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Abstract
Heavy metal-bearing waste usually needs solidication/stabilization (s/s) prior to landll 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 solidication/stabilisation process. It provides a clarication of heavy metal eects 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 eect 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 eectiveness of
cement-based s/s and extend this waste management technique.
2008 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
4.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydration of silicate phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Alite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Belite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Structure of CSH gel and its binding capacity for heavy metals.
Hydration of aluminate and ferrite . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Aluminate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Celite (ferrite) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cement hydration and heavy metal immobilisation . . . . . . . . . . . . . . . .
4.1. Hydration kinetics of cement . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Factors influencing cement-based solidification/stabilisation. . . . .
4.3. Immobilisation mechanisms of heavy metals . . . . . . . . . . . . . . .
Corresponding author. Tel.: +86 21 6779 2540; fax: +86 21 6779 2552.
E-mail address: qychen@dhu.edu.cn (Q.Y. Chen).
0956-053X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2008.01.019
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1. Introduction
2.1. Alite
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398
399
400
400
C3 S=SiO2 O H 2O Ca H2 O OH
! C3 S=SiO2 2O HO Ca CaOH2
392
Nomenclature
A
C
F
H
S
N
C
S
C3S
C2S
C3A
alumina, Al2O3
CaO
Fe2O3
H 2O
silica, SiO2
Na2O
CO2
3
SO3
tricalcium silicate, Ca3SiO5
dicalcium silicate, Ca2SiO4
tricalcium aluminate, Ca3Al2O6
C4AF
AFm
AFt
CH
CSH
ferrite, Ca2AlFeO5
monosulphate group, C4ASH12
ettringite group, C3A 3CS H32
portlandite, Ca(OH)2
calcium silicate hydrate gel of variable composition
CAH calcium aluminate hydrate gel
C3AH6 hydrogarnet, 3CaO Al2O3 6H2O
C2AH8 2CaO Al2O3 8H2O
C4AH13 4CaO Al2O3 13H2O
C4AH19 4CaO Al2O3 19H2O
consumption of C3S (Chen et al., 2003, 2007a). The accelerating eect of these metals could be attributed to: (1) the
attack of H+ resulting from hydrolyses of heavy metal ions,
and (2) the formation of double hydroxides (Ca(OH)2 xM(OH)z yH2O), which consumed calcium ions and facilitates the decomposition of C3S. However, Zn2+ retarded
the early hydration of C3S, which could arise from the precipitation of calcium zincate (CaZn2(OH)6 2H2O) (see
Eqs. (4)(6)). Calcium zincate coated C3S grains and prevented the material transport that was necessary for C3S
hydration to continue. In fact, the pH of C3S suspensionsdoped with Zn2+ (50 g/l) was below 12 and portlandite did
not precipitate even in 3 mol of hydration (Chen et al.,
2003, 2007a). At the later age, the pH rose due to the hydration of C3S (for example, the pH reached 12.5 at 1 year) and
calcium zincate dissolved. As a result, the degree of C3S
hydration increased dramatically and was higher than that
of the control sample at 1 year of age (Chen et al., 2007a).
In other words, Zn2+ promoted C3S hydration at a later period of hydration, although it retarded C3S early hydration.
The reason that calcium heavy metal double hydroxides
behave so dierently on the surface of C3S is not known at
present
2
2ZnO2
6H2 O
2 C3 S=O Ca
! C S H CaOH2
4
ZnO2
2
2.2. Belite
Dicalcium silicate, C2S or b-Ca2SiO4, is a complex material containing point defects, which undergoes inversions
on cooling, resulting in an accumulation of strain in the lattice which induces multiple twinning. Five polymorphs of
this mineral are recognised, of which the b-(orthorhombic)
is the stable form at room temperature (Lea, 1970). Belite,
393
y = 1, 2, 3, 4, . . .; Ca/Si = (6 y)/2,
Q2 species (cyclic silicates or single chain silicates):
mC3 S H2 O ! yCaOH2 Cax H2mx Sim O3m
zCaOH2 nH2 O
394
10
m = 3, 4, 5, 6, 7, 8, . . .; n > 0; z = 0, 1, 2, 3, . . .
Note that in Eq. (8), if let 5 y = x, it reduces to Glassers model of CSH (Glasser et al., 1987), whereas in Eq.
(10), if let m = 3n 1, it reduces to Richardsons model of
CSH (Richardson, 2000).
