Professional Documents
Culture Documents
Calcium Carbonate
M.M.H. Al Omari*, I.S. Rashid*, N.A. Qinna†, A.M. Jaber{,
A.A. Badwan*
*The Jordanian Pharmaceutical Manufacturing Co., Amman, Jordan
†
Petra University, Amman, Jordan
{
Philadelphia University, Amman, Jordan
Contents
1. Description 32
1.1 Nomenclature 32
1.2 Formulae 33
1.3 Elemental Analysis 33
1.4 Appearance 34
2. Methods of Preparation 34
2.1 Existence in Nature 34
2.2 Preparation of Crystalline Form 38
2.3 Preparation of Amorphous Form 46
2.4 Factors Affecting Preparation 47
2.5 Inhibitors of Precipitation 53
3. Physical Characteristics 54
3.1 Ionization Constant 54
3.2 Solubility Characteristics 54
3.3 Partition Coefficient 56
3.4 Optical Property 56
3.5 Polymorphism 56
3.6 Particle Morphology 57
3.7 Hygroscopicity 59
3.8 Molecular Modeling 59
3.9 Crystallographic Properties 61
3.10 Thermal Analysis 68
3.11 Spectroscopy 72
4. Methods of Analysis 79
4.1 Compendial Methods 79
4.2 Titrimetric Methods 87
4.3 Gravimetric Method 95
4.4 Spectroscopic Methods 95
4.5 Electrochemical Methods 99
4.6 Calcimetric Method 102
4.7 Chromatographic Methods 102
Profiles of Drug Substances, Excipients, and Related Methodology, Volume 41 # 2016 Elsevier Inc. 31
ISSN 1871-5125 All rights reserved.
http://dx.doi.org/10.1016/bs.podrm.2015.11.003
32 M.M.H. Al Omari et al.
5. Stability 104
5.1 Crystal Phase Transformation 104
5.2 Solid-State Stability 105
5.3 Stability in Solution 106
5.4 Interaction with Complexing Agents 106
6. Uses, Applications, and Pertinent History 107
7. Pharmacology 108
7.1 Pharmacokinetics 108
7.2 Mechanism of Action 109
7.3 Pharmacodynamics 110
7.4 Toxicities 110
7.5 Drug Interactions 111
References 112
1. DESCRIPTION
1.1 Nomenclature
1.1.1 Systematic Chemical Names
Calcium carbonate [1,2].
Carbonic acid calcium salt (1:1) [1].
1.2 Formulae
1.2.1 Empirical Formula, Molecular Weight, Identification Numbers
Information of empirical formula, molecular weight, and different identifi-
cation numbers of CaCO3 are listed in Table 1 [4].
O
Ca2+
–
O O–
1.4 Appearance
According to the United States Pharmacopeia (USP), CaCO3 is fine, white,
odorless, tasteless, and microcrystalline powder [9], while it is described as a
white or almost white powder in the European Pharmacopeia (Eur. Ph.) [2].
2. METHODS OF PREPARATION
2.1 Existence in Nature
CaCO3 is one of the most abundant materials found in earth’s crust and
forms the rock types like limestone and chalk [10]. Moreover, it is the most
abundant chemical sediment in modern and most ancient oceans, making up
roughly 10% of sediments [11]. CaCO3 can be a dominant sedimentary con-
stituent in virtually any environment, at any latitude, and in any depth of
water. However, it is most prevalent in warm, tropical, and subtropical seas
where the organisms that produce carbonate sediments can thrive [12]. On
the other hand, carbonates are forming extensively in many regions in the
western margins of large oceans, in both the southern and northern hemi-
spheres, at seawater temperatures ranging from about 2 to 40°C [13,14].
Nearly all the CaCO3 that makes up carbonate platforms is derived from
marine organisms. CaCO3 is also an important component in biological sys-
tems, such as shells of marine organisms, pearls, and egg shells [15]. Some of
these systems, eg, Oyster shells, have enjoyed recent recognition as a source
of dietary Ca, but are also a practical industrial source [16]. While not prac-
tical as an industrial source, dark green vegetables such as Broccoli and Kale
contain dietarily significant amounts of CaCO3 [17].
Carbonates are largely made up of skeletal remains and other biological
constituents that include fecal pellets, lime mud (skeletal), and microbially
mediated cements and lime muds. Chemical constituents, including coated
grains such as ooids and pisoids, cements, and lime mud, are common in
carbonates but are absent in most siliciclastics. Clastic grains exist in carbon-
ates, as they do in siliciclastics. In carbonates, however, these grains are
mainly clasts of intraformational, lithified sediment (intraclasts) or of
reworked, older rock (lithoclasts). Carbonates have four main components:
(1) grains, (2) matrix, (3) cement, and (4) pores.
There are many classification schemes for carbonate rocks [18–23].
Classifications for detrital carbonates were developed by Folk [18,19] and
Dunham [20]. Classifications for reef rocks were developed by Embry
and Klovan [21] and Riding [22]. A scheme to include depositional,
Calcium Carbonate 35
Figure 3 The light microscopic images show (A) the initial calcitic pat-like deposits, (B)
the maturated calcitic crystals, (C) the organized piling up of the calcitic crystals on S.
raphanus spicules (Sr-s), and (D) the tight interaction of three cells within the tissue of S.
raphanus; into which the gaps between the cells the spicules are formed.
38 M.M.H. Al Omari et al.
Supersaturation
Nucleation
CaCO3: Growth
Van der Waals
bonds Primary
particles
Gelation
Aggregation
Reorganization
Fragmentation
Recrystallization
Growth
premature precipitation, some calcites are formed but all the particles are
mainly vaterite. The vaterite particles of various shapes are aggregated and
of various shapes. When KOH is introduced into Na2CO3 solution for
the same purpose, large calcite particles and smaller aragonite needles, which
are attached to the calcite cubes, are formed [55].
The kinetics of CaCO3 precipitation is a significant tool to understand
because they relate the CaCO3 saturation, pH, and the alkalinity to the
CaCO3 precipitation potential. All of the aforementioned parameters rep-
resent key aspects which specifically affect the morphology of CaCO3 crys-
tals [57,58]. C€olfen and Qi noted that the HCO3/CO3 rate, coupled with a
change in the solution supersaturation, leads to a change in the nucleation
rate of CaCO3 [59].
Generally, the precipitation of CaCO3 is accompanied by a drop in pH
and a reduction in hardness and in total alkalinity for each mole of precip-
itated CaCO3. The CaCO3 precipitation potential increases with saturation
index and buffer intensity. Buffer intensity in turn is a function of pH and
total alkalinity. Because buffer intensity decreases with increasing pH, the
CaCO3 precipitation potential also decreases as pH is increased [60]. The
detailed kinetics of such precipitation dependence is described by
Wojtowicz [60] and Plummer and Busenberg [61].
40 M.M.H. Al Omari et al.
water until saturation was achieved [74]. Using the aforementioned princi-
ple, fine particles of calcite with controlled morphology can be synthesized
by using hydrothermal carbonation of Ca(OH)2 at high CO2 pressure (initial
pCO2 ¼ 55 bar) and at moderate and high temperatures (30 and 90°C). A
specific volume of high-purity water with electrical resistivity of
18.2 MΩ cm containing Ca(OH)2-portlandite material (7.4 g/100 mL)
with purity of 96% is placed in a titanium reactor (autoclave with internal
volume of 2 L). The Ca(OH)2 particles are immediately dispersed with
mechanical agitation. The dispersion is then heated to 90°C with a heating
system adapted to the reactor. When the dispersion temperature is reached,
CO2 gas is injected in the reactor and the total pressure in the system is
adjusted to 90 bar by Ar injection. Under these preparation conditions,
the vapor phase consists mainly of an Ar and CO2 mixture with the CO2
in a supercritical state. At the end of the experiment, the autoclave is
removed from heating system and immersed in cold water. The reaction cell
is depressurized during the water-cooling period. After water cooling at
35°C (about 15 min), the autoclave is disassembled and the solid product
is carefully recovered and separated by centrifugation. Finally, the solid
product is dried directly in the centrifugation flasks for 48 h at 60°C and
consecutively for 12 h at 110°C in order to eliminate the adsorbed water.
The metastable crystalline phases of CaCO3 (initial P ¼ 90 bar, T ¼ 90°C
after 4 h), such as vaterite and aragonite, cannot be identified during the Ca
(OH)2 carbonation process, except when the reactor is depressurized after
the water-cooling stage at 35°C. For this case, crystalline aragonite can be
also detected. However, the carbonation of Ca(OH)2 in the presence of
supercritical or gaseous CO2 led to the precipitation of submicrometric iso-
lated particles (<1 μm) and micrometric agglomerates (<5 μm) of calcite.
mixing zone in the forms of CaCO3, ie, calcite, aragonite, and vaterite; mag-
nesite (MgCO2); and dolomite (CaMg(CO)3)2.
Precipitation of carbonate minerals can cause pore blockage and lead to
decreased porosity and permeability. This is beneficial within the caprock
and may increase the integrity of the injection. Moreover, carbonate precip-
itation can impact in situ remediation of groundwater contaminants (Sr, Pb,
Cd, Cu, and UO2) through coprecipitation of carbonates and contaminants
[88–90].
2.2.10 Wollastonite
The direct dry (gas–solid phase) carbonation of wollastonite (CaSiO3) can be
carried in a continuously stirred tank reactor at 25°C and atmospheric pres-
sure for 0–600 h. The main drawback of this method is the slow rate at ther-
modynamically set temperatures [97].
CaCO3 can be prepared by direct wet carbonation by: (1) leaching
of Ca, (2) dissolution of CO2 and subsequent conversion of bicarbonate
species, and (3) nucleation and growth of CaCO3. The main disadvantage
related to aqueous carbonation is the high energy consumption and cost
[97].
CaCO3 can be also prepared indirectly by dissolving wollastonite in HCl
to form CaCl2. The Ca(OH)2 produced (via CaCl2) is then dissolved in
water and then reacted with CO2 to produce CaCO3. The major drawbacks
of such method are the energy demand for the acid recycling stage and the
very large water demand for the carbonation stage [97].
Another indirect method to prepare CaCO3 is by extracting Ca ions
from wollastonite using CH3COOH [70,97]. CO2 is then injected into
the solution, which causes CaCO3 to crystallize.
2.2.11 Dolomite
The thermal decomposition of dolomite occurs in air in two steps from
CaCO3 and CaO, respectively [98]. The process can be controlled precisely
only at a temperature of 800°C due to the two-step reaction of dissociation.
The main drawback of this method is the adsorption and precipitation of
AsCO3 and AsO.
2.4.3 Magnesium
It has been reported that the precipitated CaCO3 polymorphs are related
to the Mg/Ca ratio [122–124] whereby low-Mg calcite, then high-Mg
calcite and aragonite, then aragonite, are the sequence of phases com-
monly precipitated from fluids with increasing Mg/Ca ratio. Furthermore,
Mg/Ca ratio of about five was considered as the threshold of the forma-
tion of low-Mg calcite to high-Mg calcite and aragonite [123]. Sandberg
[125] and Milliken and Pigott [126] attributed the inferred differences
in cortical mineralogies in Phanerozoic seas to the variations in marine
Mg/Ca ratio.
With respect to CaCO3 morphology, calcite progresses from angular
to spherical with increasing Mg concentration in solution, while by
Calcium Carbonate 49
2.4.5 Antiscalants
Synthetic antiscalants including pentasodium salt of aminotrimethylene
phosphonic acid, and hepta-sodium salt diethylenetriamine pentamethylene
phosphonic acid, in addition to a copolymer containing acrylic acid,
methacrylic acid, and itaconic acid were found to be better suited for adsorp-
tion and prevention of CaCO3 precipitation [130].
2.4.7 Polyelectrolytes
Anionic polyelectrolytes were found to lengthen the induction time and
to reduce the size of CaCO3 nanocrystals precipitated from super-
saturated solution. The extent of time depends on the interaction efficiency
between the polymer anionic repeating units and the Ca ions [132]. Further,
nanocrystals having vaterite structure give spherical CaCO3, while nano-
crystals having calcite structure lead to either acicular or flower shapes
of CaCO3.
