CRYSTAL

GROWTH
Calcium Carbonate Morphology and Structure in the Presence of & DESIGN
Seawater Ions and Humic Acids
2009
G. Falini,*,†,‡ S. Fermani,† G. Tosi,† and E. Dinelli‡ VOL. 9, NO. 5
Dipartimento di Chimica “G. Ciamician”, Alma Mater Studiorum UniVersità di Bologna, Via Selmi 2, 2065–2072
I-40126 Bologna, Italy, and Laboratori di Scienze Ambientali “R. Sartori”, Alma Mater Studiorum
UniVersità di Bologna, Via Sant Alberto 167, I-48100 RaVenna, Italy

ReceiVed March 20, 2008; ReVised Manuscript ReceiVed February 16, 2009

ABSTRACT: The effectiveness of some seawater components, such as magnesium, potassium, sodium, sulfate and chloride ions,
and humic acid, in the control of calcium carbonate composition, morphology, and phase distribution was studied. These components
were tested singularly, in pairs, and all together. It was observed that magnesium ions phase distribution control is influenced by the
presence of other ions and that in the presence of a high content of magnesium ions monohydrocalcite precipitates. Moreover, in the
presence of magnesium or potassium ions the calcite crystals show modified rhomohedral morphologies, while the presence of
sulfate ions favors their aggregation. Humic acids have an inhibition effect on calcium carbonate precipitation, induce the formation
of empty spheres of vaterite, and modify the calcium carbonate phase distribution. The isomorphic substitution of magnesium to
calcium in the calcite structure is favored by some seawater ions and enhanced by the presence of humic acids.

