You are on page 1of 8

Construction and Building Materials 44 (2013) 743–750

Contents lists available at SciVerse ScienceDirect

Construction and Building Materials
journal homepage:

Durability and leaching behavior of mine tailings-based geopolymer
Saeed Ahmari, Lianyang Zhang ⇑
Department of Civil Engineering and Engineering Mechanics, University of Arizona, Tucson, AZ, USA

h i g h l i g h t s 
Systematically studied durability and leaching behavior of MT-based geopolymer bricks. 
Immersion in pH = 4 and 7 solutions leads to substantial strength loss. 
Immersion in pH = 4 and 7 solutions leads to minor water absorption and weight loss. 
MT-based geopolymer bricks effectively immobilize the heavy metals in MT. 
FRDM can satisfactorily describe the leaching behavior of heavy metals.

a r t i c l e

i n f o

Article history:
Received 12 December 2012
Received in revised form 19 March 2013
Accepted 22 March 2013
Available online 24 April 2013
Mine tailings
Heavy metals
Leaching kinetics

a b s t r a c t
Disposal of mine tailings (MT) in impoundments may have adverse environmental impacts such as air
pollution from dust emissions and release of heavy metals to surface and underground water. Geopolymerization as an environmentally-friendly and sustainable method has been used to stabilize MT so that
they can be used as construction material. In this paper, the durability and leaching behavior of MT-based
geopolymer bricks are studied by measuring unconfined compression strength (UCS), water absorption,
weight loss, and concentration of heavy metals after immersion in pH = 4 and 7 solutions for different
periods of time. Microscopic/spectroscopic techniques, SEM, XRD and FTIR, are also employed to investigate the change in microstructure and phase composition of MT-based geopolymer bricks after immersion in the solutions. To describe the leaching behavior of MT-based geopolymer bricks, the first order
reaction/diffusion model (FRDM) is used to analyze the leaching test data. The results indicate that
although there is a substantial strength loss after immersion in pH = 4 and 7 solutions, the water absorption and weight loss are small. The strength loss is mainly due to the dissolution of geopolymer gels as
indicated by the microscopic/spectroscopic analysis results. The leaching analyses show that the heavy
metals are effectively immobilized in the MT-based geopolymer bricks, which is attributed to the incorporation of heavy metals in the geopolymer network. The FRDM can satisfactorily describe the leaching
behavior of heavy metals in the MT-based geopolymer bricks and the analysis results indicate that the
solubility or reaction rate is an important factor controlling the leaching behavior.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Mine tailings (MT) are a major waste material generated by
mining operations. In current practice, MT are transported in slurry
form to and deposited in storage impoundments. Storage of MT in
such impoundments leads to occupation of large areas of land,
costly construction and maintenance, and potential environmental
and ecological risks. MT can cause air pollution due to dust emissions resulted from surface erosion. MT can also pollute surface
and underground water due to the leaching of heavy metals. The
sulfide minerals in MT such as pyrite (FeS2), pyrrhotite (Fe1xS),
⇑ Corresponding author. Tel.: +1 520 6260532; fax: +1 520 6212550.
E-mail address: (L. Zhang).
0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.

and chalcocite (Cu2S) oxidize in the presence of air and water,
yielding sulphuric acid and releasing metallic oxides such as FeO
[1]. This phenomenon, known as acid mine drainage (AMD), leads
to the drop of pH and results in further leaching of heavy metals
such as Cd, As and Cu [2]. AMD has caused serious contamination
of surface and underground waters in the United States [3]. Therefore, it is vital to take measures to reduce the risk of environmental
contamination by MT.
Generally, there are three methods to reduce the potential environmental hazards imposed by MT: (1) isolation of MT, (2) chemical stabilization of MT, and (3) a combination of these two
methods [2,4]. The isolation techniques include containment of
MT from the surrounding environment such as capping the tailings
impoundment surface. This can be achieved by designing and