Poly(allylamine HCl) as a cationic polyelectrolyte strongly influences
CaCO3 precipitation and induces the formation of calcite thin films and
fibers by counterion-induced phase separation [133]. Furthermore, CaCO3
50 M.M.H. Al Omari et al.
2.4.9 Surfactants
In the presence of cetyltrimethylammonium bromide (CTAB), crystal
agglomeration of CaCO3 increases and the irregular calcite rhombohedral
crystals are numerous. At high concentrations of CTAB (8.5 mM), the
number of spherical particles is smaller and the majority of the particles is
rhombohedral and consists of calcite crystals [143].
In the case of sodium dodecyl sulfate (SDS), at low concentrations
(5 mM), which is greater than the critical micellar concentration of SDS
in 0.1 M NaCl (1.5 mM at 25°C) [144], the crystals are primarily flower
shaped and only few rhombohedral and spherical particles are obtained.
When the concentration is increased, eg, 10 times, very small crystals result.
At very high SDS concentration, the aspect of the crystals and their magni-
tude are changed dramatically, but not the polymorphism of CaCO3 because
even in the presence of SDS the form obtained is calcite [143].
Calcium Carbonate 51
Kojima et al. [174] have also investigated the effect of frequency and
amplitude on the morphological of vaterite at high supersaturation without
additives. Kirboga et al. [175] showed that the higher amplitude, the higher
relative vaterite fraction. Moreover, specific surface area increases gradually
with the increase in the sonicator amplitude in the presence of biopolymer
carboxymethyl inulin. The presence of biopolymer affects the specific sur-
face area of CaCO3 crystals prepared not only with magnetic stirring [176]
but also with ultrasound waves [175].
3. PHYSICAL CHARACTERISTICS
3.1 Ionization Constant
Chemical equilibria of CaCO3 in aqueous solution can be described as
H2CO3 undergoing dissociation to give H+, HCO 2
3 , and CO3 ionic spe-
cies [195]. The corresponding dissociation constants pKa1 and pKa2 are 6.35
and 10.32 at 25°C, respectively [61]. Fig. 5 shows the distribution of carbon-
ates species (H2CO3, HCO 2
3 , and CO3 ) as a function of pH. However, the
presence of Ca ions leads to the formation of CaHCO+3 , CaCO3, and
CaOH+ in solution with association constants pKCaHCO3 + , pKCaOH + , and
pKCaCO3 of 1.26, 1.49, and 3.22 at 25°C, respectively [61,196].
1.00
0.75
Mole fraction
CO32–
0.50 H2CO3 –
HCO3
0.25
Table 5 Solubility Products (log pKsp) for the Various Forms of CaCO3 at 25°C [197]
Form Structure 2log pKsp
Amorphous (monohydrate) — 6.40
Ikaite (hexahydrate) Monoclinic 6.62
Vaterite (anhydrous) Hexagonal 7.91
Aragonite (anhydrous) Orthorhombic 8.34
Calcite (anhydrous) Rhombohedric 8.48
56 M.M.H. Al Omari et al.
80
46
40
20
3.8 0.005
0.13
0
2 4 6 8 10 12 14
pH
Figure 6 The calculated and measured solubility of CaCO3 as a function of pH of solu-
tion open to the atmosphere at room temperature. The pH of aqueous solutions
adjusted with HCl or NaOH (0.1–10 M) depending on the pH needed.
3.5 Polymorphism
CaCO3 exists naturally in six different forms: three crystalline polymorphs,
calcite, aragonite, and the metastable vaterite; two hydrate phases,
monohydrocalcite and ikaite; in addition to amorphous CaCO3 [202].
Calcium Carbonate 57
A B
C D
Figure 7 The SEM images of CaCO3 forms: (A) amorphous calcite, (B) layered and rhom-
bohedral calcite, (C) spherical vaterite, and (D) needle aragonite.
Table 7 Reported Particle Size, Specific Surface Area, and Pore Size of CaCO3
Specific Surface
Form Particle Size (μm) Area (m2/g) Pore Size (cm3/g) References
Calcite — 0.99 0.068 [205,206]
0.1 30 — [207]
Aragonite — 3.6 0.16–3.8 nm [208,209]
Vaterite 5 77 0.068 [206]
3–5 9–15 10 nm [62,210]
Amorphous 0.04 65 — [104]
0.086–0.31 12–42 — [205]
0.19–0.41 9–19 — [205]
Natural 1–3 4–10 — [211]
Precipitated 0.07 17–25 2.5 [212,213]
Calcium Carbonate 59
With regard to specific gravity and Mohs scale of CaCO3, all crystalline
forms showed similar values recorded as 2.54–2.95 and 3–4, respectively
[214,215].
3.7 Hygroscopicity
Amorphous and ikaite forms of CaCO3 exist as mono- and hexahydrate,
respectively, while vaterite, aragonite, and calcite exist as anhydrous.
According to USP and Eur. Ph. [1,2], CaCO3 does not loss more than
2% upon drying at 200°C, while in Japanese Pharmacopeia (JP) [216], it does
not loss more than 1% upon drying at 180°C.
A B C
Figure 8 The molecular dynamic simulation of calcite: (A) the initial, (B) the final with
a constant volume simulation (298K and density of 2.71 g/cm3), and (C) the final with a
constant stress simulation (298K and 1 bar pressure). Carbonate ions are shown with
a stick representation for the bonds between carbon and oxygen atoms. The projection
is along the b-axis.
60 M.M.H. Al Omari et al.
A B C
Figure 9 The molecular dynamic simulation of aragonite: (A) the initial, (B) the final
with a constant volume simulation (298K and density of 2.944 g/cm3), and (C) the
final with constant stress simulation (298K and 1 bar pressure). Carbonate ions are
shown with a stick representation for the bonds between carbon and oxygen atoms.
The projection is along the a-axis.
simulation (Fig. 9B) in comparison with the initial configuration (Fig. 9A).
The agreement between experimental and simulated pair distribution func-
tions would suggest that the force field reproduces the structural features of
calcite and aragonite when using constant volume simulations. However,
the constant volume/shape constraints may have had the effect of stabilizing
metastable structures [217].
Fig. 8C shows the final system configuration of the constant stress sim-
ulation for calcite. Comparing this with the starting configuration (Fig. 8A),
it is evident that the calcite structure is not greatly altered by relaxation in the
simulation constraints. The final and initial configurations of aragonite
(Fig. 9C and A, respectively) do show some differences. The equilibrated
structure from the constant stress simulation indicates that the carbonate ions
had rotated through an angle of c.60 degree, although the Ca and carbon
center-of-mass positions did not change appreciably. The differences in
the simulation outcomes can be associated with differences in the carbonate
anion geometries between the calcite and aragonite natural crystalline forms.
Furthermore, the equilibrium unit cell parameters of calcite calculated from
the constant stress simulation show a close agreement with the X-ray crys-
tallographic values. Aragonite, however, shows greater differences in the
unit cell dimensions. All three lengths, a, b, and c, were longer so that the
density was lower, in fact quite close to the calcite, suggesting that the ara-
gonite phase is tending toward this structure in an attempt to relieve stress on
the system [217].
Calcium Carbonate 61
A B
Figure 10 The hexagonal representation of a calcite unit cell: (A) side view and (B) top
view (Ca ¼ green (light gray in the print version), O ¼ red (dark gray in the print version),
C ¼ gray).
A B
Figure 11 The orthorhombic double cells of aragonite: (A) side view and (B) top view
(Ca ¼ green (light gray in the print version), O ¼ red (dark gray in the print version),
C ¼ gray).
3.9.1.2 Aragonite
Aragonite has an orthorhombic crystal structure with space group Pmcn. The
experimental structure parameters found by Dickens and Bowen are:
a ¼ 4.960 Å, b ¼ 7.964 Å, c ¼ 5.738 Å, and α ¼ β ¼ γ ¼ 90 degree, containing
four CaCO3 molecules [220]. The theoretical crystal parameters a
(5.0192 Å), b (8.0393 Å), and c (5.7952 Å), as obtained by USPEX simula-
tion method are almost close to the experimental values [118].
The Ca ion (green (light gray in the print version) spheres in Fig. 11) is
very close to the limiting value for transition making aragonite’s
orthorhomobic structure fairly easy to shift into the thermodynamically
Calcium Carbonate 63
A B
C D E
Figure 12 The crystal structures of CaCO3: (A) postaragonite, (B) phase I, (C) phase II, (D)
phase III, and (E) phase IV (Ca ¼ red (dark gray in the print version), O ¼ green (gray in the
print version), C ¼ blue (dark gray in the print version)).
64 M.M.H. Al Omari et al.
3.9.1.4 Vaterite
Its crystal structure differs from those of calcite and aragonite in terms of
symmetry, orientation of CO3 ions, and coordination environment of Ca
ions. There is general agreement that the carbonate planes are parallel to
the c-axis and that the Ca atoms are in eightfold coordination with oxygen
atoms. In contrast, the CO3 ions in calcite and aragonite are perpendicular to
the c-axis, and the Ca atoms have sixfold coordination in calcite and ninefold
in aragonite [81,230,231].
Meyer first reported an orthorhombic unit cell with a space group Pbnm
and Z ¼ 4 (Fig. 13A) for vaterite crystal structure derived from single-crystal
X-ray diffraction experiments [232]. On the other hand, Kamhi [81] found a
structure with hexagonal symmetry and space group P63/mmc using the
same XRD technique (Fig. 13B).
Later, Meyer [232] provided a structure mainly consistent with Kamhi’s
structure [81], which has the same space group but different carbonate site
symmetry. Furthermore, Lippmann [225] developed an idealized structure
from the vaterite-type high-temperature phase of YbBO3 [233] with space
group P6322. Spectroscopic methods have been applied to resolve the con-
troversy on the vaterite structure and focused on space group and site sym-
metry. However, the results are inconsistent, often due to impurities in the
samples, mode assignments, and differences of group theory analysis. For
example, Sato and Matsuda’s infrared spectra [234] support Kamhi’s
Calcium Carbonate 65
A B
Figure 13 Crystal structures of vaterite: (A) orthorhombic structure with space group
Pbnm and (B) hexagonal structure with space group P63/mmc (Ca ¼ black, O ¼ light gray,
C ¼ gray).
structure [81]. Behrens et al. [235] argued that none of the proposed struc-
tures, P63/mmc or P6322, is consistent with the Raman spectra, while
Gabrielli et al. [236] show that Meyer’s structure [232] is consistent with
the Raman spectra. On the other hand, Anderson [237] favors both Kamhi’s
[81] and Lippmann’s [225] structures. Deer et al. [223] reported that vaterite
is hexagonal with space group P63 and a ¼ b ¼ 4.13 Å, c ¼ 8.48 Å, α ¼ β ¼ 90
degree, and γ ¼ 120 degree.
Wang and Becker used MD simulation with temperature annealing to
study the structure and carbonate orientation of vaterite, in addition to esti-
mate the relative stability of the structures proposed in the literature [238].
The investigation revealed that the orthorhombic crystal structure of vaterite
proposed by Meyer [232] cannot be confirmed by quantum-mechanical cal-
culations and by the experiments by Kamhi [81]. Thus, partial occupancy
and disordering are unavoidable for correctly describing the vaterite
structure.
Subsequently, the temperature-annealing MD simulation of vaterite
structure at the end of the annealing cycle at room temperature (300K) shows
that the orientations of CO3 ions are disordered (Fig. 14A) and there are three
preferred orientations with an angle of 120 degree between CO3 planes.
However, the structure lacks long-range orientational order [238]. This
disordered structure (Fig. 14A), when taking a space average, is consistent with
Kamhi’s structure [81], in which each lattice site of the CO3 ion is partially
occupied and all atoms of the CO3 ions are randomly distributed among three
positions. An ordered hexagonal superstructure with space group P6522 or
P3221 appeared at the end of about 7 ns of simulated annealing with a final
66 M.M.H. Al Omari et al.
A B
A B
Figure 15 The structure of monohydrocalcite (CaCO3H2O) viewed down {001}: (A) the
P3121 subcell structure showing the disordered carbonate groups and (B) the super-
structure P31 model (Ca ¼ large gray, O ¼ large black, C ¼ small black, H ¼ small gray).
