead, mercury and arsenic entering the UK environment from human activities. Sci. Total Environ., 57, 129-50.) which estimated that annual inputs to UK landfills from coal fly ash are c. 60 t Cd and 1270 t Pb. However, it is argued that metals associated with MSW ashes are potentially of greater environmental significance than in coal ashes, because they are much more available and present at much higher concentrations.     

Trace metal emissions from co-combustion of refuse derived and packaging derived fuels in a circulating fluidized bed boiler

Energy recovery from refuse derived fuels (RDF) and packaging derived fuels (PDF) is one option in integrated waste management. Nine RDF and PDF co-combustion tests with peat and coal in a circulating fluidized bed boiler were carried out in this work. Heavy metal emissions in flue gas and fly ash were measured. Multivariate data analyses were used to find out the most important parameters affecting metal emissions in the flue gas.

The results showed that total heavy metal emissions were low. Although RDF and PDF had more heavy metals than peat and coal, the multivariate data analysis showed that an increase of the RDF or PDF share in the fuel mixture up to 20% did not correlate directly with the metal emissions in the flue gas. Distribution of Cd, Cu, Zn and Sn between flue gas and fly ash correlated with each other. Injection of limestone to bind sulphur and chlorine did not have a significant effect on heavy metal emissions in the flue gas. Heavy metals concentrated on the fly ash, but all fly ashes passed the EPA-TCLP tests.