The compacted specimens were compressed with an ELE Tri Flex 2 loading machine at different loading rates to ensure that the duration to reach the specified forming pressure was about 10 min for all the specimens. The results indicate that by properly selecting the preparation condition (initial water content.71 1.068 0. the hardened surface acts as a capping system which isolates the underlying tailings from the surrounding environment [14].06 1. the MT were mixed with NaOH solution.8 7. 100 90 80 Percent passing (%) 744 70 60 50 40 30 20 10 0 1 10 100 Particle size (μm) Fig.33 7.33–38].2.009 0.22.034 0.000286 0.90 3.0007 0. Geopolymer is an amorphous binder with a polymeric network structure consisting of repeating units of ASiAOAAlAOA and is formed by alkali activation of silica and alumina containing materials at high pH and room or slightly elevated temperature [19].17. in the meantime.1.52 4. An extensive research has been conducted on fly ash-.26 2. and. Of these different methods. researchers have studied other stabilization methods to stabilize MT [1.163 0. Table 1 shows the chemical composition of the MT. Ahmari. After compression. slag and aluminum are also studied by researchers [12. Due to the generated heat. Arizona.31 0. excellent durability. Fig. geopolymer gels are produced on the MT particle surface and the newly formed gels bind the particles together. de-ionized water. The mixture’s consistency varied from semi-dry to semi-paste as the water content increased from 8% to 18%.23 0. For chemical stabilization. [18] studied the feasibility of using MT-based geopolymer paste as a cover system for tailings dam.18]. poor immobilization of contaminants at high concentrations.93 0. The NaOH solution was prepared by adding NaOH flakes to de-ionized water and stirring for at least five minutes. For example.012 0. Since the stabilization of MT based on the reaction with calcium has a number of limitations. In current practice. MT-based geopolymer bricks can be produced to meet the ASTM requirements on physical and mechanical properties. and more importantly high-energy usage and greenhouse gas emissions related to production of Portland cement [15. It can be seen that the MT consist of mainly silica and alumina with substantial amount of calcium and iron.83. The nitric acid (HNO3) was manufactured by BDH and supplied by VWR. water glass and Portland cement to improve surface erosion resistance and reduce water infiltration. Silva et al. Materials The materials used in this investigation include copper mine tailings (MT).076 0. L. enough time was allowed for the solution to cool down to room temperature before it was used. Geopolymer binder offers superior mechanical properties.66 0. forming pressure and curing temperature). The sodium hydroxide (NaOH) flakes were obtained from Alfa Aesar Company in Ward Hill.70 0. NaOH concentration. 2. a Chemical compound Contenta (%) Standard deviation (%) SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O 64. The mean particle size is around 120 lm with 36% particles passing No. Massachusetts.08 4.022 0. The MT were received as dry powder from a local mine company in Tucson.06 0. The sodium hydroxide solution is prepared by dissolving the sodium hydroxide flakes in de-ionized water. such as inferior mechanical properties.24. geopolymerization is a promising one to effectively stabilize MT in an economical and environmentally-friendly way. The results indicated that fly ash and as much as 65–70% MT can be used to produce geopolymeric material suitable for capping mine tailings. 2. The specific gravity of the MT particles is 2. pozzolanic materials such as cement and lime are commonly used to stabilize MT [1. Preparation of brick samples First. 1000 . Table 1 Chemical composition (wt. and BDH Aristar Plus (67–70%) nitric acid.28–32] and MT-based geopolymer has recently attracted attention of researchers worldwide [18.003 0. Ahmari and Zhang [39] studied the production of eco-friendly bricks based on geopolymerization of copper MT. Experimental 2. 1 shows the particle size distribution curve. and metakaolin-based geopolymers [21. The isolation and stabilization techniques can also be used simultaneously. In this paper.6–11] although other materials such as fly ash. the durability and leaching behavior of the copper MT-based geopolymer bricks are studied. The NaOH solution was slowly added to the dry MT and mixed for 10 min to ensure the homogeneity of the mixture.5 mm height with minor compaction. Zhang / Construction and Building Materials 44 (2013) 743–750 constructing a closure system similar to that used for landfills [5]. Pacheco-Torgal et al. reagent grade 98% sodium hydroxide (NaOH).13. In this method. Particle size distribution of MT powder. [34] studied the stability of CTMTG immersed in water and reported disintegration after a certain period of time mainly due to deficient geopolymeric reaction. The mixture was then placed in Harvard miniature compaction cylindrical molds of 33. and effective immobilization of heavy metals [19–28]. Giannopoulou and Panias [33] showed that the compressive strength of mixed fly ash and MT-based geopolymer increases with the fly ash content and the concentrations of leached heavy metals in neutral and acidic solutions are all below the Greek Standard limits.%) of mine tailings. low acid resistance.13]. Van Jaarsveld et al. the tailings surface can be treated by binders such as organic polymers. [22] evaluated the durability and environmental performance of calcined tungsten MT-based geopolymer (CTMTG) and reported that the CTMTG binder exhibits better durability than Portland cement binder and the concentrations of released heavy metals are all below the DIN limits.4 mm diameter and 72.16].42 Trace elements Pb Zr Mo Zn Cu Mn Ti 0. The generated mixture exhibited varying consistency depending on the initial water content.08 0. slag-. focusing on their physical and mechanical properties. 1.001 0.213 0.009 0.006 The values are the average of seven tailings samples. chemicals or cementitious materials are added to immobilize the heavy metals in MT through physical encapsulation and/or chemical reactions. the specimens were de-molded and placed uncovered in an oven for curing until tested. 200 (75 lm) sieve. Grain size distribution analysis was performed on the MT using mechanical sieving and hydrometer analysis following ASTM D6913 and ASTM D422.S.