Introduction
Calcium carbonate crystallization is a ubiquitous process in
numerous terrestrial and aquatic ecosystems.1 The bulk of
calcium carbonate precipitation in seawater is skeletal. Organ-
isms orchestrate crystal nucleation and growth processes (biom-
ineralization) through a sophisticated regulation of an internal
chemistry that departs significantly from the “constant ionic
medium” of seawater.2 However, the interest in abiotic calcium
carbonate formation, and dissolution, in the ocean is increasing,
also because of the central role that these reactions will play in
the ocean’s response to the increasing partial pressure of carbon
dioxide (pCO2) in the atmosphere.3
The most important calcium carbonate polymorphs in sea-
water reactions are aragonite and calcite.1,4 Aragonite constitutes
a major phase of marine sediments, occurring both as marine
cement and as the principal skeletal component of many marine
taxa.2a,5 Marine calcite usually contains variable amounts (10
to >30 mol %) of MgCO3 in solid solution and is generically
termed magnesian calcite.4c,6 Other calcium carbonate phases
are of far less abundance and importance. Vaterite is metastable
with respect to calcite and aragonite and it is limited to minor
biogenic occurrences;7 hydrated CaCO3 phases (mainly mono-
hydrocalcite) are found only in the presence of high concentra-
tions of ions and/or microrganisms.8
Surface seawater is supersaturated with respect to calcite and
aragonite, and thermodynamic calculations indicate that this
supersaturation should be reduced by a massive precipitation
of inorganic aragonite.9 However, the inorganic precipitation
is limited and almost absent. This has been attributed to the
presence of soluble organic matter interacting onto surface of
crystals. It may act by two mechanisms: (i) as an organic sheath,
which prevents the nuclei growth by chemical-physical isola-
tion, and (ii) by adsorption on sites where crystal growth would
have occurred.10
Many studies on the precipitation of calcium carbonate in
seawater have been carried out. The effects of pressure of carbon
* Author for correspondence. E-mail: giuseppe.falini@unibo.it. Fax: ++39
051 2099456.
†
Dipartimento di Chimica “G. Ciamician”.
‡
Laboratori di Scienze Ambientali “R. Sartori”.
10.1021/cg8002959 CCC: $40.75  2009 American Chemical Society
Published on Web 03/24/2009
dioxide, salinity, ionic strength, main inorganic ions, and organic
matter have been investigated in depth.1-8,10 Magnesium ions
are the mainly responsible in controlling the kinetics and
thermodynamics of the calcium carbonate precipitation. The
precipitation of calcite at ambient temperature is both thermo-
dynamically and kinetically favored from solutions containing
low amounts of magnesium ions. However, in the presence of
magnesium ions in high concentrations relative to calcium ions,
the precipitation of aragonite is favored. Interestingly, the density
of aragonite is higher than that of calcite. However, magnesium
ions are not incorporated in the denser lattice of aragonite as a
solid solution, in spite of Mg2+ being a smaller ion than Ca2+.
Although the understanding of the mechanism of magnesium
incorporation is still limited to preclude definitive statements,
this occurs presumably because magnesium has a tightly bound
hydration shell, and its removal during crystal growth is
energetically unfavorable. Thus, hydrated Mg2+ ions may be
incorporated inside the calcite lattice destabilizing its structure
and favoring the precipitation of aragonite.6,11 The role of other
seawater ions has also been investigated deeply. Sulfate ions
are recognized as significant coprecipitating anions in marine
biogenic calcites (1 mol % in magnesia calcites), and their effect
on calcite precipitation has been investigated in solutions similar
to seawater. It has been shown that an increase of sulfate activity
reduces the precipitation rate as a function of the saturation
state.12 The interactions of organic matter, such as humid acids,
with calcium carbonate surfaces in marine systems have been
studied primarily because of their effects on the kinetics of
carbonate reactions.10d It is known that naturally occurring
dissolved organic matter acts as an inhibitor in nucleation and
growth of calcium carbonate crystals. However, it is not well-
known which chemical and physical processes are involved,
because of the complexity and variability of chemistry and
structure of the dissolved organic matter.13
In general, the research on the biotic precipitation of calcium
carbonate phases in seawater has mainly addressed kinetic and
thermodynamic studies of the processes, and relatively low
attention has been paid to structural and morphological features
of precipitates.1c,7d
The goal of this study is to examine the effectiveness of
seawater ions, such as magnesium, sulfate, potassium, sodium
2066 Crystal Growth & Design, Vol. 9, No. 5, 2009
Table 1. Molar Ratio Concentrations between the Sea Water Ions
and the Calcium Ions Used in the Crystallization Experiments of
Calcium Carbonatea
C1 C2 C3 C4 C5 A(H)b
Mg 2+
1 2 3 5 7 5
SO42- 1 5 10 5 the amount of precipitated carbonate and calcium ions.11 So,
Na+c 12c 22 32 42 12
Cl-c 12 22 32 42 11
K+ 1 2 3 1
H. acidsd 10 20 30 40 80 (40)
a
The concentration of calcium ions and carbonate ions was 3.3 ×
10-2 M. b A indicates a mixture containing all the studied seawater ions
in concentration close to that one present in seawater. A(H) indicates
that humic acids (40 ppm) has been added to the A mixture. c The
sodium and chloride ions are also the counterions of carbonate and
calcium ions, respectively. d The concentration of humic acids is
reported in ppm.
and chloride, and humid acids in the control of calcium
carbonate composition, morphology, and phase distribution.
These additives were tested singularly, in pairs, and all together.
Results and Discussion
In this study the role of the main seawater ions, such as
magnesium, potassium, sodium, chloride and sulfate, and humid
acids on the control of composition, phase distribution, and
morphology of calcium carbonate was investigated. These
additives were studied singularly, in pairs, and all together
(Table 1). Each ion was used in a range of concentrations around
the value of concentration that is present in seawater (Table 1,
last column), while humid acids were used up to the concentra-
tion (80 ppm) at which there was inhibition of precipitation.
Since chemical constraints were not adopted during the experi-
ments (carbonic acid system), the kinetic of precipitation
processes was not followed. The precipitates were weighed and
characterized by X-ray powder diffraction, Fourier transform
infrared spectroscopy, and scanning electron microscopy.
Almost stoichiometric amounts of rhombohedral calcite
crystals precipitated from the mixture of calcium chloride and
sodium carbonate solutions, the control experiment (Table 2,
Figures 1, Ctrl, and 7, Ctrl). In the presence of additional ions
and/or humic acids the amount of precipitate decreased (Table
2). This effect was clear using humic acids and less obvious
using high concentrations of sodium ions. When all the studied
sea ions were present, the amount of precipitate was reduced
to about 30% with respect to the control. The addition at this
mixture of humic acids (40 ppm) reduced the amount of
precipitate of about 50% (Table 3, last row). A correlation is
observed between the amount of precipitate and the final solution
pH; in general, the higher the pH was (around 8.1) the lower
the amount of precipitate became (Tables 2 and 3). This
observation can be explained considering the increase of salt
solubility with the solution ionic strength and the inhibition of
crystal nucleation and/or growth due to a poisoning of the calcite
crystal nuclei by additional ions (magnesium or potassium) and
humic acids.1,6,10,11 Moreover, the precipitation of calcium
carbonate phases more soluble than calcite implies an increase
of the concentration of carbonate ions in solution, and as
consequence of the pH.7b,d
In the control experiment pure calcite precipitated. The
addition of seawater ions and humic acids changed the phase
distribution of the precipitates. The presence of low concentra-
tion of magnesium ions ([Mg2+]/[Ca2+] ) 1, 2) provoked the
precipitation of magnesian calcite. Aragonite and magnesian
calcite were detected precipitating from solutions with [Mg2+]/
[Ca2+] ) 3 and monohydrocalcite precipitated with them using
Falini et al.
a solution with [Mg2+]/[Ca2+] ) 5. From a solution with [Mg2+]/
[Ca2+] ) 7 the precipitation of monohydrocalcite and aragonite
was detected (Table 2, Figure 1). These phase transitions can
be explained considering that the strongly hydrated magnesium
ions poison the growth sites on the calcite crystals reducing
as a consequence of this, solution supersaturation and pH
increase (Table 2), as already reported.7b,d This should be the
cause of the precipitation of stable calcium carbonate phases
having higher solubility than calcite, such as aragonite and
monohydrocalcite.8,11 In the presence of sulfate ions, sodium
(chloride) ions, potassium ions or low concentrations of humic
acids (up to 30 ppm) only calcite was detected in the precipitates
(Table 2, Figure 2, SO4, Na, K, H20). When 40 ppm of humic
acids were used vaterite (25% w/w) precipitated together with
calcite (Table 2, Figure 2, H40), while a complete inhibition of
precipitation was observed using 80 ppm of humic acids (Table
2). The detection of vaterite, which is a metastable phase, implies
its stabilization by the humic acids. Indeed, it is known that in
solution pure vaterite transforms into calcite by a dissolution-
precipitation process.7b Thus, the humic acids may reduce the
solubility (dissolution) of vaterite making a layer that envelops
(or covers) the crystals. At high concentrations the humic acids
may already adsorb on crystal nuclei, blocking their growth and
the following precipitation process. Unfortunately, the complex
chemistry of humic acids does not allow the formulation of any
mechanism on their interaction with calcium carbonate crystals
(or nuclei). However, because they are rich with charged
functional groups, mainly carboxylates,13 nonspecific electro-
static interactions should occur. Humic acids could also interfere
with the precipitation processes by chelating calcium ions in
solution. However, this process, which should reduce the
solution saturation, does not justify the formation of vaterite
that is the most soluble calcium carbonate polymorph. Moreover,
it does not agree with reported studies showing that inhibition
on calcium carbonates precipitation arises from a reduction of
growth sites on crystal surface.14 The FTIR spectra of these
precipitates did not show any clear absorption band that could
be related to the presence of organic material. In them only the
characteristic absorption bands of the calcium carbonate phases
were clearly observed (Figure 5).15 This is expected considering
the low starting amounts of humic acids used. Thus, a low
amounts of humic acids should be enough to stabilize vaterite.
The effect of pairs of additional ion species was studied using
concentrations similar to those ones present in seawater (Table
1, last column). In the presence of magnesium ions as unique
additive and at a [Mg2+]/[Ca2+] ) 5 the precipitation of
aragonite (80% w/w), magnesian calcite (10% w/w) and
monohydrocalcite (10% w/w) was detected (Table 2). The
presence of a second additive (ions or humic acids) with
magnesium ions changed the phase distribution of the precipi-
tates (Table 3). In the copresence of sulfates ions ([SO42-]/[Ca2+]
) 5) magnesian calcite (15% w/w) and aragonite (85% w/w)
precipitated (Table 3, Figure 3, Mg/SO4); in the copresence of
sodium ([Na+]/[Ca2+] ) 12) or potassium ions ([K+]/[Ca2+] )
1) aragonite and monohydrocalcite (20% w/w and 10% w/w,
respectively) precipitated (Table 3, Figure 3, Mg/K); and in the
copresence of humic acids (HA ) 40 ppm) magnesian calcite
(20% w/w), vaterite (10% w/w) and aragonite (70% w/w)
precipitated (Table 3, Figure 3, Mg/H). The comparison of these
data indicates that the presence of sulfate ions slightly favors
the precipitation of magnesian calcite with respect to monohy-
drocalcite. This observation has been reported in a different
system, and explained considering the formation of strong ionic
Calcium Carbonate Morphology and Structure Crystal Growth & Design, Vol. 9, No. 5, 2009 2067

