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Eect of Al source and alkali activation on Pb and Cu immobilisation in y-ash based geopolymers
J.W. Phaira,*, J.S.J. van Deventera, J.D. Smithb
a

Department of Chemical Engineering, The University of Melbourne, 3010 Victoria, Australia b School of Chemistry, The University of Melbourne, 3010 Victoria, Australia Received 29 November 2002; accepted 30 June 2003 Editorial handling by R Fuge

Abstract Solidication/stabilisation technologies are attracting great interest from mining and energy industries alike, to solve their pressing waste disposal problems. Geopolymers, in particular, are becoming one of the more popular solidication/stabilisation methods since they can be applied to a variety of waste sources at low cost, yielding added-value products. However, the eect of Al source on the solidication/stabilisation of heavy metals within y ash-based Geopolymers, has received little attention. This study examines the eect of variable Al source and alkali-activator on the nal properties of y ash-based Geopolymers as characterised by compressive strength testing, infrared and X-ray diraction analyses. Leaching tests were performed to determine the eciencies of Pb and Cu immobilisation, which were compared to the initial properties of the Al source (e.g. particle size, cation exchange capacity, total extractable cation concentration and suspension yield stress). It was observed that Pb was generally better immobilised than Cu. In addition, the total extractable cation concentration of the Al source greatly aected the eciency of Pb immobilisation while the physical properties of the Al source (suspension yield stress and eventual compressive strength) determined the eciencies of Cu immobilisation. For both metals, NaOH activation was the most favourable method for metal immobilisation, however, a clear mechanism of adsorption remains elusive. # 2003 Elsevier Ltd. All rights reserved.

1. Introduction Industrialised societies are producing progressively more waste as a result of their burgeoning mining and energy industries (Inyang and Bergeson, 1992). These wastes are amassing to such an extent that giga-scale disposal is becoming a common phenomenon (Scheetz et al., 1999). Often, giga-scale wastes such as mine tailings have low-level amounts of heavy metals (e.g. Pb) associated with them that must either be extracted or immobilised before proper disposal can occur. If immo-

* Corresponding author at present address: Turner-Fairbank Highway Research Center, FHWA, McLean VA 22101, USA. Fax: +1-202-493-3086. E-mail address: john.phair@fhwa.dot.gov (J.W. Phair).

bilisation or xation of the heavy metals within the waste source itself does not occur, these hazardous materials require a special landll consisting of double plastic and clay liners as well as a comprehensive leachate collection system (Camobreco et al., 1999). These are mandatory requirements to ensure the waste is disposed of acceptably. Such geotechnical solutions are, however, very expensive and time-consuming to install, requiring constant maintenance and monitoring for the rst 30 years after installation (Dijkema et al., 2000). Given the large quantities of materials being disposed of, it is often easier to treat the waste in situ and prevent its interaction with the environment, rather than to separate the heavy metals from the material or install geotechnical infrastructure. Solidication/stabilisation presents itself as a highly practical method of immobilisation, since it can be applied to a wide variety of waste

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sources containing heavy metals. Out of the various solidication/stabilisation techniques available, y ashbased geopolymers are attracting signicant commercial interest for their cost-eectiveness and exibility. For instance, geopolymers have already been used to immobilise and stabilise low-level radioactive waste of pure or contaminated (mixed waste) forms (Mollah et al., 1992) as well as heavy metals (Van Jaarsveld et al., 1997). When adequately xed, the new waste form can nd subsequent service in construction and road/pavement applications as an added-value product, closing the loop on the material life-cycle. The purpose of this present study is to further evaluate and substantiate the wide applicability of y ashbased geopolymer binders, by investigating the eect of variable Al source on the leaching properties. This will not only establish which and why particular Al sources work best within the geopolymers, but will help to develop a set of criteria for predicting whether a new Al source would be suitable for immobilisation.

