Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of 29Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research on the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique.     

The disposal of radioactive ferric floc

An iron hydroxide floc is used as treatment for adsorbing low amounts of actinides during nuclear fuel re-processing. This waste is cemented only after pre-treatment with Ca(OH)(2). Characterisation of all simulant material has been undertaken using XRD, TGA and SEM/EDS. The floc is a moderately alkaline colloidal slurry containing approximately 15wt% solids, with the main particulate being an amorphous hydrated iron oxide. The main phase formed during pre-treatment appears to be an X-ray amorphous hydrated calcium-ferrate phase. Embedded within this are small amounts of crystalline Ca(OH)(2), calcite, Fe(6)(OH)(12)(CO(3)), Ca(6)Fe(2)(SO(4))(3)(OH)(12).26H(2)O and Ca(3)B(2)O(6), and can form depending on concentrations of Ca(OH)(2) and time. Apart from Ca(OH)(2) and calcite, none of the crystalline phases detected during pre-treatment are detected when the floc is encapsulated in an OPC/PFA composite cement hydrated for 90 days. The main crystalline phase detected in the hardened wasteform is a solid solution hydrogarnet, Ca(3)AlFe(SiO(4))(OH)(8), known as C(3)(A,F)SH(4) in cement chemistry nomenclature.     

Alteration of municipal solid waste incineration bottom ash focusing on the evolution of iron-rich constituents

Municipal solid waste incineration (MSWI) bottom ash contains a considerable amount of Fe-rich constituents. The behaviors of these constituents, such as dissolution and precipitation, are quite important as they regulate the distribution of a series of ions between the liquid (percolated fluid) and solid (ash deposit) phases. This paper studied both fresh and weathered MSWI bottom ash from the mineralogical and geochemical viewpoint by utilizing optical microscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), and powder X-ray diffraction. The analysis results revealed that for the fresh bottom ash, iron preferentially existed in the chemical forms of spinel group (mainly Fe(3)O(4), and a series of Al- or Ti- substituted varieties), metallic inclusions (including Fe-P, Fe-S, Fe-Cu-Pb), hematite (Fe(2)O(3)) and unburned iron pieces. In the 1-20 years weathered bottom ash collected from a landfill site, interconversions among these Fe-rich constituents were identified. Consequently, numerous secondary products were developed, including goethite (α-FeOOH), lepidocrocite (γ-FeOOH), hematite, magnetite, wustite (FeO), Fe-Si-rich gel phase. Of all these transformation products, hydrous iron oxides were the most common secondary minerals. Quantitative chemical analysis of these secondary products by SEM/EDX disclosed a strong association between the newly formed hydrous iron oxides and heavy metals (e.g. Pb, Zn, Ni, and Cu). The results of this study suggest that the processes of natural weathering and secondary mineralization contribute to reduction of the potential risks of heavy metals to the surrounding environments.     

Alterations of municipal solid waste incineration residues in a landfill

Fresh municipal solid waste incineration residues (MSWIR) and a drilling core of 2-10 years old landfilled MSWIR were investigated to determine the alterations due to weathering in a landfill. Physical and geochemical properties and transformations of major components and heavy metals were analyzed for fresh and landfilled residues. Carbonates and hydroxides (10-12vol%) as major mineralogical compositions in the 8-10 years weathered MSWIR were observed by modal analysis of thin sections. Three step sequential extractions indicated that reducible phases, mainly the Fe, Al and Mn hydroxides increased with depth in the landfill. A pH controlled leaching test (including availability test and pH dependent leaching test) was then conducted. Results indicated lower concentrations of leachable contents at pH values from 6 to 10 for the four elements (Pb, Zn, Al and Fe) in the 8-10 years landfilled residues than in the fresh and 1-2 years landfilled residues. This means that 8-10 years weathered MSWIR became more stable than fresh landfilled residues. The reasons for the stabilization of these elements might be the hydration of Al and Fe during weathering in the landfill, which then results in the heavy metals adsorptions of these minerals.     

