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Geochimica et Cosmochimica Acta 74 (2010) 6344–6356

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An experimental study of magnesite dissolution rates at neutral

to alkaline conditions and 150 and 200 °C as a function of
pH, total dissolved carbonate concentration, and chemical affinity
Giuseppe D. Saldi ⇑, Jacques Schott, Oleg S. Pokrovsky, Eric H. Oelkers
Géochimie et Biogéochimie Expérimentale, LMTG – CNRS – OMP – Université de Toulouse, 14, Avenue Edouard Belin, 31400 Toulouse, France

Received 19 October 2009; accepted in revised form 8 July 2010; available online 17 July 2010

Abstract

Steady-state magnesite dissolution rates were measured in mixed-flow reactors at 150 and 200 °C and 4.6 < pH < 8.4, as a
function of ionic strength (0.001 M 6 I 6 1 M), total dissolved carbonate concentration (104 M < RCO2 < 0.1 M), and dis-
tance from equilibrium. Rates were found to increase with increasing ionic strength, but decrease with increasing temperature
from 150 to 200 °C, pH, and aqueous CO32 activity. Measured rates were interpreted using the surface complexation model
developed by Pokrovsky et al. (1999a) in conjunction with transition state theory (Eyring, 1935). Within this formalism, mag-
nesite dissolution rates are found to be consistent with
  
þ 4 4A
rd ¼ k Mg f> MgOH2 g 1  exp ;
RT
where rd represents the BET surface area normalized dissolution rate, f> MgOH2 þ g stands for the concentration of hydrated
magnesium centers on the magnesite surface, kMg designates a rate constant, A refers to the chemical affinity of the overall
reaction, R denotes the gas constant, and T symbolizes absolute temperature. Within this model decreasing rates at far-
from-equilibrium conditions (1) at constant pH with increasing temperature and (2) at constant temperature with increasing
pH and RCO2 stem from a corresponding decrease in f> MgOH2 þ g. This decrease in f> MgOH2 þ g results from the increas-
ing stability of the > MgCO3  and >MgOH° surface species with increasing temperature, pH and CO32 activity. The de-
crease in constant pH dissolution rates yields negative apparent activation energies. This behavior makes magnesite
resistant to re-dissolution if formed as part of mineral carbon sequestration efforts in deep geologic formations.
Ó 2010 Elsevier Ltd. All rights reserved.

1. INTRODUCTION Martin, 2004; Morse et al., 2007). More recently a number

This work is part of a systematic study aimed at the
characterization of carbonate mineral reactivity in natural
environments. The low-temperature dissolution behavior
of Mg- and Ca-carbonates has been studied for more than
40 years (cf. Morse and Arvidson, 2002; Duckworth and
⇑ Corresponding author. Present address: Earth Sciences Divi-
sion, Lawrence Berkeley Laboratory, 1 Cyclotron Road, Berkeley,
CA 94720, USA. Tel.: +33 5 61 33 26 32; fax: +33 5 61 33 25 60.
E-mail addresses: saldi@lmtg.obs-mip.fr (G.D. Saldi), oelkers@
lmtg.obs-mip.fr (E.H. Oelkers).
of studies have focused on the dissolution behavior of car-
bonates at high temperature and elevated CO2 partial pres-
sures, mainly motivated to better understand the reactivity
of these minerals at conditions relevant to CO2 sequestra-
tion (Talman et al., 1990; Jordan et al. 2007; Zhang et al.,
2007; Pokrovsky et al., 2009a,b).
The reactivity of magnesite is of particular interest as
this mineral could provide a long-term CO2 storage host
in the absence of Ca (cf. Oelkers and Schott, 2005; Hänchen
et al., 2008; Oelkers and Cole, 2008; Oelkers et al., 2008a,b;
Saldi et al., 2009). Previous studies have measured magne-
site dissolution rates over wide ranges of pH and solution

0016-7037/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.gca.2010.07.012
 Magnesite dissolution kinetics
composition at 25 °C (Chou et al., 1989; Pokrovsky and
Schott, 1999; Pokrovsky et al., 2005). At higher tempera-
tures, magnesite dissolution kinetics have been investigated
at acidic to near to neutral pH using batch and mixed-flow
reactors at high pCO2 (Pokrovsky et al., 2009b) and in the
presence of various organic ligands (Pokrovsky et al.,
2009a). Magnesite dissolution rates and mechanisms were
also investigated by atomic force microscopy between 60
and 100 °C (Jordan et al., 2001, 2007; Higgins et al.,
2002). To date all magnesite dissolution rates measured at
elevated temperatures have been performed at far-from-
equilibrium conditions. The goal of this study is to expand
our knowledge of high-temperature magnesite dissolution
kinetics to neutral and alkaline pH. Towards this goal mag-
nesite dissolution rates have been measured at 150 and
200 °C, and 4.6 < pH < 8.4 as a function of aqueous CO2
concentration, ionic strength, at both near and far-from-
equilibrium conditions. The purpose of this paper is to pres-
ent the results of this experimental study which illuminates
the durability of magnesite at conditions relevant to carbon
sequestration in the subsurface.
2. THEORETICAL CONSIDERATIONS
The standard state adopted in this study is that of unit
activity for pure minerals and H2O at any temperature
and pressure. For other aqueous species the standard state
is of unit activity in hypothetical 1 molal solution refer-
enced to infinite dilution at any temperature and pressure.
Aqueous solution speciation and saturation indexes with re-
spect to solid phases were calculated using PHREEQC
(Parkhurst and Appelo, 1999) together with its llnl thermo-
dynamic database after adding to it formation constants for
the MgOH+ aqueous complex taken from (Shock et al.,
1997) and changing the logarithm of the equilibrium con-
stant for the magnesite dissolution reaction
MgCO3ðcÞ ¼ Mg2þ ðaqÞ þ CO3 2 ðaqÞ ð1Þ
from 10.51 to 10.04 at 150 °C and from 11.70 to
11.23 at 200 °C. This latter change is required so that
all the reactive solutions in which magnesite dissolution oc-
curred in this study are undersaturated with respect to mag-
nesite. The need to make this <0.5 log unit change in the
equilibrium constant for reaction (1) in the llnl database
likely stems from uncertainties among the large number
of equilibrium constants required to calculate the magnesite
saturation state in the reactive fluids at elevated tempera-
ture. Note that changing the equilibrium constant of reac-
tion (1) does not change the distribution of measured
rates as a function of chemical affinity, but only the origin
where chemical affinity equals zero.
Carbonate dissolution kinetics can be quantified using
the surface complexation model (SCM) developed by Van
Cappellen et al. (1993) and Pokrovsky et al. (1999a,b). This
model, which is based on zeta-potential and surface titra-
tion measurements, molecular dynamic simulations, and
spectroscopic observations (Pokrovsky et al., 2001; Ville-
gas-Jiménez et al., 2009), represents a significant improve-
ment compared to the classic mechanistic models of
carbonate dissolution (e.g., Plummer et al., 1978; Busen-
6345
berg and Plummer, 1982; Chou et al., 1989; Wollast,
1990; Alkattan et al., 1998; Gautelier et al., 1999). Within
the SCM model dissolution rates are related directly to
the concentration of surface species, allowing quantification
of role on rates of species that adsorb on the carbonate
surface.
The SCM assumes the existence of two primary hydra-
tion sites at the carbonate–aqueous-fluid interface,
>MeOH° and >CO3H°. Hydration and reactions with min-
eral constituting ions lead to the formation of the following
surface species: >MeOH2+, >MeOH°, >MeO, >MeH-
CO3°, >MeCO3–, >CO3–, >CO3H° and >CO3Me+. Previ-
ous studies of carbonate dissolution indicate that rates are
controlled by protonated carbonate groups (>CO3H°) at
pH < 5, whereas rates are controlled by the hydrolysis of
metal centers (>MgOH2+) at pH > 6 (Pokrovsky and
Schott, 1999, 2002; Schott et al., 2009). Following this for-
malism, magnesite overall dissolution rates can be de-
scribed within the framework of the transition state
theory by (Pokrovsky and Schott, 1999):
 
