Characteristics of PCDD/F content in fly ash discharged from municipal solid waste incinerators

Different from most previous studies with quantity-limited data, this paper presents PCDD/F content characterization in the fly ash discharged from sixteen large-scale commercial MSWIs. From the results with over hundreds of data using periodically sampling and analysis, it was found that the PCDD/F contents in the fly ash were from 9.07 to 46.68 ng/g, d.w., and if based on international toxicity equivalent quantity, they were from 0.78 to 2.86 ng I-TEQ/g, d.w. The higher chlorinated PCDDs likely dominated more than lower chlorinated PCDDs, but this tendency was not for PCDFs. The OCDD had the highest contribution to the total PCDD/F content, but if based on I-TEQ content, 2,3,4,7,8-PeCDF is the PCDD/F congener with the highest toxicity contribution. Moreover, the PCDD/F characteristic index (DCI) is suggested using the representative congener content of 2,3,4,7,8-PeCDF to characterize the fly ash. The DCI is 0.875 ± 7.6% for the fly ash discharged from the MSWI with the APCD assembly of SD, AC and BF. The findings obtained in this work provide overview information on the PCDD/F content characterization in fly ash. They will provide PCDD/F fingerprint information to distinguish from other PCDD/F sources, like steel refinery industry, hazardous waste incinerators, or cement kilns, and thus be applied to fly ash management in the environment.     

Thermal behaviour of ESP ash from municipal solid waste incinerators

Stricter environmental regulations demand safer treatment and disposal of incinerator fly ashes. So far no sound technology or a process is available for a sustainable and ecological treatment of the waste incineration ashes, and only partial treatment is practised for temporary and short-term solutions. New processes and technology need to be developed for comprehensive utilization and detoxification of the municipal solid waste (MSW) incinerator residues. To explore the efficiency of thermal stabilisation and controlled vitrification, the thermal behaviour of electrostatic precipitator (ESP) ash was investigated under controlled conditions. The reaction stages are identified with the initial moisture removal, volatilisation, melting and slag formation. At the temperature higher than 1100 °C, the ESP ashes have a quicker weight loss, and the total weight loss reaches up to 52%, higher than the boiler ash. At 1400 °C a salt layer and a homogeneous glassy slag were formed. The effect of thermal treatment on the leaching characteristics of various elements in the ESP ash was evaluated with the availability-leaching test. The leaching values of the vitrified slag are significantly lowered than that of the original ash.     

Thermal treatment of the fly ash from municipal solid waste incinerator with rotary kiln

Reuse of the fly ash from the municipal solid waste incinerator (MSWI) is a policy of Taiwan EPA. However, the fly ash is often classified as a hazardous waste and cannot be reused directly because the concentrations of heavy metals exceed the TCLP regulations. The main objective of this study is to investigate the continuous sintering behavior of fly ash with a rotary kiln and seek a solution to reduce the concentrations of heavy metal to an acceptable value. The partitions of the heavy metals in the process are also considered. The results of TCLP showed that among the metals of Cr, Cd, Cu and Pb, only the concentrations of Pb in raw fly ash exceeded the regulation. At sintering temperatures of 700, 800 and 900 degrees C, the concentration of Pb decreased in sintering products, however, the concentration of Pb still exceeded the limitation at 700 and 800 degrees C. Additionally, the water-washing was used to pre-treat the fly ash before sintering process. The washing treatment effectively reduced the leaching concentrations of Pb to agree the regulations. Therefore, water-washing followed by a sintering treatment is an available process for detoxifying the fly ash of MSWI.     

Preparation of alinite cement from municipal solid waste incineration fly ash

The feasibility of partially substituting ordinary raw materials with municipal solid waste incineration (MSWI) fly ash in alinite cement production was investigated by X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF) and scanning electron microscopy (SEM). The physical properties and leaching behavior of the produced cement were also evaluated. Experimental results show that good quality clinkers can be obtained by firing the raw mixes, in which the replacement of MSWI fly ash reaches to 30%, at 1200 °C for 2 h. Alinite cements have higher early strengths at all gypsum additions, while the best result having acceptable early and 28-day strengths is obtained at 5% of gypsum addition. Results also show that the leaching toxicity of heavy metals is far lower than that of the regulatory limit at all testing ages. Based on this study, MSWI fly ash is viable as an effective, alternative raw material in alinite cement production.     

