ELSEVIER The Scienceof the Total Environment 172(1995) 95-118

Is the glass phase dissolution rate always a limiting factor

in the leaching processes of combustion residues?

J. Yan”, I. Neretnieks
Department of Chemical Engineering and Technology, Royal Institute of Technology, S-l 00 44 Stockholm, Sweden

Received 6 September 1994;accepted25 January 1995

Abstract

The kinetic characteristics of waste glass phases in some coal fly ashes are simulated by the hydration free energy
approach of multiple-component glass. A geochemical model is used to calculate the dissolution processes of waste
glass in a low flow-through system for coal fly ashes. The contribution of waste glass dissolution for the leaching of
solid waste is discussed on the basis of dissolution mechanisms and kinetics of glass phases, reaction time and
disposal condition. It has been found that the dissolution rate of a glass phase is not always a limiting factor in the
leaching processes of coal fly ashes. Additional retention mechanisms may retard the release of toxic elements but
only under some limited conditions. The disposal environment together with kinetic properties of waste glass phases
need to be accounted, for the dissolution of the glass phase. Glass dissolution under some, not improbable,
circumstances may considerably contribute to the long-term release of toxic metals.

Keywords: Waste glass phase; Solid waste; Coal fly ash; Dissolution mechanism and kinetics; Geochemical modeling;
Release of toxic metals

1. Introduction Neretnieks, 1993b). According to current esti-

The glass phase is one of the most important
parts of solid wastes, especially combustion, incin-
eration or smelting residues such as fossil fuel
combustion wastes, municipal solid waste (MSW)
ash and slags that may be a main constituent of
industrial and municipal solid wastes (Gut&rez et
al., 1993; Kirby and Rimstidt, 1993; Yan and
* Corresponding author.
mates, the production of combustion residues is
70 million tons annually for coal ash, 4 million
tons annually for municipal waste combustion
(MWC), and 1 million tons annually for wastewa-
ter sludge incineration (WSI) ashes in the U.S.
(Theis and Gardner, 1990). Although recycling or
reuse of these waste materials is possible in some
instances, most of them are usually disposed of in
landfills. Therefore, one of the major environ-
mental concerns in the disposal of the waste
residues is their leaching characteristics. More

0048-9697/95/$09.50 0 1995 Elsevier ScienceBV. All rights reserved.

SSDI 0048-9697(95)04727-I
96 J. Yan, I. Neretnieks /The
information is required to permit a thorough as-
sessment of leachability for this kind of solid
waste with the ultimate objective of defining envi-
ronmentally sound waste management practices.
In general, many solid wastes are heteroge-
neous materials. This heterogeneity mainly de-
pends on distribution of mineral elements in the
solid wastes (Yan and Neretnieks, 1993b). There
are close relationships between the dissolution
behavior of a species and its distribution. The
relationships determine the dissolution mecha-
nisms of a species in certain conditions. This is
the basis for connecting the intrinsic physical and
chemical properties of the wastes with their disso-
lution characteristics. During the dissolution
processes of solid wastes, some fractions (slats or
soluble oxides) of solid waste are easily leached in
a short period of time, some fractions (acid-solu-
ble components) may be dissolved under certain
conditions and the others (glass phases and some
magnetic fractions) will take a relatively long pe-
riod of time to be altered and dissolved (Yan and
Neretnieks, 1994b). Dissolution behavior of the
species varies due to the differences in dissolution
mechanisms and rates of species that exist in
various fractions of solid waste.
There are two dominant features of glass phases
present in the solid wastes. One is their high
percentage of wastes. For example, the glass phase
constitutes 60 to 90% of most coal fly ashes (Roy
et al., 1985). Some MWC ashes have been found
to contain a glass phase (Kirby and Rimistidt,
1993; Eighmy et al., 1994) as have some commer-
cial slags (Eberendu and Daugherty, 1984). The
other is that more toxic elements, heavy metals,
for example, may be enriched in the glass phase
as compared to other phases of solid waste (Hulett
et al., 1980; EPRI, 1981, 1983; Norton et al., 1986;
Rai et al., 1987). In combustion residues, some
toxic elements contained in the glass phase may
be as high as over 90% (Yan and Neretnieks,
1994b). The glass phase is generally considered as
a host of these trace elements in solid waste
(Norton et al., 1986; Hemming and Berry, 1988).
Many toxic elements are incorporated into the
glass phase by becoming part of the random
three-dimensional glass network. Dissolution of
the silicate matrix is a necessary precursor to the
Science of the Total Environment 172 (1995) 95-118
leaching of the toxic elements, or does at least
occur simultaneously with leaching of other com-
ponents. Therefore, the degree of dissolution of
the glass phase may be a reasonable measure of
the potential for release of the toxic elements
from the solid wastes.
Glass phases should be considered metastable
solids. In thermodynamics they have a higher free
energy than an assemblage of crystals of the same
bulk composition. Most glass phases exhibit a
tendency to react with aqueous solutions to form
more stable assemblages of hydrated phases
(White, 1988). With respect to the kinetics, on the
other hand, the glass phases have a stability that
works against re-crystallization and further reac-
tions with aqueous solutions. For solid waste in
which the glass phase is a main component, the
durability of the glass phase must account for the
thermodynamics and kinetics, particularly for
long-term leachability of the solid waste. It is not
very clear, however, how the glass phase dissolu-
tion contributes to the leachability of the solid
waste. There are several reasons for knowing
little about the properties of the glass phases in
leaching processes of the solid wastes. Owing to
the relative stability of the glass phase, long-term
observations are needed to understand the leach-
ability of the glass phase. This time factor is
difficult to simulate by present laboratory leach-
ing tests if the kinetics of the glass phase has to
be considered. In laboratory leaching tests, an
aggressive leachant or a high ratio of the solution
volume to solid volume (or weight) is often used
to accelerate the leaching progresses, but this
does not provide a correct relationship between
the results of the short-term leaching tests and
long-term leaching behaviors of a solid waste. In
this kind of leaching test, the kinetic factors of
the solid phase dissolution are easily ignored.
Besides the limits of current laboratory leaching
tests for dissolution of the glass phase, few long-
term field observations of leaching characteristics
of the solid wastes are available, though a four-
year natural weathering test (Andrade et al., 1990)
and a seven-year large-scale lysimeter test
(Hjelmar, 1990) for coal fly ash have been re-
ported. On the other hand, the complexity of
dissolution and alteration of glass phase also
 J. Yan, I. Neretniekx /The
makes it difficult to distinguish the dissolution or
alteration (or changing from metastable phase
into stable phase) characteristics of glass phase
itself in the leaching process of solid waste. The
dissolution or alteration of the glass phase often
appears with formation of secondary phases. This
makes the alteration processes of glass phase very
difficult to be directly observed from the changes
of the solution chemistry by current laboratory
test methods and field investigations.
Because of the limited understanding of the
dissolution behavior of waste glass, the glass
phases in solid waste are usually considered as an
inert phase (van der Sloot et al., 1985; Kosson et
al., 1991). According to this assumption, the disso-
lution rate of waste glass is so low that there is
little or no contribution for release of toxic ele-
ments during leaching of solid waste. In fact,
whether the dissolution rate of the glass phase is
always a limiting factor in leaching processes of
solid wastes is still an open question. In this
paper, we try to take into account dissolution
kinetics of the waste glass phase, the time factor
and possible conditions of waste disposal in order
to understand the contribution of waste glass for
dissolution of solid wastes.
2. Dissolution mechanisms and kinetics of waste
glass phase
The current theoretical and experimental stud-
ies of glass corrosion mainly involve fields includ-
ing commercial glasses, non-crystalline solid ma-
terials, natural glasses and nuclear waste glasses
(Adams, 1988). In recent decades, most of the
fundamental work focuses on nuclear waste
glasses. The field of rock/water interaction, espe-
cially the reaction of silicate minerals with aque-
ous solutions, also provides essential understand-
ing of the glass dissolution and surface chemistry.
Since most waste glass phases belong to the
multi-component non-crystalline silicate, this
similarity in chemical composition and structure
provides a basis for studying their reaction mech-
anisms and kinetics in an aqueous solution by
using the basic theory and experimental tech-
nology of glass corrosion. All of these promote
the development of unifying concepts of the reac-
Science of the Total Environment 172 (1995) 95-118 97
tion mechanisms and prediction of long-term
chemical durability, in particular for multi-com-
ponent waste glasses.
2.1. Dissolution mechanisms of waste glass phase
Regarding waste disposal, the primary concern
is the reactivity of the glass phase with water or
other aqueous solutions, and the potential for
release of toxic elements. The interaction of a
multi-component waste glass phase with an aque-
ous solution is a complicated process. The disso-
lution of multi-component silicate glass phases,
primarily involve selective leaching (Doremus,
1975; McGrail et al., 1984; Lee and Clark, 1986;
Drad et al., 1988); pH drift (Barkatt et al., 1986;
Hench, 1988); matrix dissolution (Adams, 1988;
Advocat et al., 1991); formation of a reaction
layer (gel layer) (Ewing and Jercinovic, 1987;
Abrajano et al., 1989; Cunnane et al., 1993);
precipitation of insoluble species dissolved from
the glass in or on the gel layer (Michaux et al.,
1992); and surface alteration and formation of
secondary phase (Ewing and Jercinovic, 1987;
Abrajano et al., 1990). Since glass is a metastable
phase it may reach a metastable saturation with
an aqueous solution as a development of the
surface reaction process. It cannot be in thermo-
dynamic equilibrium with an aqueous solution,
Therefore, glass will continue to react with an
aqueous medium, although the reaction rate may
be low (White, 1986). The glass phase dissolution
phenomena and mechanisms have been discussed
in detail in our early work (Yan and Neretnieks,
1993a; Yan and Neretnieks, 1994a). Regarding
dissolution kinetics of waste glasses, the most
important mechanisms may be the selective leach-
ing, matrix dissolution, phase alteration and for-
mation of secondary phase in or on the interfaces
between solution and glass surface.
2.2. Dissolution kinetics of waste glass phase
Several rate-controlling processes are involved
in dissolution of the complex waste glasses. In
general, these fundamental processes may be
grouped into mass transport, surface reaction and
solubility limit of the secondary phase. For most
silicate glasses, dissolution in an aqueous solution
exhibits two limiting stages (Nogues et al., 1985;
98 I. Yan, I. Neretnieks / The Science of the Total Environment 172 (1995) 95-118
Bunker et al., 1988). At short dissolution times, a
mobile element (for example, alkali metals or
boron) release is consistent with a transport (dif-
fusion) controlled process. After the initial tran-
sient period and for long-term dissolution, the
species release may be consistent with a rate
limiting step involving the reactions occurring at
the interface between the reacted glass phase and
the bulk glass before the concentration of the
species reaches a saturation limit. Many studies
provide evidence that the surface dissolution re-
action controls the overall dissolution rate of
complex silicate glasses including natural glasses
and waste glasses (Chick and Pederson, 1984;
Conradt et al., 1985; Grambow, 1985; Crovisier et
al., 1987; Lutze, 1988; Mouche and Vernaz, 1988;
Advocat et al., 1990; Bourcier et al., 1990; Knauss
et al., 1990; Bourcier, 1991; Cunnane et al., 1993).
In most situations the surface layer of the reacted
glass phase exhibits little or no effect of a diffi-
sion barrier. There is, however, evidence that the
surface layers may be important under some cir-
cumstances (Grambow et al., 1992). In a closed
system or for a sufficiently long reaction time, the
rate controlling process of complex silicate glasses
may be complicated by precipitation of secondary
phases from the solution or by in situ altering of
the gel layer. The composition and property
changes of surface layers, particularly the alter-
ation of metastable phases, may affect transport
processes or thermodynamic equilibrium limits,
and thus the overall dissolution rate of glass
phases.
An approach assuming surface reaction control
is widely used to model the dissolution processes
of waste glasses. This approach is developed on
the basis of the theory of water/mineral interface
reaction. On the basis of the transition state
theory and surface complex chemistry, a general
rate law (Lasaga, 1981, 1984; Aagaard and
Helgeson, 1982; Helgeson et al., 1984; Murphy
and Helgeson, 1987) is proposed to account for
the silicate hydrolysis at constant pressure and
temperature:
where r is the rate of reaction, n the number of
moles of reactant mineral in the system, t the
time, s the effective surface area, k the rate
constant, a, the activity of the ith species in the
system, ii,,j the reaction coefficient of the ith
species other than the activated complex in the
jth activation reaction forming the activated com-
plex, A the chemical affinity for overall hydrolysis
reaction, R the gas constant, T the absolute
temperature, u the ratio of the rate of decompo-
sition of the activated complex to that of the
overall reaction. According to the general hydrol-
ysis theory of silicate mineral as mentioned above
and reaction kinetics of silica with water (Rims-
tidt and Barnes, 1980), Grambow developed a
model that accounts for dissolution behaviors of
waste glasses and experimental observations. This
model has been widely applied to modeling of
dissolution of waste and natural glasses under
various environmental conditions (Freude et al.,
1985; Grambow, 1985, 1987; Grambow et al.,
1985a, 1985b, 1986, 1987; Croviser et al., 1985;
Grambow and Strachan, 1988; Iseghem and
Grambow, 1988; Zwicky et al., 1989). Grambow’s
model assumes that the surface reaction (matrix
dissolution) controls the overall dissolution
process and considers the influences of chemical
affinity and solubility effects on the dissolution
rate. This model also considers the diffusion ef-
fect of silicic acid through the alteration layers on
the glass surface and an empirical long-term dis-
solution rate. A general rate equation for matrix
dissolution of glass is shown as follows:
rm = k+(l-exp(g))
where r, is the rate of glass matrix dissolution,
k, the forward rate constant, and A* the affinity
of the rate limiting reaction.
where IAP”is the activity product and K*is the
stability constant for the rate-limiting reaction. In
the most simple case for glass dissolution, the
 J. Yan, I. Neretnieks / The Science of the Total Environment 172 (199.5) 95-118 99