The average C/S ratio for CSH in Portland cement is
1.75 (Berner, 1992; Zhang et al., 2000). CSH gel may
contain Al, Fe and Mg due to sorption or co-precipitation
(Taylor, 1993; Andersen et al., 2003). It is reported that
minor components can modify the crystal growth by substitution in the lattice of the calcium silicate hydrates
(Kwan et al., 1996; Kulik and Kersten, 2001). Almost all
calcium in natural crystalline phases of calcium silicate
hydrate such as tobermorite (C5S6H5) and xonotlite
(C5S5H) can be replaced with heavy metals, for example,
cobalt or nickel (Viehland et al., 1996, 1997). These metals
may, therefore, substitute for Ca2+ at the CSH surface.
Chromium can be chemically incorporated into all of the
cement hydration products, primarily substituting for both
calcium and silicon in CSH (Ivey et al., 1990; Lin et al.,
1997). According to Omotoso et al. (1998), Cr3+ could be
also bound into the silica matrix itself as Cr(OH)3 xSiO2.
The immobilisation of heavy metals by CSH has been
described by the RichardsonGroves model (Richardson
and Groves, 1993, 1997; Richardson, 1999, 2000; Richardson et al., 2002). When pH approaches to 12.5 during C3S
hydration in the presence of heavy metals, portlandite precipitates from solutions. If the amount of heavy metal is
sucient, precipitation and co-precipitation of heavy metal
and calcium can occur, forming amorphous structures of
hydroxides. Heavy metal hydroxides could substitute for
Ca(OH)2 in CSH gel. We suggested a model for heavy
metal incorporation in CSH, as shown in Eq. (11). Like
the structure of glass, heavy metals may act as network
modiers or network intermediates (Chen, 2004)
mC3 S M2 H2 O ! yM; CaOH2
Cax H2m1x Sim O3m1
ZM; CaOH2 nH2 O
11
m = 3, 4, 5, 6, 7, 8, . . .; n > 0; z > 1.
3. Hydration of aluminate and ferrite
3.1. Aluminate
Tricalcium aluminate, C3A or Ca3Al2O6, is the only
cement compound not to show polymorphic transformations with temperature. In C3A, Ca2+ coordination numbers are not all equal (specically, 6 and 12). In Portland
cement tricalcium aluminate is substantially modied in
12
C3 A CH H2 O ! C4 AH19 C4 AH13
! C3 AH6 AlOH3
13
assembled thermodynamic data for relevant solids and calculated equilibriums in the CaOAl2O3SO3H2O system
and compared them with experimental results
C3 A; F CSH2 H2 O ! C6 A; FS3 H32
14
15
2+
Sr
Ba2+
Pb2+
Cd2+
Co2+
Ni2+
Zn2+
Al3+ site
3+
Cr
Si4+
Fe3+
Mn3+
Ni3+
Co3+
Ti3+
2
2
site (Poellmann et al., 1993;
CrO2
4 for SO4 on the X
Lin et al., 1993). The layer structure of AFt and AFm can
incorporate variable amounts of compounds including carbonates, hydroxide and silicate (Gougar et al., 1996). Tashiro et al. (1977, 1979) have studied the eects of heavy metal
oxides such as Cr2O3, PbO and ZnO as well as Cu(OH)2 on
the formation of ettringite and properties of cement mortar.
16
17
C4 AF C6 A; FS3 H32 H2 O
! C4 A; FSH12 AlOH3 FeOH3
18
Table 1
Reported ion substitution in ettringite
Ca2+ site
395
SO2
4 site
CO2
3
Cl
OH
CrO2
4
AsO3
4
NO
3
SO2
3
Portland and other types of cement, for example, calcium aluminate cement, slag cement, pozzolanic cement,
are often used as binders in the solidication and stabilisation of wastes (Zhou et al., 2006). Portland cement clinker
is made by heating a mixture of limestone and clay to a
temperature of about 1450 C. Fluxes, notably aluminium
and iron oxides, are used, although their eect on the nal
clinker composition has to be carefully controlled. The
396
Table 2
Hydration kinetics of cement
Stages
Reactions
Remarks
Initial period
Induction
period
Acceleration
period
Deceleration
and
hardening
Curing period
a- and c-CaSO4) is added as a set-controlling agent of aluminate. Note that destructive expansion from reaction with
sulphates can occur if the latter is present in high concentration in cement (Zhang and Odler, 1996; Scrivener
et al., 1999).
Calcium oxide is certainly one of the most important
factors determining the thermodynamics and kinetics of
CSH formation. It also inuences the morphological
and structural features of CSH (Dweck and Buchler,
2000; Hill and Sharp, 2002; Dweck et al., 2003). The calcium hydroxide consuming process such as carbonation
or the displacement of solubility equilibrium of portlandite
(e.g., change of temperature, addition of calcium salts or
alkalis) might change the characteristics of CSH
(Abderlraxig et al., 1999). Other alkali compounds, in general, accelerate the rate of the early hydration of cement
and give higher early compressive strength, although the
nal strength is lower than that of the low alkali cement.