3.9.1.5 Monohydrocalcite
The generally accepted structure of monohydrocalcite is that of Effenberger
et al. [219]. The structure from single-crystal diffraction is solved in P3121
(Fig. 15A) with cell parameters a ¼ 6.0931 Å and c ¼ 7.5446 Å, which
requires orientationally disordered carbonate groups. A superstructure that
determines the orientation of water oxygen, one carbonate oxygen, and the
hydrogen atoms is solved in P31 (Fig. 15B) with a ¼ 10.5536 Å and
c ¼ 7.5446 Å, on the basis of weak super-lattice reflections, in which the car-
bonate groups are orientationally ordered. The positions are mapped from
Calcium Carbonate 67
the P3121 substructure, and the ordered orientations of the carbonate groups
are refined using rigid bodies.
Monohydrocalcite consists of eightfold coordinated Ca2+ ions, in which
some of the oxygen coordination is direct to carbonate groups and some
to water molecules. The eightfold Ca coordination consists of bonding to
four neighboring carbonate groups and two water molecules. Two of the
carbonate groups are involved in two bonds from Ca to two separate O
atoms, and two others are involved in one bond from Ca.
3.9.1.6 Ikaite
Ikaite tends to form very steep or spiky pyramidal crystals, often radially
arranged, of varied sizes from thumbnail size aggregates to gigantic salient
spurs. Upon synthesis, CaCO3H2O crystallizes in well-defined rhombohe-
dral crystals in the size range 10–40 mm. It crystallizes in the monoclinic
crystal system in space group C2/c with lattice parameters a 8.87 Å,
b 8.23 Å, c 11.02 Å, and β 110.2 degree [239]. The structure of ikaite
consists of an ion pair of (Ca2+CO2 0
3 ) surrounded by a cage of hydrogen-
bonded water molecules which serve to isolate one ion pair from another
(Fig. 16) [240].
Figure 17 XRPD patterns of different CaCO3 forms including calcite, vaterite, aragonite,
monohydrocalcite (CaCO3H2O), ikaite (CaCO36H2O), and amorphous.
of 0.02 degree 2θ and a counting time of 1 s per step [76,77]. XRPD patterns
of these prepared CaCO3 were shown in Fig. 17 and their corresponding
crystallographic data including 2θ, d-spacing, hkl indices [241,242], and %
intensity are listed in Tables 9 and 10. The interplaner d-spacing is calculated
from the Bragg equation (2d sin θ ¼ nλ), where λ (¼1.5406 Å) is the wave-
length of the X-ray (Cu Kα radiator).
As shown in Fig. 17, the XRPD patterns of the three crystalline forms of
CaCO3 (calcite, aragonite, and vaterite), prepared according to the above
conditions, represent their pure phases with no other crystalline phases
detected. Also monohydrocalcite can be clearly identified by XRPD in a
phase-pure form. Ikaite form has only one major and sharp peak at 2θ of
about 17 and 2 minors around 35. However, amorphous can be distin-
guished from other forms by a halo broad peak (Fig. 17).
Table 9 The Crystallographic Data from the X-Ray Powder Diffraction Patterns of
Anhydrous Crystalline CaCO3 Forms Calcite, Aragonite, and Vaterite
Scattering Angle (2θ) d-Spacing (Å) hkl Indices Relative Intensity (%)
Calcite
23.0 3.8637 {012} 10.0
29.4 3.0356 {104} 100.0
35.9 2.4995 {110} 15.0
39.5 2.2796 {113} 20.0
43.1 2.0971 {202} 17.5
47.5 1.9126 {024} 17.5
48.5 1.8755 {018} 20.0
57.5 1.6015 {112} 7.5
Aragonite
21.1 4.2071 {110} 12.2
26.3 3.3834 {111} 100.0
27.3 3.2618 {021} 51.2
31.2 2.8689 {002} 4.9
33.2 2.6931 {012} 29.3
36.2 2.4821 {200} 34.1
37.3 2.4076 {031} 34.1
37.9 2.3708 {112} 22.0
38.5 2.3394 {130} 39.0
41.3 2.1833 {221} 17.1
43.0 2.1036 {220} 36.6
46.0 1.9722 {221} 87.8
48.3 1.8821 {202} 41.5
50.2 1.8159 {132} 24.4
52.5 1.7425 {113} 22.0
53.1 1.7233 {231} 17.1
Continued
70 M.M.H. Al Omari et al.
Table 9 The Crystallographic Data from the X-Ray Powder Diffraction Patterns of
Anhydrous Crystalline CaCO3 Forms Calcite, Aragonite, and Vaterite—cont'd
Scattering Angle (2θ) d-Spacing (Å) hkl Indices Relative Intensity (%)
Vaterite
21.0 4.2269 {004} 11.4
24.9 3.5730 {110} 75.0
27.0 3.2997 {112} 100.0
32.7 2.7364 {114} 84.1
44.5 2.0343 {211} 79.5
49.0 1.8575 {304} 25.0
50.0 1.8227 {300} 45.5
56.0 1.6408 {224} 22.7
Table 10 The Crystallographic Data from the X-Ray Powder Diffraction Patterns of
Hydrate CaCO3 Forms Monohydrocalcite (CaCO3H2O) and Ikaite (CaCO36H2O)
Scattering Angle (2θ) d-Spacing (Å) Relative Intensity (%)
Monohydrocalcite
20.8 4.2671 46.7
29.0 3.0765 46.7
32.0 2.7946 100.0
36.0 2.4927 13.3
38.0 2.3660 20.0
42.0 2.1495 40.0
45.5 1.9919 60.0
47.0 1.9318 53.3
52.0 1.7572 20.0
56.0 1.6408 20.0
Ikaite
17.5 5.0637 100.0
34.0 2.6347 40.0
34.5 2.5976 40.0
Calcium Carbonate 71
A
10
–20
–30
–40
–50
400 500 600 700 800
Temperature (°C)
B
100
90
Weight (%)
80
70
60
50
40
200 400 600 800 1000
Temperature (°C)
Figure 18 (A) The DSC and (B) TGA thermograms of CaCO3 calcite form recorded at a
heating rate of 10°C/min in an air flow.
CaCO3 into CaO. Both aragonite and vaterite forms show almost similar
DSC patterns to calcite with endothermic peaks at around 800 (heating rate
of 10°C/min per Ar gas) and 775°C (heating rate of 5°C/min per air flow),
respectively [244,245]. In the case of vaterite, two additional exothermic
peaks obtained at 481 and 488°C are unambiguously attributed to the trans-
formation of vaterite into calcite [245].
100 Exo 15
99 10
98 5
0
–5
96
–10
95
–15
94
–20
93 –25
92 Step 1 Step 2 –30
3.11 Spectroscopy
3.11.1 Ultraviolet/Visible Spectroscopy
The ultraviolet/visible (UV/VIS) spectrophotometry was used for direct
measurement of carbonate ions (CO2 3 ) concentration. For example,
CO23 absorbs light at wavelengths of less than 250 nm, this facilities
acidimetric titration with UV detection of most carbonate-containing nat-
ural waters and observe an increase in % transmittance [246]. Ariponnammal
reported that CaCO3 has three characterized wavelengths at 233.42, 254.91,
and 356.52 nm [247]. Furthermore, Nangare described direct UV/VIS
method for simultaneous determination of CaCO3 and aspirin in tablet dos-
age form [248]. Fig. 20 represents the UV/VIS spectrum of CaCO3 in 0.1
NaOH, recorded by a Shimadzu model 1700 double beam UV/VIS spec-
trophotometer, which shows a maximum at about 240 nm.
Calcium Carbonate 73
1490 856
1420 875
713 Calcite
1475 1418
866 Amorphous
00 00 0 0 0 0 0 0 0 0
90 85 80 75 70 65 60 55 50
0
20 15
Wavenumber (cm-1)
Figure 21 The FTIR spectra of different CaCO3 forms.
10,000
Calcite
Aragonite
Vaterite
B
Raman intensity (a.u.)
Calcite
Aragonite
Vaterite
the spectrum are a weak lattice vibration at 212 cm1 and traces of ν1 at
880 cm1 [254]. For amorphous CaCO3, the typical Raman spectrum is
shown in Fig. 23B. The amorphous character is initially confirmed by the
low intensity for all Raman bands when compared to other crystalline forms.
Furthermore, the main Raman band of the carbonate ion (ν1 at 1085 cm1)
is shifted toward lower wavenumbers (1079.87 cm1) and is broader than
for well-crystallized forms [255,256].
76 M.M.H. Al Omari et al.
Table 11 The Wavenumbers (cm1) and Vibrational Mode of the Raman Absorption
Bands of Different CaCO3 Forms
Form Wavenumber (cm21)
υ1 υ2 υ3 υ4
Lattice Symmetric Out-of-Plane Asymmetric In-Plane
Mode Stretching Bending Stretching Bending
Calcite 284 1086 — 1434 1747
Aragonite 151, 206, 275 1085 853, 910 1460, 1570 —
Vaterite 267, 300, 325 1074, 1090 874 1445, 1485, 1749
1550, 1595
Figure 23 The Raman spectra of (A) monohydrocalcite (CaCO3H2O) and (B) amorphous
CaCO3. The wavenumbers at 914.90 and 1371.26 cm1 correspond to Ne emission lines,
(C and D) ikaite (CaCO3 6H2O) at pressures from 0.14 to 4.08 GPa in a diamond anvil cell
in the ranges of 200–1100 and 2800–4000 cm1, respectively.
Calcium Carbonate 77
* * Vaterite
Intensity
* *
Monohydrocalcite
* * Amorphous
water. The peaks between 1.5 and 2.5 for the amorphous are due to traces of
a mobile water fraction containing hydroxide ions.
13
3.11.3.2 C MAS NMR Spectrum
Solid-state carbon NMR spectroscopy was performed on a Bruker ASX 400
spectrometer with a 100.623 MHz resonance frequency. For all solid-state
spectra, MAS was applied at a frequency of 4000 Hz in a 7-mm rotor and
direct excitation of 13C nuclei was induced by a single 30 degree pulse of
5.75 μs duration [76].
The 13C MAS NMR spectra of all hydrated and anhydrous CaCO3
forms are shown in Fig. 25. All samples show carbonate or hydrogen carbon-
ate peaks in the range of 156–174 ppm. The crystalline, water-free phases
calcite and aragonite show very narrow NMR peaks, whereas the water-
containing phases all showed broad peaks [76,261]. The linewidth of the
amorphous peak is large due to the disordered structure. There is a clear dis-
tinction between the regions of carbonate peaks (about 166–174 ppm) and
hydrogen carbonate peaks (below 166 ppm). The foregoing indicates that
the majority of the carbon atoms in amorphous are present as carbonate
and not as hydrogen carbonate, with some similarity of the chemical envi-
ronment to the highly hydrated phase ikaite.
Calcite
* *
* * Aragonite
* * Vaterite
PTFE
Monohydrocalcite
* *
Intensity
Ikaite
*
Amorphous
* *
For aragonite, there is a single peak at 169.9 ppm; for calcite, there is a
single peak in the range of 167.4–167.9 ppm with a full width at half max-
imum (fwhm) of 1–1.1 ppm; for vaterite containing 9% calcite, there is a
single peak at 168.7 ppm (fwhm 1.9 ppm). Ikaite shows a slow decomposi-
tion during the NMR experiment, even if it is carried out at 20°C as it
partially converts to calcite (confirmed by X-ray powder diffraction) [76].
4. METHODS OF ANALYSIS
4.1 Compendial Methods
4.1.1 Calcium Carbonate
CaCO3 monograph is listed in the Eur. Ph. [2], United States Pharmaco-
peia–National Formulary (USP–NF) [1], and JP [216]. Table 12 shows a
summary of its specifications and methods of analysis.