2.9 16/0. Results and discussion 3. In the current study. Therefore. The SEM imaging was performed in the SE conventional mode using the FEI INSPEC-S50/ThermoFisher Noran 6 microscope.3. there was not much change in the microstructure after immersion.45 lm membrane filter.0 78.6 4 6. in addition to the partial geopolymerization. XRD.5 specimens and thus less strength loss was observed. A liquid to solid mass ratio of 15 was used for all the specimens throughout the experiment. at 2. The ELE Tri Flex 2 loading machine was used for the compression test at a constant loading rate of 0.1 7 6. XRD.40–42].4 5. or any sign of cracking was observed on any specimen. This can be clearly seen from Fig.5 specimen. at initial water content of 16% and 18%. The XRD analysis was performed with a Scintag XDS 2000 PTS diffractometer using Cu Ka radiation.43.3. [43] argued that geopolymers possessing Si/Al < 1.5 and 0. water absorption and weight loss measurements. the high Si/Al and unreacted alkali could also be a factor for the strength loss of the geopolymer specimens after immersion in water.1 measured UCS.9 11.1 59. 3. After 4 months.0 53.5 later on) were selected to study the durability and leaching behavior.3 7. The optimum forming pressure is related to the initial water content as shown in Fig. After specified immersion times.5 specimens. For each condition. and forming pressures varying from 0 to 35 MPa. the highest UCS values were obtained at a forming pressure respectively of 0. For example. The total amount of extraction from the solutions was less than 5% of the total solution to ensure that the solid to liquid ratio does not substantially change during the experiment. The spectrometer covers wavelengths from 600 to 4000 cm1. SEM.0 8. at least three specimens were tested and the average of the measured UCS values was used.00° with 0. 2. 2.4% at pH = 4 and 75. Initial Water Content (%) 30 5 10 15 20 25 30 35 Forming Pressure (MPa) Fig. The geopolymer brick specimens prepared at initial water content/forming pressure respectively of 12%/25 MPa and 16%/0. [34] on CTMTG which showed substantial strength loss after immersion in water mainly due to insufficient degree of geopolymerization.9 75. 5. weighed. The filtrate was diluted with 1% nitric acid and the concentration of metals in the diluted extracted sample was measured based on the ICP-MS (inductively coupled plasma mass spectrometry) technique. Zhang / Construction and Building Materials 44 (2013) 743–750 2. and dried at 110 °C for 24 h. and weight loss of the specimens after immersion in the solutions for four months.00°/min ranging from 10. Table 2 Physical and mechanical properties of geopolymer bricks after immersion in pH = 4 and 7 solutions for 4 months.600 s count time.0 pH UCS after immersion(MPa) UCS loss (%) Water absorption (%) Weight loss (%) 4 6.5 specimen. 3.5 27. The choice of nitric acid was motivated by the necessity of compensating the pH raise due to the release of unreacted NaOH from the geopolymer specimen. To study the effectiveness of geopolymerization on immobilization of heavy metals in MT.3 7. Static leaching test was also used by a number of researchers to study the leaching behavior of geopolymer binders [30. The end surfaces of the cylindrical specimens were polished before testing to ensure that they are accurately flat and parallel. FTIR spectra were obtained using Thermo Nicolet 370 FTIR/EZ Omnic with a smart performance ATR ZnSe crystal. The pH was monitored during the experiment at least twice a day and was adjusted by adding nitric acid to the solution to keep the pH constant to the predefined value. Duxson et al. a large amount of geopolymer gel was washed off the surface after immersion. leading to a more porous structure.2% at pH = 7 for the 16/0. the initial mixture had a Si/Al of 7.2 MPa.1 mm/min.3% at pH = 4 and 53. Leaching test Static leaching test was performed by soaking MT powder and geopolymer brick specimens in two different solutions.73 respectively for the 12/25 and 16/0. . UCS vs. the leaching test results from the MT powder and the solid geopolymer specimens were compared with each other.1. water absorption. however. The immersed specimens were monitored continuously. ICP-MS.3% at pH = 7 for the 12/25 specimen and 78. 21. Specimen UCS before immersion (MPa) 12/25 15.0 exhibit tendency to dissolve in water due to high Na/Al ratio and presence of alkali in the structure of the geopolymer product and suggested that the composition range be narrowed to 1 < Si/Al < 5 and Na/Al not too far from 1. and FTIR analyses on the specimens after UCS test.5 specimen resulted from the formation of more geopolymer gel. The Na/Al of the 12/25 specimens was closer to unity than the 16/0.1 11. 14. the dried specimens were weighed and tested to measure the weight loss and the new UCS. The specimens were prepared at a NaOH concentration of 15 M. 7. 90 and 105 days.5 MPa was studied. Ahmari. 59. Microscopic/spectroscopic analyses The change of micro/nanostructure and phase composition of the geopolymer matrix due to exposure to neutral and acidic environment was studied by performing SEM.5 7. efflorescence. forming pressure and curing temperature on the physical and mechanical properties of MT-based geopolymer bricks was studied systematically in [39]. L. The results indicate that 15 M NaOH concentration and 90 °C curing temperature are the optimum condition for producing MT-based geopolymer bricks. 3 which compares the SEM micrographs of the specimens before and after immersion in the pH = 4 solution. Table 2 presents the 8 25 10 20 0 1 2 12 3 Forming Pressure (MPa) 25 14 16 20 18 15 10 5 0 0 2. and FTIR. the durability of only the specimens prepared at respectively 12%/25 MPa and 16%/0. For both types of specimens. NaOH concentration.745 S. Experiments UCS (MPa) 35 35 30 UCS (MPa) The experiments performed in this study consist of unconfined compression tests.5 MPa (denoted respectively as 12/25 and 16/0. no obvious disintegration.8 7 7. The specimens were soaked in pH = 4 and 7 solutions for 4 months and then taken out from the solution. 28. the UCS after immersion decreased substantially. 1.76 and a Na/Al of 0. In current study. Durability The effect of initial water content. without altering the leachability of heavy metals through complexation reactions. The UCS increased with higher initial water content (meaning larger amount of NaOH at the same NaOH concentration) because more geopolymer gels were produced at larger amount of NaOH.1. one at pH = 4 and the other at pH = 7. 40 2.86 and 1. Finally.3.00° to 70. The other reason for the lower strength loss of the 12/25 specimens is that the compact structure of the 12/25 specimens resulted from the higher pre-compression pressure was more resistant to the acid attack than the compact structure of the 16/0.2 6. a solution sample less than 5 ml was taken and then filtered with a 0.44]. For the 12/25 specimen. The unconfined compression tests were first performed to measure the 7-day unconfined compressive strength (UCS) of the geopolymer brick specimens produced at different conditions.0 or >5. For the 16/0. moisture contents varying from 8% to 18%. forming pressure for specimens prepared at different initial water contents and 15 M NaOH concentration and cured at 90 °C for 7 days (from [39]). This is possibly due to the partial geopolymerization of mine tailings and the chemical composition of the formed geopolymer gels [34. All the analyses were performed on multiple specimens and at various locations on each specimen. a curing temperature of 90 °C. Similar results were also reported by Silva et al.