In the presence of gypsum and an alkali, some phases such
as U-phase (C4A0.9(SO4)1.1N0.5H16) will form and may
cause deleterious eects, in particular, causing expansion
(Glasser et al., 1999).
Calcium chloride is a typical accelerator of cement
hydration. It can reduce the setting time and double early
compressive strength, although the nal strength may be
reduced. In the presence of gypsum and calcium chloride,
Kuzels salt (C3A 0.5CaCl2 0.5CaSO4 10H2O) or Friedels salt (C3A CaCl2 12H2O) may form, depending
on the activity of those species in solution (Glasser et al.,
1999).
Organics may exhibit an anity towards cement particles
or cement hydration products by adsorption due to the electrostatic force, hydrogen-bonding interaction, chemical
bonding, and hydrophobic force. Adsorbed organics will
alter surface properties of the cement particle and thus its
interactions with the solution as well as with other cement
particles. They may interfere with the bonding of wastes
with cement binders, decrease unconned compressive
strength and impair short-term or long-term durability
(Cheng and Bishop, 1992; Trussel and Spence, 1994). Organics can also inuence the interactions of anhydrous clinkers
or cement hydration products and heavy metals. Despite
considerable research, the mechanisms of accelerating and
retarding eects of organic admixtures are not fully understood. This is partially due to the wide choices of experimental conditions available, including varying cement
compositions, types and dosages of admixtures. The performance of admixtures is too complicated to predict from the
chemical composition at present. The inuence of the same
species may vary, depending on the concentration and the
chemical environment (Conner and Hoener, 1998).
4.3. Immobilisation mechanisms of heavy metals
The complexity of cement-based s/s results from the variability of wastes, combined eects of the solution equilibrium and kinetic processes coupled with the surface and
397
398
Table 3
The solubility product of metal hydroxides
Metal ions
2+
Ca
Mg2+
Cu2+
Pb2+
Zn2+
Cr3+
Al3+
Fe3+
5.19
11.15
19.32
15.1
16.6
29.8
33.5
38.8
6.67
12.75
20.91
16.52
18.17
32.19
35.97
41.2
than on the surface of silica. Some heavy metals, for example, Zn2+, Cd2+, and Pb2+, form hydroxides and deposit on
calcium silicate minerals (Komarneni et al., 1988).
For the interest of identication of heavy metal compounds, heavy metal-doped suspensions of calcium oxide,
C3S or Portland cement have been investigated (Chen
et al., 2003, 2007a). In addition to Cu(OH)2, Zn(OH)2,
and Pb(OH)2, layered double hydroxides of calcium and
copper, chromium or zinc such as Ca2Cr(OH)7 3H2O,
Ca2(OH)4 Cu(OH)2 mH2O and CaZn2(OH)6 2H2O
were detected by XRD. The presence of these compounds
as amorphous structures in the corresponding hydrated
pastes was conrmed via the comparison of DTA/TG analysis results (Chen et al., 2007a). At an earlier time, Omotoso et al. (1998) found that Cr3+ associates with regions of
high calcium content in the form of calciumchromium
crystalline precipitates. They deduced that hydrous calcium
chromate (Ca2Cr2O5 6H2O) may be present.
Heavy metal compounds could be occluded (physically
encapsulated) by CSH. It is suggested that nickel and
cadmium hydroxides are incorporated into hydrated
cement matrices, whereas mercury may remain in its original oxide form and be incorporated into hydrated cement
matrices (Ortego et al., 1989; Frey et al., 1990).
4.4. Durability of cement-based solidied and stabilised
waste
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The vulnerability depends to a large extent on factors such
as permeability, chemical and mineralogical composition
and micro-structure (Ortego and Barroeta, 1991). When
exposed to air, they will suer attacks from carbon dioxide,
sulphate, chloride, water, and degradation products of
organic substances (Bonen and Sarkar, 1995). The chemical process such as further hydration, carbonation, ettringite or thaumasite formation, would result in the change of
porosity, volume and solidied waste performance (Klich
et al., 1990; Taylor et al., 2001; Wang and Scrivener,
2003; Purnell et al., 2003). They may cause expansion,
cracking as well as strength loss. Aggressive solutions
attack may cause secondary mineralisation and ultimately
may decompose treated waste (Park and Batchelor, 1999;
Malmstrom et al., 2000; Matsuyama and Young, 2000).
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