Crystal-chemistry of alteration products of vitrified wastes: implications on the retention of polluting elements

Alteration products of vitrified wastes coming from the incineration of household refuse (MSW) are described. Two vitrified wastes containing 50% and 70% of fly ash and a synthetic stained-glass with a composition close to that of an ancient glass (medieval stained-glass) were altered under different pH conditions (1, 5.5 corresponding to demineralized water and 10) during 181 days. Under acidic condition, the alteration layer is made of an amorphous hydrated silica gel impoverished in most of the initial elements. A minor phase MPO(4)*nH(2)O, where M represents Fe, Ti, Al, Ca and K cations, also constitutes the altered layer of the synthetic stained-glass. Under neutral and basic conditions, the altered layer is made of an amorphous hydrated silica gel and a crystallized calcium phosphate phase. The silica gel is depleted in alkalis and alkali-earth elements but contains significant amounts of aluminium, magnesium and transition elements, whereas the calcium phosphate is a hydroxylapatite-like phase with P-Si substitutions and a Ca/P ratio depending on the pH of the solution. This study shows: (i) the strong influence of pH conditions on the crystal-chemistry of alteration products and thus on the mechanisms of weathering resulting in different trapping of polluting elements, and (ii) that glass alteration does not necessary produce thermodynamically stable phases which has to be taken into account for the prediction of the long-term behavior.     

Impacts of natural weathering on the transformation/neoformation processes in landfilled MSWI bottom ash: a geoenvironmental perspective

Natural weathering processes are significant mechanisms that noticeably affect the fundamental nature of incineration ash residues. To provide a greater understanding of these processes, a MSWI (mono)landfill site in the north east of the US was selected as the target for systematic investigation of the natural weathering of bottom ash residues. Samples of various ages were collected from locations A (1 yr), B (10 yrs), C (13-14 yrs) and D (20 yrs) of the landfill in 2009. We investigated the phase transformation of the collected bottom ash particles, neoformation processes as well as the behavior and distribution of certain heavy metals (Cu, Pb, Zn, Ni, and Cr) in the neoformed phases using optical microscopy, SEM-EDX, and bulk examinations. Key findings: at the preliminary stage, the waste metallic particles (Al, Fe, and Cu) and unstable minerals such as lime, portlandite, ettringite and hydrocalumite convert to oxide and hydroxide (hydrate) phases, calcite, alumina gel and gypsum. At the intermediate stage, the decomposition of melt products including magnetite spinels and metallic inclusions is triggered due to the partial dissolution of the melt glass. At the longer time horizon it is possible to track the breakdown of the glass phase, the extensive formation of calcite and anhydrite, Al-hydrates and more stable Fe-hydrates all through the older ash deposits. Among the dominant secondary phases, we propose the following order based on their direct metal uptake capacity: Fe-hydrates>Al-hydrates>calcite. Calcite was found to be the least effective phase for the direct sorption of heavy metals. Based on overall findings, a model is proposed that demonstrates the general trend of ash weathering in the landfill.     

Predicting the mobility of Zn, Fe, Cu, Pb, Cd from roasted sulfide (pyrite) residues—A case study of wastes from the sulfuric acid industry in Sweden

Leachates from roasted sulfide residues, which are the wastes from the production of sulfuric acid at Falun, Sweden, have low pH and high concentrations of Zn, Fe, and SO₄. The minerals are mainly hematite and maghemite and, because the various sulfides in the feed behave differently during the roasting process, the residual sulfides minerals are pyrrhotite and sphalerite. Oxidation of the residual sulfides contributes acidity, Zn, Fe, Cu, Cd, and sulfate to the effluents from the waste deposits. The dissolution of sphalerite is most likely accelerated in acid solution rich in Fe (III). The formation of Pb-sulfate coatings on galena may provides an armoring effect which slows the oxidation of the galena. Residual sulfides are source phases controlling long-term contaminant release. Other source minerals for Zn, Fe, Pb, Cu, Cd and SO₄ in the effluents are iron oxides which retained percentage quantities of SO₄, roast-derived alteration rims of Zn oxides on sphalerite, alterated silicates formed during the roasting process, and secondary minerals (e.g. Zn, Fe, Cu sulfates, iron hydroxides) that were precipitated by in-site oxidation in the waste dumps. The Zn, Fe, and Cu sulfates most likely control short-term changes in the chemistry of the leachate, while Pb concentration in the leachates may be controlled predominantly by Pb-release from the altered silicates. The mineralogical and geochemical data provide fundamental information essential for the remedial management of this type of industial waste.     

