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Waste Management 29 (2009) 390403


www.elsevier.com/locate/wasman

Immobilisation of heavy metal in cement-based


solidication/stabilisation: A review
Q.Y. Chen a,*, M. Tyrer b, C.D. Hills c, X.M. Yang a, P. Carey c
a
School of Environmental Science and Engineering, Donghua University, Shanghai 200051, PR China
Department of Materials, Imperial College of Science, Technology and Medicine, London SW7 4AZ, UK
c
Centre for Contaminated Land Remediation, Medway School of Science, University of Greenwich, Chatham Maritime, Kent ME4 4TB, UK
b

Accepted 18 January 2008


Available online 25 March 2008

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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Q.Y. Chen et al. / Waste Management 29 (2009) 390403

5.
6.

4.4. Durability of cement-based solidified


Evaluation method of solidified waste . . . .
Summary and conclusions . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . .

and stabilised waste . . . . .


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1. Introduction

2. Hydration of silicate phases

Industrial activities in the production of materials and


chemicals give rise to very large quantities of heavy
metal-bearing wastes each year. Heavy metals may exist
in a variety of forms, for example, chloride, sulphate, and
uoride. Most of them are toxic, mutagenic, and carcinogenic. As the concentration of heavy metals in wastes varies
in a wide range and may exceed the acceptance limit of the
environment, heavy metal-bearing wastes pose a serious
threat to human and animal health and need treatment
(Bozkurt et al., 2000).
Solidication/stabilisation (s/s) of heavy metal-bearing
sludge, industrial residues and contaminated soil is an
attractive technology to reduce their toxicity and facilitate
handling prior to landll (Valls and Vazguez, 2000; Collier
et al., 2006). In terminology, stabilisation is a process of
converting a toxic waste to a physically and chemically
more stable form, that is, alters hazardous waste chemically to produce a less toxic or less mobile form. It involves
chemical interactions between waste and the binding agent.
By comparison, solidication converts liquid waste, semisolid sludge or a powder into a monolithic form or granular material that will allow relatively easy handling and
transportation to landll sites (Conner, 1990; Glasser,
1997; Poon et al., 2004). It does not necessarily imply
any form of chemical reaction has occurred.
The objectives of solidication/stabilisation are to
achieve and maintain the desired physical properties and
to chemically stabilise or permanently bind contaminants.
The high strength, low permeability and relatively high
durability of hydraulic cement make it a good binder
for this waste management technique (Conner, 1990).
Cement-based solidication/stabilisation has been widely
used in the world for about 50 years (Alunno and Medici,
1995; Conner and Hoener, 1998; Malviya and Chaudhary, 2006), which improves the handling characteristics
and lowers the leaching rates of wastes by a combination
of solidication and stabilisation.
The overall process of cement hydration includes a combination of solution processes, interfacial phenomena and
solid-state reactions. It is extremely complex, especially in
the presence of heavy metals. The selection of cements
and operating parameters depends upon an understanding
of the chemistry of the solidication/stabilisation process.
This paper examines interactions between cement phases
and heavy metals, mechanisms of heavy metal immobilisation and factors controlling the eectiveness of cementbased solidication/stabilisation.

2.1. Alite

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398
399
400
400

Tricalcium silicate, C3S or Ca3SiO5, is pseudo trigonal/


triclinic and a solid solution of CaO in dicalcium silicate
proposing the formula (Ca2SiO4  CaO). In cement, alite
is tricalcium silicate containing Mg2+, Al3+, Fe3+ and other
ions, and may appear as sub-hexagonal (pseudomorphic
remnants of high temperature trigonal) structure (Taylor,
1997). In alite, Ca2+ coordination number is 6 (lower than
normal), and Al3+ or Mg2+ ions distort the structure.
These structures readily allow water interaction, as CaO
provides a favoured site for water attack. It reacts with
water to produce calcium silicate hydrate gel (CSH)
and portlandite (CH, Ca(OH)2). Alite is considered to be
the most signicant constituent phase with respect to
strength development up to 28 days.
Skalny and Young (1980) proposed a mechanism for the
early stage of C3S hydration. They considered the initial
dissolution to be incongruent and that calcium and hydroxyl move rapidly into solution leaving the surface layers
rich in silica. In doing so the surface layer adopts a negative
zeta potential that strongly adsorbs calcium ions to it. They
suggested that this adsorbed layer and its correspondingly
low silicate concentration account for the lack of immediate hydration products seen on the surface.
Several models have been put forward to explain the
hydration of C3S (Yousuf and Mollah, 1995; Mollah
et al., 1995). According to the gel model, when C3S is in
contact with water, a membrane of CSH gel is formed
on the surface of C3S grains, which permits the inward ow
of water molecules and the outward migration of mainly
Ca2+ and silicate ions due to the dierence of osmotic
potential on both sides of the membrane. The membrane
ruptures periodically and re-forms by extruding concentrated silicate solution. As a result, an excess of portlandite
will accumulate on the uid side of the membrane (see Eqs.
(1) and (2)). The gel model has been demonstrated to be
useful in explaining the retardation of setting of cement
in the presence of heavy metals. The retarding eect is
due to the formation of insoluble gelatinous hydroxyl compounds of metals in an alkaline medium.
C3 S=SiO2  3O  Ca H2 O
! C3 S=SiO2 O  H  2O  Ca Ca2 OH