rd ¼ k CO3 f> CO3 H gm þ k Mg f> MgOH2 þ gn
  n 
Q
 1 ; ð2Þ
K MgCO3
which can be also expressed in terms of far-from-equilib-
rium dissolution rate r+ by (cf. Lasaga, 1981; Aagaard
and Helgeson, 1982; Oelkers et al., 1994):
  n    
Q nA
r d ¼ rþ  1  ¼ rþ  1  exp  :
K MgCO3 RT
ð3Þ
where
 
rþ ¼ k CO3 f> CO3 H gm þ k Mg f> MgOH2 þ gn : ð4Þ
Note that at pH > 6 where magnesite rates are controlled
by hydrated metal centers
  n 
Q
r d ¼ rþ 1  ¼ k Mg f> MgOH2 þ gn
K MgCO3
  
Q
 1 : ð5Þ
K MgCO3
In the four equations written above, k CO3 and k Mg represent
rate constants, m and n denote the reaction orders, Q cor-
responds to the ion activity product and K MgCO3 stands
for the equilibrium constant for reaction (1), R represents
the gas constant, T stands for the absolute temperature,
and A defines the chemical affinity of the dissolution reac-
tion. The ratio between Q and K MgCO3 represents the satu-
ration state of the aqueous solution with respect to
magnesite and it is usually designated X. Previous studies
of magnesite dissolution kinetics at 25 °C showed that the
values of both n and m are approximately equal to 4, indi-
cating that magnesite dissolution requires the full proton-
ation/hydration of the four surface sites surrounding the
rate controlling site (Pokrovsky and Schott, 1999). It fol-
lows that the description of magnesite dissolution rates with
Eq. (5) requires knowledge of the concentration of the
>MgOH2+ surface species. In accord with Pokrovsky
et al. (1999a) three species dominate magnesium speciation
6346 G.D. Saldi et al. / Geochimica et Cosmochimica Acta 74 (2010) 6344–6356

on magnesite surfaces at alkaline conditions: >MgOH°, This equation suggests that a negative apparent activation
>MgOH2+ and >MgCO3. Reactions among these species energy and rates that decrease with increasing temperature
can be written: for magnesite at pH > 6 could result from the strong de-
crease in f> MgOH2 þ g with increasing temperature. Nega-
> MgOH þ H2 O ¼> MgOH2 þ þ OH ; ð6Þ
tive apparent activation energies have been reported by
and Pokrovsky et al. (2009b) for calcite, dolomite, and magne-
site in acidic to neutral pH at 100 < T < 150 °C.
> MgCO þ 2
3 þ H2 O ¼> MgOH2 þ CO3 ; ð7Þ
The laws of mass action for these reactions can be expressed 3. EXPERIMENTAL METHODS
as
f> MgOH2 þ gaOH 3.1. Magnesite samples
K OH ¼ ; ð8Þ
f> MgOH g
Both natural and synthetic magnesite were used in this
and study. Synthetic magnesite was produced by placing
f> MgOH2 þ gaCO3 2 20 g of analytical grade hydrated Mg-carbonate, 250 ml
K CO3 ¼ ; ð9Þ of deionized water, and 15–20 g of solid CO2 into a rocking
f> MgCO3  g
400 ml Ti-autoclave. The autoclave was sealed and temper-
where KOH and K CO3 stand for the equilibrium constants ature was increased to 200 °C. After 3 weeks, the solids
for reactions (6) and (7), respectively. Combining Eqs. (8) were recovered, rinsed in deionized water, and dried in a
and (9) with Eq. (5) and expressing the conservation of me- stove at 60 °C. The synthesized magnesite powders con-
tal sites at magnesite surface by sisted of cubic to rhombohedral shaped crystals of 4–
s ¼ f> MgOH2 þ g þ f> MgCO3  g þ f> MgOH g; ð10Þ 40 lm in size. Five distinct magnesite powders were synthe-
results in sized: Mag-1, Mag-2, Mag-II, Mag-V, and Mag-VIII (see
!n Table 1). A SEM photomicrograph of a representative syn-
K CO3 K OH thetic magnesite powder is shown in Fig. 1a. XRD and
rþ ¼ kþ
Mg ; ð11Þ
K CO3 K OH þ K OH aCO2 þ K CO3 aOH EDS analyses confirm that these powders are pure magne-
3
site. These synthetic magnesite powders were used in disso-
where k þ
Mg is a rate constant including the total concentra- lution experiments without further treatment.
tion of Mg-sites ðk þMg ¼ k Mg  sÞ. Eq. (11) enables descrip- Natural magnesite samples used in this study were of
tion of magnesite dissolution rates as a function of two different origins. The first specimen was from Satka
aqueous CO3 2 and OH activities. Eq. (11) will be used be- (Russia) and was previously characterized by Pokrovsky
low to model measured dissolution rates. et al. (1999a). The second specimen originated from the
The temperature dependence of mineral dissolution rate Huaziyu deposit (Liaoning province, China). This deposit
(r+) is generally interpreted within the framework of the was described in detail by Jiang et al. (2004). Electron
Arrhenius equation. In accord with this equation the rate microprobe and LA-ICP-MS analyses performed on this
constant is related to the activation energy, Ea by (e.g., Eyr- sample provided the results shown in Table 2. XRD and
ing, 1935; Oelkers and Schott, 1999; Carroll and Knauss, EDS analyses of all natural samples used in this study con-
2005; Oelkers et al., 2008a,b): firm that they are pure magnesite. Natural magnesite sam-
kþ Ea =RT ples were ground in an agate mortar with a pestle and
Mg ¼ Aa e ð12Þ
sieved. The size fraction between 50 and 100 lm was ultra-
where Aa is a pre-exponential factor. In the absence of a sonically cleaned in alcohol to remove the fine particles,
mechanistic interpretation, some investigators have chosen rinsed repeatedly with deionized water, dried for 5 days at
to relate the rate to an apparent activation energy, E0a using 60 °C then retained for dissolution experiments. A SEM im-
(cf. Casey and Sposito, 1992) age of the Huaziyu magnesite powder is shown in Fig. 1b.
0 The specific surface area of all magnesite powders used in
rþ ¼ A0a  eEa =RT ; ð13Þ
the present study was determined by multi-point krypton
where A0a
is a pre-exponential factor. It follows from Eqs.
(5), (12), and (13) that
! Table 1
o ln k þ
Mg
Ea ¼ R ; ð14Þ Specific surface areas of the magnesite samples dissolved in this
oð1=T Þ study, as determined by krypton adsorption (SBET).

