Applied Geochemistry 39 (2013) 69–77

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Do organic ligands affect forsterite dissolution rates?

Julien Declercq, Olivier Bosc, Eric H. Oelkers ⇑
GET/Université Paul Sabatier, Observatoire Midi-Pyrénées, UMR 5563 (CNRS/UPS/IRD/CNES), 14 Avenue Edouard Belin, 31400 Toulouse, France

a r t i c l e i n f o a b s t r a c t

Article history: Far-from equilibrium, steady state forsterite dissolution rates were measured at pH 3 and 25 °C in aque-
Received 8 November 2012 ous solutions containing 0.1 m/kg NaCl and up to 0.1 mol/kg of 13 distinct dissolved organic ligands in
Accepted 27 September 2013 mixed-flow reactors. The organic ligands considered in this study include those common in Earth surface
Available online 4 October 2013
environments and those considered as potential catalysts for use in CO2 sequestration efforts: acetate,
Editorial handling by M. Hodson
oxalate, citrate, EDTA4, glutamate, gluconate, malonate, aspartate, tartrate, malate, alginate, salycilate
and humate. The presence of up to 0.1 mol/kg of each organic ligand altered forsterite dissolution rates
less than 0.2 log units, which is the estimated uncertainty of the measured rates. Results obtained in this
study, therefore, suggest that the presence of aqueous organic anions negligibly affects forsterite far-from
equilibrium dissolution rates in most natural environments, and indicate that forsterite carbonation may
not be appreciably accelerated by organic ligand catalysis.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction on an industrial scale (e.g. O’Connor et al., 2000a,b; Wolf et al.,

A significant number of studies have been aimed at characteriz-
ing forsterite dissolution rates at various solution compositions
and temperatures (Luce et al., 1972; Sanemasa et al., 1972; Grand-
staff, 1978, 1986; Murphy and Helgeson, 1987, 1989; Blum and
Lasaga, 1988; Van Herk et al., 1989; Wogelius and Walther, 1991,
1992; Casey and Westrich, 1992; Jonckbloedt, 1998; Awad et al.,
2000; Chen and Brantley, 2000; Rosso and Rimstidt, 2000; Pokrov-
sky and Schott, 1999, 2000a,b; Oelkers, 2001; Giammar et al.,
2005; Golubev et al., 2006; Hänchen et al., 2006; Olsen and Rims-
tidt, 2008; Rimstidt et al., 2012; Saldi et al., 2013; Wang and Gaim-
mar, 2013). There has been increased recent interest in these rates
owing to the potential application of forsterite in carbon capture
and storage efforts (e.g. Giammar et al., 2005; Oelkers and Schott,
2005; Marini, 2007; Kelemen and Matter, 2008; Oelkers et al.,
2008; Dufaud et al., 2009; Prigiobbe et al., 2009; Garcia et al.,
2010; King et al., 2010a,b; Daval et al., 2011; Guyot et al., 2011;
Olsson et al., 2012). Forsterite is commonly thought of as the best
source of the divalent metal cations required for mineral carbon-
ation due to its fast dissolution rates and global abundance. The
carbonation of forsterite in CO2-rich fluids can occur via
Mg2 SiO4ðsÞ þ2CO2 þ 2H2 O ¼ 2MgCO3ðsÞ þH4 SiO4ðaqÞ
Forsterite
Magnesite
where the resulting aqueous silica could eventually precipitate as
amorphous silica or other silicate minerals (cf. Weres et al., 1981;
Teir et al., 2007; Orlando et al., 2001). Numerous studies have fo-
cused on the application of reaction (1) to carbon sequestration
⇑ Corresponding author. Tel.: +33 561332575.
E-mail address: oelkers@get.obs-mip.fr (E.H. Oelkers).
2004; Giammar et al., 2005; Maroto-Valer et al., 2005; Chen et al.,
2006; Gerdemann et al., 2007; Oelkers et al., 2008; Broecker,
2012). Reaction (1) involves the coupling of two processes: forste-
rite dissolution and magnesite precipitation. The overall rate of car-
bonation reaction (1) is, therefore, a function of these two processes
(e.g. Saldi et al., 2013). Catalysis which could accelerate the rates of
forsterite dissolution thus may also accelerate its carbonation in ac-
cord with reaction (1).
A vast number of past studies have suggested that organic li-
gands can increase the dissolution rates of silicate minerals sub-
stantially (e.g. Huang and Kiang, 1972; Manley and Evans, 1986;
Mast and Drever, 1987; Bennett et al., 1988; Welch and Ullman,
1993, 1996; Poulson et al., 1997; Cama and Ganor, 2006; Golubev
and Pokrovsky, 2006; Golubev et al., 2006; Ganor et al., 2009;
Pokrovsky et al., 2009; Schott et al., 2009). The effect of the pres-
ence of organic ligands on forsterite dissolution has been consid-
ered in detail by Grandstaff (1986), Wogelius and Walther
(1991), Hänchen et al. (2006), Olsen and Rimstidt (2008) and
Prigiobbe and Mazzotti (2011). Grandstaff (1986) reported an in-
crease of forsterite dissolution rates when the reactive aqueous
fluid contained citrate, EDTA, oxalate, tannic acid, succinate and
phthalate at 25 °C and pH 3.5 and 4.5. Wogelius and Walther
ð1Þ
(1991) reported that the addition of either 0.05 mol/kg potassium
phthalate or 103 mol/kg ascorbic acid increases forsterite disso-
lution rates at 25 °C by 0.75 log units at pH 4, but this effect de-
creased with decreasing pH. Hänchen et al. (2006) reported that
103 mol/kg citric acid increased forsterite dissolution rates at
90 °C by 0.25 log units at pH 3.4 and 0.5 log units at pH 4.5. Ol-
sen and Rimstidt (2008) reported that 104 mol/kg oxalic acid in-
creases forsterite dissolution rates by a factor of 6 at 25 °C and
2.5 < pH < 6.5.