2. Background Geopolymers are a diverse group of ceramic-like materials formed by a geosynthetic reaction of aluminosilicate minerals in the presence of an alkali solution at low temperatures ( < 100  C) (Davidovits, 1991). The series of geochemical reactions that comprise this process are complex and include mineral dissolution, aluminosilicate polycondensation and structural re-organisation (Phair et al., 2001, Xu and Van Deventer, 2000a). A schematic of typical geochemical reactions associated with mineral polymer (polysialate) and geopolymer formation is provided in Fig. 1. Eorts continue to

improve the fundamental theory while developing and rening practical applications. Fly ash-based geopolymers are growing in commercial potential due to their reliance on cheap and readily available waste y ash as the main feedstock (Phair and Van Deventer, 2002a; Swanepoel and Strydom, 2002; Van Jaarsveld et al., 1998a). In addition, y ash-based geopolymers consist of an Al-rich additive or source to improve material performance. The term Al source here refers to an aluminosilicate mineral with a layered structure and high Al content ( > 30% Al). Initially in geopolymer synthesis, this was restricted to metakaolin but has since been extended to include kaolin (Van Jaarsveld et al., 1997), feldspar (Xu and Van Deventer, 2000b) and stilbite (Xu et al., 2001). A typical y ashbased geopolymer mix now consists of approximately 60% mass dry y ash and approximately 12% mass dry Al source (Phair and Van Deventer, 2002a; Swanepoel and Strydom, 2002; Van Jaarsveld et al., 1998a). The rest of the mix is the alkali silicate mixing solution although in most large-scale commercial operations this amount is substantially reduced. It has previously been reported how small variations in compositional factors such as the pH of the alkali activator and the nature of the setting additive (Ca rich source), greatly aect the eciency of metal immobilisation within y ash-based geopolymers (Phair and Van Deventer, 2001, 2002b). However, the role of the Al source in optimising metal immobilisation and other material properties of y ash-based geopolymers, has received little attention. The present work, therefore, aims to determine the eect of variable Al source (kaolinite, metakaolinite, K-feldspar and y ash), on the immobilisation of heavy metals (Pb and Cu) within y ash-based geopolymers. Through examining the mate-

Fig. 1. Schematic of geopolymerisation reactions according to Davidovits et al. (1991).

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rial properties of the starting materials (eg. surface area, cation-exchange capacity, mineralogy, particle size and suspension properties), explanations for the nal material and leaching properties of the geopolymers can be given as a function of Al source. An important aspect of this work will also be to evaluate the eect of the Al source on the mechanism of immobilisation of heavy metals in comparison to other compositional variables and established theories. First discussions on the mechanism of immobilisation by geopolymers relied upon comparisons to zeolitic materials for adsorbing/binding heavy metals (Comrie et al., 1988; Khalil and Merz, 1991). Immobilisation of heavy metals within Geopolymers were subsequently proposed to include a mechanism whereby the species were locked within the geopolymeric matrix (Van Jaarsveld et al., 1998a). Kinetic studies, which examined the eect of pore and particle size of crushed y-ash based geopolymers on leaching, continued to speculate that immobilisation of heavy metals occurs via adsorption onto a zeolite-like backbone (Van Jaarsveld and Van Deventer, 1999; Van Jaarsveld et al., 1997, 1998a). However, given the anionic speciation of the metals at high pH, the existence of a strict electrostatic adsorption mechanism is debatable. Nonetheless, it may still be possible for some form of adsorption to occur to a foreign substrate if both surface and solution reactions are included in its description. By adding heavy metals to the Al source (typical heavy metal adsorbents) prior to wet mixing, it will be possible to focus attention on the role of adsorption in the immobilisation of heavy metals within y ash-based geopolymers.