and MgCO3 powders Sample origin SBET (cm2/g)

  ! Huaziyu A Natural 1281
þ 4
o ln rþ o lnðk þ
Mg fMgOH2 g Þ Huaziyu B Natural 971
E0a ¼ R ¼ R : ð15Þ
oð1=T Þ oð1=T Þ Satka Natural 1260
Mag-1 Synthetic 2882
Combining Eqs. (14) and (15) leads to Mag-2 Synthetic 2241
! Mag-II Synthetic 1723
0 o lnðfMgOH2 þ g4 Þ Mag-V Synthetic 1791
Ea ¼ E a  R : ð16Þ
oð1=T Þ Mag-VIII Synthetic 2007
 Magnesite dissolution kinetics 6347

Fig. 1. SEM photomicrographs of magnesite samples used during dissolution experiments: synthetic magnesite sample Mag-II (left);
magnesite from the Huaziyu deposit, ‘Huaziyu A’ (right).

Table 2 sium concentration and alkalinity. Mg was measured by

Chemical composition of the Huaziyu magnesite used in this study. flame atomic absorption spectroscopy (AAS) with an
Note that the percent concentration of CO2 was calculated by
uncertainty of ±2% and a detection limit of 6  107 M,
difference from the other measured oxides.
whereas the alkalinity was determined by standard HCl
Major carbonate oxidesa (wt%) Trace elementsb (ppm) titration with an uncertainty of ±2% and a detection limit
MgO 47.32 Na 33.5 of 5  105 eq/L. Solution pH measurements were per-
CaO 0.32 Si 288.4 formed at 25 °C for inlet solutions as well as for outlet solu-
MnO 0.02 Cl 307.0 tions immediately after sampling using a standard glass
FeO 0.10 P 220.9 electrode, previously calibrated with 4.01, 6.86, and 9.18
SrO — K 25.7 NIST pH buffers. Solution pH was also measured in situ
BaO — Cr 3.2
during selected experiments performed at 150 °C using a so-
CO2 51.7
lid contact Li–Sn alloy commercial pH electrode coupled
a
Determined by EMPA, average of 20 points. with either a home-made Ag/AgCl reference electrode,
b
Determined by LA-ICP-MS, average of seven punctual which provides a constant potential in Cl rich solutions,
analyses.
as described by Pokrovsky et al. (2005, 2009b), or a Na-
selective glass electrode providing a constant potential in
Na+-rich solutions. The former reference electrode was
adsorption according to the BET method (Brunauer et al.,
used successfully for Cl concentrations 0.01 M; at Cl
1938). Results of these measurements are reported in
concentration P0.1 M its low stability allowed pH mea-
Table 1.
surements for only one or two experiments after calibra-
tion, and thus the latter reference electrode was used in
3.2. Experiments, solution analyses, and thermodynamic
such cases. Descriptions of potentiometric measurements
calculations
using these electrodes are provided by Saldi (2009). Poten-
tials measured with either set of electrodes generated pH
Steady-state magnesite dissolution rates were deter-
values having uncertainties not higher than 0.02–0.05 pH
mined from mixed-flow reactor experiments using 200 and
units.
300 ml titanium reactors similar to those previously de-
Mixed-flow reactor experiments were run in series. Each
scribed by Dove and Crerar (1990), Gautier et al. (1994),
series consisted of experiments with distinct fluid flow rates
and Devidal et al. (1997). Inlet solutions were stored in
and/or a distinct inlet solution with a single magnesite pow-
compressible polyethylene containers and injected into the
der. Each experimental series is noted by a distinct prefix in
reactor through a 2 lm titanium filter by a HPLC pump
Tables 3–5. Steady-state dissolution rates, indicated by a
allowing flow rates ranging from 0.1 to 10 ml/min. The
constant outlet Mg concentration, were calculated using
reactive solution inside the reactor was stirred at a constant
rate by a Parr magnetic stirrer and kept at constant temper- rd ¼ q  D½Mgtot =S ð17Þ
ature ±1 °C by a Parr controlled furnace. The fluid left the
reactor through a 2 lm titanium filter and was cooled be- where q represents the fluid flow rate, D[Mg]tot stands for
fore reaching a back-pressure regulator that maintained a the difference between the outlet and inlet solution Mg con-
constant pressure throughout the system. centration (in mol/kg) and S refers to the total mineral sur-
Inlet solutions were prepared with high purity deionized face area. The surface area used to calculate these rates was
H2O (18.2 MX cm) and reagent grade NaCl, Na-Acetate, the BET surface area of unreacted powders. Post-experi-
NaHCO3, HCl, NaOH, and MgCl2. Na-Acetate was used ment measurement show that these surface areas changed
only in a few experiments to buffer solution pH at circum- by no more than 10% during the experimental series.
neutral values. Experiments were performed at ionic Constant Mg concentrations in the outlet solution were
strengths varying from 0.001 to 1 M. The compositions of obtained after an elapsed time of 4 h to 6 days, depending
all inlet solutions used in the experiments are summarized on the flow rate. Steady-state was verified with a minimum
in Tables 3 and 4. All solutions were analyzed for magne- of three constant Mg concentrations of the outlet fluid
6348 G.D. Saldi et al. / Geochimica et Cosmochimica Acta 74 (2010) 6344–6356