rate limiting reaction is considered as: Therefore, the dissolution kinetics of a waste
glass is described by four major parameters:
SiO, + 2H,O -+ H,SiO, (4)
. the forward rate constant k,
Then: . the stability constant for silica control K*
. the final dissolution rate yfin
0 the diffusion coefficient of silicic acid through
the surface 1ayersD

where aH,sio 4 is the activity of silicic acid in the

solution.
Considering the influence of silica transport
through the surface layers on dissolution rate, the
transport rate rt can be given by a modification of
Fick’s first law:
rt = g(aS -ah> + rain
where D is the diffusion coefficient for silica, L
the thickness of the transport barrier (For a
growing surface layer, L is calculated from the
amount of glass reacted at each reaction step and
for the Nerst’s film, a fixed value for the film
thickness may be used (Grambow, 1987)), a, and
a,, are the activities of silicic acid at the glass
surface and in bulk solution, respectively, and rfin
the final rate of reaction, The last term accounts
for the experimental observation that the dissolu-
tion of glass still continues even under saturated
conditions. In this case, rt = rfin. At a steady
state, i.e., rt = r, and an,sio = a,
,-k+~l-~~=r(U~-li,i,,;
3. Prediction of the kinetic properties of waste
glass phases
According to the theories of dissolution mecha-
nisms and kinetics of waste glass, the dissolution
behaviors of a waste glass phase can be de-
(6) termined by its kinetic properties and environ-
mental conditions. The main kinetic parameters
of waste glasses can be obtained from experimen-
tal measurements or theoretical prediction and
estimation. So far, many dissolution kinetic data
are available for nuclear waste glasses and some
natural glasses but little is known about other
waste glasses. Because the glass phases in conven-
tional solid wastes such as combustion residues
usually are mixed with other constituents, it is
difficult to separate the glass phases from the
solid waste for measurement of their kinetic
properties even when the composition, structure
and fractions of the glass phases have been de-
termined by various methods. Reasonable theo-
retical prediction and estimation may, however,
provide a way to study the dissolution kinetics of
(7) the waste glass phases.

then 3.1. A thermodynamic approach for prediction of

chemical durability of wasteglassphases
A thermodynamic approach has been success-
abg + (K” - ab> + rfi,
fully proposed for prediction of the chemical
a, = (8)
durability of various glasses. This approach is
;K* + k,
based on the hydration theory of glass (Paul,
1977, 1990). The glass phase is assumed to be a
and mechanical mixture of orthosilicate and oxide
components. The long-term chemical resistance
of a glass is mainly determined by the thermody-
g(K* - ab> + rfi,
rm=K+ namic activity and stability of its component ox-
(9)
;K* + k, ides in an aqueous solution. The thermodynamic
stability of a glass can be considered to be the
 100 J. Yan, I. Neretnieks /The Science of the Total Environment 172 (1995) 95-118
stability of its component oxides, which in turn is
a function of the activity of the particular oxide in
glass and the equilibrium constants of hydration,
ionization and complexation. This approach as-
sumes that the calculated free energy of hydra-
tion of the glass is the chemical driving force for
glass alteration or dissolution. The chemical po-
tential, pi, of component i in the glass is the free
energy of formation of the component. The
chemical potential of the hydrated form of com-
ponent i is assumed to be the free energy of
formation of the hydrated species.
Pi,glass = AGf,i,glass
k,hydrated = AGf,i,hydrated
The chemical driving force for glass hydration,
A lFthydratj,,n,is given by:
n
A phydration = C ( f4,glass - &hydrated) (12)
i=l
A ~hydration = f: AGi,hydration
i=l
The calculated free energy of hydration of the
glass is related to the free energies of hydration
of its component oxides by the following equa-
tion:
AGglass,hydration = i (AGi,hydrationoXi)
i=l
where AGglass,hydration is the free energy of the
glass, AGi,hydration the free energy of component i
in the glass, and Xi the mole fraction of compo-
nent i in the glass.
Plodinec et al. (1984a, 1984b) applied this ap-
proach to predict the chemical durability of vari-
ous types of glasses covering a broad range com-
positions. The relative durabilities of over 300
natural and man-made glasses (including natural
obsidians, tektites, basalt, pure SiO,, modern
window glass, simulated medieval window glasses
and nuclear waste glasses) have been compared
based on their relative thermodynamic stabilities,
expressed as the free energies of hydration
(Jantzen, 1988a; 1988b). The linear relationships
between the free energy of hydration of a given
glass and the logarithm of the normalized mass
loss of component i (usually SiO,), Li, under a
standard leaching testing condition have been
determined:
AGglass,hydration = c l Log Li (15)
where C is the constant of proportionality. This
empirical relationship connects the intrinsic
chemical durability of a glass phase with its com-
position. There is experimental evidence that a
constant and maximal dissolution rate may be
(10) obtained at infinite dilution or at a high flow rate
and constant temperature and pH (Lutze, 1988).
(11)
The rate is only dependent on glass composition
and structure. It can therefore be considered to
be one of the intrinsic kinetic properties of glasses.
According to the surface reaction controlling
mechanism, the initial dissolution rate may be
measured in conditions far from solution satura-
tion. According to the standard leaching test con-
(13) dition (Strachan et al., 1981), the property of
normalized mass loss, Li, reflects the initial disso-
lution behavior (forward dissolution rate) of the
glass phase in pure water. This approach can
provide a simple way to take the intrinsic kinetics
of the glass phase as a function of the chemical
composition of glass phase under certain condi-
tions.
(14)
3.2. Prediction of the dissolution behaviors of the
glass phases of coal fly ashes in an aqueous solution
There is a proportion of glass phase in coal fly
ashes. Compared with other glass phases of solid
wastes, the glass phases contained in coal fly ash
have been studied in their compositions, struc-
tures, density distribution and individual particles
(Hulett et al., 1980; Ramsden and Shibaoka, 1982;
Roy et al., 1985; Hemmings and Berry, 1986;
Hemmings et al., 1987; McCarthy et al., 1987;
Hemmings and Berry, 1988; Odler and Zysk,
1989). We take the glass phase of coal fly ash as
an example to study the dissolution or alteration
characteristics of waste glass phases in aqueous
solutions.
It is known that the composition of glass phases
in coal fly ashes may vary from ash to ash and
 J. Yan, I. Nerehieks / The Science of the Total Environment 172 (1995) 95-118 101