Biotoxicity assessment on reusability of municipal solid waste incinerator (MSWI) ash

This study provides a first attempt of dose-response analysis and margin of safety using Escherichia coli DH5alpha, Bacillus subtilis as indicator microorganisms to put forward, in general terms and explanations, the toxicity rankings of various ashes of municipal solid waste incinerator (MSWI) for feasibility in further applications. Since the MSWI ash often contains cations of Si, Ca, Al and Fe, it is frequently considered to be recycled for construction building-materials. Growth inhibition of E. coli DH5alpha occurred at concentrations over 0.156, 0.625 and 0.0195 g/L for bottom ash (BA), cyclone ash (CA), scrubber ash (SA), respectively, suggesting the toxicity ranking of SA>BA>CA. In contrast, except for SA (ca. 0.313 g/L), almost same inhibitory levels of ashes to cell growth were also observed in Bacillus subtilis. Evidently, biotoxicity responses were strongly dependent upon the characteristics of indicator microorganism. Based on DH5alpha, the margins of safety (MOS) were thus 0.195, 1.56 and 6.25 mg/L for SA, BA and CA, respectively. Nearly identical levels of MOS were also suggested by B. subtilis, except for SA (3.13 mg/L). Although MSWI residual ashes qualified EPA's standard test of Toxicity Characteristic Leaching Procedure (TCLP), they might still contain other toxic residues (e.g., chloride ions and/or anions) to cause existing toxicity as indicated in this toxicity study.     

Carbon dioxide sequestration in municipal solid waste incinerator (MSWI) bottom ash

During bottom ash weathering, carbonation under atmospheric conditions induces physico-chemical evolutions leading to the pacification of the material. Fresh bottom ash samples were subjected to an accelerated carbonation using pure CO2. The aim of this work was to quantify the volume of CO2 that could be sequestrated with a view to reduce greenhouse gas emissions and investigate the possibility of upgrading some specific properties of the material with accelerated carbonation. Carbonation was performed by putting 4mm-sieved samples in a CO2 chamber. The CO2 pressure and the humidity of the samples were varied to optimize the reaction parameters. Unsieved material was also tested. Calcite formation resulting from accelerated carbonation was investigated by thermogravimetry and differential scanning calorimetry (TG/DSC) and metal leaching tests were performed. The volume of sequestrated CO2 was on average 12.5L/kg dry matter (DM) for unsieved material and 24 L/kg DM for 4mm-sieved samples. An ash humidity of 15% appeared to give the best results. The reaction was drastically accelerated at high pressure but it did not increase the volume of sequestrated CO2. Accelerated carbonation, like the natural phenomenon, reduces the dangerous nature of the material. It decreases the pH from 11.8 to 8.2 and causes Pb, Cr and Cd leaching to decrease. This process could reduce incinerator CO2 emissions by 0.5-1%.     

Utilization of municipal solid waste incineration (MSWI) fly ash in blended cement Part 1: Processing and characterization of MSWI fly ash

This paper is the first of a series of two articles dealing with the processes applied to MSWI fly ash with a view to reusing it safely in cement-based materials. Part 1 presents two stabilization processes and Part 2 deals with the use of the two treated fly ashes (TFA) in mortars. Two types of binder were used: an Ordinary Portland Cement (OPC) containing more than 95% clinker (CEM I 52.5R) and a binary blend cement composed of 70% ground granulated blast furnace slag and 30% clinker (CEM III-B 42.5N). In this first part, two stabilization processes are presented: the conventional process, called "A", based on the washing, phosphation and calcination of the ash, and a modified process, called "B", intended to eliminate metallic aluminum and sulfate contained in the ash. The physical, chemical and mineralogical characteristics of the two TFA were comparable. The main differences observed were those expected, i.e. TFA-B was free of metallic aluminum and sulfate. The mineralogical characterization of the two TFAs highlighted the presence of large amounts of a calcium aluminosilicate phase taking two forms, a crystalline form (gehlenite) and an amorphous form. Hydration studies on pastes containing mixed TFA and calcium hydroxide showed that this phase reacted with calcium hydroxide to form calcium aluminate hydrates. This formation of hydrates was accompanied by a hardening of the pastes. These results are very encouraging for the reuse of such TFA in cement-based materials because they can be considered as pozzolanic additions and could advantageously replace a part of the cement in cement-based materials. Finally, leaching tests were carried out to evaluate the environmental impact of the two TFAs. The elements which were less efficiently stabilized by process A were zinc, cadmium and antimony but, when the results of the leaching tests were compared with the thresholds of the European landfill directive, TFA-A could nevertheless be accepted at landfills for non-hazardous waste. The modifications of the process led to a significant reduction in the stabilization of chromium, selenium and antimony.     