Magnesium Dissolve 1.0 g in 12 mL of dilute HCl R. Boil Mix 1.0 g with 35 mL of water. Carefully add 3 mL of Dissolve 1.0 g in 20 mL of water and
and alkali the solution for about 2 min and add 20 mL of HCl, heat the solution, and boil for 1 min. Rapidly add 10 mL dilute HCl, boil, neutralize with
metals water R, 1 g of ammonium chloride R and 40 mL of oxalic acid TS and stir vigorously until ammonia TS, and add ammonium
0.1 mL of methyl red solution R. Add dilute precipitation is well established. Add immediately to the oxalate TS until precipitation of calcium
ammonia R1 until the color of the indicator warm mixture 2 drops of methyl red TS and then 6 N oxalate is completed. Heat the mixture
changes and then 2 mL in excess. Heat to ammonium hydroxide, dropwise, until the mixture is just on a water bath for 1 h, cool, dilute with
boiling and add 50 mL of hot ammonium alkaline. Cool to room temperature, transfer to a 100-mL water to 100 mL, shake well, and filter.
oxalate solution R. Allow to stand for 4 h, dilute graduated cylinder, dilute with water to 100 mL, mix, and To 50 mL of the filtrate add 0.5 mL of
to 100 mL with water R, and filter through a allow to stand for 4 h or overnight. Filter, and to 50 mL of H2SO4, evaporate to dryness, and ignite
suitable filter. To 50 mL of the filtrate add the clear filtrate in a platinum dish add 0.5 mL of H2SO4, at 600°C to constant mass (the mass of the
0.25 mL of H2SO4 R. Evaporate to dryness on a and evaporate the mixture on a steam bath to a small residue is not more than 5 mg)
water bath and ignite to constant mass at 600°C. volume. Carefully heat over a free flame to dryness and
The residue weighs not more than 7.5 mg continue heating to complete decomposition and
(NMT 1.5%) volatilization of ammonium salts. Finally, ignite the
residue to constant weight (NMT 1.0%; the weight of the
residue is NMT 5 mg)
Heavy metals 12 mL of solution S complies with limit test A Mix 1.0 g with 5 mL of water, slowly add 8 mL of 3 N Mix 2.0 g with 5 mL of water, slowly add
for heavy metals. Prepare the standard using lead HCl, and evaporate on a steam bath to dryness. Dissolve 6 mL of dilute HCl, and evaporate on a
standard solution (1 ppm Pb) R the residue in 20 mL of water, filter, and add water to the water bath to dryness. Dissolve the
(see Section 2.4.8, Test A) (NMT 20 ppm) filtrate to make 25 mL h231i (NMT 20 ppm) residue in 50 mL of water, and filter. To
25 mL of the filtrate add 2 mL of dilute
acetic acid, 1 drop of ammonia TS and
water to make 50 mL, and perform the
test using this solution as the test solution.
Prepare the control solution as follows:
evaporate 3 mL of HCl on a water bath
to dryness, add 2 mL of dilute acetic acid,
2.0 mL of standard lead solution and
water to make 50 mL h1.07i
(NMT 20 ppm)
Mercury — Mercury stock solution and Standard Mercury solution: Proceed —
as directed in Mercury h261i
Standard solution: Proceed as directed in Mercury h261i,
except use 3 mL of HCl instead of 3 mL of H2SO4
Sample stock solution: 4.0 g in a 100-mL beaker, and
cautiously dissolve in 14 mL of 6 N HCl
Sample solution: Proceed as directed in Mercury h261i
using the Sample stock solution, except use 3 mL of HCl
instead of 3 mL of H2SO4
Analysis samples: Standard solution and sample solution
proceed as directed in Mercury h261i method IIa
(NMT 0.5 ppm)
Fluoride — [Prepare and store all solutions in plastic containers] —
Solution A: 294 mg/mL of sodium citrate dentate in water
Standard solution: Combine 20.0 mL of the standard stock
solution (1.11 mg/mL of USP NaF RS in water) with
50.0 mL of solution A, and dilute with water to 100.0 mL
Electrode system: Use a fluoride-specific ion—indicating an
electrode and a silver–silver chloride reference electrode
connected to a pH meter capable of measuring potentials
with a minimum reproducibility of 0.2 mV h791i
Standard response line: Transfer 50.0 mL of solution A and
4.0 mL of HCl to a beaker, and add water to make
100 mL. Add a plastic-coated stirring bar, insert the
electrodes into the solution, stir for 15 min, and read the
potential (mV). Continue stirring, and at 5-min intervals
add 100, 100, 300, and 500 μL of the standard solution,
reading the potential 5 min after each addition. Plot
the logarithms of the cumulative fluoride ion
concentrations (0.1, 0.2, 0.5, and 1.0 μg/mL)
vs potential (mV)
Analysis: Transfer 2.0 g to a beaker containing
a plastic-coated stirring bar, add 20 mL of
water and 4.0 mL of HCl, and stir until dissolved.
Continued
Table 12 The Summary of the Compendial Methods of CaCO3—cont'd
Test Eur. Ph. USP-NF JP
Maulood et al. used back titration for CaCO3 determination in soil sam-
ples using 0.5 N HCl to dissolve the samples, followed by back titration with
0.2 N NaOH [279]. The results were found to be comparable with those
obtained using calcimetric method.
4.2.2 Complexometry
Ethylenediaminetetraacetic acid (EDTA) is used as a complexing agent to
determine CaCO3 in its pure form [1,2,216] or in different dosage forms
including tablets [262], chewable tablets [263], and oral suspension [265].
Full detailed procedures are mentioned in Tables 12–15.
Previously, micro- and macrodeterminations of serum Ca by direct titra-
tion with EDTA with ammonium purpurate as the indicator [280,281]. The
end point is determined by changing the indicator color to purple [280] or
graphically from spectrophotometric readings at 620 nm taken during the
titration [281]. Also Beale and Bostrom used a microtitration of Ca in the
presence of Mg in serum and urine, with EDTA as titrant and Corinth
Ca (Plasmocorinth B) as indicator [282].
Garvey et al. analyzed Ca in dietary supplements using complexometric
titration with EDTA and then, following ion exchange of the Ca ion present
for hydronium ion, by acid–base titration with NaOH [283]. Also statistical
comparison of both methods was adopted.
94 M.M.H. Al Omari et al.
4.2.3 Oxidometry
In direct oxidometric determination of Ca in solution containing also Mg,
phosphates and small amounts of Fe, or in the ash of food or feces has been
reported [284]. The method is based upon the formation of calcium oxalate,
followed by immediate titration of oxalate in acid media with standard
K2MnO4. The microdetermination of Ca in whole blood, plasma, serum,
urine, and stools was also performed by direct precipitation of calcium oxa-
late and then titration with 0.01 N K2MnO4 [285,286]. Furthermore, an
improvement in the method by using new washing solution for calcium
oxalate precipitation of 2% NH3 in equal parts of alcohol, ether, and water
is introduced to prevent flotation and permit washing of the precipitate
without appreciable loss of Ca [287].
4.2.4 Amperometry
Indirect amperometric titration of Ca using dropping mercury electrode has
been reported [288]. The method is based upon the precipitation of Ca as
picrolonate and followed by back titration of excess picrolonate with meth-
ylene blue.
4.2.5 Spectrophotometry
Sweetser and Bricker were the first to use spectrophotometric measurements
to determine the end points of EDTA titrations, which they applied to Ca
and Mg in two stages of analysis [289].
4.2.6 Coulometry
Caughey and Barcelona used this technique for the determination of total
inorganic carbon (TIC) using 2 N HClO4 with the UIC 5130/5011 mod-
ules coulometer [290].
Coulometry is still used, more than 25 years later, by the Integrated
Ocean Drilling Program for shipboard analysis of CaCO3 concentration
[291]. M€ orth and Backman described a practical approach for acquiring
accurate measurements of the carbonate content in sediments by using an
UIC Inc. coulometer [292]. The coulometer readings are absolute; ie, the
total amount of available carbon is converted by HCl to CO2 gas and the
output reading (counts) of the instrument is in μg C. In this work, they
investigated the effect of sample weight, sampling tool, preparation proce-
dure, and use of a multipoint regression analysis on the precision of the
method.
Calcium Carbonate 95
Dabke et al. used the coulometric back-titration method for the deter-
mination of CaCO3 in antacid tablets [293]. The sample was dissolved in
excess acid and the remaining acid was back titrated against the coulomet-
rically generated OH ions. The amount of acid neutralized by CaCO3 was
determined from the difference in the anodic and cathodic charge.
4.4.2 Colorimetry
An indirect colorimetric method for measuring blood Ca has been devel-
oped, which is based upon the precipitation of Ca as phosphate, and the
determination of the latter by the MoO3 colorimetric procedure [298].
96 M.M.H. Al Omari et al.
4.4.4 Fluorometry
Lerga and O’Sullivan reported a fluorometric method for a simultaneous
combined determination for Ca and Mg (water hardness) using a
98 M.M.H. Al Omari et al.
4.5.2 Polarography
Cohn and Kolthoff used picrolonic acid to precipitate Ca as calcium
picrolonate and then the excess of the acid is determined polarographically
without filtering the solutions. The method yields good result in the pres-
ence of relatively large amounts of Na, K, NH3, Mg, sulfate, and phosphate
in the solutions [344]. Another indirect polarographic determination of
Ca by chloranilic acid has been also reported [345]. Ca was determined
by precipitating as chloranilate complex, followed by measuring the polar-
ographic diffusion current of the residual chloranilic acid without need of
separation of the solid complex. The interference of different cations as a
function of their concentration has been investigated. Fleet et al. also
reported indirect polarographic method based on the decrease in the height
of the anodic polarographic waves of EDTA and ethylene glycol-bis-(β-
aminoethylether)-NNN 0 N 0 -tetraacetic acid [346]. Different complexing
Calcium Carbonate 101
4.5.3 Voltammetry
In direct measurement of Ca by differential pulse stripping voltammetry has
been achieved by using hanging electrolyte drop electrode [348]. The
method is based on the transfer of Ca ions from water to nitrobenzene facil-
itated by the complex formation with the macrocyclic polyether
diamide,7,19-dibenzyl-2,3-dimethyl-7,19-diazo-1,4,10,13,16-pentaoxacy-
cloheneicosane-6,20-dione. Wang et al. described a sensitive adsorptive
stripping procedure for trace measurement Ca using their chelates with
the dihydroxyazo dye solochrome violet RS [349].
Kim used a water-soluble calix[4]arene-diquinone-diacid (CDA) to
quantify Ca in aqueous solution by forming a complex with Ca ions
[350]. Fig. 26 shows the redox changes of CDA as a function of Ca concen-
tration in aqueous buffered solution of pH 7.4.
Potential/V vs Ag/AgCl
–0.6 –0.4 –0.2 0.0 0.2 0.4 0.6
2 µA
Increase of [Ca2+]
5. STABILITY
5.1 Crystal Phase Transformation
Calcite, stable anhydrous form of CaCO3, undergoes a series of structural
transitions toward denser of calcite II–IV phases with increasing pressure
[108,110,111]. In addition to the aforementioned calcite forms, there exists
a denser form calcite VI that can be formed using shock compression exper-
iments [112]. At even higher pressures (>100 kbar), calcite is known to
undergo yet another phase transition, known as calcite IV [114–116].
However, monohydrocalcite, the hydrate form of calcite, is not stable
thermodynamically and will transform into other crystal phases upon the loss
of crystalline water (eg, calcite and aragonite) [78,240]. In addition, low con-
tent of Mg in aqueous solution will lead to its transformation to aragonite
over 25 days at ambient temperatures [373,374].
Aragonite, metastable anhydrous form of CaCO3, will remain unaltered
for tens of millions of years in dry conditions at temperatures below 400°C.
If water is present, however, aragonite will convert to calcite in a matter of
months due to its greater solubility in water. The difference in solubility is
one of the reasons why aragonite is not as common in geological beds and is
rarely found outside of organically controlled systems [225]. At standard
temperature and pressure, aragonite is thermodynamically unstable and
tends to alter to calcite [375]. At high pressure, it becomes the stable phase
[117]. A postaragonite phase in CaCO3 at a pressure of 40 GPa and a number
Calcium Carbonate 105
7. PHARMACOLOGY
7.1 Pharmacokinetics
7.1.1 Absorption
Ca is endogenously occurring substance within the body. It is actively
absorbed into the body and its level is controlled by various Ca homeostasis
mechanisms [399]. After oral administration, 18–40% of Ca is absorbed from
the small intestine by active transport and passive diffusion. Active absorp-
tion of Ca is highly dependent on vitamin D, and vitamin D deficiency
decreases the absorption of Ca [399,400]. Absorption of Ca is dose depen-
dent, with fractional absorption being highest when at doses up to 500 mg.