Table 1
Chemical composition and coal sources of coal fly ash samples

Sample Major chemical composition (%) Coal sources

SiO, Al,O, Fe@3 Fe0 CaO MgO Na,O K,O TiO others

1 59.80 22.10 3.30 10.10 1.10 2.10 0.40 0.62 1.64 Sub-bituminous coal
2 43.20 21.00 24.20 1.60 1.00 0.50 2.20 0.90 6.60 High-Fe bituminous coal
3 47.88 24.63 1.31 12.00 2.12 1.65 0.23 0.64 1.07 6.18 Bituminous coal
4 57.76 27.38 0.43 3.95 1.71 1.37 0.74 1.66 1.28 1.66 Bituminous coal
5 60.53 25.01 0.34 3.08 1.07 0.95 0.40 1.68 1.13 3.78 Bituminous coal
6 66.41 24.49 0.07 0.68 0.29 0.50 0.08 0.28 1.06 3.08 Bituminouscoal
Data sources: the composition of sample 1 is obtained from Hemmings and Berry, 1986; sample 2 is obtained from Hemmings et
al., 1987; and samples 3, 4, 5, and 6 are obtained from Ramsden and Shibaoka, 1982.

from particle to particle. In consideration of the
heterogeneity of the glass phase in composition,
the six samples of glass phases used in this study-
include that the original coals of ashes are bi-
tuminous and sub-bituminous, the types of ash
are the high-Ca and low-Fe fly ash, low-Ca and
high-Fe fly ash, and various silicon contents in
ashes. Because density fraction may reveal a
marked speciation in glass composition of coal fly
ash (Hemmings and Berry, 1986; Hemmings et
al., 19871, the glass phases in various density
fractions of an ash have been studied (samples 1
and 2). According to two types of glass particle
(solid glass and vesicular glass), the glass phases
of individual particles in coal fly ash have also
been taken into account (samples 3 to 6). The
chemical composition of ashes and the coal
sources of the samples used in this study are
listed in Table 1. The mineralogical contents for
some samples are shown in Table 2.
On the basis of the glass chemical compositions
of various ashes, density fractions and individual
particles of coal fly ashes, the forward dissolution
rates of different waste glass phases in aqueous
solution were calculated by means of the hydra-
tion free energies of the glass phases according to
the method discussed in the last section. The
thermodynamic data used to calculate the hydra-

Table 2
Major mineralogical contents of the ashes (%) for sample 1 and 2 in density fraction

Sample 1 Density fractions (g/cm31

Phases < 0.79 0.79-1.50 1.50-2.00 2.00-2.50 2.50-2.85 > 2.85

Glass 84 77 76 77 89 97
a-quartz 1 1 2 10 11 3
Mullite 15 22 22 13 0 0

Sample 2 Density fractions (g/cm3)

Phases < 0.79 0.79-1.50 1.50-2.00 2.00-2.50 2.50-2.75 2.75-2.85 2.85-3.00 > 3.00

Glass 81 61 58 862 55 63 68 34
a-quartz 0 3 7 11 24 10 5 2
Mullite 19 36 35 27 18 24 22 0
Hematite 0 0 0 0 1 1 2 29
Spine1 0 0 0 0 2 2 3 35
Data sources: the sample 1 is obtained from Hemmings and Berry, 1986; sample 2 is obtained from Hemmings et al.. 1987.
102 J. Yan, I. Neretnieks /The Science of the Total Environment 172 (1995) 95-118

tion free energies of glass phases are obtained
from Plodinec et al. (1984a and 1984b). The
chemical compositions of various glass phases and
calculation results of the dissolution rates are
given in Table 3 - Table 6. For the samples of
glass phase based on the density distribution, the
average value of dissolution rate and glass com-
position is the weighted average of all density
fractions of a sample (samples 1 and 2). For the
samples of individual glass particles, the average
dissolution rate of glass phase in a coal fly ash is
the average value of all investigated glass parti-
cles in the sample, and the glass phase that the
dissolution rate is closest to the average dissolu-
tion rate is considered as average glass in a coal
fly ash (samples 3, 4, 5, 6). Table 6 shows the
calculation results of various individual particles
for sample 5. Other samples are treated in a
similar way.
Temperature effects have been taken into ac-
count in the calculation of dissolution rates of
waste glass phases under various temperatures.
For many silicate glass phases, including waste
glasses and some natural glasses and silicate min-
erals, the dissolution rates usually follow the Ar-
rhenius temperature dependence in dilute aque-
ous solutions:
k = Aexp( -E,/RT)
where k is the reaction rate constant, A is a
constant, E, the activation energy constant, R
the gas constant, and T the absolute temperature.
Table 7 shows some apparent activation energies
of waste and natural glass phases. In this study,
we use 65 kJ/mole as apparent activation energy
to calculate the temperature effects on forward
dissolution rates for all glass phases of the coal fly
ashes.
Another important kinetic parameter of waste
glass dissolution is the final dissolution rate. This
parameter reflects the alteration property of the
glass phase when the aqueous phase reaches satu-
ration with respect to the major component (usu-
ally Si) of the glass phase. According to the simi-
larity of multi-component silicate glass phases in
dissolution kinetics, we compare the final dissolu-
tion rates with corresponding forward rates for
some multi-component silicate glasses (Table 8).
The two dissolution rates differ by two to three
orders of magnitude. Therefore, we assume that
the final dissolution rate is lower by 2.5 orders of
magnitude than the forward dissolution rate for
the glass phase of coal fly ash. The final dissolu-
tion rates of the six samples are given in Table 9.
4. Simulation of the dissolution behaviors of waste
glass phase
In order to assess the dissolution behaviors of
(16) waste glass phases in possible disposal environ-
ments, particularly for long-term dissolution or
alteration of the glass phase, the geochemical
modeling of dissolution of waste glass phases is
performed based on the dissolution kinetics of

Table 3
Dissolution rates calculated for the glasses of high-Ca and low-Fe coal fly ash according to the density fraction (Sample 1)

Density Fraction Chemical composition (%)

Cg/cm3) (%I ~&rnoO ;mol/m’s)
SiO, f&O, Fe203 CaO M@ Na,O K,O Totals

Raw ash 59.8 22.1 3.3 10.1 1.1 2.1 0.4

< 0.79 1.4 64.7 23.5 3.3 2.8 1.3 3.6 0.1 99.3 9.205 2.52 x 10-l’
0.79-1.50 7.6 67.6 18.1 3.2 5.9 1.3 2.6 0.3 99.0 7.347 3.30 x 10-11
1.50-2.00 23.2 69.7 15.6 2.3 5.2 1.1 2.2 0.4 96.5 9.079 2.75 x lo-”
2.00-2.50 28.8 63.2 23.3 2.6 6.8 0.9 2.1 0.3 99.2 6.958 3.24x lo-”
2.50-2.85 29.2 51.2 20.9 4.7 17.5 1.5 2.3 0.2 98.3 - 8.507 1.76 x lo-”
> 2.85 9.9 43.1 19.2 6.4 23.9 1.7 1.7 0.3 96.3 - 17.19 4.34 x lo-l*
Average 59.6 20.0 3.6 11.1 1.2 2.2 0.3 98.0 -3.64 1.13 x 10-10

The data source of glass composition and density fraction: Hemmings and Berry, 1986; AG is the hydration free energy of glass
phase;r is the forward dissolution rate for Si in pure water and is calculated from the AG at 25°C; the average composition of glass
phase is weighted average of the density fractions.
 J. Yan, I. Neretnieks / The Science of the Total Environment I72 (1995) 95-118 103

Table 4
Dissolution rates calculated for the glasses of low-Ca and high-Fe coal fly ash according to the density distribution (Sample 2)

Density Fraction Chemical composition (%)