Extraction of metals from municipal solid waste incinerator fly ash by hydrothermal process

This work examined the extraction properties of metallic elements from municipal incinerator fly ash under hydrothermal conditions. The ash was firstly pre-washed by distilled water, then subjected to hydrothermal treatments. The pre-washing process was effective for Na, K, Ca extraction with extraction percentages of 67%, 76% and 48%, respectively. The optimum contact time was 30 min for the pre-washing process. Five types of acids were tested for the extraction experiments and hydrochloric acid was found to be most effective for metal extraction from the ash. Compared to room condition, hydrothermal treatment accelerated the dissolution of the ash, thus promoted the reaction of acid with hazardous metals such as Cr, Cd, Pb, and furthermore, the consumption speed of acid was slowed down under hydrothermal condition. The acid simultaneously reacted with all the metal in the ash under hydrothermal condition but preferentially reacted with Ca at room condition. The optimum hydrothermal treatment temperature, time and liquid/solid ratio were 150 degrees C, 5h and 10:1 (ml:g), respectively.     

SEM/EDS and XRD characterization of raw and washed MSWI fly ash sintered at different temperatures

The disposal of fly ash generated during municipal solid waste incineration (MSWI) may pose a significant risk to the environment due to the possible leaching of hazardous pollutants, such as toxic metals. Sintering technology attracted more attention than the vitrification process because of its low energy needed. Generally, a preliminary washing treatment of raw fly ash with water was necessary for this sintering technology. This study investigated the composition and morphology of raw fly ash (RFA) and washed fly ash (WFA) at different sintering temperatures, and examined the newly formed minerals during sintering. Toxicity characteristic leaching procedure (TCLP) tests were carried out to investigate the effect of the washing treatment and sintering process on the leaching performance of heavy metals in fly ash. Results showed that, with an increase of sintering temperature more complex aluminosilicates were formed; the incorporation of Mg, Fe and Pb into the aluminosilicates occurred during the sintering process at higher temperatures (800 and 900 degrees C). The washing treatment reduced the leachable concentration of Cd, Pb and Ni, but increased that of Cr. A CaCrO(4) compound was considered as a potential soluble species.     

Melting of municipal solid waste incinerator fly ash by waste-derived thermite reaction

This work describes a novel approach for melting municipal solid waste incinerator (MSWI) fly ash, based on self-propagating reactions, by using energy-efficient simulated waste-derived thermite. The self-propagating characteristics, the properties of the recycled alloy and slag and the partitioning of heavy metals during the process are also studied. Experimental results demonstrate that the mix ratio of fly ash to the starting mixture of less than 30% supports the development of the self-propagating reaction with a melting temperature of 1350-2200 degrees C. Furthermore, metallic iron (or alloy) and the slag were retrieved after activation of the thermite reactions among the starting mixtures. It was noted that more than 91wt.% of iron was retrieved as alloy and the rest of non-reductive oxides as slag. During the thermite reactions, the partition of heavy metals to the SFA and flue gas varied with the characteristics of the target metals: Cd was mainly partitioned to flue gas (75-82%), and partition slightly increased with the increasing fly ash ratio; Pb and Zn, were mainly partitioned to the SFA, and the partition increased with increasing fly ash ratio; Cu was partitioned to the SFA (18-31%) and was not found in the flue gas; and moreover stable Cr and Ni were not identified in both the SFA and flue gas. On the other hand, the determined TCLP leaching concentrations were all well within the current regulatory thresholds, despite the various FA ratios. This suggests that the vitrified fly ash samples were environmental safe in heavy metal leaching. The results of this study suggested that melting of municipal solid waste incinerator fly ash by waste-derived thermite reactions was a feasible approach not only energy-beneficial but also environmental-safe.     

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.     