An investigation on the potential of metal recovery from the municipal waste incinerator in Taiwan

This study aimed to identify distribution of metals and to estimate the amount of these metals that can be potentially recovered from incineration residues. First, the partitioning behavior of Cr, Cu, Fe, Cd, Al, Zn, and Pb in bottom ash and fly ash was investigated in one large municipal waste incinerator in Taiwan. In addition, the material flow analysis (MFA) method was used to estimate the material flux of metals within incinerator plant, and to calculate the amount of metal recovery. According to the findings of this study, six metals (Fe, Al, Cu, Zn, Cr, and Pb) concentrated in bottom ash mostly, while Cd existed primarily in fly ash. The weight percentages of Fe (4.49%), Al (5.24%), Cu (1.29%), Zn (2.21%), and Pb (0.58%) in incinerator ash are high, and even higher than the compositions of natural minerals. Finally, the amount of Cr, Cu, Fe, Cd, Al, Zn and Pb that can be potentially recovered from incineration residues will reach 2.69 x 10(2), 1.46 x 10(4), 4.91 x 10(4), 6.92 x 10(1), 5.10 x 10(4), 1.85 x 10(4) and 4.66 x 10(3) ton/yr, respectively.     

Influences of chemical activators on incinerator bottom ash

This research has applied different chemical activators to mechanically and thermally treated fine fraction (<14 mm) of incinerator bottom ash (IBA), in order to investigate the influences of chemical activators on this new pozzolanic material. IBA has been milled and thermally treated at 800 degrees C (TIBA). The TIBA produced was blended with Ca(OH)(2) and evaluated for setting time, reactivity and compressive strength after the addition of 0.0565 mole of Na(2)SO(4), K(2)SO(4), Na(2)CO(3), K(2)CO(3), NaOH, KOH and CaCl(2) into 100g of binder (TIBA+Ca(OH)(2)). The microstructures of activated IBA and hydrated samples have been characterized by X-ray diffraction (XRD) and thermogravimetry (TG) analysis. Thermal treatment is found to produce gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)) phases. The thermally treated IBA samples are significantly more reactive than the milled IBA. The addition of Na(2)CO(3) can increase the compressive strength and calcium hydroxide consumption at 28-day curing ages. However, the addition of Na(2)SO(4), K(2)SO(4), K(2)CO(3), NaOH and KOH reduces the strength and hydration reaction. Moreover, these chemicals produce more porous samples due to increased generation of hydrogen gas. The addition of CaCl(2) has a negative effect on the hydration of TIBA samples. Calcium aluminium oxide carbonate sulphide hydrate (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33)(H(2)O)(11)) is the main hydration product in the samples with activated IBA, except for the sample containing CaCl(2).     

Mechanical properties and leaching modeling of activated incinerator bottom ash in Portland cement blends

In the present study the evolution of mechanical strength and the leaching behavior of major and trace elements from activated incinerator bottom ash/Portland cement mixtures were investigated. Chemical and mechanical activation were applied with the purpose of improving the reactivity of bottom ash in cement blends. Chemical activation made use of NaOH, KOH, CaCl₂ or CaSO₄, which were selected for the experimental campaign on the basis of the results from previous studies. The results indicated that CaCl₂ exhibited by far the best effects on the evolution of the hydration process in the mixtures; a positive effect on mechanical strength was also observed when CaSO₄ was used as the activator, while the gain in strength produced by KOH and NaOH was irrelevant. Geochemical modeling of the leaching solutions provided information on the mineral phases responsible for the release of major elements from the hardened materials and also indicated the important role played by surface sorption onto amorphous Fe and Al minerals in dictating the leaching of Pb. The leaching of the other trace metal cations investigated (Cu, Ni and Zn) could not be explained by any pure mineral included in the thermodynamic database used, suggesting they were present in the materials in the form of complex minerals or phase assemblages for which no consistent thermodynamic data are presently available in the literature.     