0883-2927/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apgeochem.2013.09.020
70 J. Declercq et al. / Applied Geochemistry 39 (2013) 69–77

There have been a number of distinct interpretations of the ob-

served effect of organic ligands on silicate dissolution rates. Stumm
and collaborators (Furrer and Stumm, 1986; Stumm and Wollast,
1990) proposed that a parallel organic ligand promoted dissolution
pathway catalyzes the formation of organic anion surface species
leading to enhanced rates. Oelkers and Schott (1998) proposed that
organic ligands enhance silicate dissolution rates by forming aque-
ous complexes with those aqueous metal cations that would other-
wise slow rates. Yet others have suggested the formation of surface
chelates by organic ligands as a rate promoting mechanism (e.g.
Wogelius and Walther, 1991).
This study aims to further understanding of organic ligands on
mineral reactivity by measuring the effect of the presence of organ-
ic ligands on forsterite dissolution kinetics at 25 °C and pH 3. The
ligands investigated included acetate, oxalate, citrate, EDTA4, glu-
tamate, gluconate, malonate, aspartate, tartrate, malate, alginate,
salycilate and humate. The purpose of this paper is to report the re-
sults of this experimental study and to use these results to further
illuminate the effect of the presence of organic ligands on forsterite
dissolution rates in natural and carbon storage processes.

2. Materials and methods

2.1. Materials

Xenoliths containing forsteritic (Fo89) olivine were collected

from the San Carlos volcanic field east of Globe, AZ, USA. The xeno-
liths were crushed and forsterite was recovered by handpicking.
This forsterite was then ground and sieved to obtain the 100–
200 lm size fraction. X-ray diffraction analysis of this material re-
vealed it to be pure forsterite, free of clays and secondary phases.
Following the protocol established by Olsen and Rimstidt (2008),
the ground forsterite was first ultrasonically cleaned in 0.01 M
HCl for 10 min, left to settle for 5 min, and washed with alcohol
to remove the fine particles. The resulting forsterite was then dried
and used in the experiments without further treatment. The BET
surface area was measured by N2 adsorption using an Absorb-1
Quantachrome™ and calculated to be 980 cm2/g (±10%). Micro-
scopic analysis of fresh and altered forsterite surfaces was per-
formed using a Jeol JSM840a scanning electron microscope. A
photomicrograph of the forsterite prior to the experiments is
shown in Fig. 1a. The surfaces are free of both fine particles and
secondary phases.
Forsterite was dissolved in mixed flow reactors in fluids pre-
pared from 18 MX ultrapure water (MilliQ Plus system), 0.1 mol/
Fig. 1. SEM images of the forsterite powder. Image A shows the forsterite before
dissolution experiments while image B shows the forsterite powder after it had
been dissolved during experimental series 6. Note the initial forsterite is free of fine
particles, and appears to have sharp edges while the reacted mineral powder
exhibits rounded edges.
kg NaCl, sufficient HCl or NaOH to adjust the pH to 3, and from
0.0001 to 0.1 M of acidic acid, apartic acid, citric acid, EDTA diso-
dium salt dehydrate, sodium gluconate, L-glutamic acid, malic acid,
malonic acid, oxalic acid, salicylic acid, tartaric acid, or humic acid.
All chemicals used in the preparation of inlet fluids were analytical
grade and purchased from either Fluka, Sigma, or Sigma–Aldrich.
The organic acids or salts were used as purchased except for the
humic acid, which was pre-dissolved using techniques reported
by Pokrovsky et al. (2005). A list of the acids or salts used in this
study and their chemical formulas is provided in Table 1.