Comparison of the characteristics of bottom and fly ashes generated from various incineration processes

This study analyzed and compared the characteristics of bottom and fly ashes from three municipal solid waste incinerators (MSWIs) in Taiwan. Different incineration furnaces were investigated, including: (1) fluidized bed, (2) mass-burning, and (3) mass-burning linked rotary kiln. The particle size distribution, morphology, mineralogical and chemical composition, and leaching behavior of heavy metals of ash samples were evaluated. The results revealed that three types of incineration processes have different characteristic for ashes due to transportation and mixing system inside furnace. Particle size distribution indicated that 28.5% of MSWI-B bottom ash has lower than 180 microm and 61.2% of MSWI-A fly ash has larger than the 250 microm. The leaching concentration of Pb exceeded the regulatory level set by the Taiwan EPA in fly ashes from MSWI-B and MSWI-C, and thus must be considered hazardous wastes. Specifically, the leaching concentration of heavy metals of fly ashes from MSWI-A (fluidized bed incinerator) was lower than that of the others, and was corresponded to the regulatory levels. Therefore, a fluidized bed incineration process appears a potential of handling heavy metals for ashes. The result was also provided the valuable information for incinerator design and operation.     

Application of microwave-assisted extraction to the analysis of PCBs and CBzs in fly ash from municipal solid waste incinerators

Polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs) are two classes of dioxin precursors formed in municipal solid waste incinerators (MSWIs) producing negative health effects similar to those of dioxins. Reducing the analytical time required for determining the concentrations of these compounds in MSWIs is important for quickly evaluating their importance and associated health risks. In the present study, microwave-assisted extraction (MAE) is compared with traditional Soxhlet extraction (SE) to determine the extraction efficiencies attained for PCB and CBz analysis. The efficiencies of MAE are compared with those of SE under various experimental conditions, using fly ash spiked with standards. Water is used as a safe and environmentally friendly solvent in MAE for PCB and CBz analyses and MAE has high extraction efficiency for spiked fly ash compared with that of SE. Furthermore, the extraction time and organic solvent consumption are reduced with MAE compared with SE. The optimum conditions for MAE established in this study are using a 30-ml volume of toluene/acetone (1/1) or a 15-ml volume of toluene, samples with less than 60% water content (WC), and an irradiation time of 15 min.     

Polychlorinated biphenyls removal from weathered municipal solid waste incineration fly ash by collector-assisted column flotation

Polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are highly toxic micropollutants emitted from municipal solid waste incineration (MSWI), in particular, concentrated in the unburned carbon (UC) of MSWI fly ash. Because of concerns over their adverse health effects, a number of countries have classified MSWI fly ash as hazardous material and required further treatment before its final disposal in landfills. The technologies for removing the toxic chlorinated micropollutants in the MSWI fly ash have been studied, however, until now no mature technique has been obtained in this purpose. In this research, we used a technique of collector-assisted column flotation to remove PCBs-enriched UC from MSWI fly ash. We found that 36.9% PCBs could be removed from fresh MSWI fly ash with 61.7% UC removal efficiency, whereas only 21.7% PCBs could be removed from weathered MSWI fly ash with a low UC removal efficiency of 33.7%. By adding a mixture of two kinds of surfactants: sorbitan mono-oleate and polyoxyethylene (20) sorbitan mono-oleate to the weathered fly ash slurry as the collector assistant, 39.3% PCBs was removed at the hydrophile–lipophile balance (HLB) value of 13.5, while the UC removal efficiency increased to 49.0%. The results showed that the collector assistant could enhance PCBs and UC removal efficiencies during the column flotation process, and the mechanism has been discussed in detail. Higher PCBs and UC removal efficiencies could be expected by further optimizing the conditions of collector-assisted column flotation.     

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.     