Table 2. Crystallization Experiments of Calcium Carbonate in the Presence of Single Sea Water Ion Specie or Humic Acids at the
Concentrations (C1-5) Reported in Table 1a
C1 C2 C3 C4 C5
pHb nmc ccpd - % ucv pH nm ccp - % ucv pH nm ccp - % ucv pH nm ccp - % ucv pH nm ccp - % ucv
Mg2+ 7.7 0.96 C - 100 366.2 7.7 0.93 C - 100 365.8 8.0 0.95 A - 32 226.2 8.0 0.87 A - 80 225.9 8.0 0.90 A - 70 225.9
C - 68 364.6 C - 10 360.2 M - 30 242.0
M - 10 242.0
SO42- 7.7 0.97 C - 100 367.9 7.8 0.96 C - 100 367.8 7.8 0.95 C - 100 367.9 e e e e e e e e
Na+(Cl-) 7.7 0.93 C - 100 367.8 7.8 0.88 C - 100 367.7 7.9 0.83 C - 100 367.6 8.0 0.80 C 367.9 e e e e
K+ 7.7 0.95 C - 100 367.9 7.7 0.93 C - 100 367.8 7.8 0.89 C - 100 367.8 e e e e e e e e
H. acids 7.8 0.82 C - 100 367.7 7.8 0.81 C - 100 367.5 7.9 0.74 C - 100 367.6 8.1 0.70 C - 75 367.8 8.2 f f f
V - 25 125.2
a
For each crystallization experiment the final pH of the solution (pH), the normalized mass of the precipitate (nm), the calcium carbonate phases
(ccp) detected in the precipitate and their weight percentage (%), and the unit cell volume (ucv/Å3) of each phase are reported. b In the control
experiment, in which only calcium chloride and sodium carbonate were mixed, the final pH was equal to 7.7. c Mass of the precipitate normalized to the
mass of precipitate obtained from the control experiment (324 mg). d A, C, M, and V indicate aragonite, calcite, monohydrocalcite and vaterite,
respectively. Their unit cell volumes are 226.17 Å3, 367.85 Å3, 242.57 Å3 and 125.41 Å3, respectively. e These concentrations were not studied. f No
precipitation was observed after a crystallization time of 5 days.