(g/cm3) (%o) Totals kY/rnof) ;mol/m’ s)
SiO, Also, Fe203 CaO WO Na,O K,O

Raw ash 43.2 21.0 24.2 1.6 1.0 0.5 2.2

< 0.79 0.3 59.4 22.7 8.2 0.6 1.6 0.7 5.5 98.7 4.862 3.95 x lo-”
0.79-1.50 1.8 66.7 9.8 12.0 0.8 1.8 0.8 6.2 98.1 2.038 6.30 x 10-l’
1.50-2.00 3.8 67.0 4.5 16.1 1.1 1.7 0.9 6.3 97.6 9.079 2.75 x lo-l1
2.00-2.50 8.0 66.9 8.4 14.5 1.2 1.3 0.8 4.8 97.9 5.372 4.17 x 10-11
2.50-2.75 9.0 60.8 9.8 18.6 2.3 1.5 0.8 3.9 97.7 3.720 4.65 x 10-l’
2.75-2.85 52.8 54.7 12.1 20.3 2.8 1.8 1.0 4.7 97.4 - 0.644 7.16 x 10-l’
2.85-3.00 8.7 51.1 11.4 25.2 2.9 1.6 0.8 3.9 96.9 - 0.782 6.81 x lo-”
> 3.00 15.6 44.0 29.9 13.7 4.4 1.9 0.5 2.1 96.5 1.895 4.21 x lo-l1
Average 54.9 14.0 18.7 2.7 1.7 0.9 4.3 97.2 0.651 6.13 x 10-l’
The data source of glass composition and density fraction: Hemmings et al., 1987; AG is the hydration free energy of glass phase;
Y is the forward dissolution rate for Si in pure water and is calculated from the AG at 25°C; the average composition of glass phase
is weighted average of the density fractions.

waste glass. Because the initial (forward) and final the model are:
dissolution rates represent two limits of kinetic
properties of waste glass during dissolution l The state of the system is mainly controlled by
processes, the modeling is focused on these limit kinetic parameters of glass dissolution and
situations. The surface layer of the reacted glass reaction time.
phase is considered to have little or no effect as a
diffusion barrier. Trace heavy metals, Zn, Cu, Pb
and Cr, have been incorporated with the glass Water Inflow

u
phase to examine the release of the trace ele-
ments during the dissolution of the glass phase.
The content of every trace element in the glass
phases is about 0.1% (weight percentage), close ‘..:..:..:..:..:. .:..:. *:. .:. -:. .:.
I , ::...:.-.‘. ..‘...‘. *.a. ..‘. ..>:
to the higher content of the elements in coal fly . . . . . . . . . .. . . . . . . .

ash (Theis and Gardner, 1990; Murarka et al., Equilibrium

1991). A landfill is considered to be the disposal reactions
environment of solid waste. About 10% of the in aqueous
average precipitation (0.5-0.8 m3/m2 year in phase
Sweden) is assumed to flow through the waste
deposit site in the simulation.

4.1. Simulation system and geochemical modeling

A volume unit in a combustion residue monofill
is considered as a fixed bed flow through reactor.
Glass phase dissolution takes place together with
I I~:::‘::::i
1~::~::~
......*
..,.....
release of other components of solid waste in the
reactor. The dissolution process of waste glass is
evaluated by aqueous phase composition of the
system outflow when the system reaches a steady
state. This system is shown in Fig. 1. A simple
u
outflow
model is proposed for simulation of dissolution of Fig. 1. A fixed bed flow-through reactor system used to simu-
the waste glass phase. The major assumptions of late dissolution of waste glass.
 5

s
3
ts,
21
3
Table 5 3
Dissolution rates calculated for the glass phases according to the individual particles in coal fly ash (Samples 3, 4, 5 and 6) &
Samples Chemical composition(%) AG(kJ/mol) r(mol/m* s> X lo-” k
SiO, ~2% NO Fe203 FeOa K,O Na,O CaO TiO, Totals Mean S.D. Mean S.D. p.
3 Raw ash 47.88 24.63 1.65 1.31 12.00 0.64 0.23 2.12 1.07
Average glass 47.33 23.75 3.55 24.84 0.52 - 2.42 1.41 103.8 - 8.447 11.13 29.74 26.75
4 Raw ash 57.76 27.38 1.37 0.43 3.95 1.66 0.71 1.74 1.28
Average glass 58.07 32.05 1.52 .\ 3.91 3.35 0.61 0.26 1.17 100.9 8.786 10.85 11.00 20.53
5 Raw ash 60.53 25.01 0.95 0.34 3.08 1.68 0.40 1.07 1.68
Average glass 63.61 25.20 0.56 4.25 5.23 0.33 0.25 0.24 99.67 6.874 11.13 0.6630 0.9979
6 Raw ash 66.41 24.49 0.50 0.07 0.68 0.28 0.08 0.29 1.06
Average glass 61.09 31.58 0.31 0.21 2.56 0.09 0.25 0.53 96.62 15.70 4.777 1.643 1.711
aTotal iron is expressed as Fe0 for the glass phases; AG is the hydration free energy of glass; r is the forward dissolution rate for Si in pure water and is calculated
from the AG at 25°C; S.D. means standard deviation; The data source of chemical compositions of glass particles: Ramsden and Shibaoka, 1982 (sample 3 is the
Liddell fly ash; sample 4, the Munmorah fly ash; sample 5, the Vales Point fly ash; and sample 6, the Wallerawang fly ash).
 J. Yan, I. Neretnieks /The Science of the Total Environment 192 (1995) 95-118 105

Table 6
Dissolution rates calculated for the glass phases according to the individual particles in coal fly ash (Sample 5)

Particle No Chemical composition (%) AG(KJ/mol) r(mol/m3s>

SiO, Also, MS FeOa K,O Na,O CaO TiO,

Solid glass 1 32.17 12.97 2.08 44.43 0.40 0.26 1.16 1.84 - 18.24 3.51 x 10”
2 40.54 15.79 0.43 1.31 3.75 0.72 0.51 38.10 26.40 1.81 x lo-l3
3 41.91 18.74 12.56 17.00 1.83 0.12 0.05 5.20 - 15.95 3.44 x lOWI
4 44.47 19.75 4.43 26.85 0.89 0.21 0.78 1.12 - 13.45 2.68 x lo-l1
5 46.06 33.33 8.10 0.62 0.57 0.10 11.13 0.22 9.761 1.76 x lo-l1
6 51.01 32.14 6.17 5.62 1.76 0.50 0.05 2.65 2.000 4.55 x 10-12
7 52.12 33.86 0.51 10.53 0.92 0.20 0.43 0.39 7.477 2.39 x 10-”
8 54.52 23.73 0.69 4.68 2.72 0.41 1.04 9.59 12.70 1.31 x lOW12
9 54.68 19.49 0.57 1.42 4.72 0.48 0.35 17.64 16.87 7.88 x lo-l3
10 57.49 23.06 5.52 2.22 0.53 0.29 8.91 1.55 - 2.397 8.88 x 10-12
11 65.87 18.56 0.04 0.10 12.05 2.30 0.22 0.34 - 2.088 9.83 x 10-l’
12 66.70 13.05 0.54 16.37 0.81 0.10 0.55 0.36 4.506 4.41 x 10-12
13 71.45 20.93 0.47 0.90 7.67 0.57 0.24 0.20 6.807 3.56 x 1O-‘2

Vesicular glass
14 47.46 41.62 0.66 0.74 0.71 0.38 0.20 0.12 14.98 8.60 x 10-13
15 53.17 44.25 0.58 1.08 0.89 0.26 0.21 0.00 15.23 9.36 x lo-r3
16 54.72 39.88 0.43 1.36 1.72 0.24 0.87 0.40 13.51 1.19 x 10-12
17 56.96 31.99 1.82 5.65 0.71 0.24 0.37 1.44 10.68 1.76 x lo-l2
18 58.52 26.86 0.48 1.43 1.50 0.53 0.50 1.03 14.64 1.11 x lo@12
19 65.25 21.53 0.72 1.05 9.49 0.30 0.11 0.87 3.376 4.96 x lo-”
20 65.36 15.65 0.30 1.51 1.22 0.00 0.87 14.33 22.27 4.83 x lo-l3
21 65.53 21.25 0.44 1.00 1.46 0.33 0.74 0.60 15.60 1.10 x 10-12
22 65.63 24.46 0.59 1.94 2.19 0.17 0.58 2.81 14.71 1.23 x lo-l2
23 67.26 20.82 0.70 1.32 7.11 0.22 0.07 0.12 7.109 3.22 x 10ml’
24 67.68 24.91 0.73 1.61 2.80 0.48 0.31 0.84 13.24 1.52 x lo-=
2.5 70.45 18.59 0.91 1.20 4.70 0.04 0.08 0.81 11.69 1.19 x lOW’2

aTotal iron expressed as FeO; AG is the hydration free energy of glass; r is the forward dissolution rate for Si in pure water and
is calculated from the AG at 25°C; The data source of chemical compositions of glass particles: Ramsden and Shibaoka, 1982.

o Dissolution of the glass phase takes place in a
pH buffering environment (because of the re-
lease of buffering components during dissolu-
tion of solid waste).
o Dissolution of the waste glass is congruent for
all glass components including trace metals.
o Except for the dissolution reaction of the glass
phase, other reactions quickly reach equilibria
in the system.
A geochemical computer code-STEADYQL is
used to simulate the dissolution processes of the
waste glass phases. This computer program is
based on a quasi-steady-state model that con-
siders chemical processes in three time scales:
fast reversible processes in the aqueous phase,
described in terms of chemical equilibrium; slow
solid dissolution processes described by kinetic
equation and the steady-state solution is found;
and very slow processes, which are considered to
be invariant in time for the solution of the sys-
tem. The numerical algorithm incorporates these
principles and is formulated by: mass action equa-
tions, rates of slow processes and fluxes, and flux
balance and mole balance. A mathematical de-
scription is given by Furrer et al. (1989, 1990) in
more detail.
4.2. Simulation parameters and conditions
The samples used for simulation are the same
as ones in section 3.2. The simulation parameters
and conditions may be divided into system
parameters, kinetic parameters and dissolution
reactions. Most of the parameters are selected on
 106 J. Yan, I. Neretnieks / The Science of the Total Environment I72 (1995) 95-118

Table 7
Apparent activation energies of dissolution for silicate glass phases

Glass phases Activation energy Conditions Ref.