Characterization of alkali-activated thermally treated incinerator bottom ash

The fine fraction (<14mm) of incinerator bottom ash (IBA) obtained from a UK energy from waste plant has been milled and thermally treated at 600, 700, 800 and 880 degrees C. Treated materials have been activated with Ca(OH)(2) (10wt%) and the setting times and compressive strengths at different curing times measured. In addition to decomposition of CaCO(3) to CaO, thermal treatment increases the content of gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)). Thermally treated samples were significantly more reactive than milled IBA and heating to 700 degrees C produced a material which rapidly set. Silica, gehlenite and wollastonite were the main crystalline phases present in hydrated samples and a mixed sulphate-carbonate AFm-type phase (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33).11H(2)O) formed. Significant volumes of gas were generated during curing and this produced a macro-porous microstructure that limited strength to 2.8MPa. The new materials may have potential for use as controlled low-strength materials.     

Petrogenetic characteristics of molten slag from the pyrolysis/melting treatment of MSW

MSW slag materials derived from four pyrolysis melting plants in Japan were studied from the viewpoint of petrology in order to discriminate the glass and mineral phases and to propose a petrogenetic model for the formation process of molten slag. Slag material is composed of two major components: melt and refractory products. The melt products that formed during the melting process comprise silicate glass, and a suite of minerals as major constituents. The silicate glass is essentially composed of low and high silica glass members (typically 30% and 50% of SiO(2), respectively), from which minerals such as spinels, melilite, pseudowollastonite, and metallic inclusions have been precipitated. The refractory products consist mainly of pieces of metals, minerals and lithic fragments that survived through the melting process. Investigations demonstrated that the low silica melts (higher Ca and Al contents) were produced at upper levels of high temperature combustion chamber HTCC, at narrower temperature ranges (1250-1350 degrees C), while the high silica melts formed at broader temperature ranges (1250-1450 degrees C), at the lower levels of HTCC. The recent temperature ranges were estimated by using CaOAl(2)O(3)SiO(2) (CAS) ternary liquidus diagram that are reasonably consistent with those reported for a typical combustor. It was also understood that the samples with a higher CaO/SiO(2) ratio (>0.74-0.75) have undergone improved melting, incipient crystallization of minerals, and extensive homogenization. The combined mineralogical and geochemical examinations provided evidence to accept the concept of stepwise generation of different melt phases within the HTCC. The petrogenesis of the melt products may therefore be described as a two-phase melt system with immiscible characteristics that have been successively generated during the melting process of MSW.     

Stabilization of As, Cr, Cu, Pb and Zn in soil using amendments--a review

The spread of contaminants in soil can be hindered by the soil stabilization technique. Contaminant immobilizing amendments decrease trace element leaching and their bioavailability by inducing various sorption processes: adsorption to mineral surfaces, formation of stable complexes with organic ligands, surface precipitation and ion exchange. Precipitation as salts and co-precipitation can also contribute to reducing contaminant mobility. The technique can be used in in situ and ex situ applications to reclaim and re-vegetate industrially devastated areas and mine-spoils, improve soil quality and reduce contaminant mobility by stabilizing agents and a beneficial use of industrial by-products. This study is an overview of data published during the last five years on the immobilization of one metalloid, As, and four heavy metals, Cr, Cu, Pb and Zn, in soils. The most extensively studied amendments for As immobilization are Fe containing materials. The immobilization of As occurs through adsorption on Fe oxides by replacing the surface hydroxyl groups with the As ions, as well as by the formation of amorphous Fe(III) arsenates and/or insoluble secondary oxidation minerals. Cr stabilization mainly deals with Cr reduction from its toxic and mobile hexavalent form Cr(VI) to stable in natural environments Cr(III). The reduction is accelerated in soil by the presence of organic matter and divalent iron. Clays, carbonates, phosphates and Fe oxides were the common amendments tested for Cu immobilization. The suggested mechanisms of Cu retention were precipitation of Cu carbonates and oxy-hydroxides, ion exchange and formation of ternary cation-anion complexes on the surface of Fe and Al oxy-hydroxides. Most of the studies on Pb stabilization were performed using various phosphorus-containing amendments, which reduce the Pb mobility by ionic exchange and precipitation of pyromorphite-type minerals. Zn can be successfully immobilized in soil by phosphorus amendments and clays.     

