Heavy metal speciation and leaching behaviors in cement based solidified/stabilized waste materials

A circuit board printing factory sludge containing high concentrations of copper, zinc and lead was stabilized and solidified (S/S) with different portions of ordinary Portland cement (OPC) and pulverized fly ash (PFA). The chemical speciation and leaching behavior of heavy metals in these cement-based waste materials were studied by different sequential extraction procedures, standard toxicity characteristic leaching procedure (TCLP) and progressive TCLP tests. The sequential extraction results showed that more than 80% of Cu, Pb and Zn were associated with Fraction 2 (weak acid soluble, extracted with 1M NaOAc at pH 5.0 with a solid to liquid ratio of 1:60). This indicated that the heavy metals could exist in the S/S matrix as metal hydrated phases or metal hydroxides precipitating on the surface of calcium silicate hydrates (C-S-H), PFA and sludge particles. The progressive TCLP test results and MINTEQA2 calculation also showed the importance of Cu and Zn oxides during the leaching process. The leaching behaviors of these metals in the S/S waste materials were mainly controlled by the alkaline nature and acid buffering capacity of the S/S matrix. During the progressive TCLP tests, the alkaline conditions and acid buffering capacity of the matrix decreased with the dissolution of calcium hydroxide and C-S-H, therefore, the leaching of heavy metals in the S/S waste materials increased. The leaching of heavy metals in the S/S materials can be considered as a pH dependent and corresponding metal hydroxide solubility controlled process.     

垃圾焚烧炉渣-粉煤灰复合水泥的性能研究

研究了垃圾焚烧炉渣及粉煤灰单掺和复掺时硬化水泥浆体的力学性能和水化机理,比较了两者的活性,探讨了两者作为辅助性胶凝材料利用的可行性.研究表明:掺有垃圾焚烧炉渣及粉煤友的复合水泥,其强度均有不同程度的下降,它们的掺入在一定程度上延缓了水泥的水化过程,且垃圾焚烧炉渣的水化反应活性稍高于粉煤灰;掺垃圾焚烧炉渣及粉煤灰的复合水泥中重金属离子浸出量小,在等掺20%的条件下,浸出量远低于国家标准,说明在一定的情况下,焚烧炉渣及粉煤灰作为辅助性胶凝材料使用是安全的.     

Utilization of MSWI fly ash for stabilization/solidification of industrial waste sludge

This work investigated the potential for utilization of MSWI incineration fly ash as solidification binder to treat heavy metals-bearing industrial waste sludge. In the study, Municipal Solid Waste Incineration (MSWI) fly ash was used along with ordinary Portland cement to immobilize three different types of industrial sludge while MSWI incineration fly ash was stabilized at the same time. The results showed that the matrixes with heavy metals-bearing sludge and MSWI fly ash have a strong fixing capacity for heavy metals: Zn, Pb, Cu, Ni and Mn. Specimens with only 5-15% cement content was observed to be sufficient to achieve the target compressive strength of 0.3 MPa required for landfill disposal. An optimum mix comprising 45% fly ash, 5% cement and 50% of the industrial sludge could provide the required solidification and stabilization. Addition of MSWI can improve the strength of matrix. Meanwhile, the main hydration products of new S/S matrix are ettringite AFt, Friedel's salt and C-S-H. These hydration products play an important role in the fixing of heavy metals. The co-disposal of MSWI fly ash with heavy metals-bearing sludge can minimize the enlargement of the landfill volume and stabilize the heavy metals effectively.     

Disposal of MSWI fly ash through a combined washing-immobilisation process

The objective of this work was to investigate the feasibility of a combined washing-immobilisation process as a means of optimising the disposal of fly ash resulting from municipal solid waste incineration (MSWI) in cementitious matrices. Two different types of Italian MSWI fly ash and an ordinary Portland cement (ASTM Type I) were used. Washing pre-treatment of fly ash with water always produces a wastewater that can be successfully treated by reducing the pH to values of 6.5-7.5. This treatment is capable of removing the detected contaminants (Al, Cd, Pb, Zn) through two different mechanisms: precipitation of aluminium hydroxide and adsorption of cadmium, lead and zinc ions onto floc particles of Al(OH)(3). Setting and leaching tests on cementitious mixes prove that the hazardous sludge produced from wastewater treatment can be completely mixed with washed fly ash and this mixture can be incorporated into cementitious matrices to a great extent (75 wt.% of total solid) without the risks of an unacceptable delay of cement setting and an excessive heavy metals leachability from solidified products. The better performance of the combined washing-immobilisation process as compared to the immobilisation process of unwashed fly ash may be ascribed primarily to the ability of the washing step in promoting the formation of hydrate phases that incorporate and/or convert heavy metal compounds into less reactive forms and, secondarily, to its ability of removing significant amounts of alkali chlorides and sulphates from fly ash. As a result, MSWI fly ash is transformed into a material that adversely affects cement hydration to a much lower extent than unwashed fly ash.     