Table 1
List of the dissociation constants and chemical formula for the organic ligands and the identity of the acid or salt used to make the inlet fluids used in this study. With the
exception of humate, dissociation constants were compiled from Perrin et al. (1981) and Ullman and Welch (2002).

Ligand Formula pKaa Salt or acid used Salt formula

Acetate C2 H3 O
2 4.76 Acidic acid CH3COOH
Alginate (C6H8O6)n 3.5 Alginic acid (C6H8O6)n
Aspartate C2 H3 ðNH2 ÞðCOOÞ2
2
2.0–3.9 Aspartic acid C2H3(NH2)(COOH)2
Citrate C6 H5 O3 3.14–4.75–6.40 Citric acid C6H8O7
7
EDTA4 C10 H12 N2 O4 2.0–2.7–6.2–10.3 EDTA disodium salt dihydrate C10H14N2Na2O8
8
Gluconate C6 H11 O
7 3.86 Sodium gluconate C6H11NaO7
Glutamate C3 H5 ðNH2 ÞðCOOÞ2 2.1–4.1 L-Glutamic acid C3H5(NH2)(COOH)2
2
Malate C4 H4 O2 3.4–5.2 Malic acid C4H6O5
5
Malonate CH2 ðCOOÞ2 2.85–5.70 Malonic acid CH2(COOH)2
2
Oxalate C2 O2 1.2–4.2 Oxalic acid C2H2O4
4
Salicylate C7 H5 O
3 2.97 Salicylic acid C7H6O3
Tartrate C4 H4 O2 3.0–4.3 Tartaric acid C4H6O6
6

Data for humic acid is not available.

a
Where more than one value is given the values refer to the equilibrium constants sequentially for the first, second, third, and fourth deprotonation reaction where
relevant.
 J. Declercq et al. / Applied Geochemistry 39 (2013) 69–77 71

Table 2
Results of all experiments performed in the absence of aqueous organic ligands.

Exp cSi (mol/kg)  105 cMg (mol/kg)  105 cMg/cSi pH Flow (mL/min) m (g) log r+,Si (mol/cm2/s) log r+,Mg (mol/cm2/s)
1.s 12.9 26.21 2.03 3.33 0.14 0.49 8.65 8.60
1.f 15.1 31.01 2.05 3.37 0.14 0.49 8.58 8.53
2.s 11.1 20.51 1.85 3.42 0.10 0.31 8.66 8.65
2.f 7.57 15.35 2.03 3.05 0.10 0.31 8.82 8.78
3.s 17.2 31.44 1.83 3.34 0.15 0.31 8.29 8.28
3.f 4.46 8.35 1.87 2.97 0.15 0.31 8.87 8.86
4.s 14.5 27.01 1.86 3.04 0.12 0.30 8.45 8.44
4.f 3.60 7.21 2.00 3.00 0.14 0.30 8.98 8.94
5.s 20.7 33.72 1.63 3.38 0.15 0.30 8.20 8.24
5.f 4.75 8.61 1.81 3.01 0.16 0.30 8.80 8.80
6.s 3.28 6.75 2.06 3.12 0.40 0.31 8.58 8.53
6.f 1.87 4.29 2.29 3.11 0.40 0.31 8.83 8.73
7.s 14.7 26.02 1.77 3.06 0.22 0.50 8.41 8.40
7.f 4.82 9.42 1.95 3.08 0.22 0.50 8.89 8.93
8.s 14.8 26.09 1.76 3.49 0.14 0.31 8.59 8.60
8.f 4.68 8.06 1.72 3.04 0.10 0.31 9.03 9.05
9.s 9.27 10.04 1.08 3.24 0.15 0.33 8.56 8.78
9.f 1.90 3.56 1.87 3.09 0.14 0.33 9.32 9.31
10.s 4.29 8.67 2.02 3.04 0.15 0.31 8.88 8.83
10.f 7.72 13.39 1.73 3.00 0.15 0.31 8.62 8.64
11.s 4.66 9.09 1.95 3.03 0.20 0.30 8.72 8.69
11.f 5.02 8.86 1.76 2.90 0.20 0.30 8.69 8.70
12.s 1.93 4.14 2.15 2.90 0.30 0.35 8.93 8.86
12.f 1.61 2.86 1.78 2.90 0.30 0.35 9.01 8.96
13.s 1.64 3.21 1.95 2.90 0.17 0.35 9.25 9.21
13.f 2.25 4.10 1.82 2.97 0.17 0.35 9.11 9.11

