Chemical Geology 151 Ž1998.

247–258

General implications of aluminium speciation-dependent kinetic

dissolution rate law in water–rock modelling
´ ´ Gerard
Frederic ´ ),1
´
, Bertrand Fritz, Alain Clement, Jean-Louis Crovisier
´
Centre de Geochimie de la Surface, CNRS UPR 6251. 1, rue Blessig, 67084 Strasbourg, France

Abstract

Recent experimental and theoretical work has demonstrated that the dissolution rates of many aluminosilicate minerals
are inversely proportional to the activity of aqueous Al 3q. The consequences of these observations on the rates of natural
geochemical processes have been calculated by the KIRMAT hydrochemical code. Comparisons are performed at the steady
state limit of the pure advective transport through a homogeneous semi-infinite isothermal porous media at 25 and 1508C.
K-feldspar, albite, and muscovite dissolution kinetics are studied over a broad range of initial pH Ž2–10. and aluminium
concentration Žfrom 1 = 10y9 to 1 = 10y3 molal. matching most the natural conditions. Regardless of the mineral, the
characteristic distance requires to reach equilibrium Ž l eq . is two and three orders of magnitude larger and lower than
predicted using the standard Transition State Theory ŽTST. law, respectively. The maximum decrease in muscovite and
alkali-feldspar dissolution rates due to aqueous aluminium at 258C is found at near to neutral pH, and at 1508C it is found at
basic pH. The maximum dissolution rate increase at 258C at acid pH, but at 1508C it is found at basic pH. These results
demonstrate that consideration of the effect of the aluminium speciation on aluminosilicate dissolution rates is required to
improve the accuracy in water–rock interaction modelling. q 1998 Published by Elsevier Science B.V. All rights reserved.

Keywords: Reactive transport; Modelling; KIRMAT; Kinetic dissolution; Transition State Theory; Aluminium speciation

1. Introduction rate laws for mineral dissolution and growth Že.g.,

For several years, much effort has been placed on
hydrochemical or reactive transport computer mod-
elling in porous media. A large number of programs
simulating coupled chemical and mass transport in
porous media are currently available. The most ad-
vanced of these hydrochemical codes employ kinetic
)
Corresponding author. Fax: q33 3 83 39 40 69; e-mail:
gerard@nancy.inra.fr
1
Present address: INRA, Centre de Nancy, Equipe Cycles
´
Biogeochimiques, F-54280 Champenoux, France.
Coudrain-Ribstein, 1988; Steefel and Lichtner, 1994;
Steefel and Lasaga, 1994; White, 1995..
Far more silicate dissolution experiments have
been performed than mineral growth experiments.
Silicate dissolution kinetics are surface controlled to
hydrothermal temperatures. According to Transition
State Theory ŽTST. ŽEyring, 1935., the rate limiting
step of the overall reaction is the formation of an
activated complex at high energy surface sites
ŽLasaga, 1981; Aagaard and Helgeson, 1982; Helge-
son et al., 1984.. It is commonly assumed that the
concentration of activated complex is proportional to
a precursor complex at the mineral surface and both