&J/m00

General waste glasses 60-90 Various compositions 1

High-silica glass 73.2 + 6.3 Distilled water, 6-70°C 2
Tholeiitic glass 65 Seawater, 3-60°C 3
Basaltic glass 60 Aqueous solution, 50-200°C 4
Tektite glass 79.6 o-100°C 5
Quartz 67.4-76.6 Aqueous solution, O-300’% 6
cu-Cristobalite 68.7 Aqueous solution, 0-300°C 6
P-Cristobalite 65.0 Aqueous solution, 0-300°C 6
Amorphous silica 60.9-64.9 Aqueous solution, 0-300°C 6
References: (1) White, 1986; (2) Barkatt et al., 1981; (3) Crovisier et al., 1985; (4) Guy and Schott, 1989; (5) White, 1988; (6)
Rimstidt and Barnes. 1980.

the basis of the environments of waste disposal 2 6.13 x lo-r1 1.94 x lo-l3
and the physical and chemical properties of coal 3 2.97 x 10-l’ 9.40 x lo-l3
fly ashes. 4 1.10 x lo-l* 3.48 x lo-l3
The systemparameters: 5 6.63 x lo-l2 2.10 x lo-l4
6 1.64 x lo-r1 5.19 x lo-l4
l Reactor depth H = l(m) Dissolution reactions:
0 Inflow rate R, = 2 x lo-’ (m3m-%-r) Samples Reactions
0 Inflow H,COt CH,COg y = lo-’ (mol dmp3)
(Pco, = 10-3.50 atm) Glass + 1.879Hf --f SiO, (aq) + 0.396AIf3
. Buffering system pH = 9 + 0.046Fe3+ + 0.200Ca2+ + O.O78Na+ +
. Porosity of the ash in reactor 19= 0.5 0.031Mg2+ + 0.0019Cr3+ + 0.0016Cu2+ +
0 Bulk density of the ash p = 1.25 (g cme3> 0.0005Pb2+ + 0.0015Zn2+ + 0.9395H 0
. Specific surface area S, = 0.5 (rn’g-‘> Glass + 1.951H+ + SiO, (aq) + 0.3iOf+~l+~
+ 0.236Fe3+ + 0.054Ca2+ + O.l28Na+ +
0.047Mg2+ + 0.0019Cr3+ + 0.0016Cu2+ +
The kinetic parameters: 0.0005Pb2+ + 0.0015Zn2+ + 0.9755H20
Dissolution rates of the waste glasses (mol Glass + 3.442H+ -+ SiO, (aq) + 0.592Al+3
rn-‘s-l) + 0.435Fe3+ + 0.055Ca2+ + O.O14Na+ +
Samples Forward rates Final rates 0.112Mg2+ + 0.0019Cr3+ + 0.0016Cu2+ +
1 13 x lo-lo 3.57 x lo-l3 0.0005Pb2+ + 0 OO15Zn2+ + 1.72lH,G
Glass + 2.313H’ + SiO, (aq) + 0.650AI+3
Table 8 + 0,056Fe3’ + 0.005Ca2’ + O.O94Na+ +
The final dissolution rates compared with corresponding 0.039Mg2+ + 0.0019Cr3+ + 0.0016CuZf +
forward rates for multi-component silicate glasses 0.0005Pb2+ + 0.0015Zn2’ + 1156H,O
Glass + 1.727H’ + SiO, (aq, + 0.466Al+3
Glasses SAN60 SM58 JSS-A SRL-131 PNL76-68 Basalta
+ 0.056Fe3’ + 0.004Ca2’ + 0.114Naf +
r&/m2 d) 1.5 1.7 1.5 3.0 1.8 3-20a 0.013Mg2+ + 0.0019Cr3+ + 0.0016Cu2+ +
rs,,(g/m2 d) 0.005 0.003 0.0025 0.033 0.0075 O.la 0.0005Pb2+ + 0.0015Zn2+ + 08635H,O
300 570 600 90 240 30-200
rfor/rfin Glass + 1.933Hf -+ SiO, (aq) + 0.610AIf3
ameans natural basalt glasses and the dissolution rates are + 0.003Fe3’ + 0.004Ca2’ + 0.056Na’ +
expressed as wm/lOOO years;rf,,.. the forward dissolution rate; 0.008Mg2 + + 0.0019Cr3+ + 0.0016Cu2’ +
rti: the final dissolution rate (at Si-saturation). Data sources: 0.0005Pb2+ + 0.0015Zn2+ + 0.9665H20
Grambow et al., 1985b; Grambow et al., 1986; Grambow and
Strachan, 1988; Iseghem and Grambow, 1988.
 J. Yan, I. Neretnieks / The Science
Table 9
Estimation of the final dissolution rates for the glass phases of coal fly ashes
Samples 1 2
rsn (mol/m%) 3.57 x lo- l3 1.94 x lo- l3
4.3. Simulation results
In order to investigate the dissolution or alter-
ation behaviors of waste glass phases during a
long-term period, the results of simulation of
waste glass dissolution are given in two forms.
One shows the potential contribution of waste
glass dissolution for the concentrations of re-
leased species in the aqueous phase of system
outflow (Table 10). It can be used to evaluate the
influence of glass dissolution or alteration on
release concentration of a species. The potential
concentration stands for the available concentra-
tion of a species dissolved due to glass dissolution
if other reactions do not affect the concentration
of the species in the system. In this way, the glass
dissolution or alteration can be separated from
other additional reactions, for example precipita-
tion or adsorption, in the complex processes. Only
the results for the forward dissolution rates are
shown. For the final dissolution rate, the concen-
trations are 316 times (2.5 orders of magnitude)
lower.
Another form of the simulation results is given
in the specific flux of dissolution or alteration of
the glass phase with respect to the cross section
area of the reactor (Table 11). The specific fluxes
of various species of the glass phase express the
relationships between the amount of dissolution
or alteration of waste glass and reaction time in
the system. These values are obtained under the
dissolution reaction having reached steady state
in the system and at two limited dissolution ki-
netic conditions. The values are shown in Table
11, only for the forward dissolution rates.
One of the most important behaviors of toxic
elements (heavy metals) during glass dissolution
is that these species may be retarded into the
aqueous solution by various kinds of trapping or
retention effects. If the dissolution of glass phase
is not a limiting factor, their release rates should
be lower than that of glass matrix dissolution.
of the Total Environment 172 (1995) 95-118 107
3 4 5 6
9.40 x 10-13 3.48 x lo- l3 2.10 x lo- l4 5.19 x lo- l4
Solubility limit, co-precipitation (Grambow, 1982;
Petit et al., 1989,199O) and adsorption (Barkatt et
al., 1981; Lee and Clark, 1986; Petit et al., 1990)
are considered as main mechanisms that account
for the retardation mechanisms. In this study, we
only assess the solubility limit for glass con-
stituents after glass network degradation. An
equilibrium program PHREEQE (Parkhurst et
al., 1980) is used to evaluate the aqueous chem-
istry and potential precipitation of secondary solid
phases for the system outflow. The selection of
complexation reactions in aqueous phase and dis-
solution/precipitation reactions of the potential
minerals is based on Rai et al., 1987 (Rai and
Zachara, 1984; Eary et al., 1990; Mattigod et al.,
1990) and our early work (Yan and Neretnieks,
1994a). The speciation of species in aqueous phase
and the saturation states (saturation index SI =
log (LAP/K), where the IAP is the ion activity
product and the K is the solubility constant of the
mineral) can be obtained from these geochemical
calculations. The calculations are performed un-
der two situations or the alkaline condition (pH
= 9, it is the same as the system outflow) and the
weakly acidic condition (pH = 4, it simulates that
the buffering capacity of the system is consumed).
The saturation states of the outflow solutions
from simulation system are shown in Table 12 -
15.
5. Discussion
We would like to compare our simulation re-
sults with actual measured data. However, be-
cause there are some limitations in test methods,
sample separation and of difficulties to take into
account the time factor for investigation of the
glass dissolution in solid wastes and because real
waste always contains mineral phases with dif-
ferent kinetics and compositions, this has not
been possible. Furthermore the simulations are
Table 10
Simulation results for glass phase dissolution in a fixed bed flow-through reactor system for forward dissolution rate
I. The potential contribution of glass dissolution for the concentrations of an aqueous phase. (for a final dissolution rate all concentrations are 316 times lower)