3.2. Characterisation methods and sample preparation BET surface area was determined for the Al source materials used in the synthesis of the y ash-based Geopolymers, using a Micromeritics Flowsorb ASAP 2000 with a 30/70 ratio of N2 and He. Particle size of the materials was measured using a Coulter LS 130 optical particle size analyser and the density was determined using a pycnometer. Determination of cation exchange capacity and quantities of the total extractable cations for the various Al sources was conducted at pH 7 (ammonium acetate buered) (Chapman, 1965). The method was chosen since none of the solids present were acidic. Ammonium (N) concentration was determined using an Orion ammonium electrode and voltmeter. Equilibrium suspensions obtained for each Al source were analysed for elemental concentrations after centrifuging, ltering and diluting with 5% conc. HCl, by an ICP-OES PerkinElmer 3000. Yield stress measurements of concentrated suspensions of the Al sources in diluted Na-silicate were measured on a vane rheometer as described earlier (de Kretser et al., 1998). The experimental apparatus consists of a small 4-bladed vane attached to the spring-driving motor of a Haake RV-3 viscometer. Yield stress experiments were conducted on 40% solid (mass) suspensions in solutions of 2:1 ratio H2O to concentrated Na silicate. The physical and chemical characteristics of the starting materials are provided in Tables 2 and 3 respectively. The geopolymer samples were synthesised as described previously (Phair and Van Deventer, 2001, 2002a; Van Jaarsveld et al., 1998b). The samples were cast in 50mm cubes, vibrated for 2 min and set at 23  C for 7 days and thereafter stored at room temperature. Dissolved Pb(NO3)2 or Cu(NO3)2 was added to the reaction mixture. The mixes were activated with NaOH (Orica
Table 1 X-ray uorescence fusion analysis of the oxide compositions of Al source materials used in the synthesis of y ash-based geopolymers
Chemical composition (wt.%) SiO2 Al2O3 CaO Fe2O3 MgO K2O Na2O SO3 MnO P2O5 TiO2 Loss on ignition Kaolinite K-Feldspar Metakaolinite Fly ash

3. Experimental 3.1. Materials Sodium silicate (Vitrosol N(N40), P.Q. Australia Pty. Ltd, Dandenong South, Victoria) with weight% SiO2=28.7, weight ratio SiO2 : Na2O=3.22 ([SiO2]= 6.62 M) and NaOH (AR, Ajax Chemicals Australia, Sydney, NSW) were used for the alkali-activating solutions. All solutions were diluted daily from stock solution using distilled water. Fly ash used in the synthesis of all Geopolymer matrices was of coal origin and obtained from Port Augusta, South Australia. Kaolinite (HR1 Grade) and K-Feldspar were obtained from Commercial Minerals, Sydney, Australia. Metakaolinite was obtained by calcining kaolinite at 700  C for 6 h. Oxide compositions of the starting minerals (listed in Table 1) were determined on a Siemens SRS3000 sequential X-ray uorescence spectrophotometer after fusing the samples with lithium borate. Distilled water was used throughout and all other chemical reagents were of AR grade unless otherwise stated.

52.4 28.6 0.1 1.2 0.2 0.2 0.1 0 0.02 0.1 2.8 14.28

67.1 17.6 0.2 0.2 0 10.6 < 0.1 0 < 0.01 0.3 0.01 3.88

59.6 33.9 0.2 1.2 0.3 0.2 0.17 0 0.01 0.14 3.00 1.41

48.5 29.6 6.1 4.6 2.3 0.9 3.68 0.25 0.07 1.0 2.46 0.62

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Table 2 The physical characteristics of the Al source materials used in the synthesis of y ash-based geopolymers Al source Yield stress, ty (Pa) 555 397 51 105 Average particle size (mm) 0.9 0.9 11.0 1.0 Density (m2/g) 2.65 2.5 2.33 2.62 BET surface area (m2/g) 21.1 21.4 1.6 3.1