0009-2541r98r$ - see front matter q 1998 Published by Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 5 4 1 Ž 9 8 . 0 0 0 8 3 - 7
248 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258
complexes are in state of local equilibrium ŽWieland
et al., 1988; Guy and Schott, 1989.. Until recently,
precursor complexes for multi-oxide minerals were
believed to consist of either hydrogenated, hydroxe-
nated, or hydrated surface sites. Taking account of
these assumptions, TST dictates that at far-from-
equilibrium, dissolution rates only depend on pH.
The kinetic effects of solution pH on silicate dissolu-
tion has been thoroughly documented ŽHelgeson et
al., 1984; Knauss and Wolery, 1986, 1989; Tole et
al., 1986; Murphy and Helgeson, 1987; Carroll and
Walther, 1990; Acker and Bricker, 1992; Hellmann,
1994.. The abundance of data has driven most hy-
drochemical and geochemical code developers to
implement the first order, pH-dependent, rate expres-
sion in their codes to forecast silicate dissolution.
Nonetheless, except for the silica phases ŽRimstidt
and Barnes, 1980., the first order approach of the
overall dissolution rate toward equilibrium had not
been experimentally validated until recently. More-
over, other catalyticrinhibitor effects due to dis-
solved inorganic and organic species have been
pointed out for several years ŽWogelius and Walther,
1991; Amrhein and Suarez, 1992; Welch and Ull-
man, 1993; Bennett and Casey, 1994; Stillings et al.,
1996.. However, they provide no mechanistic kinetic
expression or their applicability range is too narrow
to be effective in water–rock interaction modelling.
Recently, a new mechanistic kinetic rate law con-
sistent with TST and surface chemistry was proposed
in the literature ŽGautier et al., 1994; Oelkers et al.,
1994; Schott and Oelkers, 1995.. This new rate law
takes account of the inhibitor effect of dissolved
aluminium on alkali-feldspars, kaolinite, muscovite,
and kyanite dissolution. In addition, alkali-feldspars
and kaolinite apparently have a larger dissolution
rate dependence on chemical affinity than previously
assumed.
Several convincing arguments lead us to believe
that the new rate law might significantly affect the
chemical evolution of natural water–rock systems.
Above all, aqueous aluminium effects appear strong
enough to induce an apparent chemical affinity de-
pendence on rates at far-from-equilibrium conditions.
Moreover, dissolved aluminium is common in aque-
ous solutions and has a significant concentration
range. Finally, the rate of approach toward equilib-
rium is intrinsically slowed due to its larger chemical
affinity dependence. Given alkali-feldspars, and to a
lesser extent muscovite, are ubiquitous rock-forming
minerals, most water–rock reaction paths will be
modified by these effects.
The aluminium speciation-dependent dissolution
rate equation has been introduced into the KIRMAT
´
reactive transport code ŽGerard et al., 1996, 1997;
´
Gerard, 1997., which also contains the standard ki-
netic rate expression. This innovation permits the
study of effects of the aluminium speciation depen-
dent rate law in hydrochemical modelling. The large
number of factors that now influence aluminosilicate
dissolution rates suggest its effects are case depen-
dent. The goal of this study is to estimate the upper
and lower boundaries of the effect of aqueous alu-
minium on dissolution rates. These results allow
evaluation of the trends and potential implications of
this dissolution rate law on water–rock systems.
2. Theory
2.1. Kinetic equations
Mineral dissolution rate laws are commonly de-
rived from TST, assuming both that Hq, H 2 O, and
OHy are the only aqueous species involved in the
reaction forming the activated complex, and that one
mole of activated complex is formed from each mole
of mineral. These assumptions lead to the following
equation:
A Ea
ž
rd s k d SaHn q 1 y exp y ž RT // A expy RT . Ž 1.
With
A s yRT ln Ž QrK . Ž 2.
where rd is the dissolution rate Žmol sy1 ., k d the
dissolution rate constant Žmol cmy2 sy1 ., S the
reactive surface area of the mineral, a H q the in-
hibitorrcatalytic term for pH effects and n is an
experimental exponent, A denotes the chemical
affinity Žkcal moly1 ., R the gas constant Ž1.99 =
10y3 kcal moly1 Ky1 ., A the pre-exponential factor
of the Arrhenius rate law, Ea the apparent activation
energy of the reaction Žkcal moly1 ., which is a
 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258 249

function of solution pH. Finally, Q is the ionic namic constant of the precursor formation reaction.
activity product ŽIAP. of the mineral and K its The rate law derived from the above formation reac-
thermodynamic equilibrium constant. tion is given by Žfor details see Oelkers et al., 1994.:
According to TST, the exponent n is equal to the
number of protons required to form the activated a 3Hmq
complex ŽHelgeson et al., 1984; Murphy and Helge-
son, 1987.. The rate constant k d and the exponent n
usually have different values depending on pH re-
gion: pH 1 delimits the acid from the neutral pH
region and pH 2 the neutral from the basic pH region.
rd s k d S
− <
1q
m
aAl 3q

K8a H3 mq
m
aAl 3q

A Ea
This pH dependence leads to the well-known U-shape
function. Many efforts have been made to relate pH 1
with the pH of the point of zero net proton charge,
ž
= 1 y exp y ž s RT // A expy RT Ž 4.