X.s and X.f designates the first and last experiments of the series.

2.2. Experimental methods
All experiments were performed in 30 mL polypropylene
mixed-flow reactors (cf. Chaïrat et al., 2007; Flaathen et al.,
2010); schematic illustrations of the reactor design have been pre-
sented by Kohler et al. (2005). The reactors were continuously stir-
red with floating Teflon stirring bars. These reactors were
immersed in a water bath held at a 25 ± 2 °C. The fluid was injected
using a Gilson peristaltic pump, which allows fluid flow rates from
0.01 to 10 g/min. The fluid left the reactor through a 0.45 lm ace-
tate filter. No additional filtering was performed on outlet fluid
samples prior to chemical analysis. Inlet and outlet fluid pH was
measured using a combination glass electrode calibrated with NIST
buffers (pH = 4.002, 6.865, and 9.180 at 25 °C). The precision of pH
measurements was ±0.02 units. Magnesium concentrations were
determined by flame atomic absorption spectrophotometry using
a Perkin Elmer 5100 PC spectrometer equipped with an AS-90
autosampler, with an uncertainty of ±2%. Silica concentrations
were determined using the molybdate blue colorimetric method
(Govett, 1961) using a Technicon analyzer with an uncertainty of
±2% for most fluids, though some interference was evident in some
organic ligand-rich fluids, see below.
Seventy-seven mixed-flow reactor experiments were run at a
pH of 3 ± 0.4 throughout the study. To allow direct comparison be-
tween rates in the presence and absence of organic ligands, exper-
iments were organized into thirteen series. Each series is
designated by the prefix of the experiment. For example, series 2
consists of experiments 2-b, 2-1, 2-2, 2-3, 2-4 and 2-f. Each exper-
imental series was initiated by passing an organic-free, pH 3 fluid
through the reactor at a constant flow rate for approximately
6 days. Once an initial steady state was obtained and confirmed,
the original inlet fluid was replaced by a pH 3 fluid containing
104 mol/kg of a selected organic ligand until a second steady state
was obtained and confirmed. This sequence was generally repeated
using pH 3 fluids containing 103, 102, 101 and 0 mol/kg of this
organic ligand. The total run time for each complete experimental
series ranged from 3 to 6 weeks. By running the experiments in
series dissolution rates measured in the presence of organic ligands
can be compared directly to rates measured in organic ligand-free
fluids on the identical forsterite samples. After the steady-state
was obtained for the final organic ligand-free fluid, the reactor
was dismantled, the remaining forsterite powder was recovered
and the reactor cleaned. In the case of EDTA and L-glutamate, or-
ganic ligand concentrations of 0.1 M could not be achieved due
to solubility constraints. Approximately 10 mL of outlet fluid was
collected twice daily during each experiment. Steady-state was
confirmed by the outlet fluids maintaining a constant Mg and Si
concentration within analytical uncertainty for a minimum of 3
residence times. The residence time is defined as the volume of
the reactor divided by the reactive fluid flow rate, which was fixed
at 0.15–0.40 g/min in the experiments. Further details of each
experimental series are provided in Tables 2 and 3.
3. Results
An example of the reactive fluid Mg and Si concentrations mea-
sured during one experimental series is depicted in Fig. 2. This fig-
ure shows the reactive fluid evolution during experiments
designed to assess the effect of aqueous malonate on forsterite dis-
solution rates. It can be seen in this figure that the addition of the
organic ligand leads to the attainment of a new steady state condi-
tion as indicated by the dashed lines in the figure.
Forsterite steady-state dissolution rates were calculated from
the aqueous Mg and Si concentrations using the relationship:
qðc i;out  c i;in Þ
rþ;i ¼ ð2Þ
S  m  mi
where q refers to the fluid flow rate, ci,in and ci,out represent the
aqueous concentration of the ith element in the inlet and outlet, S
denotes the specific surface area, m designates the amount of for-
sterite powder introduced in the reactor at the beginning of the
experiment series and mi stands for the stoichiometric number of
moles of the ith element in one mole of dissolving forsterite.
72 J. Declercq et al. / Applied Geochemistry 39 (2013) 69–77

Table 3
Results of all experiments performed in the presence of aqueous organic ligands.