Kaolinite Metakaolinite Fly ash K-Feldspar

cover plate before being placed under the microscope. Sample thin sections were around 30 mm thick when they were analysed. An Olympus AX70 optical microscope was used and photographs were taken with a 35 mm Olympus camera. The Infrared spectra of the ground samples were recorded using the KBr pellet technique on a Bio-Rad FTS 165 FTIR spectrometer. X-ray powder diraction traces were obtained using a Phillips PW 1800 diffractometer with CuKa radiation generated at 20 mA and 40 Kv. Specimens were step scanned as random powder mounts from 570 2y at 0.02 2 steps integrated at the rate of 1.2 s per step. 3.3. TCLP leaching tests The Toxicity Characteristic Leaching Procedure (TCLP, 1990) protocol is designed to simulate the environmental conditions experienced by landll, in order to determine whether wastes are suitable for landll disposal. Usually, these tests are conducted over a relatively short period of time ( < 24 h), so they are capable of providing fundamental, mechanistic and kinetic information regarding the actual leaching process. The TCLP also allows one to describe the measured leachate concentration from a particular waste source in terms of toxicity, and subsequently determine whether the waste source is in fact hazardous. While Cu is not regarded as a toxic element by the TCLP, the maximum concentration of Pb, which is considered to be acceptable is 5 mg/l (Conner, 1990). The specic procedure of the TCLP can be found elsewhere (Fed. Regist., Appendix IIMethod 1311, 1990). In the present work, modied TCLP leaching tests were conducted to simulate a more aggressive leaching environment. Leaching analysis occurred on Geopolymers that had been cured for 28 days. Geopolymer samples were crushed and separated into various particle size fractions using ASTM standard sieves. Particles of size fraction 1000/1700 mm were placed in an acetic acid solution buered with sodium acetate at a pH of 3.3 for the leaching analysis (Conner, 1990; Van Jaarsveld et al., 1998b). A solid : liquid ratio of 1:25 was used for the leaching tests and the temperature was

Table 3 The chemical characteristics of the Al source used in the synthesis of y ash-based geopolymers
Al source CEC value (meq./100 g) Extractable Ca2+ (meq./100 g) 119 52 505 21 Total extractable cationsa (meq/100 g) 229 72 629 223

Kaolinite Metakaolinite Fly ash K-Feldspar


a

11.6 3.2 1.3 1.9

The cations were Na, K, Mg,Ca.

Aust. Pty. Ltd.), Na-silicate (PQ Aust. Pty. Ltd) or a combination of both. The SiO2: Al2O3 ratios used in the mixes followed that of previous work for kaolinite and metakaolinite (Van Jaarsveld et al., 1998b). Compositions of the synthesised y ash-based geopolymers are provided in Table 4. From Table 4 it is clear that the proportion of Al source in the matrices was held constant throughout the samples. The % mass of Nasilicate, NaOH or Na-silicate and NaOH was also held constant. After weighing three-50 mm cubes for each sample, compressive strength testing was performed according to AS 1012.9 and the average results recorded. All samples were tested after 7 days using an Amsler FM 2750 compressive strength testing apparatus. For optical microscopy, samples were taken for analysis after being cured for 7 days. Thin sections were mounted on glass slides and were polished, coated with epoxy resin and

Table 4 Composition of geopolymeric matrices prepared from Port Augusta Fly Ash (mass%) Matrix K1 L1 T1 U1 U2 U3 Al source material Kaolinite 14.0 Metakaolinite 14.0 K-Feldspar 14.0 Fly ash 14.0 Fly ash 14.0 Fly ash 14.0 Pb2+ or Cu2+ 0.5 0.5 0.5 0.5 0.5 0.5 NaOH 2.5 2.5 2.5 2.5 5 Sodium Silicate 2.5 2.5 2.5 2.5 5 H2O: y ash ratio 0.33 0.33 0.33 0.33 0.33 0.33 Al2O3/SiO2 0.60 0.60 0.52 0.61 0.61 0.61

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maintained at 21  C. All samples were stirred using overhead impellars for 18 h instead of tumblers. Tumblers are normally used to simulate the action of water seeping through waste in a landll. However, impellars can be used to simulate a more aggressive leaching environment. Sampling of the leachate solution was conducted by syringe. The extracted sample solutions were centrifuged and ltered using a 0.2 mm nylon millipore lter before dilution with acid (5% vol. Conc. HCl) and analysis of metal concentrations using a Perkin Elmer Optima 3000 ICP-AES.