Table 3
Chemical composition of inlet solutions used at 150 °C.
Exp. ID pH NaCl (mol/kg) MgCl2 (mol/kg) HCl (mol/kg) NaOH (mol/kg) NaHCO3 (mol/kg) Na-Acetate (mol/kg)
H1 8.11 0 0 0 0 1.0E02 0
H2A 7.59 0 0 0 0 1.0E03 0
H3A 7.31 0 1.045E04 0 0 1.0E03 0
H4 8.09 0 0 0 0 1.0E02 0
H4A 8.09 0 1.009E05 0 0 1.0E02 0
H4B 8.09 0 1.009E05 0 0 1.0E02 0
H5 7.22 0 1.015E04 0 0 1.0E03 0
H6 8.34 0 0 0 0 1.0E01 0
H7A 7.54 0 2.134E05 0 0 1.0E03 0
H7B 7.56 0 1.531E05 0 0 1.0E03 0
H8 8.12 0 1.911E06 0 0 1.0E02 0
H8A 8.14 0 1.911E06 0 0 1.0E02 0
H8B 8.11 0 3.057E06 0 0 1.0E02 0
H9 7.40 0.1 0 0 0 0 0
H9A 7.46 0.1 0 0 0 2.0E04 0
H9B 7.55 0.1 0 0 0 1.0E03 0
H9C 7.88 0.1 0 0 0 5.0E03 0
H10 7.22 0.1 0 5.0E05 0 0 0
H11 6.73 0.1 0 1.0E04 0 0 0
H17 7.97 0.01 0 0 0 5.0E03 0
H17A 7.55 0.01 0 0 0 1.0E03 0
H17B 7.30 0.01 0 0 0 2.0E04 0
H17C 7.32 0.01 0 0 0 0 0
H25 7.32 0.01 0 5.0E05 0 0 0
H25A 7.07 0.01 0 1.0E04 0 0 0
H25B 7.33 0.01 0 6.0E05 0 0 0
H28 7.73 1 0 0 0 5.0E03 0
H29 6.78 0.01 0 1.6E04 0 0 0
H29A 6.92 0.01 0 1.6E04 0 0 0
H30 6.44 0.1 0 1.6E04 0 0 0
H30A 6.71 0.1 0 1.6E04 0 0 0
H31 7.55 1 0 0 0 1.0E03 0
H32 7.51 1 0 0 0 2.0E04 0
H32A 7.55 1 0 0 0 0 0
H34 7.51 1 0 5.0E05 0 0 0
H34A 7.43 1 0 5.0E05 0 0 0
H35 7.34 1 0 1.0E04 0 0 0
H35A 7.39 1 0 1.0E04 0 0 0
H36 7.08 1 0 1.5E04 0 0 0
H36A 7.23 1 0 1.5E04 0 0 0
H37 7.29 0.1 0 1.6E04 0 0 0
H37A 7.17 0.1 0 2.0E04 0 0 0
H38 7.19 1 0 2.0E04 0 0 0
H38A 7.23 1 0 2.0E04 0 0 0
H39 6.99 1 0 2.5E04 0 0 0
H39A 7.06 1 0 2.5E04 0 0 0
H40 6.89 1 0 3.0E04 0 0 0
H40A 6.91 1 0 3.0E04 0 0 0
H43 6.82 0.1 0 3.0E04 0 0 0
H44 6.42 0.1 0 4.0E04 0 0 0
H45 6.30 0.1 0 5.0E04 0 0 0
H46 4.57 0.1 0 5.0E04 0 0 0
H47 6.31 0.1 0 4.0E04 0 0 0
H48 7.81 0.1 0 0 1.0E03 0 0
H48C 7.40 0.1 0 0 5.0E04 0 0
H49 6.21 0.1 0 5.0E04 0 0 0
H50 5.98 0.1 0 6.0E04 0 0 0
H51 4.61 0.11 0 7.0E04 0 0 0
H52B 7.97 0.1 0 0 0 7.0E03 0
H53 4.35 0.11 0 7.0E04 0 0 0
H53A 7.51 0.11 0 0 0 0 0
H55 4.26 0.1 0 1.0E03 0 0 0
 Magnesite dissolution kinetics 6349

Table 3 (continued)
Exp. ID pH NaCl (mol/kg) MgCl2 (mol/kg) HCl (mol/kg) NaOH (mol/kg) NaHCO3 (mol/kg) Na-Acetate (mol/kg)
H56 7.69 1 0 0 0 7.0E03 0
H56A 5.36 1 0 2.5E03 0 0 0.005
H57 7.24 0.11 0 2.6E04 0 0 0.01
H58 5.36 0.11 0 1.3E03 0 0 0.01
H59 6.12 1 0 1.3E03 0 0 0.01
M1A 7.59 0 0 0 0 1.0E03 0
M2 7.61 0.1 0 0 0 0 0
M2A 7.59 0.1 0 0 0 2.0E04 0
M2B 7.61 0.1 0 0 0 1.0E03 0
M2C 7.84 0.1 0 0 0 5.0E03 0
Mt1–8 7.25 0 0 0 0 0 0
Mt2–7 7.23 0 0 0 0 0 0
Mt4–9 7.47 0.1 0 0 0 0 0
Mt5 7.55 0.1 0 0 0 0 0
Mt5-A 7.47 0.1 0 0 0 2.0E04 0
Mt5-B 7.63 0.1 0 0 0 1.0E03 0
Mt5-C 7.90 0.1 0 0 0 5.0E03 0
Mt5-D 7.55 0.1 0 0 0 0 0
Mt7 7.28 0.1 8.133E04 0 1.8E03 0 0