Samples r Potential concentrations of the species in an aqueous phase (mol/l)

No. (mol/m2 s) SiO, Al Fe Ca Zn cu Pb Cr
Mg
1 1.13 x lo- lo 2.02 x 10 7.98 x 100 9.27 x 10-l 4.03 x 100 625 x 10-l 3.02 x lo-’ 3.22 x lo- 2 1.01 x 10-2 3.83 x lo- 2
2 6.13 x lo-” 1.10 x 101 3.32 x loo 2.61 x 10’ 5.97 x 10-l 5.19 x lo- 1 1.66 x 10-2 1.77 x lo- 2 5.53 x 10-3 2.10 x 10-2
3 2.97 x 10-l’ 4.21 X lo1 2.49 x lo1 1.83 x 10’ 2.32 x lo- ’ 4.72 X 10’ 6.32 x lo-* 6.74 x lo-’ 2.11 x 10-2 8.00 x lo-’
4 1.10 x 10-10 1.87 x 101 1.21 x 101 1.04 x 100 9.33 x 10-Z 7.27 x 10’ 2.80 x 10-Z 2.98 x lo- 2 9.33 x 10-3 3.54 x 10-Z
5 6.63 x lo-l2 1.26 x 10’ 5.85 X 10-l 7.03 x lo- 2 5.02 x 1O-3 1.63 x lo-’ 1.88 x 1O-3 2.01 x lo- 3 6.28 x lo- 4 2.39 x 1O-3
6 1.64 x lo-” 3.05 X 10’ 1.86 x 10’ 9.17 x 1o-3 1.22 x 10-Z 2.44 x lo- 2 4.58 x 10-3 4.89 x 10-3 1.53 x 10-d 5.80 x 10-3
Table 11
Simulation results for glass phase dissolution in a fixed bed flow-through reactor system for forward dissolution rate
II The amount of dissolution or alteration of the glass phase in the system per m2 of landfill area (for a final dissolution rate all data of glass dissolution or alteration
are 316 times lower)

Samples Reactor area specific fluxes of species (mol/m2 year)

No. ;mol/m2s) Zn CU Pb Cr
SiO, Al Fe Ca Mg
1.13 x lo-‘0 1.27 x lo3 5.04 x 102 5.85 x 10’ 2.54 x lo2 3.94 x 101 1.19 x 100 2.04 x 10’ 6.36 x 10’ 2.42 x 10’
6.13 x 10-r’ 6.97 x lo2 2.09 x 102 1.65 x 10’ 3.77 x 10’ 3.28 x IO’ 1.05 x 100 1.12 x 100 3.49 x 10-r 1.33 x 100
2.97 x 10-l’ 2.66 x lo3 1.57 x 103 1.16 x lo3 1.46 x 10’ 2.98 x 10’ 3.99 x 100 4.25 x 10’ 1.33 x 10s 5.05 x 100
1.10 x 10-10 1.18 x 10s 7.65 x lo2 6.59 x 10’ 5.89 x IO0 4.59 x 10’ 1.77 x 10” 1.88 x 10s 5.89 x 10-r 2.24 x 10”
6.63 x 10-l’ 7.92 x 10’ 3.69 x 10’ 4.44 x 10s 3.17 x 10-r 1.03 x 100 1.19 x 10-l 1.27 x 10-r 3.96 x lo-’ 1.51 x 10-l
1.64 x lo-” 1.93 x 102 1.18 x 10’ 5.79 x 10-l 7.71 x 10-l 1.54 x 10s 2.89 x 10-l 3.09 x 10-l 9.64 x lo-’ 3.66.x lo- ’
110 J. Yan, I. Neretnieks /The Science of the Total Environment 172 (1995) 95-118

Table 12
The saturation states of the system outflow with respect to potential minerals (for forward dissolution rate and pH = 9)

Mineral Formula Sl=log(lAP/K)

Samples 1 2 3 4 5 6

CALCITE CaCOa 0.6506 0.3337 0.5186 -0.1594 - 1.0874 -0.7732

DOLOMITE CaMg(COJ, 0.6215 1.0405 1.4758 1.0720 - 1.4778 - 1.0160
Si02a SiO,(am) 5.7680 4.7072 6.2660 5.3547 2.8084 3.3240
CHALCEDY SiO 6.6076 5.5468 7.1056 6.1943 3.6480 4.1636
GIBBSITE A&& 7.8469 6.8649 8.4458 7.8434 5.2047 5.8022
AKOH), a NOH&d 5.1569 4.1749 5.7558 5.1534 2.5147 3.1122
Fe(OH), a Fe(OH),bm) 8.0811 8.0607 9.3575 8.0653 5.8984 5.1015
KAOLINIT Al,Si,Os(OH), 30.9972 26.6863 33.2800 30.0500 19.4034 21.6531
HALLOYSI Ai,Si,O,(OH), 29.4622 25.1513 31.7450 28.5150 17.8684 20.1187
MONTMORI Ca02AI,Si,OlO(OH), 44.0306 37.0282 47.4192 41.8581 25.3426 28.7491
CHRYSOTL Mg$i,O,(OH), 28.2679 25.1632 31.4521 27.4453 14.9366 16.5136
SEPIOLIT Mg,Si,O,.s(OH)&I,O 28.7671 25.4173 31.5270 27.7759 15.7923 17.6506
NESQUEHO MgC0,3.H,0 - 4.6468 - 3.2350 - 3.9275 - 3.0455 - 3.8374 - 3.7624
L ALBITE NaAiSiaOs 32.3593 27.2527 34.2538 30.5112 18.3953 20.6602
H ALBITE NaAlSisOs 31.0493 25.9427 32.9438 29.2017 17.0853 19.3502
ANALCIME NaAlSi,O,H,O 25.3872 21.5667 26.6947 24.0660 14.7730 16.4981
CriOH); Cr(OH)s(am) 5.7174 4.8609 6.1437 5.5030 3.0098 3.4899
CdOH); Cr(OH),(x = 0.6) 7.5474 6.6909 7.9737 7.3330 4.8398 5.3199
Cr(OH); * Cr(OH),(x = 0.1) 9.3774 8.5209 9.8037 9.1630 6.6698 7.1499
cuco, - 3.8370 - 3.4404 - 3.2294 - 2.8009 - 3.9753 - 3.5321
Cu(OH), 4.4858 3.8938 4.8068 4.3006 2.3681 2.8377
TENORITE cue 6.2116 5.3944 6.6217 5.9129 3.7037 4.1975
DIOPTASE cUSiO,(OH), 10.0820 8.4293 10.9011 9.4835 5.0047 5.9899
CERRUSIT PbC03 1.4905 2.0830 2.0132 2.6798 1.4926 1.9230
MASSICOT PbO(yellow) 2.7652 2.1438 3.0903 2.6195 0.3976 0.8786
PbSiO, 12.9114 11.2292 13.1346 12.3525 7.5843 8.5808
SMITHSON ZnCOs - 2.0015 - 0.8476 - 1.5932 - 0.5937 - 0.6777 - 0.3248
Zn(OH),a Zn(OH),(am) 2.2413 2.4066 2.3630 2.4277 1.5856 1.9650
zINcITE ZnO 3.5572 3.4971 3.7679 3.6300 2.5113 2.9148
ZnSiO, 15.2234 14.1026 15.9321 14.8829 11.2180 12.1371

.~ __land Cr(OH)?*
Cr(OH)t are considered as the solid solutions Cr,Fe,,(OH)a that are formed by Cr(OH), and Fe(OH)s (Rai
and Zachara, 1988). For &OH):, x = 0.6 and Cr(OH):*, x = 0.1.

focused on two limiting situations of glass phase
dissolution. Therefore, it is difficult to compare
our modeling results directly with the current
experimental and field observation data of leach-
ing from the solid wastes. So far, only some
nuclear waste glasses and natural glasses have
been systematically studied under the well-con-
trolled laboratory conditions. Compared with nu-
clear waste glass, the glass phases in combustion
residues are mixed with other minerals or compo-
nents instead of being a relative homogeneous
phase such as nuclear glass. This characteristic
makes the dissolution behaviors of the glass phase
more difficult to investigate experimentally. For
example, the final dissolution rate of glass phase
can indirectly be measured from the solution
concentration changes of the soluble species dis-
solved from the glass matrix after the solution is
saturated with respect to silica (Freude et al.,
1985; Grambow; 1987). For the glass phases in
solid wastes, however, it is not easy to find a
soluble species that only exists in the glass phase
and can be accurately determined by current ana-
lytical methods. Similar problems also appear in
the measurements of other dissolution behaviors
of the glass phases. Another critical reason for
the absence of glass dissolution data is that the
glass phases in most investigations are considered
 J. Yan, I. Neretnieks / The Science of the Total Environment 172 (1995) 95-118 111

Table 13
The saturation states of the system outflow with respect to potentail minerals (for final dissolution rate and pH = 9)

Mineral Formula sz = log (LAP/K)