and (c and d) 16/0. After immersion 16/0. within just 1 day. Olusola and Joshua [47] reported over 16% weight loss for laterized concrete after less than 3 months’ soaking in 5% nitric acid. Ahmari. The water absorption was small for both types of specimens after immersion in pH = 4 and 7 solutions. [22] reported that the weight loss of Portland cement based concrete immersed in 5% nitric acid could be over 40% depending on aggregate type. the water absorption reached its ultimate value. [46] reported water absorption of about 15% for cemented peat bricks with 3– 4% added lime. The ASTM standards require a water absorption not over 25% for most applications [39]. about 25%.5 pH=4 Before Immersion 16/0.5 SP G AP 10 20 P P P A A A 30 G S P S 40 S S MT powder 50 60 S P 70 2θ Fig. The MT-based geopolymer bricks easily met the ASTM requirements on water absorption. The weight loss percentage of the MT-based geopolymer bricks is also low compared to the reported values for Portland cement based concrete. Pacheco-Torgal et al. P: potassium aluminum silicate (sanidine). Zhang / Construction and Building Materials 44 (2013) 743–750 Fig. This is mainly because both types of geopolymer specimens had low initial porosity and the porosity after immersion did not change substantially. . Deboucha et al. SEM micrographs of (a and b) 12/25 specimen.5 specimen before and after immersion in pH = 4 and 7 solutions for 4 months [A: sodium aluminum silicate (albite).5 specimen. 4. L. Freidin [45] showed that for fly ash-based geopolymer bricks without hydrophobic additives. G: gypsum. 3.5 pH=7 After immersion 16/0. S: quartz]. XRD patterns of MT powder and 16/0.746 S. respectively before and after immersion in pH = 4 solution for 4 months.

However. Although the crystalline phases before and after immersion are similar. After immersion. IR spectra of MT powder.2. The geopolymerization also Table 3 Infrared (IR) characteristic bands identified in MT powder and geopolymer specimens shown in Fig. In the meanwhile.100 600 wave number (cm-1) After immersion 16/0.5 specimens before and after immersion in pH = 4 and 7 solutions for 4 months. 3. 5. the spectra exhibit a significant difference between before and after immersion. the shoulder becomes weaker and the SiAO related band becomes sharper and shifts slightly to a higher wave number indicating that the amorphous geopolymer gel is dissolved and the underlain crystalline phase is exposed. the intensity of the peaks increases after immersion.5 specimen before and after immersion in pH = 4 and 7 solutions.5 pH = 4 After immersion 16/0.5 specimens before and after immersion in pH = 4 and 7 solutions.1.600 1.100 1.100 2. Ahmari. Leaching behavior 3. this band shifts toward lower wave numbers. 5 shows the IR spectra of the MT powder and the 12/25 and 16/0.600 2. 3 – the dissolution of geopolymer gel leads to exposure of crystalline MT grains. Fig.5 pH=7 Before immersion 16/0.600 3.53] [55. the band that centers around 1000 cm1 corresponds to the stretching vibrations of SiAOAT (T = Al or Si) bonds. This confirms the SEM results shown in Fig. The identified IR characteristics are summarized in Table 3. Wave number (cm1) Characteristic bands References 800–1200 872 1450 1650 2350 SiAO stretching vibrations of SiO4 ACO3 vibrations in CaCO3 ACO3 vibrations in CaCO3 Bending (m2) mode of HAOAH CAO vibrations in CO2 constrained in amorphous phase CAO vibrations in CO2 constrained in amorphous phase [48–52] [53] [54] [48.2.600 1. and (a) 12/25 and (b) 16/0. this band disappears because the carbonates dissolve in the solution. L.56] 2920 results in a new band around 1450 cm1. 5.600 [55.100 600 1.747 S. After immersion.5 MT Powder (b) 3. After geopolymerization.100 2. . which is considered as a footprint for geopolymerization.100 wave number (cm-1) Fig.56] 2. There is no evident difference between the spectra of specimens immersed in pH = 4 and 7 solutions. Zhang / Construction and Building Materials 44 (2013) 743–750 Fig. Effectiveness of immobilization of heavy metals Table 4 shows the concentration of different metals leached from the MT powder and the brick specimens after immersion in After immersion 12/25 pH = 4 After immersion 12/25 pH=7 Before Immersion 12/25 MT Powder (a) 3. which confirm the results presented earlier. the weak shoulder localized at 1070 cm1 becomes stronger. This is more evident for the reflections between 20° and 30° at pH = 4.600 3. For the MT powder. which is attributed to carbonates. 4 shows the XRD patterns of the MT powder and the 16/0.