A thermodynamic approach to the hydration of sulphate-resisting Portland cement

A thermodynamic approach is used to model changes in the hydrate assemblage and the composition of the pore solution during the hydration of calcite-free and calcite-containing sulphate-resisting Portland cement CEM I 52.5 N HTS. Modelling is based on thermodynamic data for the hydration products and calculated hydration rates for the individual clinker phases, which are used as time-dependent input parameters. Model predictions compare well with the composition of the hydrate assemblage as observed by TGA and semi-quantitative XRD and with the experimentally determined compositions of the pore solutions. The calculations show that in the presence of small amounts of calcite typically associated with Portland cement, C-S-H, portlandite, ettringite and calcium monocarbonate are the main hydration products. In the absence of calcite in the cement, however, siliceous hydrogarnet instead of calcium monocarbonate is observed to precipitate. The use of a higher water-to-cement ratio for the preparation of a calcite-containing cement paste has a minor effect on the composition of the hydrate assemblage, while it significantly changes the composition of the pore solution. In particular, lower pH value and higher Ca concentrations appear that could potentially influence the solubility and uptake of heavy metals and anions by cementitious materials.     

Evaluation of chemical stability of heavy metals in industrial waste slag by infrared spectroscopy

Our aim was to clarify the chemical bonding type and stability of heavy metals in industrial waste slag (IWS) by using Fourier transform infrared (FT-IR) spectroscopy. The chemical composition of the IWS sample used in this study was an Al/Si ratio of 0.50 with Fe, Pb, and other minor heavy metals present. The IR peak position of the Si-OSi( M) band (M: Al, Pb, or Fe) was lower for IWS (971 cm⁻¹) than for synthetic Si-Al glass with an Al/Si ratio of 0.5 (1029 cm⁻¹). This implies the formation of covalent Si-O-Pb and Si-O-Fe bonds in the IWS, which caused a shift in the peak position toward a lower wavenumber. FT-IR spectra of synthetic Si-Al-Pb and Si-Al-Fe glasses with various Pb/Si and Fe/Si ratios with a constant Al/Si ratio of 0.5 showed that the peak position of the Si-O-Si(M) band continuously shifted toward lower wavenumbers with increasing Pb/Si and Fe/Si ratios. This suggests that covalent Si-O-Pb and Si-O-Fe bonds are formed in IWS. The comparison of peak positions of the Si-O-Si(M) band between IWS and Si-Al-Fe glass indicated that not only Pb but also other minor heavy metals such as Cu and Cr were included by covalent bonds into the structure of IWS. Therefore, we concluded that most of the heavy metals in IWS formed covalent Si-O-M bodings and were chemically stable.     

Degradation of Al/SiCp composites produced with rice-hull ash and aluminum cans

The use of recycling aluminum from beverage containers and rice-hull ash (RHA) offers to be an attractive alternative for the economic production of Al/SiCp composites. However, corrosion phenomena in the composites represent technological barriers yet to be resolved before they can be exploited to their full potential. A simple methodology involving characterization by XRD, SEM, EDX, FTIR and ICP was designed in order to investigate the causes of the rapid degradation in a humid environment of Al/SiCp composites produced with RHA and aluminum cans. Results reveal that the use of RHA was beneficial to avoid degradation through the formation and subsequent hydration of the Al4C3 phase. However with condensed moisture acting as an electrolyte, localized corrosion took place with aggressive damage manifested by the disintegration of the composite into a powdery mixture. The relevant corrosion mechanism was mainly attributed to microgalvanic coupling between the Mg2Si intermetallic compound and the matrix (although other phases such as SiC, Si, MgAl2O4 could also work as microcathodes).     