EXP Ligand Ligand conc. cSi (mol/kg)  105 cMg (mol/kg)  105 cMg/cSi pH Flow m (g) log r+,Si log r+,Mg
(mol/kg) (mL/min) (mol/cm2/s) (mol/cm2/s)
1-1 Malonate 0.0001 15.8 28.9 1.83 3.38 0.14 0.49 8.55 8.54
1-2 0.0001 6.50 12.2 1.87 3.39 0.16 0.30 8.67 8.66
1-3 0.001 5.18 9.13 1.76 3.14 0.16 0.30 8.77 8.78
1-4 0.01 5.39 9.13 1.67 3.01 0.16 0.30 8.76 8.78
1-5 0.1 6.14 12.2 1.98 3.01 0.16 0.30 8.70 8.66
2-1 Acetate 0.0001 14.9 26.9 1.81 3.50 0.10 0.31 8.51 8.51
2-2 0.001 15.3 28.5 1.86 3.22 0.10 0.31 8.50 8.49
2-3 0.01 13.5 25.1 1.85 3.17 0.10 0.31 8.55 8.54
2-4 0.1 8.36 24.5 2.93 3.05 0.10 0.31 8.76 8.55
3-1 Oxalate 0.0001 11.2 21.8 1.94 3.34 0.30 0.31 8.17 8.14
3-2 0.001 8.37 16.4 1.96 3.11 0.30 0.31 8.30 8.26
3-4 0.01 8.45 16.7 1.98 2.95 0.30 0.31 8.29 8.26
3-5 0.1 1.42 5.80 4.09 3.03 0.30 0.31 9.07 8.71
4-1 Citrate 0.0001 6.86 12.1 1.77 3.17 0.30 0.30 8.38 8.39
4-2 0.001 5.75 10.9 1.90 3.13 0.30 0.30 8.46 8.44
4-3 0.01 6.76 13.2 1.96 3.04 0.30 0.30 8.39 8.35
4-4 0.1 4.12 n.d. n.d. 3.07 0.30 0.30 8.60 n.d.
5-1 EDTA 0.0001 11.0 22.9 2.09 2.95 0.30 0.30 8.17 8.11
5-2 0.001 5.71 11.2 1.96 3.10 0.30 0.30 8.45 8.42
5-3 0.01 3.82 9.01 2.36 3.20 0.30 0.30 8.63 8.51
6-1 Tartrate 0.001 3.26 6.72 2.06 3.07 0.39 0.31 8.60 8.54
6-3 0.01 3.00 5.94 1.98 3.20 0.40 0.31 8.62 8.58
7-1 Malate 0.0001 4.88 9.23 1.89 3.12 0.22 0.30 8.67 8.65
7-2 0.0001 5.11 9.79 1.92 3.13 0.30 0.30 8.51 8.65
7-3 0.001 4.63 8.52 1.84 2.99 0.30 0.30 8.55 8.55
7-4 0.01 4.93 8.85 1.79 2.99 0.30 0.30 8.53 8.53
7-5 0.1 12.4 24.1 1.94 3.08 0.14 0.50 8.67 8.65
8-1 Salicylate 0.0001 15.0 27.4 1.83 3.01 0.14 0.50 8.59 8.58
8-2 0.001 4.11 7.45 1.81 3.03 0.10 0.31 9.08 9.08
8-3 0.01 4.93 8.43 1.71 3.01 0.10 0.31 9.01 9.03
8-4 0.1 5.18 44.3 8.72 3.11 0.10 0.31 8.98 8.30
9-1 Alginate 0.0001 4.69 9.53 2.03 3.15 0.15 0.30 8.85 8.80
9-2 0.001 1.27 2.61 2.05 3.29 0.31 0.31 9.11 9.05
9-3 0.01 2.08 3.84 1.85 3.30 0.31 0.31 8.90 8.89
9-4 0.1 1.64 3.41 2.08 3.04 0.31 0.31 9.00 8.94
10-1 Humatea 0.0002 3.43 6.28 1.83 3.07 0.33 0.14 8.30 8.29
10-2 0.0006 2.92 5.43 1.86 3.04 0.30 0.31 8.76 8.75
10-3 0.0006 3.24 5.08 1.57 3.05 0.15 0.33 9.05 9.11
10-4 0.001 3.70 6.83 1.60 3.04 0.30 0.31 8.65 8.65
10-5 0.001 14.5 n.d. n.d. 3.22 0.10 0.33 8.57 n.d.
11-1 Gluconate 0.0001 4.36 9.83 2.26 3.15 0.15 0.30 9.70 8.79
11-2 0.001 1.91 4.52 2.36 3.51 0.20 0.30 9.11 8.99
11-3 0.01 2.00 4.10 2.05 3.43 0.20 0.30 9.09 9.04
11-4 0.1 3.46 6.79 1.96 3.15 0.20 0.30 8.85 8.82
13-1 Glutamate 0.0001 1.65 3.29 1.99 2.77 0.21 0.35 9.21 9.17
13-2 0.001 1.86 3.81 2.05 2.88 0.21 0.35 9.16 9.11
13-3 0.01 1.93 3.76 1.95 2.81 0.21 0.35 9.15 9.11
12-1 Aspartate 0.0001 2.20 5.07 2.30 2.92 0.20 0.35 9.11 9.01
12-2 0.001 2.08 5.07 2.43 2.95 0.20 0.35 9.14 9.01
12-3 0.01 2.00 5.07 2.53 2.92 0.20 0.35 9.15 9.01
12-4 0.1 1.80 5.07 2.82 2.92 0.20 0.35 9.20 9.01