The obtained concentrations from both equations can be superimposed to account for the dissolution/diffusion phenomenon as in many systems.1 0. In case of no sorption.0 1. It is believed that the chemical stabilization dominates the physical encapsulation because the structural breakdown of the geopolymer gel does not result in significant release of the heavy metals.0 5. the reaction rate.0 0. Mg.6 359 2998 0.5 specimens have about the same effective porosity for contaminants to migrate. The concentration of released As and Mo from the brick specimens is higher than that from the MT powder indicating that geopolymerization has an adverse effect on the immobilization of these elements.3 46.0 0.0 0.0 0.4 1.0 0.0 NA NA 1.0 0. pH Na Mg Al K Ca Cr Mn Fe Co Ni Cu Zn As Se Mo Cd Pb MT 7 4 5.0 0.0 0. Cu and Zn in acidic condition. Dobs are respectively the cumulative concentration of the contaminant. Ahmari.1 0.9 0. The obtained Dc was then substituted in the equation and fp was backcalculated by fitting Eq.8 0.0 0.5–5. K. The combined solution to the FRM and BDM models is called the first order reaction/diffusion model (FRDM).0 2. (3) was applied to fit the measured concentration vs.1 0.0 0. and D denote respectively the amount of soluble contaminant in the solid waste.1 0.7 0. (2) is reduced to the following: M ¼ Q 0 ½1  expðktÞ þ 2SC 0  1 Dc f p t 2 p ð3Þ Using the non-linear regression method with Microsoft Excel solver.0 0. and Zn is studied based on the first-order reaction/diffusion model. it may oxidize and yield FeO (ferrous iron) or Fe2O3 (ferric iron). Fe does not show considerable leaching despite its high concentration in the MT powder.0 0.8 0. and the observed diffusivity.6 0.1 36.0 1.0 3.0 0.0 NA NA NA NA NA NA NA NA 2. Kinetics of leaching In this section.0 NA NA 5. Mg.5–10. Q0.1 0.0–5. First. [30] employed the FRDM by using Deff and introducing two factors accounting for the chemical and physical retardation. The MT powder exhibits high leachability for Ca. The threshold concentrations regulated by different standards are also shown in the table. effective diffusivity (Deff) which represents only the effect of tortuous pores and their connectivity on the transport of contaminants can be used. (3) to the measured concentration data of the brick specimen.3 0. which has been shown to be sufficiently accurate for solid wastes [30.7 0.1 0. Na and trace elements Mn.7 0.0 8.9 11.8 0.0 NA NA NA NA NA 1.13 0. To separate physical from chemical retardation. [62] and Zheng et al.2 0.0 0.7 0.1 0. Cu. 6.2. Dobs can be obtained by multiplying Deff by a factor. This model explains the leaching of species out of solid specimens through a simplified mechanism. Zheng et al. the concentration of the contaminant at time t and position x. the total concentration of the contaminant in the solid specimen.2.4 0.0 0. Dc was back-calculated by fitting Eq. fp does not change largely with the specimen type. Ca. the concentration of leached Mn and Zn at pH = 4 exceeds the threshold concentrations regulated by some of the standards.0 0. Fe. Considering the low solubility of Fe in the current experiment. Zhang / Construction and Building Materials 44 (2013) 743–750 Table 4 Concentration (ppm) of leached metals from MT powder and 12/25 and 16/0. (3) can fit the experimental data very well.2 8. the concentration of many leached metals at pH = 4 is higher than that at pH = 7 because most metals have higher solubility at acidic condition [57].0 12/25 7 4 2952 3740 1. In this study.0 0. the leaching behavior is dominated by both dissolution and diffusion.0–5. Except for Al.9 0.0 0. Fe mainly exists as pyrite (FeS) or chalcopyrite (CuFeS2) and during AMD process.1 28.2–0.2 7. The major reason could be that the natural pH of the geopolymer gel is alkaline and As and Mo exhibit higher solubility in alkaline condition [58–60].5 NA 2.0 NA NA EPA limit DIN Greek pH = 4 and 7 solutions for 90 days. the surface area.6 0. L.748 S.0 NA NA NA NA NA NA 5. It can be seen that Eq. Fe3+ is most likely to be the dominant valence since Fe3+ is less soluble.4 0. By doing so.0 1.1 0. S. which indicates the chemical retardation [63].8 0. For the geopolymer brick specimens.9 497 0. Eq. For the MT powder. the leaching behavior of Al.0 0.25–0.0 NA 0. The concentration of leached metals is consistent with the chemical composition and the content of trace elements shown in Table 1. C. these heavy metals are effectively immobilized and exhibit concentrations significantly lower than the standard limits and those of MT powder. Dobs and Deff are identical. The back-calculated parameters are summarized in Table 5 and some of the fitting curves are shown in Fig. Zn and Mo.0–2.59].0 0.5 0. the initial amount of the contaminant.0 NA NA NA NA 1. Eq. In copper MT. [30] successfully predicted the leaching kinetics by using the FRDM model as the following: M ¼ Q 0 ½1  expðktÞ þ 2SC 0 Dobs t !12 p ð2Þ where M. Suzuki et al. k.1 0.0 0.2 1.0 0.1 0.6 0. The model consists of the first order reaction model (FRM) which involves dissolution of the species at the solid–liquid interface and the bulk diffusion model (BDM) which accounts for transportation of the dissolved species through the porous medium. and the coefficient of diffusion.1 0.0 0.0 16/0. 3.0 0. (3) to the measured concentration data of the MT powder with the assumption of fp = 1.2 0.0 0.6 132 592 87.0 69. However.5 7 4 4135 4858 1.1 0. indicating that the 12/25 and 16/0. For both MT powder and brick specimens.3 101 124 78.1 0.0 0. however. Cu.0 0.2 0. The MT powder contains substantial amount of Fe.3 0. Dobs represents the effect of physical barrier due to transport through the tortuous pores and chemical retardation due to sorption on the solid phase.1 0.5 NA 2. The governing differential equations for the one-dimensional FRM and BDM are as follows: dQ ¼ kQ dt @C @2C ¼D 2 @t @x ð1Þ where Q.0 0.0 0.5 specimens after immersion in pH = 4 and 7 solution for 90 days. the chemical and physical contributions to Dobs are separated by introducing a physical retardation factor (fp) and a chemical diffusion parameter (Dc) that depends only on the diffusing contaminant. .9 0.0 0.0 1. C0.8 0. Dc varies significantly with contaminants indicating that chemical retardation is an important factor affecting the leaching behavior of the brick specimens. Immobilization of heavy metals can take place chemically through incorporation into the geopolymeric structure as chargebalancing cation and/or physically through encapsulation within the geopolymer gel [61].0 0. in the case of linear sorption. time data.0 0.0 NA NA NA NA NA NA 5. However. K and Na but only trace amount of Mn.