C3 S=SiO2 O  H  2O  Ca H2 O OH
! C3 S=SiO2  2O  HO  Ca CaOH2

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Q.Y. Chen et al. / Waste Management 29 (2009) 390403

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

Taylor (1986, 1993) proposed that there is no diusion


of water molecules through either the inner or outer product layers and suggested that hydrogen ions are transferred
from one oxygen atom to another until they reach the C3S
surface. He proposed that a narrow zone exists at an interface where atomic rearrangements convert C3S into CSH
gel. As this zone moves into the hydrating grain, calcium
and silicate ions move through the product and into the
surrounding liquid to be precipitated ultimately in the
outer product layers or (for calcium) as portlandite. He
deduced that the migration of silicon is by a series of movements through the faces of the tetrahedra, from sites initially lled to those initially empty. He similarly proposed
this as a mechanism for the change of silicate anion type
both during and after CSH formation.
According to the crystal model, when C3S in contact
with water, calcium silicate minerals dissociate into
charged silicate and calcium ions (see Eq. (3)). These
charged silicate ions then concentrate as a thin layer on
the surface of C3S grains to retard the interaction of C3S
and water. The nucleation and growth of hexagonal crystals of calcium hydroxide ll up the spaces and cavities
between the grains. Meanwhile, particles of CSH precipitate out of water onto the silicate-rich layer on the C3S
grains and gradually form needles or spines. Eventually
needles from dierent grains come into contact with each
other to form sheets (Yousuf and Mollah, 1995)

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

C3 S H2 O ! Ca2 OH H4 SiO4

2
2ZnO2
6H2 O
2 C3 S=O  Ca

! C  S  H CaOH2

In the literature, heavy metals are largely considered to


be inhibitors of C3S or cement hydration based on the
observation of setting, strength development, portlandite
precipitation, or heat evolution (Cocke et al., 1989; Hills
et al., 1994; Taylor, 1997). It should be noted that hydration of C3S or cement does not necessarily result in all of
the abovementioned phenomena.
It is reported that some heavy metals such as Cu2+, Pb2+
and Cr3+ accelerated the hydration of C3S, as shown by the

Zn2 2OH ! ZnOH2




ZnOH2 2OH ! 2H2 O

4
ZnO2
2

! C3 S=O  CaZn2 OH6  2H2 O 2OH

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,

Q.Y. Chen et al. / Waste Management 29 (2009) 390403

substituted dicalcium silicate, is normally present in cement


as the polymorph, which may be stabilised by impurities in
the lattice. The grains of belite are more rounded than
those of alite; darker in thin section and often distinctively
yellow in transmitted light. Its reaction with water to form
CSH gel and portlandite is relatively slow compared with
that of alite and so it contributes little to early strength
development. However, after 1 year the compressive
strengths of hydrated alite and belite pastes are comparable. According to the crystal model, C2S hydration can
be expressed as
C2 S H2 O ! Ca2 OH H4 SiO4
! C  S  H CaOH2

2.3. Structure of CSH gel and its binding capacity for


heavy metals
The major product of silicate phase hydration, calcium
silicate hydrate gel (CSH), is a mixture of poorly crystallised particles with dierent morphologies. It has been
reported that there are four types of CSH according to
morphology: (1) brous, (2) reticular network, (3) equate
grain morphology, and (4) inner product morphology
(Xu and Viehland 1996; Taylor, 1997; Famy et al., 2002a,
b). Type 1 is a prominent product at early stages of hydration and grows up 2 lm long. Type 2 is also an early hydration product described as forming honeycombs or reticular
networks, whereas Type 3 and Type 4 are both fairly massive and seem to appear only in older pastes (Taylor, 1997).
CSH gel has been classied as high density and low
density of CSH gel (namely HD and LD CSH), which
forms as inner product (within the original cement grain
boundaries) and outer products (in-lling the pore space)
respectively (Jennings et al., 1981; Jennings, 2000). The
ratio of HD CSH and LD CSH is inuenced by phase
compositions, additives, hydration and curing conditions.
There is no obvious dierence in composition between
HD CSH and LD CSH (Jennings, 2000).
CSH gel contains the bulk of micro-porosity. The gel
pores give rise to a high surface area and largely control the
sorption properties. Hong and Glasser (2002) conrmed
that CSH gel has a strong capacity of binding metals.
The carbonation of C3S results in an increasing capacity
of retaining heavy metal cations and heavy metal hydroxyl
ions, because of the large surface area and meta-stability of
decalcied CSH gel and calcium carbonate (Chen et al.,
in press).
A number of models for adsorption have been developed to better explain the intrinsic mechanism involved
in s/s processes, for instance, the double electrostatic layer
model (bi-layer model), the triple electrostatic layer model
(tri-layer model) and the charge dispersal model. In the triple electrostatic layer model, Ca2+ ions from initial hydration form a tightly bound bi-layer with the negatively
charged CSH surface. Subsequently, the heavy metal
cations and hydroxyl anions immediately orientate to