commonly noted pH pznpc Žsee for example, Blum and
Stillings, 1995; Hochella and Banfield, 1995.. Al-
though some consistent results are obtained on sim-
ple oxides such as SiO 2 Že.g., Brady and Walther,
1989, 1990; Bennett, 1991., inconsistent results have
been obtained for more complex oxides such as
alkali-feldspars and kaolinite Žsee for instance the
where s is equal to the number of silica mole per
mole of aluminosilicate. The aqueous activity term
controls the dependence of the dissolution rate on
aluminium speciation at far-from-equilibrium condi-
tions; at close to equilibrium conditions the effects of
chemical affinity become important. When the num-
ber of precursor complexes at the mineral surface is
3m

discussion in Chen and Brantley, 1997.. Moreover, relatively small, K8am H < 1 and Eq. Ž4. can be
q

aAl 3q
as proposed by several authors Že.g., Chou and Wol- rewritten in terms of total dissolved aluminium con-
last, 1985; Garnor et al., 1995., the temperature centration Žnoted wAlx. and pH ŽOelkers et al., 1994.:
dependence of the exponent n Žsee Carroll and ym
Walther, 1990; Hellmann, 1994; compare Chou and rd s k d S w Al x Ž a3H q b 3 a2H qq b 2 aH q
q

Wollast, 1985 to Knauss and Wolery, 1986. might

m A
be due to the presence of some unrecognized in-
hibitor effects thus pointing out the failure of Eq. Ž1.
qb4 q b 1 ay1
Hq . ž 1 y exp yž s RT // . Ž 5.
to explain the dissolution kinetic of the complex Where b 1 is the thermodynamic equilibrium con-
oxides studied. Although this deviation from the stant for AlŽOH.y 3q
4 formation reaction from Al and
standard theory can be understood with the help of q
4H 2 O, b 2 for AlŽOH. 2 formation from Al 3q
and
surface chemistry Žsee Brady and Walther, 1992; 2H 2 O, b 3 for AlŽOH. 2q formation from Al 3q and
Casey and Sposito, 1992., both discrepancies can be H 2 O, and finally b4 for AlŽOH. 38 formation from
explained by taking into account the effect of dis- Al 3q and 3H 2 O.
solved aluminium. The presence of an aluminium-
deficientrsilica-rich rate controlling precursor com-
plex was considered by Gautier et al. Ž1994.; Oelkers 2.2. The code KIRMAT
et al. Ž1994., Oelkers and Schott Ž1995., Schott and
Oelkers Ž1995., and Oelkers Ž1996.. It was proposed The hydrochemical code KIRMAT ŽGerard ´ et al.,
that this precursor complex is formed by the follow- ´
1996, 1997; Gerard, 1997. has been developed by
ing exchange reaction: adding provision for chemical mass transport into the
thermodynamic and kinetic geochemical code
K8 KINDISP ŽMade´ et al., 1994.. KINDISP’s thermo-
3 m Hqq M–O m P8 q m Al 3q Ž 3. dynamic database contains the data of Helgeson et
al. Ž1978. and is used in the KIRMAT hydrochemi-
where M–O represents a potentially reactive surface cal code. The dissolution rate laws ŽEqs. Ž1. and Ž4..
site Žmetal–oxygen., m is a stoichiometric coeffi- are encoded in KIRMAT, in addition to other kinetic
cient, P8 the precursor species, and K8 the thermody- formulations for dissolution and precipitation. The
250 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258

classic explicit finite difference scheme is used to Ž1986. and Hellmann Ž1994. at 25, 70, and 1008C,
solve mass transport equations. The advective flux respectively. A good agreement is observed for m s
may be computed by either centred or upstream 1r3 ŽFig. 1., which is in accordance with that re-
weighing. The later spatial scheme allows modelling ported by Oelkers et al. Ž1994. at 1508C. The knowl-
of purely advective systems. The reaction and trans- edge of k d at different temperatures allows calcula-
port mass balance equations are fully coupled in a tion of an apparent activation energy Ž Ea ., which is
one-step algorithm. The explicit calculation method
enables us to keep the matrix rank identical to that
solved in KINDISP and, accordingly, to perform
calculations mesh by mesh. KIRMAT provides the
user with mineral volume fractions, porosity, perme-
ability, reactive surface area, and tortuosity over
geologically timeframes in a 1D finite difference
grid. The time evolution of these governing parame-
ters may be computed by either assuming the quasi-
stationary state approximation Že.g., Lichtner, 1988;
Steefel and Lasaga, 1994. or in a transient mode.