Table 4
Summary of magnesite dissolution experiments performed in this study at 200 °C. All the experiments were performed on synthetic magnesite
samples.
Exp. ID pH NaCl NaHCO3 D[Mg] Alk BET s. area MgCO3 FFRa X rd
(mol/kg) (mol/kg) (mol/kg) (eq/L) (cm2/g) mass (g) (g/min) (mol/cm2/s)
S2 7.25 0.1 2.5E04 1.22E04 4.94E04 1723 0.915 1.295 0.48 1.67E12
S2A 7.13 0.1 0 1.81E04 3.52E04 1723 0.898 1.595 0.38 3.11E12
S3 7.53 0.1 1.0E03 4.02E05 1.14E03 1723 0.900 0.892 0.66 3.85E13
S3A 7.43 0.1 5.0E04 7.71E05 6.87E04 1723 0.900 1.194 0.57 9.89E13
S4 7.74 0.1 2.5E03 1.30E05 2.54E03 1723 0.957 0.596 0.68 7.82E14
S4A 7.72 0.1 2.5E03 1.21E05 2.51E03 1723 0.955 1.197 0.61 1.47E13
S4B 7.72 0.1 2.5E03 1.09E05 2.48E03 1723 0.953 2.197 0.54 2.42E13
S4C 7.89 0.1 5.0E03 5.63E06 4.99E03 1723 0.952 0.596 0.68 3.41E14
S4D 7.88 0.1 5.0E03 5.18E06 4.94E03 1723 0.951 1.197 0.61 6.30E14
S5 7.98 0.1 7.5E03 3.57E06 7.45E03 2007 0.984 0.497 0.68 1.50E14
S5A 7.97 0.1 7.5E03 3.38E06 7.40E03 2007 0.984 0.997 0.64 2.84E14
S5B 7.23 0.1 0 1.66E04 3.66E04 2007 0.984 2.190 0.39 3.06E12
S5C 6.88 0.1 0 2.52E04 2.29E04 2007 0.959 3.474 0.21 7.56E12
S5D 6.78 0.1 0 2.26E04 1.71E04 2007 0.932 4.997 0.11 1.01E11
S5E 7.24 0.1 0 1.82E04 4.26E04 2007 0.904 1.395 0.55 2.34E12
S6 8.04 0.1 1.0E02 2.84E06 9.87E03 1791 1.293 0.395 0.73 8.09E15
a
Fluid flow rate.

samples taken over several residence times. After all data at
a given set of conditions had been obtained, inlet fluid
composition and/or fluid flow rate were changed to the next
desired experimental conditions. Some examples of attain-
ment of steady-state conditions with respect to outlet solu-
tion Mg concentration are shown in the plot of Fig. 2.
4. RESULTS
Steady-state magnesite dissolution rates measured at 150
and 200 °C are listed in Tables 4 and 5 and plotted as a
function of aCO3 2 and pH in Fig. 3. It can be seen that mag-
nesite dissolution rates decrease with increasing activity of
both CO3 2 and OH. The plots of Fig. 3a and b illustrate
the strong dependence of magnesite dissolution rates on
aqueous CO3 2 activity; rates decrease by approximately
three orders of magnitude for an increase of aCO3 2 from
107 to 103. Note, however, that some of this decrease
may stem from an approach to magnesite saturation – see
the saturation state scale on the upper x-axis of the plots
in Fig. 3. The linear regression of the rates represented by
the dashed lines drawn in Fig. 3 exhibit a slope of 1 both
at 150 and 200 °C. Inhibition of magnesite dissolution by
aqueous carbonate species was previously observed by
Pokrovsky and Schott (1999, 2001) and Pokrovsky et al.
(2005, 2009b). Despite scatter, it can be seen in Fig. 3a
and b that dissolution rates at 150 °C increase by about
one order of magnitude with ionic strength increasing from
6350 G.D. Saldi et al. / Geochimica et Cosmochimica Acta 74 (2010) 6344–6356
Fig. 2. Examples of the temporal evolution of reactive fluid Mg
concentrations during the indicated dissolution experiments per-
formed at 150 °C. The symbols represented measured concentra-
tions and the dashed lines correspond to their steady-state values.
The uncertainties on the measured concentrations are approxi-
mately equal to the symbol size.
0.01 to 1 M, consistent with the dashed lines drawn through
the symbols in Fig 3a. Less rate data were obtained at
200 °C, and they exhibit less scatter than the rates deter-
mined at 150 °C. This may be due to the fact that only pure
synthetic magnesite was used in the dissolution experiments
at 200 °C.
A similar decrease of magnesite dissolution rates is ob-
served with increasing reactive solution pH (see Fig 3c
and d). This observation suggests the inhibition of magne-
site dissolution by hydroxyl ions. Comparison between
Fig. 3a and c and b and d suggests that the impact of pH
on magnesite dissolution rates is stronger than that of
CO3 2 .
To distinguish the effect of aqueous CO3 2 and OH on
dissolution rates from that of chemical affinity, magnesite
forward dissolution rates (r+) were calculated from overall
rates (rd) using Eq. (8) and n = 4, assuming that magnesite
dissolution mechanism does not change with T (Pokrovsky
et al., 1999b, 2009b). Magnesite forward dissolution rates
(r+) obtained from this calculation are plotted as function
of aCO3 2 and pH in Fig. 4 for an ionic strength of 0.1 M.
The plots of Fig. 4 show that forward dissolution rates de-
crease with both increasing pH and carbonate activity.
Comparison of Figs. 3 and 4 suggests that both overall
and forward magnesite dissolution rates at 200 °C are the
same or lower than those measured at 150 °C. This is more
evident if forward dissolution rates determined at 150 and
200 °C are plotted on the same graph as a function of
one of these two variables (Fig. 5). This observation implies
that the apparent activation energy of magnesite dissolu-
tion is negative or zero over this temperature interval. As
mentioned above, negative apparent activation energies
have also been reported by Pokrovsky et al. (2009a) for cal-
cite, dolomite, and magnesite in acidic to neutral pH at
100 < T < 150 °C. These authors attributed this negative
apparent activation energy to a decreasing enthalpy of sur-
face carbonate site protonation reaction with increasing T.
5. MODELING MAGNESITE DISSOLUTION RATES
AS A FUNCTION OF SOLUTION COMPOSITION,
CHEMICAL AFFINITY, AND TEMPERATURE
Modeling the dependence of magnesite dissolution rates
on CO3 2 activity and pH with Eq. (11) requires the identi-
fication of the equilibrium constants for reactions (6) and
(7). Values of the constants KOH and K CO3 deduced from
surface titration and zeta-potential measurements at 25 °C
were reported by Pokrovsky et al. (1999a). These constants
are not, however, available at higher temperature. In the
absence of direct measurement, K CO3 and KOH were ob-
tained together with k þMg from the regression of dissolution
rate data at an ionic strength of 0.1 mol/kg in the present
study; this regression could not be performed for other io-
nic strengths due to limited data. Results of this regression
are found in Table 6. The values obtained for k þ Mg are equal
to 1010.5 and 109.9 mol/cm2/s at 150 and 200 °C, respec-
tively. These values are consistent with a value of Ea of
46 kJ/mol; the extrapolation of the k þ Mg values in Table 6
using the Arrhenius equation (Eq. (12)) together with this
activation energy is in good agreement with the k þ Mg value
determined at 25 °C by Pokrovsky and Schott (1999). The
quality of this regression can be gauged with the aid of
Figs. 4 and 5 which compare measured dissolution rates
as a function of pH and aCO3 2 with corresponding values
generated from Eqs. (5), (11) and the parameters listed in
Table 6. A close agreement is found between the computed
curves and the measured symbols. The quality of these
regressions is validated by the Pearson P parameters and
coefficients of determinations of these fits listed in Table 6.
A further assessment of the quality of this fit can be seen in
Fig. 6. This plot shows that rates calculated from Eqs. (5),
(11), and the parameters listed in Table 6, agree with mag-
nesite dissolution rates measured in the present study at an
ionic strength of 0.1 mol/kg rates within a 0.5 log units dif-
ference. Only three data points exhibit a difference between
measured and calculated value that is of about 1 log unit or
larger. Of these three rate data exp. H6 is not plotted on the
graph because of the large uncertainty in its degree of
disequilibrium.
The speciation of Mg on the magnesite surface pre-
scribed by the equilibrium constants listed in Table 6 is
shown in Fig. 7 for two different total dissolved inorganic
carbon concentrations in a 0.1 M NaCl solutions at
150 °C. It can be seen that increasing the solution pH from
7 to 8 reduces by more than 50% the concentration of
> MgOH2 þ , as a consequence of the formation of >MgOH°
increases in carbon-poor solutions (RCO2 6 0.01 M); the
formation of > MgCO3  becomes significant in carbon-rich
solutions (RCO2 = 0.1 M) at alkaline pH.
The dependence of measured magnesite dissolution rates
on chemical affinity is plotted in Fig. 8 for experimental data
at 150 °C. Magnesite dissolution rates decrease significantly
with chemical affinity when A 6 15 kJ/mol, approaching 0
for A = 0 kJ/mol. Also shown on this plot are rates calcu-
lated using Eq. (3), which is derived from the Plummer
 Magnesite dissolution kinetics 6351