393

the bi-layer to constitute a tri-layer (Yousuf and Mollah,


1995; Mollah et al., 1995). In the charge dispersal model,
Ca2+ ions surround the negatively charged CSH surface
and preferentially adsorb to form a layer of positive charge;
the dispersion of other complex ions surrounds the surface.
Adsorption of heavy metals inhibits homogeneous
nucleation or heterogeneous nucleation and growth of
hydration products and in some cases enhances silicate
polymerisation (Smith et al., 1997; Chen, 2004; Chen
et al., 2007a).
Since CSH is essentially amorphous, direct determination of the solid structure is dicult and inferences about
the structure have been made from indirect measurements
(Escalante-Garcia et al., 1999; Escalante-Garcia and
Sharp, 1999; Grutzeck et al., 1999). Early ideas favoured
the concept of a disordered layer structure-based primarily
on structural analogies with related calcium silicate hydrate
minerals as deduced from poorly dened X-ray diraction
patterns. It is reported that CSH (1) is similar to tobermorite and CSH (2) is somewhat like jennite (Taylor,
1986). As is well known, tobermorite (C5S6H9) is a layer
structure, bonding together by surface forces with occasional strong ionic-covalent bonds linking adjacent particles; jennite (C9S6H11) is a single layer, bonding through
solidsolid contacts with a higher Ca/Si ratio.
Spectroscopic studies using 29Si solid-state magic angle
spinning/nuclear magnetic resonance (MAS/NMR) show
that during C3S hydration, SiO4 groups from the clinker
phases re-order as dimers (Si2O7), some of which eventually
react to form larger species (mostly pentamer and octamer)
collectively termed polymer. This polymer consists of single chains or rings, but not more complex species such as
double chain or clusters (Taylor, 1986; Cong and Kirkpatrick, 1996; Sun et al., 1999). The average chain length
increases with age of cement hydration, but dimer still
makes up approximately 40% of the chains after 2030 year
(Taylor, 1997; Kirkpatrick et al., 1997).
CSH gel is a structure very far from equilibrium and is
thermodynamically unstable at ambient temperature. It
comprises a large and complex family of phases, with varying compositions (Harris et al., 2002; Gore and Milestone,
2007). It is likely that a continuous range of composition of
CSH gel may exist in C3S or cement pastes (Glasser
et al., 1987). Based on the results of 29Si NMR studies,
we deduced molecular models of CSH as follows (Chen,
2004; Chen et al., 2007a):
Q1 species (di-silicates):
C3 S yH2 O ! yCaOH2 Ca5y H2y2 Si2 O7
 CaOH2  nH2 O

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

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Q.Y. Chen et al. / Waste Management 29 (2009) 390403

m = 3, 4, 5, 6, 7, 8, . . .; n > 0; z = 0,1,2,3,... Ca/Si = (x + z) /m


mC3 S H2 O ! yCaOH2 Cax H2m1x Sim O3m1
 zCaOH2  nH2 O

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

structure and composition by the incorporation of ions,


particularly, Si4+, Fe3+, Mg2+, Ti4+, Na+, and K+. They
can constitute as much as 10% by weight in this phase
(Lea, 1970). Lea estimated the probable iron content in this
phase at around 4.1% by weight (as Fe2O3). Group I metal
substitution (for calcium) causes changes in symmetry from
the essentially cubic lattice.
The reaction of C3A with water gives the initial formation of calcium aluminate hydrate gel that increases in crystallinity to form hexagonal hydrates such as C2AH8 and
C4AH19. The latter loses bound water to become
C4AH13. These hexagonal hydrates are converted to icosahedra of the cubic hydrate C3AH6 (hydrogarnet), as shown
in Eqs. 12 and 13. The conversion from the meta-stable
hexagonal form to the stable cubic form is accompanied
by a volume change that may have detrimental eects if
it occurs in a loaded structure. In cements with a high
C3A content, the heat of hydration is normally sucient
to ensure the conversion occurs quickly (before setting).
In the presence of calcium hydroxide (CH) the formation
of C4AH19 (or C4AH13) is favoured; and the hydration rate
is generally slower and the conversion to C3AH6 is inhibited (Lea, 1970; Chen et al., 2005).
C3 A H2 O ! Ca2 OH AlOH
4
! C4 AH19 C4 AH13 C2 AH8
! C3 AH6 AlOH3