Application of fly ash on the growth performance and translocation of toxic heavy metals within Cajanus cajan L.: Implication for safe utilization of fly ash for agricultural production

The present study was undertaken to examine the influence of the application of fly ash (FA) into garden soil for Cajanus cajan L. cultivation and on accumulation and translocation of hazardous metals from FA to edible part. Numerous studies have been reported on the growth and yield of agricultural crops under FA stress; however, there is a dearth of studies recommending the safe utilization of fly ash for crop production. Pot experiments were conducted on C. cajan L., a widely cultivating legume in India for its highly nutritious seeds. C. cajan L. were grown in garden soil and amended with varying concentrations of FA in a weight/weight ratio (0%, 25%, 50% and 100%; w/w). Incorporation of fly ash from 25% to 100% in garden soil increases the levels of pH, particle density, porosity and water holding capacity from 3.47% to 26.39%, 3.98% to 26.14%, 37.50% to 147.92% and 163.16% to 318.42%, respectively, than the control while bulk density decrease respectively from 8.94% to 48.89%. Pot experiment found that accumulation and translocation of heavy metals in tested plant depends on the concentration of FA. Addition of FA at lower concentration (25%) had shown positive results in most of the studied parameters of growth and yield (14.23% than control). The experimental results confirmed that lower concentration of FA (25%) is safe for C. cajan cultivation, which not only enhanced the yield of C. cajan L. significantly but also ensured the translocation of heavy metals to edible parts within the critical limits.     

Sequential extraction for evaluating the leaching behavior of selected elements in municipal solid waste incineration fly ash

A sequential extraction method has been applied for the determination of binding forms of trace elements in the municipal solid waste incineration (MSWI) fly ash and evaluating their leaching behavior in view of their potential environmental impact. The elemental determinations in the different leachates are performed by ICP-AES and ICP-MS, respectively. The morphology and mineralogical phases after extraction step were performed by scanning electron microscopy (SEM). Total of 20 elements in the samples are investigated. A reference material of city waste incineration fly ash (BCR No. 176) is also tested to examine the applicability as well as accuracy of the proposed method. The sum of most elements present in the individual fractions shows a good agreement with the total elemental concentrations. The extraction efficiencies are generally higher than 80% except for that of Cr and V. The extractable data of most elements give information about the binding forms of various elements in both incineration fly ashes. It was found that the elements such as Ca, K, Na, Pb, Zn, Cd, Cu and Sr have exhibited a remarkable mobility in fly ash. More than half of them would be dissolved or exchanged under a mild leaching condition. The toxic elements such as Pb, Cd, Zn and Cu have a great potential to be released into the environment under normal conditions.     

Atmospheric dry deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in the vicinity of municipal solid waste incinerators

This study focuses on the atmospheric dry deposition flux of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the vicinity of the two municipal solid waste incinerators (MSWIs) located in southern Taiwan. PCDD/Fs in ambient air were taken and analyzed for seventeen 2,3,7,8-substituted PCDD/Fs during November 2004 and July 2005. Results show that the mean concentrations of PCDD/Fs in the ambient air near MSWI-GS and MSWI-RW were 0.090 and 0.097pg I-TEQ/Nm(3), respectively. Dry deposition fluxes of total PCDD/Fs were 18.0 and 23.5pg I-TEQ/(m(2)d) in the ambient air near MSWI-GS and MSWI-RW, respectively, which were considerably higher than that measured in Guangzhou, China. Annual dry deposition fluxes of total PCDD/Fs in the ambient air near MSWI-GS and MSWI-RW were 189 and 217ng/(m(2)year), respectively, which were also much higher than dry deposition of total PCDD/Fs to the Atlantic Ocean. The results of the present study strongly suggest that exposure to PCDD/Fs in this area should be reduced. In addition, parametric sensitivity shows that dry deposition flux of PCDD/Fs is most sensitive to dry deposition velocity of the particle-phase, followed by air temperature and concentration of total suspended particulate but least sensitive to dry deposition velocity of the gas-phase.     

Application of thermally activated municipal solid waste incineration (MSWI) bottom ash fines as binder substitute

Untreated municipal solid waste incineration (MSWI) bottom ash fines (0–2 mm) have poor pozzolanic properties, and contain substances which can pose an environmental risk (e.g. heavy metals and salts). This study investigates combined treatments applied on bottom ash fines (BAF) to increase their reactivity. The treated BAF is compared with both untreated BAF and cement, and its contribution to cement hydration is investigated. Additionally, the utilization of the treated BAF in mortar as cement replacement is tested. Finally, the leaching properties of mortars containing treated and untreated BAF are estimated. According to the results obtained, the 28-day compressive and flexural strengths of mortar with 30% treated bottom ash are about 16% and 6% lower than the reference mortar, respectively. The leaching of contaminants from the crushed mortars with BAF are well under the limit values imposed by Dutch legislation.