Figure 1. X-ray powder diffraction patterns of calcium carbonate
precipitated in the presence of different concentrations of magnesium
ions. (Ctrl) pure calcite; (Mg1), (Mg3), (Mg5), and (Mg7) indicate
[Mg2+]/[Ca2+] are equal to 1, 3, 5, and 7, respectively. (C), (A), and
(M) indicate the main diffraction peaks of calcite, aragonite, and
monohydrocalcite, respectively. The diffraction patterns were displaced
along the vertical axis that reports intensity in arbitrary units of counts.
couples among sulfate and magnesium ions; this reduces the
activity of magnesium ions in solution favoring the precipitation
of magnesian calcite.16 In the presence of humic acids the
deposition of vaterite could be explained taking in account the
adsorption of this organic material on the crystals, as discussed
above. The coupling of humic acids with sulfate or sodium ions
provoked the deposition of calcite only (Table 3), while in the
presence of potassium ions a small amount of vaterite (10%
w/w) was also detected (Table 3, Figure 3, H/K). The absence
of vaterite in the presence of sodium or sulfate ions may suggest
that these ions reduce the strength of the electrostatic interactions
between humic acids and crystals, which should prevent the
Figure 2. X-ray powder diffraction patterns of calcium carbonate
precipitated in the in the presence of different ions: (SO4) sulfate, (Na)
sodium, and (K) potassium. (H20) and (H40) are the diffraction patterns
of the calcium carbonates precipitated in the presence of 20 ppm and
40 ppm of humic acids, respectively. (C) and (V) indicate the main
diffraction peaks of calcite and vaterite. The diffraction patterns were
displaced along the vertical axis that reports intensity in arbitrary units
of counts. The species concentrations were the ones reported in the
last column of Table 1.
dissolution of vaterite. Thus, during these crystallization experi-
ments the metastable vaterite should transform in calcite.7b Also
in this case the amount of adsorbed organic material was very
low, because it was not revealed by the FTIR spectra of the
precipitates (data not shown). The addition of two ions among
sodium, potassium, and sulfate provoked only a reduction of
the amount of precipitated calcite, which was always the unique
phase detected (Table 3, Figure 3SO4/K).
When all the studied seawater ion species were mixed
together (Table 1, last column) the precipitation of magnesian
2068 Crystal Growth & Design, Vol. 9, No. 5, 2009 Falini et al.