12

C3 A CH H2 O ! C4 AH19 C4 AH13
! C3 AH6 AlOH3

13

Calcium aluminate hydrates (CAH) are thought to


have a structure consisting of sheets of Ca2 AlOH
6 with

or
OH
in
the
interlayer
region,
which
balance
AlOH
4
the net positive charge of the layer. Anions (such as


2
SO2
4 ; OH ; CO3 ; Cl ) substitution may partially stabilise CAH phases.
In cement, C3A is the most reactive mineral towards
water and its rapid dominance of rheological properties
of the cement paste requires the addition of gypsum to control immediate hydration. The rst hydrate to form is AFtsulphate, i.e., ettringite, producing a membrane around the
hydrating grain that impedes the diusion of ions from the
solution to the un-reacted C3A (see Eq. (14)). This reaction
will continue slowly by the repeated rupture and fresh reaction of this coating until the surrounding solution is
depleted in both calcium and sulphate ions. An osmotic
mechanism has also been proposed for the end of the dormant period in this mineral. Eventually, the stage is
reached where formation of further ettringite is not stoichiometrically favoured and a second related mineral
begins to precipitate as calcium monosulphoaluminate
hydrate (AFm-sulphate) (Glasser et al., 1999). Associated
with this precipitation is the gradual transformation of
ettringite to monosulphate by reaction within the pore
solution (Eq. (15)). Damidot and Glasser (1995) reviewed
the chemistry and mineralogy of ettringite formation. They

Q.Y. Chen et al. / Waste Management 29 (2009) 390403

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

C3 A; F C6 A; FS3 H32 H2 O ! C4 A; FSH12

15

Ettringite is one of the main components of expansive,


shrinkage-resistant, rapid hardening, high early strength
and low energy cements. The average content of ettringite
in modern cements may have increased as more sulphate
is added in order to control the set time of clinkers and
to improve early strengths (Glasser, 1997; Famy and Taylor, 2001). Morphologically, the ettringite phase is present
as prismatic and/or acicular crystals of hexagonal cross
section. Moore and Taylor (1968, 1970) observed that
ettringite tends to be in the form of stubby, prismatic crystals close to the aluminate surface while also forming away
from these surfaces.
The AFt and AFm phases are chemically and mineralogically complex, in which columns of Ca6(Al(OH)6) 
3
24H2O are lines of AlOH6 octahedrally bonded with
2+
3Ca ions. Water molecules complete the co-ordination
number of calcium. Sulphates are inter-columnar and can
occur in four dierent positions. Three of these positions
are occupied by sulphates and the remaining by two water
molecules (Moore and Taylor, 1968, 1970). The constitution of AFm and AFt is very sensitive to the cement composition as well as to chemical changes induced by
reactions of the cement solidpore water system with its
service environment (Glasser et al., 1999).
An examination of ettringite minerals provides evidence

of compositional change at Ca2 ; Al3; SO2
4 ; and OH
sites. For example, half of the sulphate content can be substi4
tuted by anions such as OH ; Cl ; CO2
3 ; and SiO4 (Tas3+
hiro and Oba, 1979). Fe or tetravalent cations (Si4+) can
replace Al3+. The maintenance of charge balance is accomplished by the substitutions even though stoichiometry has
been sacriced (Gougar et al., 1996; Glasser et al., 1999).
The extent of solid solution between aluminium and iron
oxide forms is not well established. The substitution of other
trivalent cations and a wide range of anion substitutions
(in place of sulphate) in these phases are shown in Table 1.
Ettringite has shown potential for immobilising Cr ions.
Substitution can occur for Cr3+ at the M3+ site and

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.