Stabilization of a chlorine-rich fly ash by colloidal silica solution

Fly ash from municipal solid waste incinerators (MSWI) consists of various substances, including a lot of heavy metals. In cases where fly ash contains a lot of chlorides, it is very difficult to apply general treatment methods because chlorides could hinder hydration in cementation and cause great loss in vitrification. In this study, we report a promising method for the treatment of fly ash containing a high concentration of chlorides. A colloidal silica solution was induced to stabilize the fly ash. The fly ash used in this research has a chlorine level over 35 wt.% as well as containing heavy metals, such as Pb (1120 ppm) and Zn (5430 ppm). The samples were prepared at a temperature of 600-800 degrees C for 2h after mixing with the fly ash and a 4 wt.% colloidal silica solution. The effect of the colloidal silica was evaluated by the leaching test, Toxicity Characteristic Leaching Procedure (TCLP). The solidified products with fly ash and colloidal silica at temperatures of more than 700 degrees C had an excellent resistance, with Pb(2+) <0.02 ppm, Zn(2+) <0.52 ppm, and Cd(2+), Cr(2+), Cu(2+), Mn(2+) <0.01 ppm, and it could be influenced by the phases containing Ca and Si formed above 600 degrees C and reduction of a chemically weak phase.     

Emission of Pb and PAHs from thermally co-treated MSWI fly ash and bottom ash process

Municipal solid waste incinerator (MSWI) fly ash was regarded as a hazardous material because concentrations of TCLP leaching solution exceeded regulations. Previous studies have investigated the characteristics of thermally treated slag. However, the emissions of pollutant during the thermal treatment of MSWI fly ash have seldom been addressed. The main objective of this study was to evaluate the emission of Pb and PAHs from thermally co-treated MSWI fly and bottom ash process. The experimental parameters included the form of pretreatment, the proportion of bottom ash (bottom ash/fly ash, B/F=0, 0.1 and 1) and the retention time. The toxicity of thermally treated slag was also analyzed. The results indicated that (1) Pb emission occurred only in the solid phase and that PAHs were emitted from both solid and gas phases during thermal treatment process. (2) Washing pretreatment reduced not only the TCLP leaching concentration of Pb (from 15.75 to 1.67 mg/L), but also the emission of PAHs from the solid phase during thermal treatment process. (3) Adding bottom ash reduced the TCLP leaching concentration of thermally treated slag. (4) The concentration of Pb emission increased with retention time. (5) The thermal treatment reduced the toxicity of raw fly ash effectively, the inhibition ratio of raw fly ash and thermal treated slag were 98.71 and 18.35%, respectively.     

Solidification and stabilization of asbestos waste from an automobile brake manufacturing facility using cement