4. Results and discussion 4.1. Characterisation of the Al source The Al sources examined all varied in their chemical structure and properties. Metakaolinite contains 4 coordinated Al while kaolinite and K-feldspar contain 6co-ordinated Al, although kaolinite is hydrophilic. Fly ash contains 4 co-ordinated Al in a mostly amorphous structure. Mineralogical compositions of the starting materials are presented in Table 1. Metakaolinite has the highest Al content and K-feldspar the lowest. The physical characteristics of the materials provided in Table 2 demonstrate consistent trends between the samples. Generally, the minerals with the largest surface area produced a suspension with the highest yield stress. An explanation for this is that since kaolinite and metakaolinite have a plate-like structure and hydrophilic surface, their interparticle interactions and resulting suspension yield stress are higher (Van Olphen, 1977). The chemical characteristics of the Al source are displayed in Table 3. Measured cation exchange capacities (CEC, units of meq./100 g) compare favourably with literature values (Sharma and Lewis, 1994) with kaolinite clearly having the largest value followed by metakaolinite then K-feldspar. On the other hand, y ash had the highest extractable Ca and total cation concentration followed by kaolinite, then K-feldspar. These values may provide an indication of the extent to which a material may be able to undergo rapid supercial reactions or precipitation. 4.2. Characterisation of y ash-based geopolymers Optical micrographs of geopolymeric matrices U1 and K1 are provided in Figs. 2 and 3. It is clear from Figs. 2 and 3 just how heterogeneous the particle size distribution is within these matrices. Fly ash particle sizes, for instance, range from 1 to 40 mm in diameter. Infrared spectra were recorded for all of the geopolymer samples. Spectra of NaOH/Na-silicate activated matrices of varying Al source are presented in Fig. 4,

while the peak assignments and their respective frequencies are provided in Table 5. No observable peak could be attributed to the presence of Pb or Cu. The peaks around 1009 and 1030 cm1 have been attributed to asymmetric stretching of AlO and SiO bonds (v1) while the peaks at 550 cm1 have been attributed to octahedrally co-ordinated Al (Palomo and Glasser, 1992) (v2). Peaks at approximately 460 cm1 are assigned to in-plane bending of AlO and SiO linkages (v3). Only in K (kaolinite) matrices were the two peaks at 1009 and 1030 cm1 observed suggesting that the kaolinite still maintains a structural role in the new matrix. Of further interest is the carbonate peak at  875 cm1 (Yousuf et al., 1993) which increases with the concentration of Na-silicate added. An additional carbonate peak at  1450 cm1 on the other hand, maintains consistent intensity throughout. The study of gepolymers by XRD is complicated by the extensive broad peaks associated with amorphous (y ash) structure, seen between 20 and 40 degrees 2 in Fig. 5 (Van Jaarsveld et al., 1998a). Sharp peaks are normally associated with un-reacted starting materials such as the heamatite, quartz and mullite present in the y ash. 4.3. Compressive strength Compressive strength tests were performed on the geopolymers to indirectly link the bulk material properties of the matrix to its eciency of metal immobilisation. Generally, there is accepted to be a strong link between material porosity and compressive strength. If immobilisation eciencies decrease with decreasing compressive strength, then a direct correlation with porosity can exist. If immobilisation eciency does not vary with compressive strength, this suggests that other factors are aecting the immobilisation eciency rather than pore size/distribution alone. The compressive strength and measured densities of the geopolymers are presented in Table 6. All samples had a similar density of approximately 1.6 g/cm3, however, U1
Table 5 The peak assignments for the FTIR spectra of y ash-based geopolymers synthesised according to Table 4 Matrix K1 L1 T1 U1 U2 U3 Fly ash n1 1031.3 1008.5 983.8 984.6 985.2 1028.89 986.4 1026.3 n2 541.2 558.4 564.2 559.5 560.3 558.5 550.5 n3 469 458.8 458.5 453.4 461.5 454.4 461.1
v2CO2 3

874.6 875.1

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Fig. 2. Optical micrograph of geopolymeric matrix U1 (from Table 4).