Table 5
Summary of magnesite dissolution experiments performed in this study at 150 °C. nd = not determined. Note that only five experiments were
performed using synthetic magnesite samples (series M-), all the other ones having been carried out with natural samples (series H- and Mt-).
Exp. ID pH NaCl NaHCO3 D[Mg] Alk BET s. area MgCO3 FFRa (g/min) X rd (mol/cm2/s)
(mol/kg) (mol/kg) (mol/kg) (eq/L) (cm2/g) mass (g)
H1 8.11 0 1.0E02 2.46E06 0.01 1281 0.776 0.797 0.50 3.29E14
H2A 7.59 0 1.0E03 2.04E05 0.0143 1281 1.012 0.605 0.33 1.59E13
H4 8.09 0 1.0E02 2.41E06 0.01 1281 0.812 0.495 0.56 1.91E14
H6 8.34 0 1.0E01 1.41E06 0.1 1281 1.908 0.493 0.99 4.75E15
H8 8.12 0 1.0E02 1.55E06 1.02E02 1281 1.151 0.291 0.73 5.07E15
H8A 8.14 0 1.0E02 1.72E06 1.02E02 1281 1.151 0.196 0.78 3.80E15
H8B 8.11 0 1.0E02 8.2E07 1.02E02 1281 1.151 0.196 0.80 1.81E15
H9 7.40 0.1 0.0E+00 1.40E04 2.11E04 1281 0.700 1.390 0.10 3.62E12
H9A 7.46 0.1 2.0E04 1.09E04 4.17E04 1281 0.700 1.396 0.14 2.82E12
H9B 7.55 0.1 1.0E03 4.02E05 1.08E03 1281 0.700 1.396 0.19 1.04E12
H9C 7.88 0.1 5.0E03 6.22E06 5.01E03 1281 0.700 1.200 0.26 1.39E13
H10 7.22 0.1 0 1.18E04 1.85E04 1281 1.000 3.970 0.04 6.10E12
H11 6.73 0.1 0 7.77E05 1.14E04 1281 0.888 5.470 0.006 6.23E12
H17 7.97 0.01 5.0E03 5.49E06 5.01E03 1281 0.719 1.194 0.49 1.19E13
H17A 7.55 0.01 1.0E03 2.06E05 1.04E03 1281 0.719 1.392 0.21 5.19E13
H17B 7.30 0.01 2.0E04 5.94E05 3.19E04 1281 0.719 1.390 0.11 1.49E12
H17C 7.32 0.01 0.0E+00 9.44E05 1.50E04 1281 0.719 1.390 0.08 2.38E12
H25 7.32 0.01 0.0E+00 1.03E04 1.57E04 1281 1.007 3.379 0.07 4.52E12
H25A 7.07 0.01 0.0E+00 1.03E04 1.05E04 1281 1.007 4.793 0.03 6.37E12
H25B 7.33 0.01 0.0E+00 1.03E04 1.45E04 1281 1.007 2.956 0.06 3.92E12
H28 7.73 1 5.0E03 4.28E05 5.09E03 1281 0.718 1.197 0.51 9.29E13
H29 6.78 0.01 0 1.39E04 1.19E04 1281 0.695 3.98 0.03 1.04E11
H29A 6.92 0.01 0 1.63E04 1.66E04 1281 0.675 1.6916 0.07 5.31E12
H30 6.44 0.1 0 1.02E04 nd 1281 0.725 3.976 0.001 7.24E12
H30A 6.71 0.1 0 1.31E04 nd 1281 0.708 1.689 0.01 4.07E12
H31 7.55 1 1.0E03 1.49E04 1.30E03 1281 0.717 1.403 0.29 3.80E12
H32 7.51 1 2.0E04 2.12E04 6.24E04 1281 0.658 1.394 0.16 5.85E12
H32A 7.55 1 0 2.28E04 4.56E04 1281 0.623 1.397 0.11 6.65E12
H34 7.51 1 0 3.26E04 6.02E04 1281 0.724 2.008 0.23 1.18E11
H34A 7.43 1 0 2.77E04 5.04E04 1281 0.696 4.021 0.14 2.08E11
H35 7.34 1 0 2.68E04 4.35E04 1281 0.884 5.504 0.09 2.17E11
H35A 7.39 1 0 3.06E04 5.11E04 1281 0.845 2.509 0.15 1.18E11
H36 7.08 1 0 2.32E04 3.15E04 1281 0.739 6.530 0.04 2.67E11
H36A 7.23 1 0 2.65E04 3.80E04 1281 0.707 4.481 0.07 2.18E11
H37 7.29 0.1 0 1.97E04 2.31E04 1281 1.044 2.842 0.09 6.97E12
H37A 7.17 0.1 0 1.86E04 1.72E04 1281 1.002 3.968 0.05 9.60E12
H38 7.19 1 0 2.86E04 3.71E04 1281 0.734 6.993 0.06 3.54E11
H38A 7.23 1 0 2.98E04 3.97E04 1281 0.693 5.020 0.08 2.81E11
H39 6.99 1 0 2.62E04 2.74E04 1281 0.454 7.503 0.03 5.63E11
H39A 7.06 1 0 2.80E04 3.10E04 1281 0.416 5.020 0.04 4.39E11
H40 6.89 1 0 2.78E04 2.56E04 1281 0.453 8.058 0.02 6.44E11
H40A 6.91 1 0 2.75E04 2.49E04 1281 0.413 6.091 0.02 5.27E11
H43 6.82 0.1 0 2.06E04 nd 1281 0.657 4.983 0.08 2.04E11
H44 6.42 0.1 0 2.20E04 nd 1281 0.623 5.963 0.04 2.74E11
H45 6.30 0.1 0 2.71E04 nd 1281 0.654 4.968 0.04 2.68E11
H46 4.57 0.1 0 2.22E04 nd 1281 0.625 6.429 0.001 2.96E11
H47 6.31 0.1 0 2.05E04 nd 971 0.634 6.983 0.03 3.88E11
H48 7.81 0.1 0 3.07E05 1.06E03 971 0.854 0.795 0.22 4.91E13
H48C 7.40 0.1 0 5.93E05 6.19E04 971 0.854 0.995 0.12 1.19E12
H49 6.21 0.1 0 2.53E04 nd 971 0.646 5.762 0.01 3.87E11
H50 5.98 0.1 0 2.68E04 nd 971 0.642 5.467 0.02 3.91E11
H51 4.61 0.11 0 3.14E04 nd 971 0.658 5.433 0.001 4.45E11
H52B 7.97 0.1 7.0E03 2.35E06 0.00703 971 1.421 0.992 0.16 2.81E14
H53 4.35 0.11 0 3.03E04 nd 971 0.704 5.197 0.001 3.83E11
H53A 7.51 0.11 0 1.30E04 2.40E04 971 0.637 2.788 0.06 9.01E12
H55 4.26 0.1 0 2.99E04 nd 971 0.431 6.015 0.001 7.16E11
H56 7.69 1 7.0E03 4.79E05 7.10E04 971 1.004 0.801 0.73 6.56E13
H56A 5.36 1 0 7.39E04 4.21E03 971 0.993 7.007 0.001 8.95E11
H57 7.24 0.11 0 1.76E04 1.03E02 971 0.524 5.922 0.12 3.42E11
(continued on next page)
6352 G.D. Saldi et al. / Geochimica et Cosmochimica Acta 74 (2010) 6344–6356