Currently, the generated brake lining waste dust, which contains asbestos as its major component, is disposed of into a secure landfill without any additional treatment. As an alternative to this, solidification/stabilization (S/S) disposal of the dust was investigated using Portland cement alone and Portland cement mixed with activated carbon (AC), as the binders. Toxicity Characteristics Leaching Procedure (TCLP) results on the solidified matrix showed that cement was able to immobilize the heavy metals, Ba, Zn, Cr, Pb, Cu and Fe, to within the limits set by the US EPA for TCLP. Addition of AC to the cement reduced the leaching of heavy metals by an additional 4-24% compared to cement alone. The pH of the TCLP leachate extracted from virgin cement, and from dust treated with cement with or without AC was found to increase to 10.9-12.5 as opposed to an initial value of 4.93 for the TCLP extract for the untreated dust. Results of ANS 16.1 (modified) leach protocol revealed that Ba in cement-treated samples showed the highest leach rate, followed by Zn, Pb, Cr, Cu and Fe. The leach rate of heavy metals decreased with progress in time. Cement mixed with AC exhibited similar leach characteristics, however, the leach rate was lower. The linear relationship between the cumulative fraction leached (CFL) and the square root of leaching time in all cement-based samples indicate that a diffusional process is the controlling transport mechanism for the leaching of the heavy metals. The obtained Leachability Indices (L(i)) of 7.6-9.1 and 8.3-9.5 for cement and cement with AC, respectively, were low but exceeded the guidance value of 6, which clearly indicates that all the heavy metals studied are retained well within solid matrices. Cement-based S/S hardening times increased from 30 to 96 h as the dust content increased from 40 to 70 wt.%. The resulting solid matrices exhibited a compressive strength ranging from 1 to 12 MPa, which was well above the specified limit of 414 kPa for such matrices. An economic analysis indicates that the disposal costs for the dust in the only available secure landfill would increase by 40.3% if one were to go for the cement S/S option. Addition of AC to the cement would escalate this by an additional 43.8%. Although the S/S of brake lining dust using cement effectively immobilized the heavy metals of concern, cost considerations may hinder the commercial adaptation of this technique for waste disposal unless new regulatory demands are implemented.     

Investigation into the stabilization/solidification performance of Portland cement through cement clinker phases

This research studied the influence of individual heavy metal on the hydration reactions of major cement clinker phases in order to investigate the performance of cement based stabilization/solidification (S/S) system. Tricalcium silicate (C3S) and tricalcium aluminate (C3A) had been mixed with individual heavy metal hydroxide including Zn(OH)2, Pb(OH)2 and Cu(OH)2, respectively. The influences of these heavy metal hydroxides on the hydration of C3S and C3A have been characterized by X-ray diffraction (XRD) and differential scanning calorimetry-thermogravimetry (DSC-TG). A mixture of Zn(OH)2, Pb(OH)2 and Cu(OH)2 was blended with Portland cement (PC) and evaluated through compressive strength and dynamic leach test. XRD and DSC-TG data show that all the heavy metal hydroxides (Zn(OH)2, Pb(OH)2 and Cu(OH)2) have detrimental effects on the hydration of C3A, but only Zn(OH)2 does to the C3S at early curing ages which can completely inhibit the hydration of C3S due to the formation of CaO(Zn(OH)2).2H2O. Cu6Al2O8CO(3).12H2O, Pb2Al4O4(CO3)(4).7H2O and Zn6Al2O8CO(3).12H2O are formed in all the samples containing C3A in the presence of metal hydroxides. After adding CaSO4 into C3A, the detrimental effect of heavy metals increases due to the coating effect of both calcium aluminate sulphates and heavy metal aluminate carbonates. The influence of heavy metal hydroxide on the hydration of C3S and C3A can be used to predict the S/S performance of Portland cement.     

Reuse of cement-solidified municipal incinerator fly ash in cement mortars: physico-mechanical and leaching characteristics

The reuse of cement-solidified Municipal Solid Waste Incinerator (MSWI) fly ash (solidified/stabilised (S/S) product) as an artificial aggregate in Portland cement mortars was investigated. The S/S product consisted of a mixture of 48 wt.% washed MSWI fly ash, 20 wt.% Portland cement and 32 wt.% water, aged for 365 days at 20 degrees C and 100% RH. Cement mortars (water/cement weight ratio=0.62) were made with Portland cement, S/S product and natural sand at three replacement levels of sand with S/S product (0%, 10% and 50% by mass). After 28 days of curing at 20 degrees C and 100% RH, the mortar specimens were characterised for their physico-mechanical (porosity, compressive strength) and leaching behaviour. No retardation in strength development, relatively high compressive strengths (up to 36 N/mm2) and low leaching rates of heavy metals (Cr, Cu, Pb and Zn) were always recorded. The leaching data from sequential leach tests on monolithic specimens were successfully elaborated with a pseudo-diffusional model including a chemical retardation factor related to the partial dissolution of contaminant.     