Samples 1 2 3 4 5 6

CALCITE CaCO, - 0.3560 - 0.9580 - 0.7222 - 1.7941 - 2.7712 - 2.4383

DOLOMITE CaMdCO,), - 1.3814 - 1.8413 - 0.9856 - 2.5591 - 4.9009 - 4.4450
SiO,a SiOJam) 1.4501 1.1898 1.7741 1.4171 0.2485 0.6332
CHALCEDY SiO, 2.2897 2.0293 2.6137 2.2567 1.0880 1.4727
GIBBSITE ANOH), 3.8716 3.5133 4.3396 4.0659 2.8024 3.2946
AltOH),a MOH),(am> 1.1816 0.8233 1.6496 1.3759 0.1124 0.6046
Fe(OH),a Fe(OH)&m) 4.4886 4.9428 5.7846 4.5436 3.3801 2.4928
KAOLINIT AI,Si,O,(OH), 14.0057 12.7681 15.5912 14.3283 9.4632 11.2171
HALLOYSI Al,Si,O,(OH), 12.4707 11.2331 14.0562 12.7933 7.9282 9.6821
MONTMORI Ca0.2Al,Si,01,(OH), 17.3310 15.4137 19.5547 17.3925 9.9764 12.5941
CHRYSOTL Mg&O,(OH), 10.2046 9.6938 13.1888 10.4681 3.7734 4.9487
SEPIOLIT Mg,Si30,.,(0H),H,0 10.4059 9.6322 12.9324 10.5266 4.1174 5.5419
NESQUEHO MgC0,3H,O - 4.4281 - 4.2849 - 3.6701 -4.1675 - 5.5300 - 5.4073
L ALBITE NaAISl,Os 11.5567 10.5696 12.5655 11.7342 5.9285 7.6416
H ALBITE NaAlSi,O, 10.2467 9.2596 11.2555 10.4242 4.6185 6.3316
ANALCIME NaAlSi,06H,0 9.3075 8.5812 9.9910 9.5180 4.8818 6.2101
CdOH); Cr(OH)Jam) 1.7485 1.5098 2.0406 1.7264 0.6074 0.9826
Cr(OH)il; Cr(OH),(x = 0.6) 3.5785 3.3398 3.8706 3.5564 2.4374 2.8126
Cr(OH); * Cr(OH),(x = 0.1) 5.4085 5.1698 5.7006 5.3864 4.2674 4.6426
cuco, - 5.2868 -5.4135 - 4.9780 -5.1730 - 6.2607 - 5.8871
Cu(OH), 1.0248 0.7594 1.3499 0.9880 - 0.1872 0.1988
TENORITE cue 2.3456 2.0799 2.6720 2.3088 1.1329 1.5189
DIOPTASE CuSiO,(OH)Z 2.3031 1.7774 2.9522 2.2333 -0.1105 0.6602
CERRUSIT PbCO, 0.2871 0.1846 0.5586 0.4131 - 0.6211 - 0.2572
MASSICOT PbO(yellow) - 0.8544 - 1.0960 - 0.5653 - 0.8790 - 2.0016 - 1.6252
PbSiO, 4.9739 4.4720 5.5870 4.9163 2.6251 3.3862
SMITHSON ZnCO, - 1.9047 - 2.0155 - 1.6135 - 1.7808 - 2.8438 - 2.4745
Zn(OH), a Zn(OHkJam) 0.3269 0.0775 0.6344 0.3002 - 0.8503 - 0.4687
ZINCITE ZnO 1.2378 0.9880 1.5465 1.2110 0.0597 0.4415
ZnSiO, 8.5861 8.0760 9.2189 8.5263 6.2064 6.9728

as an inert material. Little or no attempt is made
to relate their contributions to leaching of the
solid wastes. In this study, we do not primarily
aim at providing an accurate description for the
dissolution behaviors of the glass phases in the
solid wastes. We try to address an important issue
of whether the glass phases can be regarded as
inert materials or if they under landfill conditions
significantly could contribute to the release of
toxic metals. The results can be used to direct our
future work even if this answer is quasi quantita-
tive or needs to be modified. The validity must be
tested by more accurate theoretic and experimen-
tal investigations.
On the other hand, it is impossible to repro-
duce the long-term behaviors of the waste glass in
a given disposal conditions by laboratory experi-
ments. There are many reasons for this. Among
the most important are that kinetics may change
during the experiment in not observable ways,
different phases including mineral and surface
phases are present and these may react differ-
ently than the glass phases and obscure the re-
lease from the latter. The time to reach steady
state dissolution is also often much larger than
what can be allowed in experiments.
Nevertheless the type of simulations we have
made give important insights into what potential
release might be expected under long term land-
fill conditions and what factors may influence the
release from the amorphous glass phases.
112 .l. Yan, I. Neretniekx / The Science of the Total Environment 172 (1995) 95-118

Table 14
The saturation states of the system outflow with respect to potentail minerals (for forward dissolution rate and pH = 4)

Mineral Formula sz = log(i?lAP/K)

Samples 1 2 3 4 5 6

CALCITE CaCO, - 2.2505 - 2.3291 - 2.3201 - 2.8236 - 5.6706 - 3.9377

DOLOMITE CaMg(CO,), -5.1802 - 4.5876 - 4.2010 - 4.6236 - 10.5345 - 7.0637
SiO,a SiO,(am) 5.8156 5.1064 6.3258 5.7492 3.1315 4.1364
CHALCEDY SiO, 6.6552 5.9459 7.1653 6.5888 3.9710 4.9759
GIBBSITE AI( 2.1104 2.4311 2.2875 2.3343 2.3124 2.6471
AI( a Al(OH),(am) - 0.5796 - 0.2589 - 0.4025 - 0.3557 - 0.3776 - 0.0429
Fe(OH),a Fe(OH)&m) 5.0935 5.8536 6.2478 5.1690 3.6595 3.5245
KAOLINIT Al,Si,OS(OH), 19.6132 18.6119 21.0829 19.9117 14.2648 16.9681
HALLOYSI Al,Si,O,(OH), 18.0782 17.0769 19.5479 18.3767 12.7298 15.4331
MONTMORI CaO~2AI,Si,010(OH)2 29.1249 26.6080 31.5896 29.0864 18.1154 22.8454
CHRYSOTL Mg,Si,O,(OH), - 1.6055 - 2.1435 1.5731 - 1.4579 - 13.6230 - 8.0807
SEPIOLIT Mg2Si307,5(OH)3H20 8.9439 7.8888 11.7072 8.9671 - 2.7091 2.6083
NESQUEHO MgCO,.SH,O - 7.5292 -6.1855 - 6.7656 - 6.3503 -8.3111 - 6.6457
L ALBITE NaAlSi,Os 21.8981 19.8209 23.2748 21.9536 11.5715 15.4102
H ALBITE NaAISi,Os 20.5881 18.5109 21.9648 20.6436 10.2615 14.1002
ANALCIME NaAlSi,O,H,O 14.8845 13.7407 15.6559 15.0228 7.6261 10.4358
CdOH): Cr(OH),(am) 0.8534 1.1004 0.9502 0.8580 0.0303 0.8365
CdOH); Cr(OH),(x = 0.6) 2.6834 2.9304 2.7802 2.6880 1.8603 2.6665
Cr(OH);* Cr(OH),(x = 0.1) 4.5134 4.7604 4.6102 4.5180 3.6903 4.4965
cuco, -5.1628 - 4.6442 - 4.7029 - 4.1394 - 5.2788 - 4.4573
Cu(OH), - 3.9268 - 3.7113 - 3.8281 - 3.9342 - 4.1970 - 3.9440
TENORITE cue - 2.2071 - 2.2157 -2.0132 - 2.2309 - 2.8613 - 2.5842
DIOPOTASE CuSiO,(OH), 1.7170 1.2233 2.3259 1.6432 - 1.2373 0.0206
CERRUSIT PbCO, - 0.4885 0.0022 0.0027 0.5417 - 1.2827 0.1348
MASSICOT PbO(yellow) - 6.3068 - 6.3433 - 6.0816 - 6.3237 - 7.6392 - 6.7661
PbSiO, 3.8871 3.1413 4.6224 3.8037 - 0.1295 1.7485
SMITHSON ZnCO, - 4.8909 -4.3721 - 4.4309 - 3.8674 - 5.0067 -4.1854
Zn(OH), a Zn(OH),(am) - 7.7349 - 7.5192 - 7.6361 - 7.7422 - 8.0049 - 7.7521
ZINCITE ZnO - 6.4252 - 6.4336 - 6.2312 - 6.4488 - 7.0792 - 6.8023
ZnSiO, 5.2887 4.5710 5.9927 5.1986 1.9505 3.2323

From predictions of the kinetic properties of
waste glass phase, it can be found that the dif-
ference in dissolution rate is about one order of
magnitude for various density fractions of the
glass phase in a coal fly ash. High density glass
phase appears to have a higher dissolution rate.
This difference reflects the variation of chemical
composition of the glass phase in various density
fractions. The silicon content exerts one of the
most important influences on the chemical dura-
bility of the glass phase. High density glass phase
has lower silicon content and higher content of
calcium or iron oxide. These factors together
make high density glass phase have a higher dis-
solution rate because reducing the silicon content
of glass phase or raising CaO or Fe0 content, will
decrease the hydration free energy of glass phase.
This influence of chemical composition on the
durability of the glass phase is also found in the
glass phases of individual particles. Larger dif-
ferences of dissolution rates can be found between
individual particles. This may exhibit the hetero-
geneity of waste glass phase in chemical composi-
tions. However, in comparison with the chemical
compositions of the raw ashes, the composition of
the average glass phase in an ash sample is very
close to the composition of its raw ash, particu-
larly for the major components. This means that
the glass phase, which has very high or low disso-
lution rate, may only be a small fraction in the
glass phases of an ash sample. Similar character-
istics may also be found in the glass phases of
 J. Yan, I. Neretnieks /The Science of the Total Environment 172 (1995) 95-118 113