Table 5 (continued)
Exp. ID pH NaCl NaHCO3 D[Mg] Alk BET s. area MgCO3 FFRa (g/min) X rd (mol/cm2/s)
(mol/kg) (mol/kg) (mol/kg) (eq/L) (cm2/g) mass (g)
H58 5.36 0.11 0 5.02E04 7.17E03 971 0.529 6.364 0.001 1.04E10
H59 6.12 1 0 4.57E04 9.97E03 971 0.477 7.020 0.01 1.16E10
M1A 7.59 0 1.0E03 2.87E05 1.06E03 2882 0.539 0.572 0.48 2.11E15
M2 7.61 0.1 0.0E+00 1.94E04 3.87E04 2882 0.620 2.790 0.26 5.03E12
M2A 7.59 0.1 2.0E04 1.46E04 4.91E04 2882 0.620 2.790 0.28 3.78E12
M2B 7.61 0.1 1.0E03 7.55E05 1.15E03 2882 0.620 2.786 0.43 1.96E12
M2C 7.84 0.1 5.0E03 1.84E05 5.04E03 2882 0.620 2.786 0.72 4.78E13
Mt4 7.47 0.1 0 1.39E04 2.77E04 1260 0.549 1.360 0.10 4.55E12
Mt5 7.55 0.1 0 1.56E04 3.30E04 1260 0.566 1.369 0.16 5.00E12
Mt5-A 7.47 0.1 2.0E04 1.15E04 4.38E04 1260 0.566 1.417 0.16 3.79E12
Mt5-B 7.63 0.1 1.0E03 4.78E05 1.09E03 1260 0.566 1.420 0.27 1.59E12
Mt5-C 7.90 0.1 5.0E03 1.00E05 5.10E03 1260 0.566 1.423 0.44 3.34E13
Mt5-D 7.55 0.1 0 1.55E04 3.35E04 1260 0.566 1.454 0.16 5.25E12
Mt7 7.28 0.1 0 4.50E05 3.01E04 1260 0.856 0.730 0.47 5.08E13
a
Fluid flow rate.