n.d. Not determined.

a
The ligand concentration for the humates is given in units of volume fraction.

Steady-state Si and Mg outlet concentrations and the dissolu-
tion rates calculated from all experiments are provided in Tables
2 and 3. With few exceptions the molar Mg to Si ratio of all stea-
dy-state outlet flow is 1.78 ± 0.25, consistent with stoichiometric
dissolution of the forsterite. The logarithm of the dissolution rates
calculated based on Si release is plotted as a function of those
based on Mg release in Fig. 3. Only 3 experiments are significantly
non-stoichiometric: 11-1, 3-4 and 8-4, containing respectively
104 mol/kg of gluconate, and 0.1 mol/kg of oxalate and salicylate.
Tests of the molybdate blue method used to analyze dissolved Si
in this study show that the presence of 0.1 mol/kg gluconate and
oxalate significantly affected Si concentrations measured by this
method; these observations will be expanded upon in detail in
a future communication. As such, rates based on Mg release are
used for the interpretation of these experiments in the discussion
below.
All experimentally determined forsterite dissolution rates are
plotted as a function of organic ligand concentration in Figs. 4
and 5. Plots in these figures are grouped by experimental series
allowing the direct assessment of the effect on forsterite dissolu-
tion rates of each organic ligand. Measured rates are plotted in
each figure in the sequence they were measured; first rates were
measured in an organic ligand-free fluid, then rates were measured
in a sequence of fluids containing increasing organic ligand
 J. Declercq et al. / Applied Geochemistry 39 (2013) 69–77
Fig. 2. The temporal evolution of reactive fluid aqueous Si and Mg concentrations during experimental series 1. The solid symbols correspond to measured concentrations,
the vertical solid lines indicate times when the inlet fluid composition was changed, and the dashed lines indicate the steady state concentration values for each experiment.
Fig. 3. Measured far-from-equilibrium steady-state forsterite dissolution rates at
25 °C and pH 3 based on Si release as a function of corresponding rates based on
Mg release. Rates measured in the presence of aqueous organic ligands are depicted
as solid squares were whereas those measured in organic ligand-free fluids are
depicted as solid diamonds. Unfilled symbols correspond to experiments showing
an apparent non-stochiometric metal release. Note that 74 of the 77 plotted rates
are within 0.25 log unit of the 1:1 stoichiometric line.
concentrations and, finally, a second rate measurement was per-
formed in an organic ligand-free fluid. First it is evident that the fi-
nal rate measured in organic ligand-free fluids, based on Mg
73
release, is as much as 0.6 log units different from that measured
in the first organic ligand-free fluid. This difference is not system-
atic; in some experiments the final steady state forsterite dissolu-
tion rate is higher and in some the final rate is lower than the
initial rate. The origin of these variations remains unclear, but a
number of previous studies have suggested that significant tempo-
ral variations in rates during experiments are due to changes in
reactive surface area (Lüttge et al., 1999; Gautier et al., 2001; Hod-
son, 2006; Lüttge, 2006); mineral dissolution rates are commonly
assumed to be proportional to the mineral–fluid reactive surface
area, yet the variation of these surface areas as minerals dissolve
is still poorly defined (e.g. Noiriel et al., 2009). A second relevant
observation is that rates measured in the presence of organic
ligands are equal to those measured in organic ligand-free fluids
within analytical uncertainty.
4. Discussion
4.1. Comparison with past studies
Wogelius and Walther (1991) reported that the degree to
which ascorbic acid and K-phthalate affect forsterite dissolution
rates depends on pH. They observed no effect of these organic
compounds at pH 2, but reported that these ligands increased
forsterite dissolution rates by up to 0.75 log units at pH 6.
Grandstaff (1986) noted a similar pH dependence of the effect
of organic ligands on forsterite dissolution rates. Hänchen et al.
(2006) reported that the effect of citric acid on forsterite disso-
lution rate was small under acid conditions but increases with
increasing pH at 90 °C. In contrast, Olsen and Rimstidt (2008)
suggested that the presence of oxalate on forsterite dissolution
rates at 25 °C was pH independent from 2.5 < pH < 6.5. One
74 J. Declercq et al. / Applied Geochemistry 39 (2013) 69–77