Production of cement clinkers from municipal solid waste incineration (MSWI) fly ash

This communication reports the laboratory scale study on the production of cement clinkers from two types of municipal solid waste incineration fly ash (MSW ash) samples. XRD technique was used to monitor the phase formation during the burning of the raw mixes. The amount of trace elements volatilized during clinkerization and hydration, as well as leaching behaviours of the clinkers obtained from optimum compositions, were also evaluated. From the results it is observed that all of the major components of ordinary Portland cement (OPC) clinkers are present in the produced clinkers. Results also show the volatilization of considerable amounts of Na, K, Pb, Zn and Cd during the production of clinkers. However, major parts of the toxic elements remaining in the clinkers appear to be immobilized in the clinkers phases. Hydration studies of the clinkers obtained from optimum compositions show that the clinkers prepared from raw MSW ash are more reactive than the washed MSW ash based clinkers. TG/DTA analyses of the hydrated pastes show the formation of hydration products, which are generally found in OPC and OPC derived cements. The initial study, therefore, shows that more than 44% of MSW ash with the addition of very small amounts of silica and iron oxide can be used to produce cement clinkers. The amount of CaCO3 necessary to produce clinkers (approximately 50%) is also smaller than the same required for the conventional process (more than 70%).     

Physicochemical properties of slags produced at various amounts of iron addition in lead smelting

In the process of lead production from lead-bearing materials generated in copper metallurgy, a large amount of hazardous waste in the form of slag is produced. To assess the effect of the slag on the environment, its physicochemical properties were determined. In this study, the following methods were used: wavelength dispersive X-ray fluorescence (WD XRF), X-ray diffraction (XRD), and Bunte-Baum-Reerink method to determine softening and melting points, as well as viscosity examination and leaching tests. The measurements were performed on the slag produced with two different amounts of iron addition to the lead smelting process. The resulting slags, an oxide rich phase slag and a sulfide rich phase slag have different compositions and physicochemical properties. It was found that the increase in iron addition causes an increase in the softening melting point of the oxide rich phase slag by about 100 °C, and a twofold increase in the viscosity of both slag phases. The increase in iron addition also results in the decrease in As leachability and increase in Zn, Fe, and Cu leachability from the slags. Slag produced with increased iron addition has a greater impact on the environment.

     

Stabilization of heavy metals in MSWI fly ash using silica fume

The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR (²⁷Al and ²⁹Si) techniques. It was found that silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.     

Immobilization of MSWI fly ash through geopolymerization: Effects of water-wash

The present research explored the role played by water-wash on geopolymerization for the immobilization and solidification of municipal solid waste incineration (MSWI) fly ash. The water-wash pretreatment substantially promoted the early strength of geopolymer and resulted in a higher ultimate strength compared to the counterpart without water-wash.XRD pattern of water-washed fly ash (WFA) revealed that NaCl and KCl were nearly eliminated in the WFA. Aside from geopolymer, ettringite (Ca₆Al₂(SO₄)₃(OH)₁₂·26H₂O) was formed in MSWI fly ash-based geopolymer (Geo-FA). Meanwhile, calcium aluminate hydrate (Ca₂Al(OH)₇·3H₂O), not ettringite, appeared in geopolymer that was synthesized with water-washed fly ash (Geo-WFA). Leached Geo-WFA (Geo-WFA-L) did not exhibit any signs of deterioration, while there was visual cracking on the surface of leached Geo-FA (Geo-FA-L). The crack may be caused by the migration of K⁺, Na⁺, and Cl⁻ ions outside Geo-FA and the negative effect from crystallization of expansive compounds can not be excluded. Furthermore, transformation of calcium aluminate hydrate in Geo-WFA to ettringite in Geo-WFA-L allowed the reduction of the pore size of the specimen. IR spectrums suggested that Geo-WFA can supply more stable chemical encapsulation for heavy metals.Static monolithic leaching tests were conducted for geopolymers to estimate the immobilization efficiency. Heavy metal leaching was elucidated using the first-order reaction/diffusion model. Combined with the results from compressive strength and microstructure of samples, the effects of water-wash on immobilization were inferred in this study.