Table 3. Crystallization Experiments of Calcium Carbonate in the Presence of Pairs of Sea Water Ions or a Sea Water Ion and Humic Acids at
the Concentrations Reported in the Last Column of Table 1a
Mg2+ SO42- Na+ (Cl-) K+
b c d
pH nm ccp - % ucv pH nm ccp - % ucv pH nm ccp - % ucv pH nm ccp - % ucv
SO42- 7.8 0.87 A - 85 226.2
C - 15 359
Na+ (Cl-) 7.7 0.84 A - 80 226.2 7.9 0.76 C - 100 367.8
M - 20 242.1
K+ 7.8 0.88 A - 90 226.2 7.8 0.86 C - 100 367.9 7.9 0.79 C - 100 367.8
M - 10 242.0
H. acids 8.0 0.61 A - 70 226.2 8.1 0.56 C - 100 367.7 8.2 0.50 C - 100 367.6 8.2 0.55 C - 90 367.8
C - 20 356 V - 10 125.2
V - 10 125.2
Ae 8.0 0.72 A - 30 226.9 A(H)e 8.2 0.46 A - 80 226.5
C - 15 357 C - 15 354
M - 55 241.9 V-5 125.2
a
For each crystallization experiment the final pH of the solution (pH), the normalized mass of the precipitate (nm), the calcium carbonate phases
(ccp) detected in the precipitate and their weight percentage (%), and the unit cell volume (ucv/Å3) of each phase are reported. In the last row the data
concerning the crystallization experiments in which all the studied sea water ion species were used without (A) and with 40 ppm hunic acids (A(H)) are
reported. b In the control experiment, in which only calcium chloride and sodium carbonate were mixed, the final pH was equal to 7.7. c Mass of the
precipitate normalized to the mass of precipitate obtained from the control experiment (324 mg). d A, C, M and V indicate aragonite, calcite,
monohydrocalcite and vaterite, respectively. Their unit cell volumes are 226.17 Å3, 367.85 Å3, 242.57 Å3 and 125.41 Å3, respectively. e The
concentrations of the seawater ions are those ones reported in the last column of Table 1.