462 0.23E10 99. 6.32E05 1.181E01 2. Final report of a coordinated research project 2000– 2004.383 1.6 Zn 12/25 16/0. The back-predictions of the measured concentrations of Zn show that the contribution from the diffusion part of Eq.95E04 5.244E04 1. Based on the experimental results. Tariq A. but the water absorption is relatively small and weight loss is smaller than that for Portland cement-based binder.5 0. IAEA-TECDOC-1403.011 0.00 0. .80 0.703E04 1.00 Zn (pH=4) 12/25 Measured 12/25 predicted 16/0.60 1. (3) is zero.825E03 3.5 predicted 0 20 40 60 80 60 80 100 120 Time (days) 100 120 Concentration (ppm) Concentration (ppm) Time (days) 0.08 0.14 0. Conclusions The durability and leaching behavior of MT-based geopolymer brick specimens were studied.80 0.851E07 1.004 NA NA NA NA NA NA 95. This implies that the leaching kinetics of Cu is dominated by reaction and its lower immobilization efficiency is due to its higher reaction rate.60 0.  The UCS of the MT-based geopolymer bricks decreases substantially after immersion in pH = 4 and 7 solutions for four months.5 0.60 1.1 99.20 0.204E03 1.5 measured 16/0. Stabilization of sulphidic mine tailings for prevention of metal release and acid drainage using cementitious materials: a review.851E07 1.00 1.154E01 3. In other words.846E05 2.3 Fe 12/25 16/0.16 0. On the other hand.075 0.  The first-order reaction/diffusion model can be used to satisfactorily describe the leaching of heavy metals in MT-based geopolymer bricks. as discussed earlier.04 0.20 1.02 0. Element Specimen Q0 (mg/kg) k (1/h) fp Dc (m2/h) Dobs (m2/h) R2 (%) Al 12/25 16/0. This means that the leaching of Zn from MT-based matrix is controlled by early-stage chemical reaction.004 8. which indicates the physical encapsulation has not significant effect.810E03 2. the BDM or the reaction part of the equation fits into the measured curve.20 0. Fe and Zn at pH = 4. the following conclusions can be drawn: [1] Nehdi M.5 measured 0.209 0.00 0.40 Concentration (ppm) Concentration (ppm) 1.8 0.60 0.053 0. L. The long term stabilization of uranium mill tailings. The effective immobilization can be due to the incorporation of heavy metals in the geopolymeric network or physical encapsulation.6:423–36.2 94.122 9.20 0.004 0. Ahmari.2 Cu 12/25 16/0.5 predicted 0. Cu.3 98.5 measured 16/0.012 8. J Environ Eng Sci 2007.40 1.060 0.189 0.140 0.15 12/25 Measured 12/25 predicted 0.10 0.80E10 2. 2004. This is further evidenced by the same low level leachability of Fe in the MT powder as in the brick specimens.5 predicted 0. Measured and predicted concentrations of heavy metals at pH = 4 by FRDM. References 4.06 0.5 0. [2] IAEA (international atomic energy agency).00 0 20 40 60 80 100 120 0 20 40 2.05 16/0.5 predicted 0 20 40 60 80 100 120 Time (days) Time (days) Fig.08E07 96. Zn might come from the outer surface of the specimen so that it does not face any physical or chemical barrier.580E01 3.553 0.20 1. So the low leachability of Fe.  The heavy metals are effectively immobilized in the MT-based geopolymer bricks.017 0.00 0. It indicates that the solubility or reaction rate is an important factor controlling the leaching behavior.25 0. Zhang / Construction and Building Materials 44 (2013) 743–750 Table 5 Summary of back-predicted FRDM parameters for Al.80E04 98. Cu exhibits higher reaction rate and higher chemical retardation.40 0.20 Cu (pH=4) 0.846E05 2.18 0.80 1.00 Fe (pH=4) 12/25 Measured 12/25 predicted 16/0.5 measured 16/0. The strength loss is mainly due to the high initial Si/Al ratio and the partial geopolymerization of MT.1 93.40 12/25 Measured 12/25 predicted 16/0.30 Al (pH=4) 1.10 16/0. is attributed to its low chemical reaction rate.749 S. The k for Fe has the lowest value indicating that it has the lowest reaction rate with the solution.5 0.12 0.