3. Computational methods

3.1. The characteristic distance to reach equilibrium

The effect of the aluminium speciation-dependent

rate law ŽEq. Ž4.. on aluminosilicate dissolution rates
is studied by comparing the values of the characteris-
tic distance to reach equilibrium calculated with
KIRMAT with alternatively with Eqs. Ž1. and Ž4..
The characteristic distance for a mineral to reach its
thermodynamic equilibrium, l eq , is inversely propor-
tional to the average mineral reaction rate. The char-
acteristic distance to reach equilibrium was first used
by Knapp Ž1989. to assess the validity of the local
equilibrium approximation ŽLEA. for quartz dissolu-
tion by comparison of computed results with the
scale of interest Že.g., size of a sedimentary basin,
column..

3.2. Kinetic parameters of the aluminium

speciation-dependent rate law

As described in Oelkers et al. Ž1994., it is possi-

ble to reinterpret published rate data initially fitted
with the Eq. Ž1. using Eq. Ž5. and the experimental
values of the total aluminium concentration. This
method has been used on the albite dissolution data
of Chou and Wollast Ž1985., Knauss and Wolery
Fig. 1. Graphic reinterpretations of dissolution rate data with Eq.
Ž5.. Ža. Chou and Wollast Ž1985. at 258C, Žb. Knauss and Wolery
Ž1986. at 708C, Žc. Hellmann Ž1994. at 1008C.
 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258 251

Table 1 Ž s s 3.. The kinetic parameters for albite, K-feldspar

Kinetic parameters used in the dissolution rate equation given by and muscovite used in Eq. Ž4. are listed in Table 1.
Eq. Ž4. for albite, K-feldspar, and muscovite
The dissolution kinetic behaviour of kaolinite is not
Mineral Ea m K8 kd s studied because it is usually a secondary product
Žkcal moly1 . Žmol cmy2 sy1 .
at 258C rather than a primary rock-forming mineral.
Albite 3.6 1r3 0 y12.4 3
K-feldspar 3.6 1r3 0 y13.1 3
muscovite 3.8 1r3 0 y14.3 3
3.3. Kinetic parameters of the pH-dependent rate
law

The kinetic parameters of the pH-dependent rate

independent of pH. The resulting value is Ea s 3.6
kcal moly1 . This value corresponds to the lower
limit for the control by adsorption-surface precursor
formation of the overall dissolution ŽGuy and Schott,
1989.. Insufficient data is available to calculate Ea
for K-feldspar dissolution. Based on the structural
similarity of K-feldspar and albite, we assume they
have identical apparent activation energies.
The muscovite dissolution data of Knauss and
Wolery Ž1989. at 708C has also been reinterpreted
Žsee Oelkers et al., 1994.. Interestingly, the exponent
m s 1r3, and the apparent activation energy: Ea s
3.8 kcal moly1 ŽOelkers, pers. com.. is similar to
that of albite. The similar behaviour of albite and
muscovite supports the assumption that the reaction
order of muscovite dissolution is equal to three
law ŽEq. Ž1.. are listed in Table 2. The pH values
delimiting the acid from the neutral region and the
neutral from the basic regions are noted as pH 1 and
pH 2 , respectively. No apparent activation energy is
available for muscovite under neutral and basic pH
conditions. The theoretical value proposed by Lasaga
Ž1984. is accepted by default in the present study.
This value is widely used in modelling kinetic disso-
lution processes Žsee for instance, Made,´ 1991; Ben
Baccar et al., 1993; Bertrand et al., 1994; Made´ et
al., 1994.. The activation energies associated with
the standard TST rate law are larger than those
obtained for the aluminium speciation-dependent ki-
netic equation. These differences stem from the ef-
fect of dissolved aluminium on the standard dissolu-
tion rate.