Absorption of Ca is also dependent on pH (reduced in alkaline), body size,
estrogen status, vitamin D status, age, and genetic polymorphisms. The
absorption of Ca from CaCO3 is increased when taken with food [399,400].
Different Ca salts show different levels of absorption. For example,
calcium citrate is more bioavailable than CaCO3 [401–403]. Hanzlik et
al. showed that calcium formate is clearly superior to both CaCO3 and cal-
cium citrate in ability to deliver Ca to the blood stream after oral adminis-
tration [404].
Zhao et al. compared the Ca bioavailability from CaCO3-fortified
soymilk (CCSM) and tricalcium phosphate-fortified soymilk (TCPSM)
with cow’s milk in young healthy women using ICP-MS technique
[405]. They found that the fractional Ca absorption in CCSM did not differ
from that of cow’s milk, but both were higher than that of TCPSM.
Ayed and Thannoun studied the effect of phosphorus on the bioavail-
ability of Ca [406]. They concluded that CaCO3-based diet containing
0.19% Ca with 1.5:1 Ca to phosphorus ratio may give high Ca bioavailability
for growing rats which was considered as standard (control) diet for other
diet supplement. Kressel et al. showed that calcium lactate citrate and cal-
cium lactate malate may offer a very good choice for the fortification
of beverages to increase the daily Ca intake comparing with CaCO3 and
calcium gluconate [407]. The two former salts have higher water
solubility with a satisfactory Ca content and availability comparing with
the later salts.
Calcium Carbonate 109
Mueller et al. showed that daily intake of 1200 mg of Ca, as CaCO3, and
800 IU of vitamin D3, with a new chewable tablet increased the intestinal
Ca absorption compared to the results from the placebo [408].
Meiron et al. compared the solubility and fractional absorption of a
stabilized amorphous CaCO3 without and with the presence of chitosan
and crystalline CaCO3 [378]. The results demonstrated that the amorphous
is more soluble than the crystalline form. Fractional absorption was evaluated
by intrinsically labeling CaCO3 preparations with 45Ca, orally administrated
to rats using gelatin capsules. The results revealed that Ca absorption
from the amorphous preparations is up to 40% higher than from the crys-
talline form.
It was reported that Ca from nanoparticulate CaCO3 is more readily
absorbed than the microparticulate form in mice study. A slight increase
in bioavailability (by 38%) of the nanosized CaCO3 by comparison with
the micronized form in humans indicates that the absorption levels of
Ca from both forms are almost similar [4].
7.1.2 Distribution
Skeletal Ca accounts for 99% of the Ca in the body. Of the remaining 1%,
40–45% is bound to proteins, primarily albumin. About 5–10% is
complexed to phosphate, citrate, or other anions. Approximately 50% of
Ca in the serum is in the physiologically active ionized form [399,400].
7.1.3 Metabolism
As an endogenously occurring substance, Ca is not metabolized in the
traditional pharmacokinetic sense [399].
7.1.4 Elimination
Unabsorbed Ca from the small intestine is excreted in the feces. Renal
excretion depends largely on glomerular filtration and Ca tubular
reabsorption with more than 98% of Ca reabsorbed from the glomerular
filtrate, with only 2% lost as obligatory Ca loss. This process is regulated
by active vitamin D and parathyroid hormone (PTH) [399,400]. Excess
carbonate is excreted as CO2 via respiration [4].
7.3 Pharmacodynamics
Ca administration decreases the elevated rate of bone turnover typically
seen in postmenopausal women with osteoporosis. In randomized, pla-
cebo-controlled studies in postmenopausal women, Ca administration
(500–1600 mg) decreased biochemical markers of bone turnover, including
urine N-telopeptide, urine-free pyridinoline (markers of bone resorption),
alkaline phosphatase, and osteocalcin (markers of bone formation) relative to
placebo-treated women. Ca administration may transiently increase levels of
serum Ca with compensatory reductions in serum PTH and an increase in
urinary Ca. However, urinary and serum Ca levels usually remain within the
normal reference range [400].
7.4 Toxicities
Different toxicity studies have been carried out with CaCO3 in rats, mice,
and cats. They have overall not demonstrated any evidence of toxicity attrib-
utable to CaCO3 [4].
Recommendations for daily dietary Ca intake that range from 400 to
1200 mg/day depending on age and gender have been issued by governmen-
tal and nongovernmental organizations in many countries [4,399,400,404].
Total daily intake of Ca above 1500 mg has not demonstrated additional bone
benefits, while daily intake above 2000 mg has been associated with increased
risk of adverse effects, including hypercalcemia and kidney stones [399,400].
However, intake of dietary Ca equivalent to 250 or 500 mg/kg bw/day
in rats leaded to nephrocalcinosis, while in Beagle dogs at the same doses did
not show any signs of nephrocalcinosis [4]. Nephrocalcinosis was also not
observed in a recent combined repeat dose oral toxicity/reproduction/
developmental toxicity screening study with CaCO3 (having a particle size
of 60–100 nm) carried out in Wistar rats at dose levels of up to 1000 mg/kg
bw/day for up to 48 days. The only changes seen in this study were slight but
statistically significant hematological and biochemical effects in males receiv-
ing 1000 mg/kg bw/day, and significant reductions in plasma phosphate
levels in all male-treated groups. No evidence of toxicity was reported in
a study in which mice were administered CaCO3 (described as nano
CaCO3) by oral gavages at dose levels up to 1300 mg/kg bw/day [4].
Calcium Carbonate 111
REFERENCES
[1] United States Pharmacopeia Convention, United States 38/National Formulary 33
(USP 38/NF 33), Calcium Carbonate, vol. 2, USP Convention Inc., Maryland, 2015.
[2] European Pharmacopeia (Eur. Ph.), Calcium Carbonate, eighth ed., European
Directorate for the Quality of Medicines, Strasbourg, France, 2015.
[3] European Medicines Agency (EMA), CMPH/EMA Opinion on Calcitugg® and
Associated Names INN: Calcium Carbonate, Background Information, 2003.
http://www.ema.europa.eu/docs/en_GB/document_library/Referrals_document/
Calcitugg_30/WC500010592.pdf (accessed date January 2015).
[4] European Food Safety Authority (EFSA), Scientific opinion on re-evaluation of cal-
cium carbonate (E 170) as a food additive, EFSA J. 9 (2011) 2318. http://www.efsa.
europa.eu/en/efsajournal/doc/2318.pdf (accessed date January 2015).
[5] M.J. O’Neil, P.E. Heckelman, C.B. Koch, K.J. Roman, C.M. Kenny, M.R. D’Arecca,
Calcium carbonate (1697), in: The Merck Index: An Encyclopedia of Chemicals, Drugs,
and Biologicals, 14th ed., Merck & Co. Inc., Whitehouse Station, NJ, 2006.
[6] Drugs, Calcium Carbonate Brand Names. http://www.drugs.com/comments/
calcium-carbonate (accessed date January 2015).
[7] Electronic Medicines Compendium (eMC), Calcium Carbonate. https://www.
medicines.org.uk/emc/search (accessed date January 2015).
[8] Jordan Encyclopedia Drugs, Calcium Carbonate. http://drugsjo.blogspot.com
(accessed date January 2015).
[9] United States Pharmacopeia Convention, United States Pharmacopeia 38/National
Formulary 33 (USP 38/NF 33), Description and Solubility, vol. 1, USP
Convention Inc., Maryland, 2015.
[10] M. Pidwirny, Carbon Cycle, 2012. http://www.eoearth.org/view/article/150923
(accessed date January 2015).
[11] Department of Geology, Maryland University, Carbonate Sediments and Chemistry.
http://www.geol.umd.edu/jmerck/geol342/lectures/14.html (accessed date January
2015).
[12] Department of Geology, University of Puerto Rico, Sediment Patterns. http://
geology.uprm.edu/Morelock/margsedptt.htm (accessed date January 2015).
[13] A. Lees, Possible influence of salinity and temperature on modern shelf carbonate
sedimentation, Mar. Geol. 19 (1975) 159–198.
[14] C.S. Nelson, An introductory perspective on non-tropical shelf carbonates, Sediment.
Geol. 60 (1988) 3–12.
[15] D. Beruto, M. Giordan, Calcite and aragonite formation from aqueous calcium hydro-
gen carbonate solutions: effect of induced electromagnetic field on the activity of
CaCO3 nuclei precursors, J. Chem. Soc. Faraday Trans. 89 (1993) 2457–2461.
[16] Online Medical Dictionary (WebMD), Natural Oyster Shell Calcium, 2015. http://
www.webmd.com/drugs/2/drug-16642/natural-oyster-shell-calcium-ora (accessed
date January 2015).
[17] R.P. Heaney, C.M. Weaver, S.M. Hinders, B. Martin, P.T. Packard, Absorbability of
calcium from Brassica vegetables: broccoli, bok choy, and kale, J. Food Sci. 58 (1993)
1378–1380.
[18] R.L. Folk, Practical petrographic classification of limestones, AAPG Bull. 43 (1959)
1–38.
[19] R.L. Folk, Spectral subdivision of limestone types, in: W.E. Ham (Ed.), Classification
of Carbonate Rocks, AAPG Memoir No. 1, Tulsa, OK, 1962.
[20] R.J. Dunham, Classification of carbonate rocks according to depositional texture,
in: W.E. Ham (Ed.), Classification of Carbonate Rocks, AAPG Memoir No. 1,
Tulsa, OK, 1962.
Calcium Carbonate 113
[21] A.F. Embry, J.E. Klovan, A Late Devonian reef tract on northeastern Banks Island,
NWT, Bull. Can. Petroleum Geol. 19 (1971) 730–781.
[22] R. Riding, Structure and composition of organic reefs and carbonate mud mounds,
concepts and categories, Earth Sci. Rev. 58 (2002) 163–231.
[23] V.P. Wright, A revised classification of limestones, Sediment. Geol. 76 (1992) 177–185.
[24] W.M. Ahr, Geology of Carbonate Reservoirs: The Identification, Description, and
Characterization of Hydrocarbon Reservoirs in Carbonate Rocks, John Wiley &
Sons Inc., New Jersey, 2008.
[25] Global Ocean Exploration Inc, Ocean Acidification in the Western Arctic Expedition
Log, 2011. http://arcticocean.globaloceanexploration.com/?p¼104 (accessed date
January 2015).
[26] K. Caldeira, M.E. Wickett, Oceanography: anthropogenic carbon and ocean pH,
Nature 425 (2003) 365.
[27] S. Andersen, E.S. Grefsrud, T. Harboe, Effect of increased pCO2 level on early shell
development in great scallop (Pecten maximus Lamarck) larvae, Biogeosciences
10 (2013) 6161–6184.
[28] I.M. Weiss, N. Tuross, L. Addadi, S. Weiner, Mollusc larval shell formation: amor-
phous calcium carbonate is a precursor phase for aragonite, J. Exp. Zool.
293 (2002) 478–491.
[29] M. Kudo, J. Kameda, K. Saruwatari, N. Ozaki, K. Okano, H. Nagasawa, T. Kogure,
Microtexture of larval shell of oyster, Crassostrea nippona: a FIB-TEM study, J. Struct.
Biol. 169 (2010) 1–5.
[30] P. Barros, P. Sobral, P. Range, L. Chı́charo, D. Matias, Effects of sea-water acidifica-
tion on fertilization and larval development of the oyster Crassostrea gigas, J. Exp. Mar.
Biol. Ecol. 440 (2013) 200–206.
[31] J.C. Orr, V.J. Fabry, O. Aumont, L. Bopp, S.C. Doney, R.A. Feely, A. Gnanadesikan,
N. Gruber, A. Ishida, F. Joos, R.M. Key, K. Lindsay, E. Maier-Reimer, R. Matear,
P. Monfray, A. Mouchet, R.G. Najjar, G.-K. Plattner, K.B. Rodgers, C.L. Sabine,
J.L. Sarmiento, R. Schlitzer, R.D. Slater, I.J. Totterdell, M.-F. Weirig,
Y. Yamanaka, A. Yoo, Anthropogenic ocean acidification over the twenty-first
century and its impact on calcifying organisms, Nature 437 (2005) 681–686.