3.2. Celite (ferrite)


The aluminoferrite phase, Ca2(Fe1XAlX)2O5, where
0 < X < 0.7, is orthorhombic and a solid solution between
C6AF2 and C6A2F (Taylor, 1997). In cement, the ferrite
phase, tetracalcium aluminoferrite (celite, C4AF, Ca2AlFeO5), is signicantly modied by the incorporation of Si4+,
Mg2+, Ti4+, Mn4+, Cr3+, Na+, and K+ ions and variable
Al/Fe ratios. It is reported that MgO and SiO2 may substitute for (Al, Fe)2O3 up to about 10 mole% (Lea, 1970).
The reactivity of ferrite with water is variable. Essentially, the hydration products of ferrite are similar to those
of C3A, but forming much more slowly and with substantial substitution of Fe3+ for Al3+. Assuming, as is the case
in Portland cement hydration, calcium hydroxide is available, then hexagonal hydrates such as C4(A, F)H13,
C4(A, F)H19, and C2(A, F)H8 precipitate and then convert
to C3(A, F)H6 (Eq. (16)). Substituted hydrogarnets formed
when such pastes are cured at high temperature are metastable and ultimately decompose to calcium hydroxide, aluminium hydroxide and haematite. Like C3A, aluminoferrite reacts with sulphates to produce ettringite and related
phases, which ultimately convert to monosulphate (see
Eqs. 17 and 18). Thus, it is reasonable to expect some competition for available sulphate to occur between this phase
and aluminate
C4 AF H2 O ! Ca2 OH AlOH
4 FeOH3
! C4 A; FH13 C4 A; FH19 C2 A; FH8
! C3 A; FH6 AlOH3 FeOH3

16

C4 AF CSH2 H2 O ! C6 A; FS3 H32 AlOH3


FeOH3

17

C4 AF C6 A; FS3 H32 H2 O
! C4 A; FSH12 AlOH3 FeOH3

18

4. Cement hydration and heavy metal immobilisation

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

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Q.Y. Chen et al. / Waste Management 29 (2009) 390403

clinker is mixed with a few percent of gypsum and nely


ground to make Portland cement, which is a heterogeneous
mixture of four main compounds with 5070% alite, 20
30% belite, 512% aluminate, 512% ferrite, and 2%
gypsum.

permeability caused by these reaction products, that is,


the precipitation of insoluble metal colloidal gels on cement
grain surfaces.
4.2. Factors inuencing cement-based solidication/
stabilisation

4.1. Hydration kinetics of cement


The hydration of cement is a sequence of overlapping
chemical reactions between clinker compounds, calcium
sulphate and water, leading to continuous cement paste
stiening and hardening. The action rate of pure cement
phases usually can be arranged in the increasing order:
C3A > C3S  CA > C4AF > C2S. Actual cement phases
are even more reactive than pure compounds due to the
small grain size, non-regular coordination, deformation of
crystal structure and the presence of impurity metal ions.
The early behaviour of hydrating cement is governed by
reactions of aluminate phases; the setting and early strength
development behaviour is mostly dependent on the hydration of silicates, particularly alite. The formation of hydration products and the development of micro-structural
features depend on solution processes, interfacial reactions
and, ultimately, solid-state reactions, which is reported
widely in the literature (e.g., Macphee et al., 1989; Scrivener
et al., 1999; Gore and Milestone, 2007). The hydration
products of Portland cement comprise approximately 20
25% Ca(OH)2, 6070% CSH and 515% other phases,
including grains of still-unhydrated cement. It has been proposed that hydration of cement can be divided into ve
stages, as shown in Table 2 (Taylor, 1997).
Hydration of cement can be modied by heavy metals
due to coating around cement grains (Tashiro and Oba,
1979). Three-dimensional structures up to 100300 nm
thick containing heavy metal can form coatings around
cement grains (Cartledge et al., 1990; Taylor, 1997; Cannell
et al., 2000). According to Poon et al. (1985, 1986), metals
that form the least soluble hydroxides retard hydration
reactions; those that form more soluble hydroxides exhibit
only a slight degree of retardation; and metals forming soluble hydroxides behave as accelerators of cement hydration. Retardation has been attributed to the reduction in

In addition to the phase composition and structure, the


reaction rates of cement phases are variable and dependent
on temperature, particle shape and size, and the presence of
accelerators or retarding agents (Ortego et al., 1989; Hills
et al., 1994; Hills and Pollard, 1997). In cement-based
solidication/stabilisation, the most important admixtures
are gypsum, calcium chloride, sodium carbonate, calcium
hydroxide, carbon dioxide, and activated carbon (Conner,
1990).
The eect of neness on the rate of hardening of cement
is, of course, due to the fact that the larger the surface area
available for hydration, the more hydration products will
form at early ages, and the higher the initial strength developed by cement. Particle size and shape of cement grains
aect the setting rate and diusion of soluble constituents
from the interior into the inter-particle space after solidication (Glasser, 1997). It should be noted that the neness
of cement is not more important than chemical composition when considering the ultimate strength of cement.
As is well known, waste particles less than 74 lm can delay
setting and hardening of cement.
Temperature can aect the hydration degree of cement,
reaction rates and products of cement hydration. For
example, thaumasite only forms below 5 C. Temperature
inuences the transport of species in solidied waste and
causes expansion or shrinkage of solidied waste. If the
temperature exceeds 6070 C, serious loss of durability
can occur (Kiellsen, 1996; Escalante-Garcia and Sharp,
1998a; 1998b; Escalante-Garcia et al., 1999).
As mentioned earlier, aluminate reacts rapidly with
water and may cause undesirably rapid setting and the
undesirable properties of some products formed (e.g., hexagonal CAH). Calcium sulphate, gypsum (CaSO4 
2H2O) or its analogues such as bassanite (CaSO4  0.5H2O)
or anhydrite CaSO4 (including its polymorphic forms