Figure 4. X-ray powder diffraction patterns of calcium carbonate

Figure 3. X-ray powder diffraction patterns of calcium carbonate
precipitated in the presence of pairs of seawater ion species or a specie
of seawater ions and humic acids at the concentrations reported in the
last column of Table 1. (SO4/K) sulfate and potassium ions; (H/K)
humic acids and potassium ions (Mg/H); magnesium ions and humic
acids; (Mg/SO4) magnesium and sulfate ions (Mg/K) magnesium and
potassium ions. (C), (A), (V), and (M) indicate the main diffraction
peaks of calcite, aragonite, vaterite, and monohydrocalcite, respectively.
The diffraction patterns were displaced along the vertical axis that
reports intensity in arbitrary units of counts.
calcite (15% w/w), aragonite (30% w/w), and monohydrocalcite
(55% w/w) was detected (Table 3, Figure 4A). The high content
of monohydrocalcite in the precipitate is consistent with what
reported for induced calcium carbonate precipitation in natural
seawater.8a The addition of humic acids (40 ppm) at the solution
containing all the seawater ions changed the phase distribution
precipitated in the presence of all the studied seawater ions without
(A) and with humic acids (A(H)). The concentrations are those ones
reported in the last column of Table 1. (C), (A), (V), and (M) indicate
the main diffraction peaks of calcite, aragonite, vaterite, and monohy-
drocalcite, respectively. The diffraction patterns were displaced along
the vertical axis that reports intensity in arbitrary units of counts.
of the precipitate. A mixture of aragonite (80% w/w), vaterite
(5% w/w), and magnesian calcite (15% w/w) was detected
(Table 3, Figure 4, A(H)). Thus, humic acids favor the
precipitation of vaterite and rule against the precipitation of
monohydrocalcite, as already observed in the previous experi-
ments. The X-ray powder diffraction patterns of the precipitates
from the solutions containing all the seawater ions and the humic
acids showed a marked broadening of the diffraction peaks
(Figure 4) with respect to that one observed in diffraction peaks
from the other precipitates (Figures 1-3). This indicates a
reduction in the crystallinity of mineral phases,17 which could
be related to the high number of additives in the precipitation
solutions.
The X-ray diffraction patterns and the FTIR spectra of the
precipitates did not show any signal that could be associated
with the presence of amorphous calcium carbonate.18 Thus, this
phase is absent, present in low amounts, or has been transformed
into crystalline phases during the precipitates’ handling.19
Calcium Carbonate Morphology and Structure
Figure 5. FTIR spectra of calcium carbonate precipitated in the absence
of additives (Ctrl), in the presence of 40 ppm of humic acids (H40) in
the presence of all the considered seawater ions without (A) and with
(A(H)) humic acids. The peaks at 1485, 1420, and 1408 cm-1
correspond to the ν3 absorption band of carbonate ions. The peaks at
876 and 713 cm-1 correspond to ν2 and ν4 absorption bands of calcite,
respectively. The peak at 860 cm-1 (ν2) and 745 cm-1 (ν4) are diagnostic
of aragonite and vaterite, respectively. All spectra were normalized to
the peak intensity of the band ν3 of carbonate and were displaced along
the vertical axis that reports absorption in arbitrary units. The
concentrations of the species were those ones reported in the last column
of Table 1.
The isomorphic substitution of ions in the calcium carbonate
crystalline structures was evaluated by lattice parameters. Those
ones of aragonite, monohydrocalcite, and vaterite were almost
constant (Tables 2 and 3). Only the lattice parameters of the
magnesian calcite changed, as a function of the additive(s) in
solution. In general, the isomorphic substitution of magnesium
to calcium in calcite increased increasing the magnesium content
in solution (Figure 6). When solutions with [Mg2+]/[Ca2+] equal
to 1, 2, and 3 were used the precipitated magnesian calcite had
an isomorphic substitution of magnesium to calcium of 1.2, 2.6,
and 4.2, atom %, respectively. When a [Mg2+]/[Ca2+] ) 5 was
used an isomorphic substitution of magnesium to calcium of
about 7 atom % was detected in the magnesian calcite structure.
This isomorphic substitution was increased by the copresence
of sulfate ions and humic acids, which provoked an isomorphic
substitution to 8 and 10 atom %, respectively (Figure 6). A
plausible explanation of this observation is that these additives
weaken the hydration sphere of magnesium ions favoring their
entrance into structure of calcite.11 In the presence of all the
studied ions the magnesium substitution to calcium in the
structure of calcite was about 9 atom % and increased to about
13 atom % when humic acids were added (Figure 6). This effect
due to of humic acids may be explained considering that they
are rich with carboxylate groups which may contribute to a
reduction of the hydration of magnesium ions. Moreover, the
inhibition of humic acids versus the precipitation of calcium
carbonates should lead to high levels of supersatutation, in
agreement with final pH of solutions. In this condition, probably
through the formation of an amorphous precursor, the precipita-
tion of magnesian calcite with high content of magnesium is
favored.20 Interestingly, the observed values of isomorphic
substitution of magnesium to calcium ions in the calcite structure
Crystal Growth & Design, Vol. 9, No. 5, 2009 2069
Figure 6. Isomorphic substitution (atom %) of magnesium to calcium
in the calcite structure as function of the concentration of magnesium
ions in solution. (() Only magnesium ions were present in solution:
Mg1, Mg2, Mg3 and Mg5 indicate [Mg2+]/[Ca2+] molar ratio equal to
1, 2, 3 and 5, respectively. (9) Mg/SO4: Sulfate and magnesium ions
were present in solution. (2) Mg/H: Magnesium ions and humic acids
(40 ppm) were present in solution. (×) all the considered seawater ions
(A) were present in solution; (x’s with vertical line) all the considered
seawater ions and 40 ppm humic acids (A(H)) were present in solution.
The concentrations of the species are those ones reported in the last
column of Table 1.
are lower than those ones reported in magnesian calcites
precipitated from natural seawater.1c,4,21
Calcium carbonate precipitated as single crystals and crystal-
line aggregates whose morphology and shape were modified
by the presence of seawater ions and humic acids (Table 4,
Figures 7 and 8). These forms showed a wide range of sizes
that did not allow any clear correlation with the kind of additive
which was present in the crystallization solution. Rhombohedra
of calcite showing only {104} faces precipitated in the presence
of sodium or sulfate ions, as observed in the control experiment
(Figure 7, Ctrl). However, in the presence of sulfate ions the
crystals were aggregated (Figure 7, SO4); the higher ion
concentration was the higher aggregation occurred, as previously
reported.16 The presence of potassium ions stabilized crystalline
{hk0} faces on the {104} rhombohedral calcite crystals (Figure
7K). Magnesian calcite crystals showed also a modified {104}
rhombohedral morphology in which {11j0} crystalline faces were
observed (inset in Figure 7, Mg3).6a,b The stabilization of new
crystalline faces on calcite by magnesium ions (specific) and
potassium ions (nonspecific) implies a preferential interaction
of these ions with specific crystal plane(s) of the calcite structure,
otherwise unstable. The specificity of these ions is probably
related to their ionic radius, charge density, and hydration
sphere.6a,b,22 Aragonite appeared as spherical aggregates formed
by small needle-like crystals, while monohydrocalcite appeared
as spherulites (insets in Figure 7, Mg7). Vaterite, which
precipitated only in the presence of humic acids, formed void
globular spherulites (Figure 7, H40’). These spherulites were
polycrystalline material (optical microscope observation, data
not reported) that showed a wide distribution of sizes and a
wall thickness of about 1 µm. Similar shapes for vaterite have
been already observed in the presence of templating carboxy-
lated polypeptides or in crystallization processes in which an
amorphous precursor quickly converted in the crystalline
phase.23 In the presented experiments a templating effect due
to humic acids cannot be excluded, although they are present
in small amounts (40 ppm).
2070 Crystal Growth & Design, Vol. 9, No. 5, 2009 Falini et al.