[32] J. Raven, K. Caldeira, H. Elderfield, O. Hoegh-Guldberg, P. Liss, U. Riebesell,
J. Sheperd, C. Turley, A. Watson, Ocean Acidification due to Increasing Atmospheric
Carbon Dioxide, The Royal Society, The Clyvedon Press Ltd, Cardiff, UK, 2005.
[33] S. Marshak, Essentials of Geology, third ed., W.W. Norton & Company, New York,
2009.
[34] L.A. Melim, H. Westphal, P.K. Swart, G.P. Eberli, A. Munnecke, Questioning
carbonate diagenetic paradigms: evidence from the Neogene of the Bahamas, Mar.
Geol. 185 (2002) 27–53.
[35] D. Archer, An atlas of the distribution of calcium carbonate in sediments of the deep
sea, Glob. Biogeochem. Cycles 10 (1996) 159–174.
[36] D. Archer, A data driven model for the lysocline, Glob. Biogeochem. Cycles 10 (1996)
511–526.
[37] J.I. Hedges, F.S. Hu, A.H. Devol, H.E. Hartnett, E. Tsamakis, R.G. Keil, Sedimentary
organic matter preservation: a test for selective degradation under oxic conditions, Am.
J. Sci. 299 (1999) 529–555.
[38] D.E. Archer, J.L. Morford, S.R. Emerson, A model of suboxic sedimentary diagenesis
suitable for automatic tuning and gridded global domains, Glob. Biogeochem. Cycles
16 (2002) 17-1–17-21.
[39] J.W. Morse, R.A. Berner, Dissolution kinetics of calcium carbonate in seawater: II. A
kinetic origin for the lysocline, Am. J. Sci. 274 (1972) 638–647.
114 M.M.H. Al Omari et al.
[40] J.W. Morse, Dissolution kinetics of calcium carbonate in sea water: VI. The near--
equilibrium dissolution kinetics of calcium carbonate-rich deep sea sediments, Am.
J. Sci. 278 (1978) 344–353.
[41] R.S. Keir, The dissolution kinetics of biogenic calcium carbonates in seawater,
Geochim. Cosmochim. Acta 44 (1980) 241–252.
[42] B. Hales, S. Emerson, Calcite dissolution in sediments of the Ontong-Java Plateau: in
situ measurements of pore water O2 and pH, Glob. Biogeochem. Cycles 10 (1996)
527–541.
[43] J.W. Morse, Formation and diagenesis of carbonate sediments, in: D. Heinrich, K. Karl
(Eds.), Treatise on Geochemistry, Elsevier Ltd, Amsterdam, Netherlands, 2003.
[44] A. Sigel, H. Sigel, R.K.O. Sigel, Biomineralization: From Nature to Application,
Metal Ions in Life Sciences, vol. 4, John Wiley & Sons Inc., New Jersey, 2008.
[45] J. Kazmierczak, S. Kempe, W. Altermann, Microbial origin of Precambrian carbon-
ates: lessons from modern analogues, in: P.G. Eriksson, W. Altermann, D.R. Nelson,
W.U. Müller, O. Catuneanu (Eds.), The Precambrian Earth: Tempos and Events,
Elsevier, Amsterdam, Netherlands, 2004.
[46] R.S. Harmon, C.M. Wicks, D.C. Ford, W.B. White, Perspectives on Karst Geomor-
phology, Hydrology, and Geochemistry: A Tribute Volume to Derek C Ford and
William B White, Geological Society of America, Colorado, 2006.
[47] J.W. Morse, R.S. Arvidson, A. Lüttge, Calcium carbonate formation and dissolution,
Chem. Rev. 107 (2007) 342–381.
[48] S. Lindskog, Structure and mechanism of carbonic anhydrase, Pharmacol. Ther.
74 (1997) 1–20.
[49] K. Simkiss, K. Wilbur, Biomineralization, Cell Biology and Mineral Deposition,
Academic Press, California, 1989.
[50] W.E.G. Müller, U. Schlossmacher, H.C. Schr€ oder, I. Lieberwirth, M. Korzhev,
M. Neufurth, X. Wang, G. Glasser, Enzyme-accelerated and structure-guided crystal-
lization of calcium carbonate: role of the carbonic anhydrase in the homologous
system, Acta Biomater. 10 (2014) 450–462.
[51] D. Gebauer, A. V€ olkel, H. C€ olfen, Stable prenucleation calcium carbonate clusters,
Science 322 (2008) 1819–1822.
[52] E.M. Pouget, P.H.H. Bomans, J.A.C.M. Goos, P.M. Frederik, G. With,
N.A.J.M. Sommerdijk, The initial stages of template-controlled CaCO3 formation
revealed by cryo-TEM, Science 323 (2009) 1455–1458.
[53] D.E. Jacob, A.L. Soldati, R. Wirth, J. Huth, U. Wehrmeister, W. Hofmeister, Nano-
structure, composition and mechanisms of bivalve shell growth, Geochim.
Cosmochim. Acta 72 (2008) 5401–5415.
[54] X. YiDong, X. XuRong, T. RuiKang, Influence of viscosity on the phase transfor-
mation of amorphous calcium carbonate in fluids: an understanding of the medium
effect in biomimetic mineralization, Sci. China Chem. 53 (2010) 2208–2214.
[55] J. Schlomach, K. Quarch, M. Kind, Investigation of precipitation of calcium carbonate
at high supersaturations, Chem. Eng. Technol. 29 (2006) 215–220.
[56] J.-P. Andreassen, Formation mechanism and morphology in precipitation of vaterite-
nano-aggregation or crystal growth, J. Cryst. Growth 274 (2005) 256–264.
[57] B. Cheng, M. Lei, J. Yu, X. Zhao, Preparation of monodispersed cubic calcium
carbonate particles via precipitation reaction, Mater. Lett. 58 (2004) 1565–1570.
[58] J. Yu, M. Lei, B. Cheng, X. Zhao, Effects of PAA additive and temperature
on morphology of calcium carbonate particles, J. Solid State Chem. 177 (2004)
681–689.
[59] H. C€ olfen, L. Qi, A systematic examination of the morphogenesis of calcium carbonate
in the presence of a double-hydrophilic block copolymer, Chem. Eur. J. 7 (2001)
106–116.
Calcium Carbonate 115
[60] J.A. Wojtowicz, Calcium carbonate precipitation potential, J. Swim. Pool Spa Ind.
2 (2001) 23–29.
[61] L. Plummer, N.E. Busenberg, The solubilities of calcite, aragonite and vaterite in
CO2–H2O solutions between 0 and 90 °C, and an evaluation of the aqueous model
for the system CaCO3–CO2–H2O, Geochim. Cosmochim. Acta 46 (1982)
1011–1040.
[62] L. Brečević, D. Kralj, On calcium carbonates: from fundamental research to applica-
tion, Croat. Chem. Acta 80 (2007) 467–484.
[63] M. Dittrich, P. Kurz, B. Wehrli, The role of autotrophic picocyanobacteria in calcite
precipitation in an oligotrophic lake, Geomicrobiol. J. 21 (2004) 45–53.
[64] M. Dittrich, M. Obst, Are picoplankton responsible for calcite precipitation in lakes?
Ambio 33 (2004) 559–564.
[65] M.A. Borowitzka, Calcification in algae: mechanisms and the role of metabolism, Crit.
Rev. Plant Sci. 6 (1987) 1–45.
[66] C.R. Heath, B.C.S. Leadbeater, M.E. Callow, Effect of inhibitors on calcium carbon-
ate deposition mediated by freshwater algae, J. Appl. Phycol. 7 (1995) 367–380.
[67] R.H. Crist, J.R. Martin, D. Carr, J.R. Watson, H.J. Clarke, Interaction of metals and
protons with algae. 4. Ion exchange vs adsorption models and a reassessment of
Scatchard plots, ion-exchange rates and equilibria compared with calcium alginate,
Environ. Sci. Technol. 28 (1994) 1859–1866.
[68] E. Kiefer, L. Sigg, P. Schosseler, Chemical and spectroscopic characterization of algae
surfaces, Environ. Sci. Technol. 1 (1997) 759–764.
[69] W. Bao, H. Li, Y. Zhang, Preparation of monodispersed aragonite microspheres via a
carbonation crystallization pathway, Cryst. Res. Technol. 44 (2009) 395–401.
[70] M. Kakizawa, A. Yamasaki, Y. Yanagisawa, A new CO2 disposal process via artificial
weathering of calcium silicate accelerated by acetic acid, Energy 26 (2001) 341–354.
[71] C.N. Fredd, H.S. Fogler, The influence of equilibrium reactions on the kinetics of
calcite dissolution in acetic acid solutions, Chem. Eng. Sci. 53 (1998) 3863–3874.
[72] E.D. Economou, T.C. Vaimakis, E.M. Papamichae, The kinetics of dissolution of the
carbonate minerals of phosphate ores using dilute acetic acid solutions: the case of pH
range from 3.96 to 6.40, J. Colloid Interface Sci. 245 (2002) 133–141.
[73] S. Teir, S. Eloneva, C. Fogelholm, R. Zevenhoven, Dissolution of steelmaking slags in
acetic acid for precipitated calcium carbonate production, Energy 32 (2007) 528–539.
[74] G. Montes-Hernandez, F. Renard, N. Geoffroy, L. Charle, J. Pironon, Calcite pre-
cipitation from CO2–H2O–Ca(OH)2 slurry under high pressure of CO2, J. Cryst.
Growth 308 (2007) 228–236.
[75] H. Tang, J. Yu, X. Zhao, H.L.D. Ng, Creation of calcite hollow microspheres with
attached bundles of aragonite needles, Cryst. Res. Technol. 43 (2008) 473–478.
[76] H. Nebel, M. Neumann, C. Mayer, M. Epple, On the structure of amorphous calcium
carbonates—a detailed study by solid-state NMR spectroscopy, Inorg. Chem.
47 (2008) 7874–7879.
[77] H. Nebel, M. Epple, Continuous preparation of calcite, aragonite and vaterite, and of
magnesium-substituted amorphous calcium carbonate (Mg-ACC), Z. Anorg. Allg.
Chem. 634 (2008) 1439–1443.
[78] M. Neumann, M. Epple, Monohydrocalcite and its relationship to hydrated amor-
phous calcium carbonate in biominerals, Eur. J. Inorg. Chem. 2007 (2007) 1953–1957.
[79] C.A. Weiss, K. Torres-Cancel, R.D. Moser, P.G. Allison, E.R. Gore,
M.Q. Chandler, P.G. Malone, Influence of temperature on calcium carbonate poly-
morph formed from ammonium carbonate and Ca(CH3COO)2, J. Nanotech. Smart
Mater 1 (2014) 1–6.
[80] L.F. Wang, I. Sondi, E. Matijevic, Preparation of uniform needle-like aragonite par-
ticles by homogeneous precipitation, J. Colloid Interface Sci. 218 (1999) 545–553.
116 M.M.H. Al Omari et al.
[81] S.R. Kamhi, On the structure of vaterite CaCO3, Acta Crystallogr. 16 (1963)
770–772.
[82] I. Gaus, M. Azaroual, Reactive transport modeling of the impact of CO2 injection on
the clayey cap rock at Sleipner (North Sea), Chem. Geol. 217 (2005) 319–337.
[83] F. Gherardi, T. Xu, Numerical modeling of self-limiting and self-enhancing caprock
alteration induced by CO2 storage in a depleted gas reservoir, Chem. Geol. 244 (2007)
103–129.
[84] B. Cantucci, G. Montegrossi, Geochemical modeling of CO2 storage in deep
reservoirs: the Weyburn project (Canada) case study, Chem. Geol. 265 (2009)
181–197.
[85] S.G. Sayegh, F.F. Kraus, Rock/fluid interactions of carbonated brines in sandstone res-
ervoir: Pembina Cardium, Alberta, Canada, SPE Form. Eval. 5 (1990) 399–405.