Table 2
Hydration kinetics of cement
Stages

Reactions

Remarks

Initial period

Surface wetting, dissolution of cement phases, nucleation of ettringite and


hexagonal crystals of Ca(OH)2, which occurs homogeneously from the
solution phase, or heterogeneously at solid solution interfaces
Growth of ettringite needles, precipitation of CSH gel onto the silicate-rich
layer on the cement grains, which gradually forms needles or spines
Disruption of the hydrate protective layer by osmotic pressure or
transformation of the hydrates; CSH and CH growth rapidly
AFt transformation into AFm

015 min, chemical reaction control, heavy metals


may inuence the nucleation of CSH, Ca(OH)2
and ettringite
15 min4 h, chemical reaction control, heavy metals
may show accelerating or retarding eects
48 h, chemical reaction control, heavy metals may
co-precipitate with CSH, CH and ettringite
824 h, diusion control, heavy metals may
inuence this conversion process and setting, and
promote atmospheric carbonation
A few days, diusion control, Heavy metals may
inuence the mechanical strength and permeability

Induction
period
Acceleration
period
Deceleration
and
hardening
Curing period

Further hydration, conversions of hydration products

Q.Y. Chen et al. / Waste Management 29 (2009) 390403

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

near surface of cement phases. The possible immobilisation


mechanisms of heavy metals could be (1) sorption, (2)
chemical incorporation (surface complexation, precipitation, co-precipitation, diodochy), and (3) micro- or
macro-encapsulation (Trussel and Spence, 1994; Glasser,
1997).
Sorption of heavy metals on cement hydration products
includes physical adsorption and chemical adsorption.
Physical adsorption phenomena occur when contaminants
in the solution (pore water) are attracted to the surfaces of
particles because of the unsatised charges of the particles.
Chemical adsorption refers to high anity and specic
adsorption, which generally occurs through covalent bonding. The surface charges, chemical reactions involving surface functional groups and specically adsorbed ions
greatly modify the binding capacity of hydration products
of cement for toxic metals (Tamas et al., 1992; Cheng and
Bishop, 1992). In the precipitation of cement hydration
products, heavy metal ions may be adsorbed on their surfaces and then enter the lattice to form a solid solution,
altering their structures (crystallinity, particle size) and solubility (Kitamura et al., 2002).
In most cases of cement-based s/s systems, the dominant
xation mechanism for heavy metals is through the chemical precipitation of low solubility species. The saturation
indices of heavy metal compounds are usually very high
and the homogeneous or spontaneous nucleation of these
compounds occurs very quickly. If heterogeneous nucleation and secondary nucleation are taken into account,
the nucleation time could be even shorter (Cannell et al.,
2000; Salhan et al., 2003). As a result, the nucleation and
aggregation of heavy metal compounds occur very rapidly.
For species may not have sucient mobility or enough
time to undergo adequate orientation and alignment, heavy
metal compounds are inclined to form amorphous structures or poorly ordered structures in cement pastes (Cannell et al., 2000). According to Ostwalds rule, the
structure with highest entropy develops rst and then
transforms to more stable crystalline phases subsequently.
It is not surprising that heavy metal compounds in the
solidied waste are not stable.
According to the knowledge of chemistry, in cementbased s/s systems, heavy metals can be precipitated as
hydroxides, carbonates, sulphates and silicates (Hills
et al., 1994; James, 1996; Conner and Hoener, 1998).
Hydroxide precipitation occurs when the pH of a solution
of dissolved metal ions is raised to some optimum level for
a specic metal. The optimum pH is dierent for each
metal and for dierent valence states of a single metal. Carbonate precipitation sometimes has an advantage over
hydroxide precipitation when metal carbonates are less soluble than corresponding hydroxides (Asavapisit et al.,
1997; Lange et al., 1996). Heavy metal compounds precipitate on the surface of a solid more readily than from bulk
solution (James and Healy, 1972; Kulik and Kersten,
2001). As shown in Table 3, the solubility product, Ksp of
the metal hydroxides in bulk solution is considerably less

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Q.Y. Chen et al. / Waste Management 29 (2009) 390403

Table 3
The solubility product of metal hydroxides
Metal ions
2+

Ca
Mg2+
Cu2+
Pb2+
Zn2+
Cr3+
Al3+
Fe3+

log Ksp (in solution)

log Ksp (on the surface of silica)

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
Cement-based solidied and stabilised wastes are vulnerable to physical and chemical degradation processes.
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).