Table 2
Kinetic parameters used in the dissolution rate equation given by Eq. Ž1. for albite, K-feldspar, and muscovite dissolution
Mineral log k dŽH q. log k dŽH 2 O . log k dŽOH y. pH 1 pH 2 n ŽpH - pH 1 . n ŽpH ) pH 2 .
Žmol cmy2 sy1 . a Žmol cmy2 sy1 . a Žmol cmy2 sy1 . a
Albite y14.0 y15.7 y18.3 5 8 0.36 y0.32
K-feldspar y14.2 y15.8 y18.2 5 8 0.3 y0.27
muscovite y15.3 y18.0 y19.5 5 7 0.54 y0.21

Mineral EaŽH q. EaŽH 2 O . EaŽH q. s

Žkcal moly1 . Žkcal moly1 . Žkcal moly1 .
Albiteb 21.3 16.5 20.3 1
K-feldspar b 12.4 8.6 13.9 1
muscovite 6d 14.3 d 14.3 e 1
a
At 258C: Chou and Wollast Ž1985. for albite; Made´ Ž1991. for K-feldspar and Knauss and Wolery Ž1989. for muscovite.
b
Hellmann Ž1994..
c
Blum and Stillings Ž1995..
d
Nagy Ž1995..
e
Theoretical value for a reaction control by the formation of an activated complex ŽLasaga, 1984..
k dŽH q. , k dŽH 2 O . and k dŽOH y. stand for dissolution rate constants, EaŽH q. , EaŽH 2 O . and EaŽOH . for the apparent activation energies in acid
ŽpH - pH 1 ., neutral ŽpH 1 - pH - pH 2 ., and basic pH conditions, respectively.
252 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258
3.4. Modelling strategy
Aluminosilicate dissolution rates are function of
pH and chemical affinity variations along the reac-
tion path, whatever the kinetic formulation em-
ployed. For rates that follow Eq. Ž4., however, aque-
ous aluminium concentration affects not only the
affinity term but also the activity term. Aluminosili-
cate dissolution rates are thereby self-inhibited by
the aluminium release during dissolution. Because
secondary products usually contain silica and alu-
minium, they can affect the average mineral dissolu-
tion rate by altering the aluminium concentration in
addition to chemical affinity and pH along the flow
path. It follows that the identity of the secondary
product minerals will have a large effect on alkali-
feldspar and muscovite dissolution rates. For in-
stance, a secondary product with a high aluminium
to silica ratio Že.g., kaolinite. should decrease to a
lesser extent alkali-feldspar and muscovite dissolu-
tion rates than the precipitation of pure silica.
The above discussion demonstrates that a larger
number of factors affects the average dissolution rate
when controlled by Eq. Ž4.. In particular, both pre-
cipitation and dissolution of secondary minerals have
an additional influence on alkali-feldspar and mus-
covite dissolution rates. As a consequence, a multi-
step approach is followed to evaluate the effect of
rate expressions on dissolution rates. The first step is
to compute dissolution rates of single minerals alter-
natively with Eqs. Ž1. and Ž4. using KIRMAT. The
second step is to add provision for secondary mineral
precipitation to these systems. The third step is to
add to the system other dissolving minerals with
different stoichiometries and reaction rates.
3.5. Computational conditions
KIRMAT calculations are done assuming steady
state over a 1D homogeneous semi-infinite system.
Pure advective mass transport is considered to keep
the comparisons between the different l eq indepen-
dent of the dispersion effects; dispersive transport is
proportional to the concentration gradient, which
may vary with the rate law used. The range of initial
conditions is chosen to correspond to those found in
nature. The initial pH and total dissolved aluminium
concentration range from 2 to 10 and from 1 = 10y0 9
to 1 = 10y0 3 molal, respectively. A pH equal to 2
may be reached in an acid mine drainage, some ore
recovery techniques, and is caused by organic acids
during sedimentary basin evolution. For instance, the
upper pH range is attained in concrete formation
water. Concrete will be widely used in nuclear waste
storage. The spreading of a hyper-alkaline plume
may occur and its geochemical impact needs has
already been studied by modelling water–rock inter-
actions Žsee for example, Eikenberg and Lichtner,
1992; Steefel and Lichtner, 1994.. The present calcu-
lations are performed at 25 and 1508C. The most
important inhibitor effects are sought in this study.
Silica and alkali concentrations in the initial solution
are very low Ž1 = 10y2 0 molal. to have a maximum
initial chemical affinity, which results in the largest