Table 15
The saturation states of the system outflow with respect to potentail minerals (for final dissolution rate and pH = 4)

Mineral Formula SI = log (LAP/K)

Samples 1 2 3 4 5 6

CALCITE CaCO, -5.5437 - 6.2912 - 5.8785 - 7.1999 - 8.1669 - 7.8716

DOLOMITE CaMg(COJ2 - 11.7434 - 12.4982 - 11.2654 - 13.3505 - 15.6891 - 15.3055
SiO,a SiO,(am) 1.5311 1.2635 1.8911 1.5027 0.3116 0.6992
CHALCEDY SiO, 2.3707 2.1031 2.7307 2.3422 1.1511 1.5388
GIBBSITE AI( 1.4403 1.1965 1.7110 1.5835 0.7877 1.1296
ANOH), a AI( - 1.2497 - 1.4935 - 0.9790 - 1.1065 - 1.9023 - 1.5604
Fe(OH), a Fe(OH)&m) 1.8859 2.3940 3.1395 1.9254 0.9318 - 0.0031
KAOLINIT A,Si,O,(OH), 9.3050 8.2818 10.5679 9.5346 5.5601 7.0191
HALLOYSI Al,Si,O,(OH), 7.7700 6.7468 9.0329 7.9996 4.0251 5.4841
MONTMORI CaO.2Al,Si,O,,(OH), 10.2407 8.5639 12.1333 10.1879 3.7991 6.0682
CHRYSOTL Mg,Si,O,(OH), - 19.9879 -20.5224 - 16.9391 - 19.9082 - 26.3527 - 25.3177
SEPIOLIT Mg,SisO,,s(OH),H,O - 9.5875 - 10.3891 - 6.9579 - 9.5818 - 15.8616 - 14.5257
NESQUEHO MgC0,3H,O - 9.6024 - 9.6086 - 8.7936 - 9.5532 - 10.9225 - 10.8345
L ALBITE NaAlSiaOs 4.3322 3.4392 5.2513 4.4546 - 0.9194 0.6383
H ALBITE NaAlSisO, 3.0222 2.1292 3.9413 3.1446 - 2.2294 - 0.6717
ANALCIME NaAlSi,O,H,O 2.0020 1.3770 2.5597 2.1529 - 2.0292 - 0.8593
Cr(OH),a Cr(OH),(am) - 2.4038 - 2.5309 - 2.1820 - 2.4715 -3.1737 - 2.9187
CdOH); Cr(OH),(x = 0.6) - 0.5738 - 0.7009 - 0.3520 -0.6415 - 1.3437 - 1.0887
Cr(OH);* CrtOH),(x = 0.1) 1.2562 1.1291 1.4780 1.1885 0.4863 0.7413
cllco, - 6.4803 - 6.6591 - 6.2834 - 6.5357 - 7.4118 -7.1132
CdOH), -5.1125 - 5.2837 - 4.9527 -5.1715 - 6.0299 - 5.7330
TENORITE cue - 3.7917 - 3.9632 - 3.6305 - 3.8506 - 4.7098 - 4.4128
DIOPTASE CuSiO,(OH)a - 3.7532 - 4.1920 - 3.2333 - 3.8406 - 5.8901 - 5.2055
CERRUSIT PbCO, - 3.8013 - 3.9801 - 3.5069 - 3.8526 -4.7111 - 4.4223
MASSICOT PbO(yellow) - 9.8867 - 10.0582 - 9.6280 - 9.9416 - 10.7832 - 10.4959
PbSiO, - 3.9774 - 4.4165 - 3.3586 - 4.0607 - 6.0934 - 5.4185
SMITHSON ZnCO, - 6.2083 - 6.3872 - 6.0114 - 6.2637 - 7.1398 - 6.8413
Zn(OH),a Zn(OH),(am) - 8.9205 - 9.0917 - 8.7607 - 8.9795 - 9.8379 - 9.5411
ZINCITE zno - 8.0097 - 8.1813 - 7.8485 - 8.0687 - 8.9278 - 8.6310
ZnSiO, - 0.5803 - 1.0196 - 0.0591 - 0.6678 - 2.7181 - 2.0336

various density fractions of an ash sample. There- In this study, the forward dissolution rates of
fore, it is reasonable that the average glass phase glass phase of coal fly ashes are from 6.63 x
should represent the glass phases of a coal fly ash 10-i’ to 2.97 X 10-l’ mol rn-‘s-l, which have
on their chemical durabilities. been shown in Table 3 - 5. In comparison with

Table 16
Comparison with other glass phases on the dissolution rates

Glass phase r& (mol rnm2sK1) Ref.

Tholeiite basalt glass 1.31 x 10-s Guy and Schott, 1989
Synthetic basalt glass 3.92 x 10-m Byers et al., 1985
ABS118 waste glass 4.01 x lo-‘0 Christensen et al., 1986
SRL-131 waste glass 1.28 x 1O-g Lokken and Strachan, 1984
Glass of coal fly ash 2.97 x 10-10 This study (sample 3)
Glass of coal fly ash 6.63 x lo-l2 This study (sample 5)
‘rfor is the forward dissolution rates in Si (25°C) and calculated from the testing values which are obtained from the references.
114 J. Yan, I. Neretnieks /The
other glass phases that are similar to the glass
phase of coal fly ash in chemical composition, the
dissolution rates of glass phase of coal fly ashes
are close to or lower than basalt glasses and some
nuclear waste glasses (Table 16).
Our modeling results indicate that if one were
to neglect adsorption or precipitation of sec-
ondary phases, some of the metals may be re-
leased in millimolar to tens of millimolar concen-
trations from the glass phases. In some circum-
stances this may be higher than acceptable. The
primary release from the glass phase thus cannot
always be neglected.
In our simulations we have so far not ac-
counted for the formation of secondary phases or
adsorption of the toxic metals. The solubilities of
some of the metals are exceeded and secondary
precipitates might form. This means that precipi-
tation/dissolution of the secondary solid phases
may control the compositions of the leaching
solutions and solubility limit will become a reten-
tion mechanism for the release of species from
waste glass alteration. Similarly, other trapping
mechanisms such as ion-exchange and adsorption
may also play important roles in retarding some
species into aqueous solution. However there are
some limitations for these retention mechanisms,
many factors (pH, the property of the secondary
solid phase, the redox status of the system, com-
plexing ligands) affect the intensity and capacity
of these processes. For example, under acidic
conditions, the solubility limit may not be reached
for many elements, in particular for transition
metals. Comparing the saturation indices in Table
14 and 15 with these in Table 12 and 13, it is seen
that under the acidic conditions the saturation
indices with respect to many minerals will de-
crease and some minerals will be dissolved into
aqueous phase again when it becomes acid. Al-
though other retention processes may reduce the
release rates of toxic elements when the glass
dissolution is not a limiting factor, these mecha-
nisms usually are closely related to the properties
of the toxic elements themselves and environmen-
tal conditions, and can not provide a permanent
barrier against release of toxic elements because
the products of glass alteration do not have the
Science of the Total Environment 172 (1995) 95-118
durability of the glass phase and the secondary
phases are much more quickly leached than glass
phases in certain conditions. These results also
point out that the pH buffering capacity of the
combustion residues may be very important.
In addition to kinetic properties of waste glass,
the characteristics of solid waste and disposal
environments also affect the dissolution or alter-
ation of waste glass phases and contribute to the
leaching of solid waste. When coal fly ash is
disposed in a landfill, a low-flow or near closed
system provides a relatively long-term reaction
time, and the small particles of coal fly ash make
a large surface area available for glass dissolu-
tion. In this case, system parameters may be as
important as the kinetic properties of waste glass.
The dissolution kinetics of waste glass may shift
with changes of the system conditions. For exam-
ple, the dissolution rate of waste glass may rise to
near the forward dissolution rate in a fast-flow
system, but the contribution of glass dissolution
to the concentration of aqueous solution is still
decided by the flux and mass balances of the
system. Therefore, the contribution of the waste
glass phase in the leaching of solid waste should
be a function of the glass durability, time scale
and system properties. It is not enough to only
take into account the low alteration rate of waste
glass phase.
6. Conclusions
On the basis of the prediction of kinetic
properties, the chemical durabilities of the glass
phases in the coal fly ashes are similar to the
basalt glass and some nuclear glasses. According
to geochemical modeling, the glass phase dissolu-
tion is not always a limiting factor in the leaching
processes of combustion residues (coal fly ashes).
Under certain disposal conditions, the glass phase
in combustion residues (coal fly ash) can not
provide a permanent barrier for release of toxic
elements. Additional reactions associated to toxic
elements influence their release behaviors. Some
retention mechanisms such as precipitation of
secondary phase may become controlling factors
but only under some limited conditions. In the
leaching processes of combustion residues, the
 J. Yan, I. Neretnieks / The Science
contribution of glass phases is decided not only by
their kinetic behaviors but also by their other
properties related to dissolution reactions and
disposal environment. Special experimental meth-
ods need to be developed for investigation of
waste glass dissolution in solid waste in order to
provide more information to modify the research
approaches.
Acknowledgements
The financial support of the Swedish Waste
Research Council (AFR) is gratefully ac-
knowledged.
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