Fig. 4. Forsterite far from equilibrium dissolution rate conditions at 25 °C and pH 3 measured in the present study as a function of the concentration of the indicated organic
ligand concentration. Rates obtained in the presence of aqueous organic ligands are shown as solid diamonds. Rates obtained at the beginning and end of the corresponding
experimental series in organic ligand-free fluids are plotted as filled triangles at a log organic ligand concentration of 5 and 0, respectively, to illuminate the effect of the
ligands on rates.

possible reason why this latter study is inconsistent with the of forsterite dissolution experiments can be inconsistent with the
previous studies is that their conclusions were based on forste- longer-term steady state rates.
rite dissolution experiments that lasted only 2 h. As can be seen Rates in the present study demonstrate that at pH 3 forsterite
in Fig. 2, the Mg and Si release rates during the first few hours dissolution rates are negligibly impacted by the presence of a wide
 J. Declercq et al. / Applied Geochemistry 39 (2013) 69–77
Fig. 5. Forsterite far from equilibrium dissolution rates at 25 °C and pH 3
measured in the present study as a function of aqueous humate concentration.
Rates obtained in the presence of aqueous humate are shown as solid diamonds.
Rates obtained at the beginning and end of the experimental series in organic
ligand-free fluids are plotted as filled triangles at an aqueous humate concentration
of 0 and 0.0011, respectively, to illuminate the effect of the aqueous humate on
rates.
variety of organic ligands at 60.1 mol/kg. These observations are in
general agreement with the previous reports that aqueous organic
ligands have at most a small effect on forsterite dissolution rates in
strongly acidic conditions but may have an effect at higher pH. A
reason for the contrasting effects of aqueous organic ligands on
steady-state forsterite dissolution rates with increasing pH may
stem from their aqueous speciation. As can be seen in Table 1,
many of the organic ligands considered in this study have a first
dissociation constant near pH 3. As such these organic species tend
to be present as neutral aqueous species at acidic pH, but as nega-
tively charged aqueous species in mildly acidic and neutral condi-
tions. Another possible reason for the contrasting effect of organic
ligands on forsterite dissolution rates with increasing pH is the
composition of the forsterite surface. Both the charge and Mg/Si ra-
tio of forsterite surfaces are strong functions of pH, factors which
could affect its reactivity (Pokrovsky and Schott, 2000a,b; Oelkers
et al., 2009).
4.2. Implications for carbon capture and storage
One of the major goals of this study is to assess the degree to
which the addition of organic ligands might accelerate Mg release
from forsterite thus aiding mineral carbonation efforts. The pH of
CO2-charged water depends on the partial pressure of CO2 in the
system; the pH of CO2 saturated water decreases from 3.9 to 3.0
with increasing CO2 partial pressure from 1 to 64 bars (Gíslason
et al., 2010). The results summarized above suggest that the addi-
tion of most organic ligands will have little effect on Mg release
from forsterite in these CO2-charged waters. This conclusion agrees
with those of Wolff-Boenisch et al. (2006, 2011) who concluded
that the addition of various organic ligands negligibly affected
the rates of peridotite dissolution at 25 °C and pH 3.6. As forsterite
dissolves in CO2 charged waters, however, the fluid will neutralize
(e.g. Siever and Woodfort, 1979). Under such conditions, previous
studies suggest that some acceleration of Mg release could be at-
tained from the presence of a number of organic ligands. The pres-
ence of these organic ligands, however might inhibit the ultimate
precipitation of carbonates either through increasing the solubility
of these minerals (Innskeep and Bloom, 1986; Lebrón and Suárez,