Carbon dioxide attack is probably the most common


degradation mechanism in cement-solidied waste. Carbonation lowers pH due to the reaction between dissolved
CO2 and the phases in the paste, which consumes Ca(OH)2
and CSH (Johannesson and Utgenannt, 2001). The
incorporation of heavy metals results in a decrease of the
Ca(OH)2 content of the cement paste and increases its vulnerability to carbonation and acidic corrosion (Chen and
Wu, 2000; Chen, 2004). McWhinney et al. (1990),
McWhinney and Cocke (1993) have studied the solidication of metal ion pollutants, namely Ba, Zn, Cr, Pb, Cd,
and Hg, and noted that the carbonation degree was greater
for the zinc, cadmium and mercury-doped cement pastes
compared with the control cement paste.
There is disagreement in the literature about eects of
carbonation on cement-based solidication/stabilisation.
Degradation of the principal binding phases (CSH gel)
will lead to considerable strength loss (Taylor, 1997). There
are, however, reports that accelerated carbonation
increases the compressive strength of solidied waste
(Lange et al., 1996). Carbonation has been shown to alter
the rate at which some hazardous components leach from
industrial wastes and Portland cement solidied/stabilised
waste streams (Smith et al., 1997; Macias, 1997; Dias,
2000). Carbonation reduced permeability that would be a
desirable attribute in a matrix used to conne toxic wastes
(Lange et al., 1996). In addition, carbonation reduces the
alkaline nature of the hydrated cement paste and reduces
the availability of some metals through their precipitation
as sparingly soluble salts. Lange et al., (1996) reported that
accelerated carbonation lowered the leaching of heavy metals. Based on dynamic leaching tests using pure water and
0.5 N acetic acid, Walton et al. (1997) reported that accelerated carbonation of mature cement s/s products could be
detrimental. The leaching rates of metals, such as calcium,
cadmium, lead and cobalt, from carbonated waste forms
were higher compared with non-carbonated analogues.
The inference from the work is that atmospheric carbonation can degrade cement-based solidied wastes and
increase the release of heavy metals to the environment
with time. Sweeney et al. (1998) studied the accelerated carbonation of Portland cement and used it to stabilise heavy
metal-bearing wastes. The work reported that concentrations of chromium in leachates associated with non-carbonated samples were generally higher than those of their
carbonated analogues. They also reported that copper concentrations were similar for both carbonated and non-carbonated samples. Their results showed that carbonated
samples demonstrated higher concentrations of zinc at
the low acid addition and similar concentrations at the
higher acid addition compared with non-carbonated
samples.
5. Evaluation method of solidied waste
There are many test methods applied to the solidied
product evaluation. Physical evaluation methods, for

Q.Y. Chen et al. / Waste Management 29 (2009) 390403

example, measurements of bulk density, porosity, and


moisture content, are used to determine the engineering
properties and the volume change factor for a solidication
process. Chemical evaluation methods, including leaching
tests and measurements of acid neutralisation capacity,
address the solubility and reactivity of contaminants when
exposed to dierent reagents and environments (Brindle
et al., 1987; Stegemann and Cote, 1990; Lo et al., 2000).
Chemical evaluation can also give useful information on
the binder in stabilising heavy metals (Ortego and Barroeta, 1991; Cheeseman et al., 1993; Mckinley et al., 2001; Van
Eijk and Brouwers, 2001).
The overall release of soluble species contained in a porous cement block in contact with water is a result of complex and coupled phenomena, for example, dissolution of
species in the pore water and transportation of species in
the leaching solution. The mass transfer during leaching
can be described by a diusion mechanism, which only
takes into account Ficks diusion law (Wang and Vipulanandan, 2000; Li et al., 2001). More recently, models
accounting for more than one eect, for example, diusion
and chemical reactions or mass transfer at an interface,
have been reported by Baur et al. (2001), Kosson et al.
(2002), and Kumpiene et al. (2008). Problems that arise
principally are the paucity of transport data relevant to
cementitious materials, which are necessary to support
such calculations. Nonetheless, considerable eort in coupling chemical and transport codes has produced a plethora of tools available with which to undertake
calculations (Read and Falck, 1996; Adenot et al., 2001).
Accelerated leaching tests characteristically used are (1)
elevated temperatures, (2) high specic surface areas perhaps achieved by crushing or grinding the matrix, and (3)
acidication and renewal of leachant (Van Herck and Vandecasteele, 2001; Chen et al., 2007b). Each method has its
own attractions and penalties and at the time of writing,
there is considerable worldwide eort expended in harmonising leach test methods (Van der Sloot et al., 1997; Adenot
et al., 2001; Munoz et al., 2007).
Most research on solidication/stabilisation has been
conducted via treatability studies and technology demonstrations. Although experiment and observation remain
essential, obvious spatial and temporal constraints prevent
their application over the life of a stabilised waste form.
The results of treatability studies and small-scale applications alone are no guarantee of the eectiveness of the technology at a large-scale or especially, in the longer term, as
there are no reliable data on performance extant. The evaluation of the long-term performance of stabilised processes
requires modelling, depending on the environmental level
of exposure corresponding to the considered scenario
(Atkins and Bennett, 1992; Berner, 1992; Stronach and
Glasser, 1997; Thomas and Jennings, 1998; Van Eijk and
Brouwers, 2001). It is, therefore, of critical importance that
stabilisation and solidication formulations are considered
from a thermodynamic standpoint. This approach shows
the sequence of chemical evolution that a system is likely