Characterisation and management of ash produced in the hospital waste incinerator of Athens, Greece

Bottom and fly ash samples (BASH and FASH) from the APOTEFROTIRAS S.A. medical waste incinerator (Athens, Greece) were investigated. Powder-XRD data and geochemical diagrams showed BASH to be an amorphous material, analogous to basaltic glass, and FASH consisting of crystalline compounds (mainly CaClOH). Bulk analyses by ICP-MS and point analyses by SEM-EDS indicated a high content of heavy metals, such as Fe, Cu and Cr, in both samples. However, BASH was highly enriched in Ni while FASH was additionally enriched in Zn and Pb. Gamma-ray measurements showed that the radioactivity of both ash samples, due to natural and artificial radionuclides ((137)Cs, (57)Co), was within the permissible levels recommended by IAEA. According to EN-type leaching tests, BASH was practically inert with regard to the mobility of the hazardous elements in aqueous media. FASH, however, showed a relatively high EN (and TCLP) leachability with regard to Pb and Zn. Finally, the stabilisation method, suggested for the treatment of FASH, included compression of the powder into briquettes using an appropriate machine and embedding the briquettes into pozzolanic cement blocks. After this treatment, TCLP and EN-type tests showed minimal release of Pb and Zn, thereby demonstrating a reliable management of ash waste.     

MSW fly ash stabilized with coal ash for geotechnical application

The solidification and stabilization of municipal solid waste (MSW) fly ash for the purpose of minimizing the geo-environmental impact caused by toxic heavy metals as well as ensuring engineering safety (strength and soaking durability) are experimentally evaluated. The mixtures of MSW fly ash stabilized with cement and fluidized bed combustion coal fly ash (FCA) were used for unconfined compressive strength tests, leachate tests, and soaking tests. The behavior of soluble salts contained in the MSW fly ash significantly affects strength development, soaking durability, and the hardening reaction of the stabilized MSW fly ash mixtures. The cement stabilization of the MSW fly ash does not have enough effect on strength development and soaking durability. The addition of cement only contributes to the containment of heavy metals due to the high level of alkalinity. When using FCA as a stabilizing agent for MSW fly ash, the mixture exhibits high strength and durability. However, the Cd leachate cannot be prevented in the early stages of curing. Using a combination of cement and FCA as a MSW fly ash stabilizer can attain high strength, high soaking durability, and the containment of heavy metals. The stabilized MSW fly ash with cement and FCA can be practically applied to embankments.     

Optimization of the solidification/stabilization process of MSW fly ash in cementitious matrices

The solidification/stabilization (S/S) process of municipal solid waste (MSW) fly ash in cementitious matrices was investigated in order to ascertain the feasibility of a washing pretreatment of fly ash with water as a means of maximizing the ash content of cementitious mixtures. Four types of fly ash resulting from different Italian MSW incineration plants and ASTM Type III Portland cement were used in this study. Ash-cement mixtures with different fly ash/cement (FA/C) ratios were made using untreated and washed fly ash. Washing of fly ash with water was realized by a two-stage treatment (liquid/solid=25; mixing time=15 min for each stage). The cementitious mixtures were characterized for water demand, setting time, mechanical strength, and heavy metals leachability. Comparison between the above properties of mixtures incorporating untreated and washed fly ash (particularly, setting characteristics), coupled with economical evaluation of the S/S process when applied to untreated and washed fly ash, proved the feasibility of washing pretreatment as a means of maximizing the incorporation of MSW fly ash in cementitious matrices (ash content up to 75%-90% by weight of total solid).     

Leaching characteristics of slag from the melting treatment of municipal solid waste incinerator ash

This study investigated the composition and leaching characteristics of municipal solid waste incinerator (MSWI) ash and slag. The modified slags were characterized after the melting of MSWI ash mixtures at 1400 degrees C for 30 min. The ash mixtures were composed of different types of MSWI ash, including cyclone ash, scrubber ash and bottom ash, in various proportions. The results indicate that the Cd leaching concentration of the cyclone ash and the Pb leaching concentration of the scrubber ash reached 1.82 and 8.7 mg/L, respectively, which exceeds the ROC EPA's current regulatory thresholds, and can thus be classified as hazardous. The results of the analysis of the metal content and the leaching behavior of heavy metals, showed high concentrations of Cu and Zn, but a low leaching ratio of these metals. Concerning the characteristics of the modified slags, the X-ray diffraction patterns of the MSWI fly ash slag showed that it contained large amounts of glass. The toxicity characteristic leaching procedure (TCLP) leaching concentrations of the target metals of all the slags, met the ROC EPA's regulatory thresholds. The leaching concentrations of heavy metals in the F- and B1-slag were lower than those in the cyclone and the bottom ash, because there was a high amount of SiO(2), which formed a net-like structure in the bottom ash.     