Fig. 3. Optical micrograph of geopolymeric matrix K1 (from Table 4).

seemed slightly denser which could be attributed to the extensive hydration of y ash in the absence of any other Al source. This would cause more water to be retained within the matrix and increase the observed density. Geopolymers containing kaolinite and metakaolinite were found to be the strongest under compressive strength testing while y ash lacked any considerable strength alone. At this stage, it is also possible to make a correlation between the viscosity of the Al source and the nal strength of the matrix with the more viscous clay sus-

pensions yielding higher compressive strengths. The increased strength may not be attributable to the viscosity directly, but since the viscosity is related to the clays physical structure and morphology, it may indirectly indicate the Geopolymers compressive strength. 4.4. Leaching Leaching tests are probably the single-most important measure of the eciency of heavy metal immobilisation within y ash-based Geopolymers. Accordingly, the

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Fig. 4. FTIR spectra of NaOH/Na-silicate activated matrices.

Fig. 5. The XRD spectra for y ash and y ash based Geopolymer matrices (U1, U2, U3) dened in Table 4.

Table 6 The compressive strength and density of y ash-based geopolymers synthesised according to Table 4 Geopolymer matrix K1 L1 T1 U1 Compressive strength (MPa) 32.7 26.8 13.9 7.7 Density (g/cm3) 1.6 1.61 1.58 1.63

Toxicity Characteristic Leaching Procedure (TCLP) of the EPA was the leaching method of choice due to its wide recognition and established use for evaluating solidication/stabilisation technologies. Not only were equilibrium concentrations of heavy metals measured after the leaching, but equilibrium concentrations of Si and Al were also determined. The TCLP is typically designed for assessing whether a particular waste is safe for disposal by landll. However, more aggressive leaching conditions were used to assess the suitability of the stabilised waste form for other applications (e.g. roads), which have more rigorous leaching standards.

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The nal solution concentrations of Pb after the leaching tests are shown in Fig. 6. It is readily apparent that the alkali activator had a consistent eect on the eciency of immobilisation (minimum concentration of Pb in equilibrium solution) for all Al sources. NaOH was determined to be the most eective activator while Na-silicate was determined to be the least eective.

Nevertheless, all matrices were generally found to be highly ecient in retaining Pb within the matrix with the following order of eectiveness established: y ash > kaolinite > K-feldspar > metakaolinite. This trend can be directly correlated with the liberation of Si and Al from y ash-based Geopolymers according to the data in Figs. 7 and 8. No correlations, however, could

Fig. 6. Equilibrium concentrations of Pb in leachate after leaching of y ash-based geopolymers (dened in Table 4) for 18 h.

Fig. 7. Equilibrium concentrations of Si in leachate after leaching of y ash-based geopolymers (dened in Table 4) for 18 h.

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Fig. 8. Equilibrium concentrations of Al in leachate after leaching of y ash-based Geopolymers (dened in Table 4) for 18 h.

be observed between the eciency of Pb immobilisation and the compressive strength (porosity) or the viscosity of the matrices. In contrast to NaOH being the most eective activator for minimising the quantity of Pb leached out, Na-silicate was determined to be the most eective activator for retaining Al and Si. The fact that less Al and Si is leached out in the presence of silicate activator alone is most likely due to the fact that it is less alkaline than NaOH and, therefore, does not dissolve the mineral ingredients as much. This result suggests that immobilisation of Pb requires reaction with species dissolved from the starting materials in order to form a new phase. Its immobilisation eciency is lowest when Na-silicate alone is used as the activator. The new phase in which Pb is immobilised requires Al, Si and possibly other minerals and cannot simply rely upon the excesses of Si made available using Na-silicate. The total extractable cation content of the mineral source was found to be the single chemical characteristic that correlated best with Pb immobilisation data. This suggests that the higher the amount of available cations on the surface, the greater the ability for insoluble metal hydroxide/silicate compounds to undergo further reactions. These subsequent reactions result in new aluminosilicate phase formation, which immobilises Pb more eectively. No correlation was observed between the cation exchange capacity of the various mineral samples and the eciency of immobilisation indicating that direct electrostatic adsorption does not occur. This is most likely due to the high pH ( > 13) used in geopoly-