aluminium concentration at equilibrium. A more re-
alistic initial solution composition, a silica concentra-
tion to quartz or amorphous silica saturation for
example, would lead to intermediate results by low-
ering aluminium concentration at equilibrium.
The formation of polynuclear dissolved alu-
minium species ŽAl 2 ŽOH. 4q Ž . 5q
2 , Al 3 OH 4 , Al 13 when
.
the aluminium concentration is high has not been
considered in the calculations. These species are
absent from the KIRMAT thermodynamic database.
Furthermore, the current knowledge is insufficient in
thermodynamic parameters ŽPlyasunov and Grenthe,
1994; Ohman and Sjoberg, ¨ 1996., which prevents
their addition to the database in keeping its consis-
tency. Moreover, it is uncertain that the formation of
the polymer Al 13 from Al 3q is not kinetically con-
strained ŽHem and Roberson, 1990; Furrer et al.,
1992.. By the same token, the formation of aqueous
complexes between alkali ŽNa, K. and AlŽOH.4 y
has also been ignored in the present study. The state
parameters are known ŽPokrovskii and Helgeson,
1995; Diakonov et al., 1996. but only a negligible
amount is formed over the temperature and concen-
tration ranges considered.
The approximation leading to Eq. Ž5. is assumed
valid for the three aluminosilicates with the tempera-
ture and pH ranges considered in this study. The
above experimental reinterpretations performed with
Eq. Ž5. have shown that K8 ™ 0 at various tempera-
tures and a large pH range. None of the laboratory
experiments performed on albite and K-feldspar at
1508C have led to a different finding ŽOelkers et al.,
1994; Gautier et al., 1994..
 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258
4. Results
4.1. Single mineral systems
The results obtained with KIRMAT at steady state
by assuming that only the presence of a single
Fig. 2. The l eq ratio vs. initial pH. The l eq ratio is defined as the
characteristic distance to reach equilibrium calculated with Eq. Ž4.
divided by that calculated with Eq. Ž1.. Ža. K-feldspar, Žb. albite,
Žc. muscovite. Open symbols: T s 258C; filled symbols: T s
1508C; the dashed lines stand for the results with wAlx init.s1=
10y0 9 molal, continuous lines for wAlx init.s1=10y0 3 molal.
253
Fig. 3. Initial Qr K ratio for K-feldspar vs. the initial pH. The
chemical affinity A is related to Qr K through Eq. Ž2.. Open
symbols: T s 258C; filled symbols: T s1508C; the dashed lines
stand for the results with wAlx init.s1=10y0 9 molal, continuous
line for wAlx init.s1=10y0 3 molal.
aluminosilicate reacting in an aqueous solution are
illustrated in Fig. 2. The characteristic distance to
reach equilibrium, l eq , calculated with Eq. Ž4. di-
vided by that calculated with Eq. Ž1., referred as the
l eq ratio, is plotted as a function of the initial pH at
25 and 1508C and for a total initial dissolved alu-
minium concentration ŽwAlx init. . of 1 = 10y0 3 and
1 = 10y0 9 molal. Among the three aluminosilicates
studied, K-feldspar shows the maximum l eq ratio at
258C. This ratio is close to 100 at pH init.s 6 and wAlx
y0 3
init.s 1 = 10 molal. The minimum l eq ratio is
close to 10 for albite and muscovite at acid pH
ŽpH s 2. and T s 1508C. The later result is indepen-
dent of total initial dissolved aluminium concentra-
tion. Regardless of the temperature and mineral, the
l eq ratio is insensitive to initial aluminium concentra-
tion at pH init.s 2. The same result is obtained at
basic pH and 1508C. The dissolved aluminium con-
centration at equilibrium plays a key role in these
results. The chemical affinity change required to
reach equilibrium Ži.e., the mineral solubility. con-
trols the final wAlx value and depends on pH ŽFig. 3..
At 1508C, the maximum initial chemical affinity is
attained at acid and basic pH conditions, while at
258C this maximum initial affinity exists only at acid
pH. This relation between log ratio mineral solubility
and initial pH outlines the weak pH variation during
the reaction path.
The solubility is not the only factor affecting the
l eq ratio ŽFig. 2.. The initial dissolution rates strongly
affect the l eq ratio. As shown in Fig. 4, the ratio of
the initial dissolution rates computed using Eq. Ž1.
254 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258