Investigation of the stability of hardened slag paste for the stabilization/solidification of wastes containing heavy metal ions

We have studied the effect of chromium ions and lead ions on the chemical stability of hardened slag paste with toxic wastes during the stabilization/solidification process. The influences of Cr and Pb ions on the hydration of slag were also investigated. Sodium silicate (Na(2)SiO(3)), 5 wt.% of slag, was used as an alkali activator for slag hydration. The physical stability of hardened paste containing partial replacement of slag with fly ash and gypsum was also examined.When gypsum was added to slag, the compressive strength of hardened slag paste developed, accompanying the activation of alumino-ferrite-tricalciumsulfate (Al(2)O(3)-Fe(2)O(3)-3CaSO(4), AFt) and alumino-ferrite-monocalciumsulfate (Al(2)O(3)-Fe(2)O(3)-CaSO(4), AFm) phase generation. Those phases caused densification of the microstructure. Concurrently, the leaching amount of heavy metal ions was decreased. When fly ash was added to slag, the compressive strength increased and the leaching amount decreased with both active formation of aluminate hydrates and ion substitution. Lead ions were mostly stabilized through physical encapsulation by the hardened slag paste's hydrate matrix. In the case of chromium ions, we observed that it was mainly solidified through the formation of a substitutional solid solution with aluminum atoms in the structure of aluminate hydrates.     

Sintering of MSWI fly ash by microwave energy

This study presents the sintering of municipal solid waste incineration (MSWI) fly ash assisted by microwave energy. The composition of fly ash was investigated by chemical sequential extraction and modified microwave digestion method. Effects of process time, container materials, aging time and salt contents were also discussed. The major elements of fly ash are Ca, Cl, Na, Si, K, Al, Mg, and Zn, and the metal species, Zn, Cr, Pb, Ca, and Cu, are mainly in the oxide phase. Under microwave processing, the fly ash was sintered into a glass-ceramics and the leaching concentrations of heavy metals were restrained. The stabilization efficiency increased with an increase in processing time in most of the cases. Better stabilization efficiency of fly ash was discovered by using the SiO(2) or Al(2)O(3) container than by using the graphite plate/SiC plate. The presence of salt in the fly ash could enhance the sintering and stabilization of fly ash. During the aging time of 0-30 days, negligible Pb in the sintered fly ash was leached out, and the leaching concentration was lower than the criterion.     

Influence of flue gas SO2 on the toxicity of heavy metals in municipal solid waste incinerator fly ash after accelerated carbonation stabilization

The influence of CO₂ content and SO₂ presence on the leaching toxicity of heavy metals in municipal solid waste incinerator (MSWI) fly ash was studied by examining the carbonation reaction of MSWI fly ash with different combinations of simulated incineration flue gases. Compared with raw ash, the leaching solution pH of carbonated ash decreased by almost 1 unit and the leaching concentrations of heavy metals were generally lower, with that of Pb decreasing from 19.45 mg/L (raw ash) to 4.08 mg/L (1# carbonated ash). The presence of SO₂ in the incineration flue gas increased the leaching concentrations of heavy metals from the fly ash to different extents after the carbonation stabilization reaction. The pH of the leaching solution was the main factor influencing the leaching concentrations of heavy metals. The increase in buffer capacity with the pH of carbonated ash caused an increase in heavy metal stability after the carbonation reaction. Accelerated carbonation stabilization of MSWI fly ash could reduce its long-term leaching concentrations (toxicity) of Cu, Pb, Se, and Zn. The leaching concentrations of heavy metals from carbonated ash also likely had better long-term stability than those from raw ash. The presence of SO₂ in the incineration flue gas increased the proportion of exchangeable state species of heavy metals; slightly increased the long-term leaching toxicity of Cu, Pb, Se, and Zn; and reduced the long-term stability of these metals in the fly ash after the carbonation reaction.     