[86] K.A. Bowker, P.J. Shuler, Carbon dioxide injection and resultant alteration of the
Weber Sandstone, Rangely Field, Colorado, AAPG Bull. 75 (1991) 1489–1499.
[87] N. Assayag, J. Matter, Water–rock interactions during a CO2 injection field-test:
implications on host rock dissolution and alteration effects, Chem. Geol. 265
(2009) 227–235.
[88] L.A. Warren, P.A. Maurice, Microbially mediated calcium carbonate precipitation:
implications for interpreting calcite precipitation and for solid-phase capture of inor-
ganic contaminants, Geomicrobiol. J. 18 (2001) 93–115.
[89] Y. Fujita, G.D. Redden, Strontium incorporation into calcite generated by bacteria
ureolysis, Geochim. Cosmochim. Acta 68 (2004) 3261–3270.
[90] V. Achal, X. Pan, Bioremediation of Pb-contaminated soil based on microbially
induced calcite precipitation, J. Microbiol. Biotechnol. 22 (2012) 244–247.
[91] K.N. Islam, M.Z.B.A. Bakar, M.E. Ali, M.Z.B. Hussein, M.M. Noordin,
M.Y. Loqman, G. Miah, H. Wahid, U. Hashim, A novel method for the synthesis
of calcium carbonate (aragonite) nanoparticles from cockle shells, Powder Technol.
235 (2013) 70–75.
[92] J. Warren, Dolomite: occurrence, evolution and economically important associations,
Earth Sci. Rev. 52 (2000) 1–81.
[93] G.E. Seil, Study of literature on separation of magnesia from lime in dolomite and
similar materials, J. Am. Ceram. Soc. 26 (1943) 218–238.
[94] Y. Wu, E.J. Anthony, J. Wang, L. Jia, Simultaneous hydration/carbonation of FBC ash
by low-frequency sonication, Chem. Eng. Process. Process Intensif. 47 (2007) 9–16.
[95] J.A.H. Oates, Use of quick and slaked lime in the production of chemicals, in: Lime
and Limestone: Chemistry and Technology, Production and Uses, Wiley-VCH
Verlag GmbH, Weinheim, Germany, 1998.
[96] M. Hassibi, An overview of lime slaking and factors that affect the process, in: 3rd
International Sorbalit Symposium, New Orleans, LA, USA, November 3–5, 1999.
[97] A.E. Peks, Investigation of viability of storage options of CO2 in calcium silicates,
MSc thesis, Department of Applied Earth Sciences, Delft University of Technology,
Netherlands, 2010.
[98] Y. Salameh, A.B. Albadarin, S. Allen, G. Walker, M.N.M. Ahmad, Arsenic (III, V)
adsorption onto charred dolomite: charring optimization and batch studies, Chem.
Eng. J. 259 (2014) 663–671.
[99] M. de Beer, J.P. Maree, L. Liebenberg, F.J. Doucet, Conversion of calcium sulphide to
calcium carbonate during the process of recovery of elemental sulphur from gypsum
waste, Waste Manage. 34 (2014) 2373–2381.
[100] N. Koga, Y.Z. Nakagoe, H. Tanaka, Crystallization of amorphous calcium carbonate,
Thermochim. Acta 318 (1998) 239–244.
€
[101] M. Faatz, F. GrOhn, G. Wegner, Amorphous calcium carbonate: synthesis and poten-
tial intermediate in biomineralization, Adv. Mater. 16 (2004) 996–1000.
Calcium Carbonate 117
[124] R.L. Folk, The natural history of crystalline calcium carbonate: effect of magnesium
content and salinity, J. Sediment. Petrol. 44 (1974) 40–53.
[125] P.A. Sandberg, New interpretations of Great Salt Lake ooids and of ancient nonskeletal
carbonate mineralogy, Sedimentology 22 (1975) 497–537.
[126] K.L. Milliken, J.D. Pigott, Variation of oceanic Mg/Ca ratio through time-implica-
tions for the calcite sea, Geol. Soc. Am. South-Cent. Meet. (1977) 64–65.
[127] L. Fernandez-Diaz, A. Putnis, The role of magnesium in the crystallization of calcite
and aragonite in a porous medium, J. Sediment. Res. 66 (1996) 482–491.
[128] Z. Zhang, Y. Xie, X. Xu, H. Pan, R. Tang, Transformation of amorphous calcium
carbonate into aragonite, J. Cryst. Growth 343 (2012) 62–67.
[129] J.D. Rodriguez-Blanco, S. Shaw, P. Bots, T. Roncal-Herrero1, L.G. Benning, The
role of Mg in the crystallisation of monohydrocalcite, Geochim. Cosmochim. Acta
127 (2014) 204–220.
[130] L.F. Greenlee, F. Testa, D.F. Lawler, B.D. Freeman, P. Moulin, The effect of anti-
scalant addition on calcium carbonate precipitation for a simplified synthetic brackish
water reverse osmosis concentrate, Water Res. 44 (2010) 2957–2969.
[131] S. Bai, G. Naren, M. Nakano, Y. Okaue, T. Yokoyama, Effect of polysilicic acid on
the precipitation of calcium carbonate, Colloids Surf. A 445 (2014) 54–58.
[132] A. Jada, K. Jradi, Role of polyelectrolytes in crystallogenesis of calcium carbonate,
Macromol. Symp. 233 (2006) 147–151.
[133] B. Cantaert, A. Verch, Y.-Y. Kim, H. Ludwig, V.N. Paunov, R. Kr€ oger,
F.C. Meldrum, Formation and structure of calcium carbonate thin films and nanofibers
precipitated in the presence of poly(allylamine hydrochloride) and magnesium ions,
Chem. Mater. 25 (2013) 4994–5003.
[134] N. Wada, K. Yamashita, T. Umegaki, Effects of divalent cations upon nucleation,
growth and transformation of calcium carbonate polymorphs under conditions of dou-
ble diffusion, J. Cryst. Growth 148 (1995) 297–304.
[135] H.M. Müller-Steinhagen, C.A. Branch, Influence of thermal boundary conditions on
CaCO3-fouling in double pipe heat exchangers, Chem. Eng. Process. 24 (1988) 65–73.
[136] P.P. Coetzee, M. Yacoby, S. Howall, S. Mubenga, Scale reduction and scale modifi-
cation effect induced by Zn and other metal species in physical water treatment, Water
SA 24 (1998) 77–84.
[137] H.J. Meyer, The influence of impurities on the growth rate of calcite, J. Cryst. Growth
66 (1984) 639–646.
[138] S. Ghizellaoui, M. Euvrard, J. Ledion, A. Chibani, Inhibition of scaling in the presence
of copper and zinc by various chemical processes, Desalination 206 (2007) 185–197.
[139] L. Wen-Jun, F. Hui, J. Ledion, W. Xing-Wu, The influence of metal ion on the scal-
ing in the mineral water tests, Ionics 14 (2008) 449–454.
[140] L. Brečević, V. N€othig-Laslo, D. Kralj, S. Popović, Effect of divalent cations on the
formation and structure of calcium carbonate polymorphs, J. Chem. Soc. Faraday
Trans. 92 (1996) 1017–1022.
[141] D. Kralj, L. Brečević, A.E. Nielsen, Vaterite growth and dissolution in aqueous solu-
tions. I. Kinetics of crystal growth, J. Cryst. Growth 104 (1990) 793–800.
[142] D. Kralj, L. Brečević, A.E. Nielsen, Vaterite growth and dissolution in aqueous solu-
tions. II. Kinetics of dissolution, J. Cryst. Growth 143 (1994) 269–276.
[143] M. Stroescu, A. Stoica-Guzun, S.I. Jinga, T. Dobre, I.M. Jipa, L.M. Dobre, Influence
of sodium dodecyl sulfate and cetyl trimethylammonium bromide upon calcium car-
bonate precipitation on bacterial cellulose, Korean J. Chem. Eng. 29 (2012)
1216–1223.
[144] H. Wei, Q. Shen, Y. Zhao, Y. Zhou, D. Wang, D. Xu, Crystallization habit of calcium
carbonate in the presence of sodium dodecyl sulfate and/or polypyrrolidone, J. Cryst.
Growth 260 (2004) 545–550.
Calcium Carbonate 119
[145] H. Wei, Q. Shen, Y. Zhao, Y. Zhou, D. Wang, D. Xu, Effect of anionic surfactant–
polymer complexes on the crystallization of calcium carbonate, J. Cryst. Growth
264 (2004) 424–429.
[146] A. Jada, E. Pefferkorn, Smooth and rough spherical calcium carbonate particles, J.
Mater. Sci. Lett. 19 (2000) 2077–2079.
[147] L. Dupont, F. Portemer, M. Figlarz, Synthesis and study of a well crystallized CaCO3
vaterite showing a new habitus, J. Mater. Chem. 7 (1997) 797–800.
[148] L.A. Estroff, L. Addadi, S. Weiner, A.D. Hamilton, An organic hydrogel for the
growth of calcium carbonate, Org. Biomol. Chem. 2 (2004) 137–141.
[149] H.Y. Li, L.A. Estroff, Porous calcite single crystals grown from a hydrogel medium,
Cryst. Eng. Comm. 9 (2007) 1153–1155.
[150] X.H. Guo, S.H. Yu, G.B. Cai, Crystallization in a mixture of solvents by using a crystal
modifier: morphology control in the synthesis of highly monodisperse CaCO3 micro-
spheres, Angew. Chem. Int. Ed. Engl. 45 (2006) 3977–3981.
[151] S.F. Chen, J.H. Zhu, J. Jiang, G.B. Cai, S.H. Yu, Polymer-controlled crystallization of
unique mineral superstructures, Adv. Mater. 22 (2010) 540–545.
[152] L.M. Qi, J. Li, J.M. Ma, Morphological control of CaCO3 particles by a double-
hydrophilic block copolymer in mixed alcohol–water solvents, Chem. J. Chin. Univ.
23 (2002) 1595–1597 (in Chinese).
[153] H.A. Lowenstam, S. Weiner, On Biomineralization, Oxford University Press, New
York, 1989.
[154] W.T. Hou, Q.L. Feng, Morphology and formation mechanism of vaterite particles
grown in glycine-containing aqueous solutions, Mat. Sci. Eng. C 26 (2006) 644–647.
[155] C.C. Shivkumara, P. Singh, A. Gupta, M.S. Hegde, Synthesis of vaterite CaCO3 by
direct precipitation using glycine and L-alanine as directing agents, Mater. Res. Bull.
41 (2006) 1455–1460.
[156] W. Hou, Q. Feng, A simple method to control the polymorphs of calcium carbonate in
CO2-diffusion precipitation, J. Cryst. Growth 282 (2005) 214–219.
[157] H. Tong, W. Ma, L. Wang, P. Wan, J. Hu, L. Cao, Control over the crystal phase,
shape, size and aggregation of calcium carbonate via a L-aspartic acid inducing process,
Biomaterials 25 (2004) 3923–3929.
[158] S. Mann, B.R. Heywood, S. Rajam, J.B.A. Walker, Structural and stereochemical
relationships between Langmuir monolayers and calcium carbonate nucleation, J.
Phys. D Appl. Phys. 24 (1991) 154–164.
[159] G. Falini, S. Fermani, M. Gazzano, A. Ripamonti, Oriented crystallization of vaterite
in collagenous matrices, Chem. Eur. J. 4 (1998) 1048–1052.
[160] E. Ruiz-Hitzky, K. Ariga, Y. Lvov, Bio-inorganic Hybrid Nanomaterials: Strategies,
Syntheses, Characterization and Applications, Wiley-VCH, Weinheim, Germany,
2007.
[161] A.M. Belcher, X.H. Wu, R.J. Christensen, P.K. Hansma, G.D. Stucky, D.E. Morse,
Control of crystal phase switching and orientation by soluble mollusk–shell proteins,
Nature 381 (1996) 56–58.
[162] J.B. Thompson, G.T. Paloczi, J.H. Kindt, M. Michenfelder, B.L. Smith, G. Stucky,
D.E. Morse, P.K. Hansma, Direct observation of the transition from calcite to
aragonite growth as induced by abalone shell proteins, Biophys. J. 79 (2000)
3307–3312.