merisation that creates negatively charged Pb species and reduces the adsorbent characteristics of the Al source. As a consequence, it is suggested that Pb is immobilised within a new phase rather than being adsorbed onto the surface of the mineral. Table 7 presents the leaching data for Cu doped y ash-based geopolymers and it is clear from the outset, that the eciency of Cu immobilisation is much lower than it is for Pb. A strong correlation can be observed between the immobilisation eciency and the compressive strength/viscosity of the Al source. This trend was not apparent for the immobilisation of Pb, which was determined to be dependent upon the total extractable cation content of the Al source. As was observed for the immobilisation of Pb (See Fig. 6), the most eective immobilisation of Cu occurred when NaOH was used as the activator. With respect to the leachate concentrations of Al and Si in Table 7, it is clear that they are both at a maximum for NaOH activation, followed by Na-silicate/NaOH and are at a minimum for Na-silicate activation. On the other hand, Na-silicate/NaOH activation was determined to produce the highest concentrations of Al and Si for Pb doped geopolymers (See Figs. 7 and 8). Nonetheless, the eect of the Al source on the leachate concentrations of Al were similar for Cu doped matrices as they were for Pb doped matrices with the following descending order of concentrations established: metakaolinite > y ash > kaolinite > K-feldspar. This trend essentially follows the Al2O3 compositions of the minerals as provided in Table 1. A similar trend for Si leachate concentrations was observed for both Cu and Pb doped matrices

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Table 7 Leaching data for y ash-based geopolymers containing Cu as a function of Al source and alkali activator (element concentrations are in units of mg/l) Element Cu Matrix K L T U K L T U K L T U Al Source Kaolinite Metakaolinite K-feldspar Fly Ash Kaolinite Metakaolinite K-Feldspar Fly Ash Kaolinite Metakaolinite K-Feldspar Fly Ash Na-Silicate/NaOH 85.7 101 116 113 1180 1800 1210 1620 842 853 679 333 Na-Silicate 128 120 122 149 469 401 229 202 539 491 245 235 NaOH 81.6 91.6 70.1 79.3 1740 2240 1430 1920 1070 997 849 979

Al

Si

with metakaolinite and kaolinite providing the highest concentrations followed by K-feldspar and y ash. 4.5. Mechanism of immobilisation of heavy metals within y ash-based geopolymers Sodium silicate based technology has widely been used for remediation processes by industry. Portland cement/soluble silicate remediation systems are based on the reaction of polyvalent metals with soluble silicates to form a 3-D polymer matrix with a structure similar to that of a natural pyroxene (Conner, 1990). In geopolymerisation, Na silicate activation alone does not attain the highest eciency in the immobilisation of Pb and Cu. Sodium silicate activation does, however, allow for a considerable reduction in the leaching of Al and Si from the matrices compared to NaOH. This is most likely due to the fact that Na silicate is less alkaline than NaOH and, therefore, does not liberate such species as readily during the hydration of the starting materials. This process is to be distinguished from Na silicate causing an apparent improvement in the susceptibility of y ash based-geopolymers to leaching conditions, thus reducing the quantities of Al and Si liberated. NaOH activation alone was determined to provide the most eective environment for immobilising both Pb and Cu. This immediately indicates the advantages of geopolymers for heavy metal immobilisation compared to techniques relying on Na silicate as the heavy metal binding agent alone. Adding more alkali is expected to increase the solubility of the metals since Cu and Pb hydroxides are more labile than a bulky polysilicate Pb or Cu precipitate, but this is oset by the advantages associated with the degradation of the mineral starting materials at