These additives were tested singularly, in pairs and all together. Their concentrations are reported in the last column of Table 1. b rhomb. indicates a rhombohedral shape. c rhomb. ag. indicates a shape generated
by the aggregation of rhomhedra. d void sph. indicates spherical shapes which are void. e m. rhomb. indicates a modified rhombohedral shape. f sp. agg. n. indicates spherical shapes generated by the aggregation of
prismatic {104} {11j0}
morph.
Table 4. Effects of Seawater Ions, Magnesium, Potassium, Sodium and Sulphate, and Humic Acids on Composition, Shape, Morphology and Phase Distribution of Calcium Carbonatea
H

sp. agg. n.
m. rhomb.
void sph.
shape

C(10)
phase

needle-like crystals. g The value in parentheses reports the isomorphic substitution of magnesium to calcium in the magnesian calcite structure. It is expressed as atom %.
{104} {hk0}
morph.

sp. agg. n. prismatic

K+

m. rhomb
void sph.
shape

spher.
phase

M
V
A
C

prismatic
morph.

{104}
{104}
Na+ (Cl-)

sp. agg. n.

m. rhomb.
a. spher.
shape

rhomb.
rhomb.

spher.

spher.
Figure 7. Scanning electron micrographs calcium carbonates precipi-

C(13)
phase

tated in the presence of single seawater ions or humic acids. (Ctrl)

M
A

A
C
C

v
pure calcite, the control experiment. (Mg3), (Mg5), and (Mg7) calcium
carbonate precipitated from a solution with [Mg2+]/[Ca2+] equal to 3,
{104} {11j0}

5, and 7, respectively. (K) and (SO4) calcium carbonate precipitated in

morph.

prismatic

the presence of potassium ions and sulfate ions, respectively. (H40)

{104}
{104}
{104}

A(H)e

and (H40′) calcium carbonate precipitated in the presence of 40 ppm

humic acids; two different magnifications are reported. In the inset in
(Mg3) a magnesian calcite crystal exposing {11j0} faces is shown. The
SO42-

sp. agg. n.

insets in (Mg7) show needle-like crystals of aragonite (A) and

m. rhomb.
shape

spherulites of monohydrocalcite (M). In the inset in (K) a calcite crystal

rhomb.
rhomb.
rhomb.

showing {hk0} faces is shown and therein the arrow indicates the c-axis
of calcite. In the inset in (H40′) empty spherulites of vaterite are shown.
The concentrations of the species were those ones reported in the last
phase

column of Table 1.
C(8)
A
C
C
C

In the copresence of sulfate and magnesium ions the crystals

of aragonite and magnesian calcite aggregated forming compact
{104} {hk0}

{104} {11j0}

spherulites (Figure 8, Mg/SO4), similarly to what observed in

morph.

prismatic

prismatic

the presence of only magnesium ions, at the same concentration

{104}
{104}
{104}

{104}

(Figure 7, Mg5). Also the crystals formed in the presence of

-

potassium ions aggregated when sulfate ions were present

(Figure 8, SO4/K). These crystals conserved the modified
rhomb. ag.c

m. rhomb.e

sp. agg. n.f

m. rhomb.

m. rhomb.
void sph.d

rhombohedral morphology, due to the presence of potassium

shape

a. spher.
rhomb.b

rhomb.

rhomb.

spher.

spher.

ions. However, the effect of potassium ions as crystal morphol-

ogy modifiers was lost when a high concentration of sulfate
ions was used ([SO42-]/[K+] ) 10) (data not shown). In the
phase

C(7)g

C(9)

copresence of potassium and sodium ions the calcite crystals

M

M
V
A

A
C
C
C
C
C

conserved the morphology observed in the presence of potas-

sium ions only (Figures 7, K and 8, Na/K). In the copresence
Na+ (Cl-)

H. acids

of magnesium and potassium ions the presence of distinct

SO42-

Mg2+

aragonite needles and monohydrocaltes sperulites was observed

Ctrl

K+

a
Ae

(Figure 8, Mg/K), while in the copresence of humic acids and

Calcium Carbonate Morphology and Structure Crystal Growth & Design, Vol. 9, No. 5, 2009 2071

Figure 8. Scanning electron micrographs of calcium carbonate precipitate in the presence of pairs of seawater ions: (Mg/SO4) sulfate and magnesium
ions; (SO4/K) potassium and sulfate ions; (Na/K) potassium and sodium ions; (H/K) potassium ions and humic acids; (Mg/K) potassium and
magnesium ions. (A) calcium carbonate precipitated from all the seawater ions. (A(H)) calcium carbonate precipitated in the presence of all seawater
ions plus humic acids. The inset in (K/H) shows a empty spherulite of vaterite. The insets in (A) and (A(H) show a low magnification view of the
corresponding precipitated aggregates. The concentrations of the species were those ones reported in the last column of Table 1.