The effects of alkaline dosage and Si/Al ratio on the immobilization of heavy metals in municipal solid waste incineration fly ashbased geopolymer. Shi H. 2nd ed. fly ash and polymeric materials. editors. Environ Geol 2002. [28] Shi C. Melbourne. Evans J.126:1004–12. Wei S. Ahmari.35:1233–46. [12] Mohamed AMO. Tsai Y-N. Technological environmental and commercial drivers for the use of geopolymers in a sustainable material industry. Construction wastes as raw materials for geopolymer binders. Lukey GC. 2000.168:711–20. Graham A. Hashim R. Properties of tungsten mine waste geopolymeric binder.6:1732–9. Greece. Environ Health Perspect 2008. Effect of immersion in water partially alkali-activated materials obtained of tungsten mine waste mud. Provis J. 24–45. p. Water Res 2002. Panias D. J Hazard Mater 2007. Cem Concr Res 2002. Cartledge K. Cocke DL.41:55–71. Evolution of disposal cell cover design used for uranium mill tailings long term containment. Constr Build Mater 2008. [60] Izquierdoa M. 2009. Castro-Gomes J. Treatment of arsenic contaminated soils II: treatability study and remediation. Hossein M. Shamaev A. Castro-Gomes JP.30:400–5.22:897–904. [55] Sakulich AR. [61] Van Jaarsveld JGS. Leaching characteristics of stabilized/solidified fly ash generated from ash-melting plant. McLearn M. Properties of concrete made with alkali-activated fly ash lightweight aggregates (AFLA). [49] Allahverdi A. Constr Build Mater 2012. Duxson P. Marutsky S. Environ Sci Technol 1996.21:12–8. Cement based solidification/stabilization of arseniccontaminated mine tailings. Jalali S. [16] Whinney HG. Grand Junction. Provis JL. van Deventer JSJ. Chem Mater 1996. [59] Engelsen CJ. Geopolymer technology. Cem Concr Res 1990. Investigations about the effect of aggregates on strength and microstructure of geopolymeric mine waste mud binders. Zhang L. 2005. Abdollahnejad Z.23:522–7. Int J Civil Eng 2009. and future direction of solidification/stabilization technologies for hazardous waste treatment. . Engineering properties of cemented peat bricks. Knowlton R. Germany: Proc Int Conf Workshop. Waste Manage 1997. Albuquerque A. Van Deventer JSJ. Synthesis and heavy metal immobilization behaviors of slag based geopolymer. Metall Mater Trans B 1998. Construct Build Mater 2012.8:2056–60.24:103–9. 1994. final report of a coordinated research project 2000– 2004. Jamshidi M. Denver Colorado. [19] Van Deventer JSJ. [23] Pacheco-Torgal F. Fumei L. J Hazard Mater 2006. Mollah A. Durability of alkali-activated binders: a clear advantage over Portland cement or an unproven issue.30:25–30. The effect of alkali and Si/Al ratio on the development of mechanical properties of metakaolin-based geopolymers. In: Merkel B. Waste Manage 2009. [30] Zheng L. [46] Deboucha S. Phytostabilization of mine tailings in arid and semiarid environments—an emerging remediation technology. [36] Pacheco-Torgal F. [44] Pacheco-Torgal F.20:79–91.137:1656–63.37:933–41. Adv Mater Res 2011.37:1590–7. [41] Tavor D. StoltenbergHansson E. Influence of sodium carbonate addition on the thermal reactivity of tungsten mine waste mud based binders. Investigations of tungsten mine waste geopolymeric binder: strength and microstructure. KY: Lexington. Solidification/stabilization of arsenic containing solid wastes using Portland cement. Durability and environmental performance of alkali-activated tungsten mine waste mud mortars. [21] Yusheng Z. [18] Van Jaarsveld JGS. Buckingham P. [22] Pacheco-Torgal F. Maier RM. Constr Build Mater 2012.10:331–4. Bussiere B. [31] Luna Y.36:156–66. The stabilisation of mine tailings by reactive geopolymerization. Stabilization/solidification of hazardous and radioactive wastes with alkali-activated cements. [38] Pacheco-Torgal F. Bittnar Z. [42] Yunsheng Z. Use of infrared spectroscopy to study geopolymerization of heterogeneous amorphous aluminosilicates. J Mater Civil Eng 2010. J Hazard Mater 2009. Mater Res 2007. present status. Alkali-activated fly ash-based geopolymers with zeolite or bentonite as additives.. Vandecasteele C. [32] Jo BW. Chemosphere 2010. Akhter H. Wolfson A. 2004. Colloids Surf A: Physicochem Eng Aspects 2007.194–196:798–801. Cocke DL. p.41:749–59. Investigations on mix design of tungsten mine waste geopolymeric binder. 1998. Chemosphere 2008.292:8–20. An FTIR and XPS investigations of the effects of carbonation on the solidification/stabilization of cement based systems-Portland type V with zinc. [26] Majidi B. IAEA-TECDOC-1403. [7] Barth FE. [27] Duxson P.24:56–60. Comans RNJ. Effect of nitric acid concentration on the compressive strength of laterized concrete. Characterization of environmentally-friendly alkali activated slag cements and ancient building materials. Van der Sloot HA. Balke K. Barnes P. Lin C. Kopecky L.29:323–31. [47] Olusola K. [15] Poon CS.42:3024–32. Vale JF. Material and structural characterization of alkali activated low-calcium brown coal fly ash. metals and materials.7:154–60. US department of energy. [50] Lee WKW. p.50:200–7. J Hazard Mater 1990. Lund W. The leaching of major and trace elements from MSWI bottom ash as a function of pH and time. Dabbs DM. [37] Pacheco-Torgal F. Joshua O. Int J Coal Geol 2012. Hess TR. Cem Concr Res 2007. Cem