Fig. 4. Ratio of initial K-feldspar dissolution rates vs. the initial
pH. rd init.Ž1. demotes the initial dissolution rate calculated with
Eq. Ž1.; rd init.Ž4. stands for the initial dissolution rate calculated
with Eq. Ž4.. Open symbols: T s 258C; filled symbols: T s1508C;
the dashed lines curves correspond to the results with wAlx init.s1
=10y0 9 molal, continuous curves for wAlx init.s1=10y0 3 molal.
Fig. 5. Effect of anorthite Ždiamonds. and quartz Žtriangles.
dissolution on the l eq ratio calculated for K-feldspar. Also shown
in this figure are computed results obtained for anorthite or quartz
free systems Žopen squares.. The dashed curves correspond to the
results with wAlx init.s1=10y0 9 molal, solid curves lines for
wAlx init.s1=10y0 3 molal.

vs. Eq. Ž4. is very close to the ratio of the character-

istic distance needed to reach thermodynamic equi-
librium ŽFig. 2.. In particular, the position of the
maximum l eq ratio for K-feldspar ŽFig. 2. is clearly
due to the difference between the initial dissolution
rates ŽFig. 4.. The l eq ratio decreases from 25 to
1508C despite the higher temperature dependence of
the standard TST proton-promoted rate law Žsee
Tables 1 and 2.. This is due to the temperature
dependence of aluminium speciation, which signifi-
cantly alters the initial dissolution rate ratio com-
puted using Eq. Ž4..
4.2. Influence of other dissolÕing minerals
mineral dissolution ŽFig. 5.. This is due to the simul-
taneous silica release, which speeds up the approach
to equilibrium and thus diminishes the effect of
aqueous aluminium on the dissolution rate. Accord-
ingly, quartz dissolution produces a more important
decrease of l eq ratio ŽFig. 5.. The faster additional
aluminium and silica are released in to solution, the
faster the approach to equilibrium, where the effect
of the affinity term supplants the inhibitorrcatalytic
effects either due to aluminium or pH. The l eq ratio
tends toward the unity when the local equilibrium
limit is approached ŽFig. 6..

Comparative calculations have been performed to

evaluate the effects of adding selected dissolving
minerals to alkali-feldspars and muscovite. The
choice of mineral added to the system is based on
their occurrence in natural systems. The aluminium
to silica ratio of the rock-forming minerals associ-
ated with alkali-feldspars and muscovite usually
ranges from the unity to zero. Therefore anorthite
and quartz are considered in the comparative calcula-
tions, stoichiometric anorthite dissolution is as-
sumed. Intermediate results are expected for the
addition of minerals possessing intermediate alu-
Fig. 6. The effect of anorthite dissolution rate on K-feldspar l eq
minium to silica ratios. ratio at T s 258C and pH init.s6. The dashed curve stand for the
Aluminium release from anorthite decreases the results with wAlx init.s1=10y0 9 molal, solid curve for wAlx init.s1
l eq ratio compared to that obtained above for single =10y0 3 molal.
 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258 255