potassium ions void spherulites of vaterite and modified
rhombohedral crystals of calcite were observed (Figure 8, H/K).
The copresence of humic acids and magnesium ions provoked
the precipitation of aggregates similar to those ones observed
in the presence of all the seawater ions and humic acids (Figure
8, A(H)).
The presence of all the studied seawater ions provoked the
precipitation of aggregates, in which it was possible to observe
the presence aragonite needles and monohydrocaltes sperulites
localized in different regions (Figure 8, A). When humic acids
were also used the aggregation of the calcium carbonate particles
increased and it was not possible anymore to discriminate among
phases (Figure 8, A(H)). Interestingly, the calcium carbonate
precipitated from seawater appears as cement in which the
different crystalline phases are closely packed.21
The results of the calcium carbonate crystallization experi-
ments in the presence of seawater ions and humic acids are
summarized in the Table 4. It reports shape, aggregation status,
and phase distribution of the precipitates obtained in the presence
of a single additive, a couple of additives, and all the additives.
From its analysis it can be seen that the effectiveness of
individual ions in the control of calcium carbonate precipitation
is modulated by the presence of other ions. Moreover, some
ions have a key role in controlling the characteristics of the
precipitate. Magnesium ions are the controllers of crystal
morphology and phase distribution, potassium ions control
crystal morphology, and sulfate ions act as controllers of crystal
aggregation. Also the humic acids have an important role
inhibiting the precipitation process and controlling the phase
distribution of calcium carbonate. Interestingly, the isomorphic
substitution of magnesium to calcium in the magnesian calcite
structure is influenced by the presence of the seawater ions and
humic acids, and reaches the highest value when all the additives
are present.
Conclusion
This study shows how seawater ions and humic acids can
control calcium carbonate composition, morphology, and phase
distribution. The control of magnesium ions over the phase
distribution is modulated by the presence of humic acids, sodium
or sulfate ions. The morphology and aggregation of calcite
crystals are controlled by magnesium ions, potassium ions, and
sulfate ions. Humic acids provoke inhibition of the calcium
carbonate precipitation, favor the formation of void spherulite
of vaterite, and modify the calcium carbonate phase distribution.
The isomorphic substitution of magnesium to calcium in the
calcite structure is favored by the presence of sulfate ions and
humic acids.
Experimental Procedures
The chemicals used, CaCl2, MgCl2, Na2CO3, NaCl, KCl, Na2SO4,
HCl, and NaOH, were analytically pure (Sigma-Aldrich) and the
solutions were made using Milli-Q water. Humic acids, as sodium salt,
2072 Crystal Growth & Design, Vol. 9, No. 5, 2009
were purchased from Sigma. 3.3 × 10-2 M CaCl2 and 3.3 × 10-2 M
Na2CO3 solutions were used as stock solutions. The solutions containing
additional solutes were prepared adding the salts to the CaCl2 or Na2CO3
stock solution. The additions were made avoiding the formation of
precipitates. Humic acids were added to the carbonate solution. The
final pH of the solutions was adjusted to 8.2 by addition of 0.1 M
NaOH or 0.1 M HCl solution. The experiments were carried out pouring
100 cm3 of the CaCl2 solution into the same volume of the Na2CO3
solution. After mixing the final solution was kept for five days in a
closed bottle at room temperature. The formed precipitate was filtered
and washed with Milli-Q water, then it was dried at 105 °C for 12 h
and finally weighed. The surnatant pH was measured. The X-ray powder
diffraction (XRD) patterns were recorded using a X’Celerator diffrac-
tometer (PANalytical) with Cu KR radiation and a Ni filter. In the FTIR
analysis each powdered sample (approximately 0.1 mg) was mixed with
about 10 mg of anhydrous KBr. The mixtures were pressed into 7 mm
diameter discs. Pure KBr discs were used as background. The analysis
was performed at 4 cm-1 resolution using a Nicolet 380 FT-IR
spectrometer. Scanning electron micrographs (SEM) of the samples
were recorded by a Philips 515 scanning electron microscope. The
samples were glued on aluminum stubs and gold sputtered prior the
observations. A Rietveld program (Quanto) for quantitative phase
analysis of polycrystalline mixtures from powder diffraction data was
used to quantify calcium carbonate phases and to evaluate the unit cell
parameters.24a The isomorphic substitution of magnesium to calcium
in the calcite structure was estimated from the unit cell parameters
according to Goldsmith et al.24b
Acknowledgment. We thank the Alma Mater Studiorum
Università di Bologna (Funds for Selected Topics), the Ministero
dell’Istruzione, dell’Università e della Ricerca (MIUR), and
Consorzio Interuniversitario di Ricerca Chimica dei Metalli nei
Sistemi Biologici (CIRCMSB) for financial support.
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