Concr Res 2005. Jalali S. Durability of geopolymer materials in sodium and magnesium sulfate solutions. Graham A. Jalali S. Lukey GC. Helling C. [62] Suzuki K. Van Deventer JSJ. [35] Pacheco-Torgal F. Adelide SA. Use of different geopolymeric agents for the stabilization/solidification (S/S) of metallurgical waste.143(1–2):206–13. Škvara F. Castro-Gomes J.143:206–13. In: 48th Institute of quarrying conference. Implementing the natural flushing strategy: a case history. J Environ Eng 2000. Van Deventer JSJ. In: International symposium of advanced processing of.29:128–35. [25] Drechsler M. Office. Aksay IA. [5] Smith GM. Hydromechanical evaluation of stabilized mine tailings. Cem Concr Compos 2007. Lorenzen L. J Wuhan Univ Technol – Mater Sci Ed 2008. Environmental resources management. [14] Gagarin A. Hills C. 241–252. [63] Park JY. Leaching behavior of elements from coal combustion fly ash: an overview. Park JB. USA: Drexel University. 2006.22:2212–9. 209–22.22:1201–11. Zhang / Construction and Building Materials 44 (2013) 743–750 [3] Metzler D. [6] Poon CS. Synthesis and heavy metal immobilization behaviors of slag based geopolymer. Qianli C. Wibetoe G. Australia. Kriven WM. Van Deventer JSJ. Freiberg. [52] Zhang Y.35:117–24. An overview of the history. Leaching characterisation and geochemical modelling of minor and trace elements released from recycled concrete aggregates. Appl Geochem 2006. [11] Choi WH. [53] Trezza MA. Cem Concr Res 2007. Castro-Gomes JP. Belem T.17:15–23. [56] Treadwell DR. [51] Mingyu H. Leaching behavior of heavy metals from the class C fly ash-based geopolymers. Long term Stewardship workshop. Lukey GC. Izquierdo M. Cem Concr Compos 2009. J Hazard Mater 2007.21:335–51. [57] LaGrega M. Hassani FP.116:278–83. A multi-component numerical leach model coupled with a general chemical speciation code. Cem Concr Res 1993. [17] Mendez MO. Baker AP. McGraw-Hill.750 S. [4] Lange L. Civil Environ Res 2012. Xiaomin Z. Constr Build Mater 2010. Peters CJ. Perry R. Sun W. Li Z. Shvarzman A. The limitation of the toxicity characteristic leaching procedure for evaluating cement-based stabilized/solidified waste forms. Development of geopolymeric materials from industrial solid wastes. Shi Y. Qianli C. Mater Technol 2009.23:773–84. Preliminary investigation into the effects of carbonation on cement-solidified hazardous wastes. Pant KK. Cementless pressed blocks from waste products of coal-firing power station. [43] Duxson P. Production of eco-friendly bricks from copper mine tailings through geopolymerization. J Hazard Mater 2006.79:665–71. Mullite (3Al2O3–2SiO2) synthesis with aluminosiloxanes. Camoes AF. [9] Miller J. Ortego JD.2:48–57. [33] Giannopoulou IP. Castro-Gomes JP. [58] Dijkstra JJ. Castro-Gomes JP. Khani EN. [34] Silva I. 2006. [20] Skváraa F. Park SK. 363–71.94:54–66. Recycling of industrial wastewater by its immobilization in geopolymer cement. Sci Total Environ 1985. Uranium mining and hydrology II. [8] Singh TS. Mechanism of metal stabilization by cement based fixation processes. Fernandez-Pereira C. Cem Concr Res 2010. Fernandez-Jimenez A. Chemical factors that influence the performance of mine sulphidic paste backfill. Immobilization mechanism of arsenic in waste solidified using cement and lime.22:1939–49. [48] Buchwald A. Alkali-activated metakaolin-slag blendsperformance and structure in dependence of their composition. In: The long term stabilization of uranium mill tailings. Van der Sloot HA.29:1766–71. PhD thesis. 2009. Hilbig H. Langmuir 2003. Ono Y.32:2782–7. Environ Sci Technol 1998. Jalali S. Park JY. Jalali S. p. Poole A.40:1639–49. world of coal ash (WOCA) conference. 1998.131:29–36. Lukey GC. Development of method of covering raising dust beaches of radioactive waste storage out of operation. Lee SR. [54] Yousuf M. Wang W. L.31:762–8.29:283–91. Smilauer V. [39] Ahmari S. Batchelor B. Ding Y. [24] Bakharev T. from fundamentals to advanced applications: a review. [29] Minarikova M. Construct Build Mater 2008. CONF-980652. Indust Eng Chem Res 2007. Aziz AA. Scient Res Essays 2011. Kaps CH. Wei S. An investigation of mercury solidification and stabilization in Portland cement using X-ray photoelectron spectroscopy and energy dispersivescopy. In: 2nd International conference on advances in mineral resources management and environmental geotechnology. Factors affecting the immobilization of metals in geopolymerized fly ash.71(5):922–32. Justnes H. The role of inorganic polymer technology in the development of ‘green concrete’. Lin C. Fixation of heavy metals in geopolymeric materials based on brown coal fly ash. [13] Benzaazoua M. Ceram  Silikáty 2006. J Mater Sci 2007. Innovative material technologies: bringing resources sustainability to construction and mining industries. hazardous waste management. Querol X. Constr Build Mater 2007.19:8726–34.46(21):6801–5. Constr Build Mater 2008. [40] Guo X. [45] Freidin C. Mallicoat SW. Infrared spectroscopy study of structural nature of geopolymeric products.32:1133–44. [10] Dutre V. In: International congress on mineral processing and extractive metallurgy (MINPREX2000). Lio KW. Jalali S. Hydration study of ordinary Portland cement in the presence of zinc ions.24:79–87.