Fig. 7. The l eq ratios at 25 and 1508C for K-feldspar, albite, and muscovite dissolution for various initial conditions as a function of initial
pH. The l eq ratio is defined as the distance required to attain steady state calculated using the aluminium speciation rate law ŽEq. Ž4..
divided by that calculated using the standard pH-dependent law ŽEq. Ž1.. with KIRMAT. The continuous curves denote the single mineral
results. The dashed and dot-dashed curves correspond to l eq ratios obtained for comparisons performed for an initial aluminium
concentration of 1 = 10y0 9 and 1 = 10y0 3 molal, respectively. These latter results were corrected so that the chemical affinity term of both
Eqs. Ž1. and Ž4. were identical Žsee text..
256 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258
4.3. Influence of the secondary products
The precipitation of secondary products produces
the reverse effect on the l eq ratio from that of the
dissolution of other mineral phases. The largest ef-
fect is found when an aluminium-rich secondary
phase rapidly precipitates. When solubility of this
secondary phase is within 1 = 10y0 9 and 1 = 10y0 3
molal, the minimum and maximum total initial alu-
minium concentrations used in this study, the ratio of
the distance to reach equilibrium is equal to that of
the initial dissolution rates ŽFig. 4.. Note that these
results should be corrected to account for the intrin-
sic higher dependence with respect to the chemical
affinity of the dissolution rate calculated with Eq. Ž4.
Žsee below..
Only pure silica precipitation increases the l eq
ratio compared to the single mineral results due to a
higher aluminium concentration at equilibrium.
However, this possibility is considered unlikely be-
cause the excessively high aluminium concentration
resulting from these calculations are inconsistent with
the ubiquity of aluminium-bearing secondary prod-
ucts in natural systems.
4.4. The maximum increase and decrease in dissolu-
tion rates due to the aluminium speciation-dependent
rate law
The maximum l eq ratio increase, which corre-
sponds to the maximum dissolution rate decrease due
to the effects of aqueous aluminium, can be graphi-
cally determined using Fig. 7. This figure illustrates
the l eq ratio for the case of single mineral dissolution
Žsolid curve. and for the case of mineral dissolution
in an initial solution containing 1 = 10y3 molal Al
Ždashed curve.. The maximum l eq ratio is given by
the higher of these two curves at any given initial
pH. The minimum increase of the l eq ratio cannot be
larger than unity, as it is set by the local equilibrium
limit. On the other hand, the lowest l eq ratio, which
corresponds to the largest dissolution rate increase,
occurs for dissolution in a solution with constant
aluminium concentration equal to 1 = 10y0 9 molal.
The effect of the higher chemical affinity depen-
dence of Eq. Ž4. is corrected by multiplying the
former curve by the l eq ratio calculated for s s 1
and s s 3, without considering aluminium specia-
tion effects.
Muscovite shows the smallest rate decrease Ži.e.,
the larger l eq ratio. over the temperature range con-
sidered ŽFig. 7.. The effect of the aluminium specia-
tion-dependent rate law is to decrease the muscovite
dissolution rate by one order of magnitude for an
initial aluminium concentration of Ž1 = 10y0 3 molal..
The maximum effect is obtained at neutral and acid
initial pH for 25 and 1508C, respectively. The alu-
minium speciation-dependent rate law lowers alkali-
feldspar dissolution rate by as much as two orders of
magnitude, for an initial aluminium concentration of
1 = 10y3 molal. This maximum is attained at 258C
for K-feldspar Žneutral pH., and at 1508C for albite
Žacid pH.. The temperature appears to have a larger
effect on l eq for the alkali-feldspars than for mus-
covite.
The maximum increase in albite dissolution rate
due to the aluminium speciation-dependent rate law
is three orders of magnitude at 258C and at acid pH.
For the other minerals tested, the maximum increase
is between two and three orders of magnitude, also at
low temperatures and at acid conditions. At 1508C, a
two orders of magnitude rate increase is observed at
basic conditions for all three minerals. According to
Eq. Ž4. these rates would increase by another one
order of magnitude lower if the initial aluminium
concentration was lowered by a factor of 1000 to
wAlx init.s 1 = 10y1 2 molal.
5. Conclusions
The effects of the aluminium speciation-depen-
dent rate law ŽEq. Ž4.. have been determined for
K-feldspar, albite and muscovite, at 25 and 1508C
and over a wide range of initial pH and dissolved
aluminium concentration. These calculations are pos-
sible by using the KIRMAT hydrochemical code and
a multi-step approach. The first step consists in
modelling single mineral systems. Some additional
dissolving and precipitating secondary silicates with
end-member reaction rates and silica–aluminium
stoichiometry were considered in additional calcula-
tions. This modelling study indicates the need to
model the reactive transport phenomena with com-
pletely validated rate equations; up to three orders of
magnitude differences in muscovite and alkali-
feldspar dissolution rates are found when using an
 ´
F. Gerard et al.r Chemical Geology 151 (1998) 247–258
aluminium speciation-dependent rate law vs. the
standard proton-promoted rate equation. In addition,
secondary product formation produces sensitive
feedbacks on alkali-feldspar and muscovite dissolu-
tion rates by controlling the dissolved aluminium and
silica concentrations. Therefore, the effects of aque-
ous aluminium concentration on rates may have a
crucial effect on basin modelling performed to evalu-
ate the permeability variations and fluid migration.
Acknowledgements
Support was from the Centre National de la
´ ´ de Secours
Recherche Scientifique and the « Societe
des Amis des Sciences ». The authors are indebted to
E.H. Oelkers for cheerful encouragement, fruitful
discussions, and thoughtful correction of the English
language.
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