Electrodialytic removal of heavy metals from different fly ashes. Influence of heavy metal speciation in the ashes

Electrodialytic remediation, an electrochemically assisted extraction method, has recently been suggested as a potential method for removal of heavy metals from fly ashes. In this work, electrodialytic remediation of three different fly ashes, i.e. two municipal solid waste incinerator (MSWI) fly ashes and one wood combustion fly ash was studied in lab scale, and the results were discussed in relation to the expected heavy metal speciation in the ashes. The pH-dependent desorption characteristics for Cr differed between the two MSWI ashes but were similar for Cd, Pb, Zn and Cu. Thus, it was expected that the speciation of Cd, Pb, Zn and Cu was similar in the two ashes. However, in succeeding electrodialytic remediation experiments significant differences in removal efficiencies were observed, especially for Pb and Zn. In analogous electrodialytic remediation experiments, 8% Pb and 73% Zn was removed from one of the MSWI ashes, but only 2.5% Pb and 24% Zn from the other. These differences are probably due to variations in pH and heavy metal speciation between the different ashes. Cd, the sole heavy metal of environmental concern in the wood ash, was found more tightly bonded in this ash than in the two MSWI ashes. Approximately 70% Cd was removed from both types of ashes during 3 weeks of electrodialytic remediation, although the total concentration was a factor of 10 lower in the wood ash. It was suggested that complex Cd-silicates are likely phases in the wood ash whereas more soluble, condensed phases are dominating in the MSWI ashes.     

Use of sulfoaluminate cement and bottom ash in the solidification/stabilization of galvanic sludge

Solidification/stabilization (S/S) process can improve the physical characteristics of wastes, reduce their leaching and limit the solubility of their heavy metals. The identification of binders able to assume the fixation of contaminants is essential for the success of the technique. In this study, calcium sulfoaluminate cement was added to another waste, bottom ash, in order to treat galvanic sludge. The properties of the resultant solid matrix (MS) were determined: setting time, compressive strength and products of hydration. Solid matrix composed of 77% waste and only 23% cement presented initial setting time lower than 4 h and 28 day-strength of 6 MPa. SEM investigations showed that contaminants present in the galvanic sludge (Cr) were encapsulated in the hydrated phases and particles of bottom ash.     

Vitrification of fly ash from municipal solid waste incinerator

Fly ash from municipal solid wastes (MSW) incinerators in Korea contains a large amount of toxic materials and requires pertinent treatments. However, since fly ash in Korea has a high chlorine concentration, it is difficult to apply cementation and chemical treatment techniques. In this study, we report the vitrification of fly ash along with the properties of the glasses and leaching characteristics of heavy metal ions.Fly ash can be vitrified by melting at 1500 degrees C for 30 min with the addition of >5 wt.% of SiO2. Glasses showed Vickers hardness of 4000-5000 MPa, bending strength of 60-90 MPa and indentation fracture toughness of approximately 0.9 MPa m(1/2). Glasses also showed the excellent resistance against leaching of heavy metal ions with Cd2+ <0.04 ppm, Cr3+ <0.02 ppm, Cu2+ <0.04 ppm and Pb2+ <0.2 ppm. These results indicate that the vitrification technique is effective for the stabilization and recycling of toxic incinerator fly ash.     

Removal of hazardous metals from MSW fly ash—An evaluation of ash leaching methods

Incineration is a commonly applied management method for municipal solid waste (MSW). However, significant amounts of potentially hazardous metal species are present in the resulting ash, and these may be leached into the environment. A common idea for cleaning the ash is to use enhanced leaching with strong mineral acids. However, due to the alkalinity of the ash, large amounts of acid are needed and this is a drawback. Therefore, this work was undertaken in order to investigate some alternative leaching media (EDTA, ammonium nitrate, ammonium chloride and a number of organic acids) and to compare them with the usual mineral acids and water.All leaching methods gave a significant increase in ash specific surface area due to removal of soluble bulk (matrix) compounds, such as CaCO₃ and alkali metal chlorides. The use of mineral acids and EDTA mobilised many elements, especially Cu, Zn and Pb, whereas the organic acids generally were not very effective as leaching agents for metals. Leaching using NH₄NO₃ was especially effective for the release of Cu. The results show that washing of MSW filter ash with alternative leaching agents is a possible way to remove hazardous metals from MSW fly ash.