higher pH. Only by liberating more Al, Si, Ca etc. species in situ, is it possible to provide the right environment to form a new phase that will adequately bind and encapsulate the heavy metal into a new, more insoluble form. While alkali activation has a consistent eect on the immobilisation of both Cu and Pb within y ash-based geopolymers, it is readily apparent that the Al source aects the immobilisation eciencies in separate ways for both Cu and Pb. While Pb immobilisation was demonstrated to be highly dependent upon the total extractable cation concentration of the Al source, Cu immobilisation eciencies depended more upon the overall physical characteristics of the Al source and its contribution to the compressive strength of the nal material. This result can be explained by the fact that Pb precipitates are larger and less labile than Cu precipitates. Therefore, they are more susceptible to subsequent reactions and may be inuenced by the presence of extra cations (from the Al source), which may stabilise the formation of new amorphous aluminosilicate phases. Furthermore, the possibility of Pb being adsorbed onto the surface of the Al through a series of complex reactions is not excluded. The immediate consequence of Cu precipitates being more labile is that their immobilisation eciencies are considerably less than for those of Pb. Thus, the relative eciencies of Cu immobilisation are dominated by the bulk physical properties of the matrix, which control the migration of Cu precipitates. Properties that have been shown to inuence the eciency of Cu immobilisation include the eventual compressive strength of the matrix and the suspension viscosity of the Al source.

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4.6. The role of the Al source in y ash-based Geopolymers The present work demonstrated that it was possible to utilise variable Al sources to successfully synthesise y ash-based Geopolymers for the purposes of heavy metal immobilisation. While the study was restricted to directly comparing only four Al sources, a list of all the Al sources that may be used in y ash-based Geopolymers is far from complete. So far, it is possible to dene three main requirements if a particular Al source is to be successfully included within a y ash-based Geopolymer. Firstly, the Al source must provide enough Al and in a form useful for Geopolymerisation reactions (Van Jaarsveld et al., 1997). This may also require the presence of minimum quantities of Si, Ca, K etc. Secondly, the Al source must be an additive that optimises (or at least does not detract) the engineering properties of the Geopolymeric matrix eg. shrinkage, compressive strength, brittleness etc. (Davidovits et al., 1990). Thirdly, if the Al source has the ability to act as an adsorptive/reactive surface when added to a wet mix containing heavy metals, then it will minimise the leaching of heavy metals or other contaminants from the waste. Special care must be given when utilising clay based materials as the Al source, since an increase in the swelling capacity and water adsorption of the mix often accompanies better metal adsorption properties. This may subsequently aect the density and strength of the nal product (Guler et al., 1995).

still produced the most favourable environment for Cu immobilisation. It is concluded that the mechanism of immobilisation of Pb and Cu not only involves a physical encapsulation mechanism, but the formation of a new phase through the reaction of the insoluble Pb or Cu compounds with Al- and Si-rich species dissolved from the Al source. Moreover, the immobilisation mechanism of Pb is directly aected by the extractable alkali cations from the Al source while the physical characteristics (suspension viscosity, nal material compressive strength) of the Al source largely control the immobilisation of Cu. New aluminosilicate phase formation is a necessity for the most ecient immobilisation of Pb and Cu and activation based on Na-silicate alone, is insucient. At this stage, for increased eciency of immobilisation it is suggested that the metal waste be pre-treated with the Al source/clay before being added to the geopolymer mix. This would maximise the sorptive capacities of the Al source. More work is required to improve the Cu immobilisation properties of y ash-based geopolymers before they can be applied to the eld.

Acknowledgements JWP acknowledges the support of a Melbourne University Research Scholarship (MRS) Award. Financial contributions from the Australian Research Council and Particulate Fluids Processing Center are also gratefully recognised.

5. Conclusions Fly-ash based geopolymers are emerging as a viable alternative for the solidication/stabilisation of bulk industrial wastes contaminated with heavy metals. By xing heavy metals in situ, it is possible to create addedvalue products, which do not necessarily have to be disposed of immediately. Examination of varying the Al source within various y ash-based geopolymers has conrmed that the geopolymers generally retain useful immobilisation properties no matter which Al source is utilised. The immobilisation of Pb in geopolymers involves a chemical immobilisation process that depends on the total extractable cation concentration of the Al source and the type of alkali activator used. Only NaOH activated matrices consistently produced a TCLP leachate within the EPA limit of 5 mg/l for Pb. K-feldspar and kaolinite exclusively, produced a TCLP leachate within the EPA guideline under NaOH/Na silicate activation. Immobilisation of Cu within y ash-based geopolymers was not as eective due to the increased lability of Cu precipitates. Nevertheless, alkali activation with NaOH

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