Fig. 3. Magnesite dissolution rates plotted against corresponding aqueous CO32 activity at 150 (a) and 200 °C (b) and as a function of the
solution pH (c and d). At both temperatures rates strongly decrease with increasing CO32 activity and increasing pH (OH activity),
indicating the inhibiting effect of these species. Plots (a) and (c) also show how dissolution rates increase with increasing ionic strength. Dashed
lines represent linear regression lines for the different groups of data points. Error bars on symbols correspond to a 0.2 log unit uncertainty in
measured rates.
 Magnesite dissolution kinetics 6353

Fig. 4. Magnesite forward dissolution rates at 150 and 200 °C calculated assuming n = 4, plotted as a function of carbonate activity (a and b)
and corresponding pH (c and d). Solid lines represent a description of these data obtained with Eqs. (5), (11), and the parameters listed in
Table 6. The larger error bar relative to the experiment H6 stems from the uncertainty of its saturation state.

Table 6
Summary of the constants used to describe magnesite dissolution
rates at 150 and 200 °C at I = 0.1 M. P and R2 in this table refer to
refers to the Pearson P parameter and the coefficient of determi-
nation for the respective fits.
T I Log K CO3 Log KOH Log k þ
Mg (mol/ P R2
(°C) (M) cm2/s)
150 0.1 3.9 ± 0.2 7.6 ± 0.3 10.5 ± 0.2 0.0055 >0.999
200 0.1 4.4 ± 0.2 7.1 ± 0.1 9.9 ± 0.1 0.0003 >0.999

et al. (1978) model (dashed line), and those obtained from

Eqs. (5), (11), and the parameters listed in Table 6 for a
RCO2 of 104 and 101 mol/kg. For both models a dissolu-
tion rate constant equal to 3.2  1011 mol/cm2/s was used
to calculate rates. It can be seen that experimental rates are
inconsistent with those predicted by Eq. (3), but are located
between the rates calculated from Eqs. (5), (11), and the
parameters listed in Table 6 for RCO2 of 104 and Fig. 5. Magnesite forward dissolution rates at 150 and 200 °C plotted
against the corresponding solution pH. Comparison of these rate data
101 mol/kg. This comparison illustrates (1) the significance
on the same diagram allows to appraise the slight decrease of rates with
of solution composition (pH and aCO3 2 ) on dissolution rates increasing temperature, which stems from increasing carbonation and
at near neutral to basic conditions and (2) the limitations of hydrolysis of rate controlling sites (>MgOH2+) in CO32-rich alkaline
the classic Plummer et al. (1978) model to describe the var- aqueous solutions. These surface reactions are thus responsible for
iation of carbonate rates as a function of solution composi- negative values of the apparent activation energy for magnesite
tion and chemical affinity. dissolution (see Eq. (16)) in the interval of temperature studied.
6354 G.D. Saldi et al. / Geochimica et Cosmochimica Acta 74 (2010) 6344–6356
Fig. 6. Comparison of measured steady-state magnesite dissolu-
tion rates at 150 and 200 °C with corresponding rates calculated
using Eqs. (5), (11), and parameters listed in Table 6. The symbols
correspond to rates and the dashed line to equal values for these
measured versus computed rates. The error bars on the symbols
represent a ±0.2 log unit uncertainty on the measured rates.
Fig. 7. Mg surface species distribution as a function of solution pH
at 150 °C, calculated using the formation constants (K CO3 and KOH)
for an ionic strength equal to 0.1 M, a Mg concentration of
105 mol/kg and for two different contents of dissolved inorganic
carbon: (a) 0.01 M; (b) 0.1 M.
Fig. 8. Magnesite steady-state dissolution rates as a function of
chemical affinity at 150 °C for the different ionic strengths. The
dashed and the solid lines represent the dissolution rates predicted
by Eqs. (3) and (11) respectively. Rates were calculated using a
dissolution rate constant of 3.2  1011 mol/cm2/s, as obtained
from the analysis of rates measured at an ionic strength of 0.1 mol/
kg M. Solid line 1 represents the rates calculated for a total
dissolved carbon (RCO2) of 104 mol/kg, whereas solid line 2 is
calculated for RCO2 equal to 0.1 mol/kg. Error bars on data
symbols correspond to ±0.2 log units.
6. CONCLUDING REMARKS
Steady-state magnesite dissolution rates have been mea-
sured at 150 and 200 °C and at neutral to alkaline pH, con-
ditions that may be present during the in situ sequestration
of carbon in deep geologic formations. Results show that
far-from-equilibrium, rates decrease (1) with increasing
temperature at constant pH and (2) with increasing aque-
ous CO32 and OH activities at constant temperature.
This atypical behavior, which is likely exhibited by all diva-
lent carbonate minerals is interpreted to stem from the
hydrolysis and carbonation of the rate controlling
> MgOH2 þ surface complex with increasing temperature.
The tendency for magnesite dissolution rates to decrease
with increasing temperature as well as with OH concentra-
tion could benefit carbon sequestration efforts by making
magnesite more resistant to dissolution in deep, hot geolog-
ical formations, thus preserving the petrophysical integrity
of deep carbonate-rich confining reservoirs. The low reac-
tivity of divalent carbonates would favor the dissolution
of other mineral phases, such as silicates, which can con-
tribute to the increase of alkalinity and of the concentration
of dissolved divalent metal cations. This process can poten-
tially promote the formation of other CO2-trapping car-
bonates, improving the storage capacity of the reservoir.
ACKNOWLEDGMENTS
We would like to thank Jean-Claude Harrichoury and Alain
Castillo for the constant technical assistance throughout the dura-
tion of the experimental work, Carole Causserand for her generous
help during the analytical part of the work, and Philippe de Pars-
eval for providing a sample of the Huaziyu magnesite. We are also
grateful to Pascale Bénézeth, Jean-Louis Dandurand, and Robert
Gout for helpful discussions during the course of this study. Sup-
port from Centre National de la Recherche Scientifique, and the
 Magnesite dissolution kinetics
European Community through the MIR Early Stage Training Net-
work (MEST-CT-2005-021120) is gratefully acknowledged.
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Associate editor: Roy A. Wogelius