1998) or by inhibiting their precipitation rates (e.g. Kitano and
75
Hood, 1965; Suess, 1970; Otsuki and Wetzel, 1972; Reddy, 1977;
Berner et al., 1978; Reynolds, 1978; Reddy and Wang, 1980; Inns-
keep and Bloom, 1986; Giannimaras and Koutsoukos, 1988; Dove
and Hochella, 1993; Katz et al., 1993; Paquette et al., 1996).
4.3. Implications for silicate dissolution models
There are at least two distinct models for the enhancement of
silicate mineral dissolution rates in the presence of organic ligands.
A number of studies have argued that organic ligands could adsorb
to the mineral surface, providing a new parallel reaction mecha-
nism for the detachment of material from the mineral surface
(e.g. Furrer and Stumm, 1986; Amrhein and Suarez, 1988). In con-
trast, Oelkers and Schott (1998) proposed that the observed accel-
eration of the dissolution rates of some silicate minerals with
organic ligand concentration stems from their ability to make
aqueous complexes with aqueous metals that would otherwise in-
hibit rates. Although the degree to which organic ligands adsorb
onto forsterite surfaces has not been measured directly in this
study, it seems likely that significant adsorption would occur be-
cause at pH 3 forsterite surfaces are positively charged (Pokrovsky
and Schott, 2000a; Oelkers et al., 2009) whereas most of the organ-
ic species considered in this study are at least partly present as
aqueous anions at this pH due to their low dissociation constants
(see Table 3). The lack of forsterite dissolution rate acceleration
in the presence of most organic ligands seems to be inconsistent
with the hypothesis that rates are accelerated by ligand adsorption.
Although aqueous Mg-organic ligand complexation does occur,
forsterite dissolution rates have been shown to be independent
of aqueous Mg2+ activity (Oelkers, 2001). As such this aqueous
Mg-organic ligand complexing would not lead to accelerated rates
according to the Oelkers and Schott (1998) hypothesis, consistent
with the observations reported above.
5. Conclusions
The results of this study suggest that the presence of organic li-
gands at concentrations of <0.1 mol/kg have at most a small effect
on forsterite dissolution rates at pH 3 and 25 °C. As this pH is char-
acteristic of the CO2 charged waters that might be found in the
subsurface during carbon storage efforts it seems unlikely that
the presence of organic ligands would enhance the availability of
those divalent metals required for mineral carbonation from ultra-
mafic rocks prior to the neutralization of this fluid. In contrast, the
presence of organic ligands have been shown to enhance the disso-
lution rates of the intermediate feldspars and basaltic glass at
acidic conditions (e.g. Blum and Stillings, 1995; Thorseth et al.,
1995; Ullman et al., 1996; Oelkers and Schott, 1998; Alt and Mata,
2000; Oelkers and Gíslason, 2001); as such the use of organic li-
gands might prove effective in accelerating mineral carbonation
in basaltic and/or rocks of intermediate composition. Nevertheless,
organic ligands may hinder mineral carbonation due to their effect
on the solubility and/or precipitation kinetics of carbonate miner-
als. As such the potential of aqueous organic ligands to enhance
carbon mineralization remains questionable.
Acknowledgements
We would like to thank Alain Castillo for technical assistance
throughout the duration of the experimental work, Carole Causser-
and for her generous help during the analytical part of the work,
and Philippe de Parseval for aid creating SEM images. We thank
Per Aagaard, Stacey Callahan, Oleg Pokrovsky, Jacques Schott, Pas-
cale Bénézeth and Morgan T. Jones for helpful discussions during
the course of this study. Support from Centre National de la
76 J. Declercq et al. / Applied Geochemistry 39 (2013) 69–77
Recherche Scientifique, and the European Community through
CARB-FIX (Collaborative Project-FP7-ENERGY-2011-1-283148) is
gratefully acknowledged.
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