399

to experience in a given environment. It can predict the


likely progression of chemical environments experienced
by the waste after emplacement (Adenot et al., 2001).
Observation of experiments and natural or industrial analogues provides snapshots of the evolution at a given time,
whilst the thermodynamic prediction is made independently of time. In combination, the two approaches oer
the best practicable approach to planning the long-term
storage of encapsulated wastes (Tyrer, 1994).
6. Summary and conclusions
The hydration of cement phases and cement clinker has
been extensively investigated and the considerable divergences of opinions have been discussed in this paper.
Hydration of cement proceeds through three successive
reactions: (1) dissolution of phases, (2) precipitation of
CSH, portlandite and other reaction products, and (3)
equilibriums of hydration products. A series of self-limiting
reactions occurring in cement hydration are probably largely controlled by the permeability of protective colloidal
coatings around reacting cement grains. The presence of
accelerators or retarding agents alters the reaction rates
and products of cement hydration.
Heavy metals often alter the course of cement hydration
reactions. Hydrolyses of heavy metals result in the reduction of pH and accelerate cement hydration. They may
inuence the formation and properties (structure and permeability) of the protective hydrated layer, and further
inuence the nucleation and growth of reaction products.
Cement-based stabilisation/solidication technology is an
attractive option for the management of heavy metal-bearing waste to facilitate handling prior to ultimate disposal
and reduces the release of contaminants into the environment. The ecacy of cement-based solidication/stabilisation can be improved by modifying cement phase
compositions and controlling temperature, water/solid
ratios, particle size, and other factors that aect setting
and strength development and long-term durability of
solidied waste forms. The potentially deleterious heavy
metals may adversely aect the cementing matrix; pretreatment to render such substances harmless, e.g., by
adsorbent addition, is necessary in some cases.
In addition to sorption and precipitation, heavy metals
may enter the lattice of the hydrates. Phases associated
with heavy metals in cement-based s/s systems are often
amorphous or poorly crystalline mixtures of varying compositions in nano-scale; the characterisations of these
phases are very dicult. Consequently, there are many
contradictory speculations about the mechanism dominating the xation of heavy metals in hydrated cement. The
literature review has highlighted several areas ripe for further investigations, for example, the phase development of
cement pastes in the presence of heavy metals, the dissolution and precipitation of stoichiometric phases and of solid
solutions, and surface phenomena controlling heavy metal
immobilisation.

400

Q.Y. Chen et al. / Waste Management 29 (2009) 390403

There is a need to develop the design and diagnostic


methods for managing dierent wastes, enabling process
operators to adjust the process parameters. But perhaps
the most urgent challenge is harmonising rapidly advancing technology with a detailed understanding of chemistry
of the system and micro-structure, which controls the
release and mobility of toxic species to the external environment. It is certain that no single solution exists to the
solidication and stabilisation of wastes by cementation.
The solubility minima (for example, as a function of pH,
redox potential, carbonate activity or temperature) exhibited by salts of heavy metals dier considerably, so no
cement formulation can be ideally matched to mixed waste
streams.
Few thorough thermodynamic studies have been published which relate the waste to its intended solidication
and stabilisation regime. The increasing regulatory pressures to justify a chosen disposal route as the best practicable environmental option have raised these issues to the
fore. It is to be hoped that the future management of hazardous wastes will be based on an increased understanding
of the system behaviour, rather than on previously tolerated practice.
Acknowledgements
We warmly thank Drs. P. Purnell, M. Derron and G.
Manby for their informative comments, which greatly improved the quality of the manuscript.
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