[163] S. Mann, D.A. Archibald, J.M. Didymus, T. Douglas, B.R. Heywood, F.C. Meldrum,
Crystallization at inorganic–organic interfaces: biominerals and biomimetic synthesis,
Science 261 (1993) 1286–1292.
[164] C.-L. Yao, W.-H. Xu, A.-M. Ding, J.-M. Zhu, Sucrose/bovine serum albumin
mediated biomimetic crystallization of calcium carbonate, J. Chem. Sci. 121 (2009)
89–93.
120 M.M.H. Al Omari et al.
[165] L. Yang, L.Y. Guo, X. Ma, Z. Hu, S. Zhu, X. Zhang, K. Jiang, Cooperativity between
pepsin and crystallization of calcium carbonate in distilled water, J. Inorg. Biochem.
15 (2003) 197–203.
[166] L. Yang, W.-J. Ding, Y.-G. An, K. Jiang, X.-Y. Zhang, Control synthesis of aragonite
calcium carbonate with glucan as the template, Chem. J. Chin. Univ. 25 (2004)
1403–1406.
[167] X.-Y. Zhang, Z.-J. Liao, L. Yang, Interaction between β-cyclodextrin and crystalli-
zation of calcium carbonate, Acta Chim. Sin. 61 (2003) 69–73. http://en.cnki.com.
cn/Article_en/CJFDTotal-HXXB200301013.htm (accessed date April 2015).
[168] G. Santomauro, J. Baier, W. Huang, S. Pezold, J. Bill, Formation of calcium carbonate
polymorphs induced by living microalgae, J. Biomater. Nanobiotechnol. 3 (2012)
413–420.
[169] Y. Mori, T. Enomae, A. Isogai, Preparation of pure vaterite by simple mechanical
mixing of two aqueous salt solutions, Mater. Sci. Eng. C 29 (2009) 1409–1414.
[170] S.H. Sonawane, S.R. Shirsath, P.K. Khanna, S. Pawar, C.M. Mahajan, V. Paithankar,
V. Shinde, C.V. Kapadnis, An innovative method for effective micro-mixing of CO2
gas during synthesis of nano-calcite crystal using sonochemical carbonization, Chem.
Eng. J. 143 (2008) 308–313.
[171] C.D. Mateescu, C. Sarbu, R. Isopescu, O. Dumitrescu, D. Ghica, Sonocrystallization
of calcium carbonate metastable polymorphs in alcoholic solutions as reaction media,
in: 18th International Symposium on Industrial Crystallization, Zurich, Switzerland,
2011.
[172] M.D. Luque de Castro, F.P. Capote, Analytical Applications of Ultrasound, first ed.,
Elsevier, Amsterdam, Netherlands, 2007.
[173] G.J. Price, M.F. Mahon, J. Shannon, C. Cooper, Composition of calcium carbonate
polymorphs precipitated using ultrasound, Cryst. Growth Des. 11 (2011) 39–44.
[174] Y. Kojima, K. Yamaguchi, N. Nishimiya, Effect of amplitude and frequency of
ultrasonic irradiation on morphological characteristics control of calcium carbonate,
Ultrason. Sonochem. 17 (2010) 617–620.
[175] S. Kirboga, M. Oner, E. Akyol, The effect of ultrasonication on calcium carbonate
crystallization in the presence of biopolymer, J. Cryst. Growth 401 (2014) 266–270.
[176] S. Kirboga, M. Oner, Investigation of calcium carbonate precipitation in the presence
of carboxymethyl inulin, Cryst. Eng. Comm. 15 (2013) 3678–3686.
[177] A.A. Al-Hamzah, C.P. East, W.O.S. Doherty, C.M. Fellows, Inhibition of homog-
enous formation of calcium carbonate by poly (acrylic acid). The effect of molar mass
and end-group functionality, Desalination 338 (2014) 93–105.
€
[178] S. Kirboga, M. Oner, The inhibitory effects of carboxymethyl inulin on the seeded
growth of calcium carbonate, Colloids Surf. B 91 (2012) 18–25.
[179] X. Guo, F. Qiu, K. Dong, X. Rong, K. He, J. Xu, D. Yang, Preparation and appli-
cation of copolymer modified with the palygorskite as inhibitor for calcium carbonate
scale, Appl. Clay Sci. 99 (2014) 187–193.
[180] K. Mann, F. Siedler, L. Treccani, F. Heinemann, M. Fritz, Perlinhibin, a cysteine-,
histidine-, and arginine-rich miniprotein from Abalone (Haliotis laevigata) Nacre,
inhibits in vitro calcium carbonate crystallization, Biophys. J. 93 (2007) 1246–1254.
[181] M.M. Reddy, Calcite growth-rate inhibition by fulvic acid and magnesium ion-possible
influence on biogenic calcite formation, J. Cryst. Growth 352 (2012) 151–154.
[182] E. Dalas, A. Chalias, D. Gatos, K. Barlos, The inhibition of calcium carbonate crystal
growth by the cysteine-rich Mdm2 peptide, J. Colloid Interface Sci. 300 (2006)
536–542.
[183] Z. Belarbi, J. Gamby, L. Makhloufi, B. Sotta, B. Tribollet, Inhibition of calcium car-
bonate precipitation by aqueous extract of Paronychia argentea, J. Cryst. Growth
386 (2014) 208–214.
Calcium Carbonate 121
[184] X. Yang, G. Xu, The influence of xanthan on the crystallization of calcium carbonate,
J. Cryst. Growth 314 (2011) 231–238.
[185] X. Yin, W. Yang, Y. Tang, Y. Liu, J. Wang, The synergistic effect of orthophosphate
and polymer on the precipitation of calcium carbonate, Desalination 255 (2010)
143–147.
[186] L. Ling, Y. Zhou, J. Huang, Q. Yao, G. Liu, P. Zhang, W. Sun, W. Wu, Carboxylate-
terminated double-hydrophilic block copolymer as an effective and environmental
inhibitor in cooling water systems, Desalination 304 (2012) 33–40.
[187] G.H. Nancollas, K. Sawada, Formation of scales of calcium carbonate polymorphs: the
influence of magnesium ion and inhibitors, J. Petrol. Technol. 34 (1982) 645–652.
[188] M.M. Reddy, Crystallization of calcium carbonate in the presence of trace con-
centrations of phosphorus-containing anions: I. Inhibition by phosphate and
glycerophosphate ions at pH 8.8 and 25 °C, J. Cryst. Growth 41 (1977) 287–295.
[189] J. Kanakis, P. Malkaj, J. Petroheilos, E. Dalas, The crystallization of calcium carbonate
on porcine and human cardiac valves and the antimineralization effect of sodium
alginate, J. Cryst. Growth 223 (2001) 557–564.
[190] F. Manoli, E. Dalas, The effect of sodium alginate on the crystal growth of calcium
carbonate, J. Mater. Sci. Mater. Med. 13 (2002) 155–158.
[191] E.K. Giannimaras, P.G. Koutsoukos, The crystallization of calcite in the presence of
orthophosphate, J. Colloid Interface Sci. 116 (1987) 423–430.
[192] Z. Amjad, Kinetic study of the seeded growth of calcium carbonate in the presence of
benzene polycarboxylic acids, Langmuir 3 (1987) 224–228.
[193] M.M. Reddy, Kinetic inhibition of calcium carbonate formation by waste water con-
stituents, in: A.J. Rubin (Ed.), Chemistry of Wastewater Technology, Ann Arbor
Science Publishers, Michigan, 1978.
[194] A.G. Xyla, J. Mikroyannidis, P.G. Koutsoukos, The inhibition of calcium carbonate
precipitation in aqueous media by organophosphorus compounds, J. Colloid Interface
Sci. 153 (1992) 537–551.
[195] M.E.Q. Pilson, Carbon dioxide, in: An Introduction to the Chemistry of the Sea,
second ed., Cambridge University Press, New York, 2013.
[196] A.P. Sincero, G.A. Sincero, Water stabilization, in: Physical–Chemical Treatment of
Water and Wastewater, IWA Publisher and CRC Press, London, UK, 2003.
[197] J.-Y. Gal, J.-C. Bollinger, H. Tolosa, N. Gache, Calcium carbonate solubility: a
reappraisal of scale formation and inhibition, Talanta 43 (1996) 1497–1509.
[198] S.L. Goss, K.A. Lemons, J.E. Kerstetter, R.H. Bogner, Determination of calcium salt
solubility with changes in pH and PCO2, simulating varying gastrointestinal environ-
ments, J. Pharm. Pharmacol. 59 (2007) 1485–1492.
[199] S. Bialkowski, Use of Acid Distributions in Solubility Problems, Utah State University,
Logan, UT, 2015. http://ion.chem.usu.edu/sbialkow/Classes/3600/Alpha/alpha3.
html (accessed date March).
[200] University of Hertfordshire, Calcium Carbonate, Pesticide Properties DataBase.
http://sitem.herts.ac.uk/aeru/ppdb/en/Reports/108.htm#none (accessed date March
2015).
[201] N. Durand, H.C. Monger, M.G. Canti, Calcium carbonate features, in: G. Stoops,
V. Marcelino, F. Mees (Eds.), Interpretation of Micromorphological Features of Soils
and Regoliths, Elsevier, Amsterdam, Netherlands, 2010.
[202] W. Sekkal, A. Zaoui, Nanoscale analysis of the morphology and surface stability of
calcium carbonate polymorphs, Sci. Rep. 3 (2013). 10 ppwww.nature.com/
articles/srep01587 (accessed date March 2015).
€ Cizer, C. Rodriguez-Navarro, E. Ruiz-Agudo, J. Elsen, D. Van Gemert, K. Van
[203] O.
Balen, Phase and morphology evolution of calcium carbonate precipitated by carbon-
ation of hydrated lime, J. Mater. Sci. 47 (2012) 6151–6165.
122 M.M.H. Al Omari et al.
[223] W.A. Deer, R.A. Howie, J. Zussman, Introduction to the Rock Forming Minerals,
Longman, Harlow, UK, 1992.
[224] Q. Wang, A computational study of calcium carbonate, Doctor of Philosophy Thesis,
University College London, UK, 2011.
[225] F. Lippmann, Sedimentary Carbonate Minerals, Springer-Verlag, Berlin, Germany,
1973.
[226] F.C. Meldrum, Calcium carbonate in biomineralisation and biomimetic chemistry,
Int. Mater. Rev. 48 (2003) 187–224.
[227] R.J. Reeder, Mineralogical Society of America, Carbonates: Mineralogy and
Chemistry, Mineralogical Society of America, Washington, DC, 1983.
[228] J. Santillán, Q. Williams, A high pressure X-ray diffraction study of aragonite and
the post-aragonite phase transition in CaCO3, Am. Mineral. 89 (2004) (2004)
1348–1352.
[229] S. Ono, T. Kikegawa, Y. Ohishi, J. Tsuchiya, Post-aragonite phase transformation in
CaCO3 at 40 GPa, Am. Mineral. 90 (2005) 667–671.
[230] J.P.R. Villiers, Crystal structures of aragonite, strontianite, and witherite, Am. Mineral.
56 (1971) 758–767.
[231] S.A. Markgraf, R.J. Reeder, High-temperature structure refinements of calcite and
magnesite, Am. Mineral. 70 (1985) 590–600.
[232] H.J. Meyer, Struktur und fehlordnung des vaterits, Z. Kristallogr. 128 (1969) 183–212.
[233] W.F. Bradley, D.L. Graf, R.S. Roth, The vaterite-type ABO3 rare-earth borates, Acta
Crystallogr. 20 (1966) 283–287.
[234] M. Sato, S. Matsuda, Structure of vaterite and infrared spectra, Z. Kristallogr.
129 (1969) 405–410.
[235] G. Behrens, T.L. Kuhn, R. Ubic, H.A. Heuer, Raman spectra of vateritic calcium
carbonate, Spectrosc. Lett. 28 (1995) 983–995.
[236] C. Gabrielli, R. Jaouhari, S. Joiret, G. Maurin, In situ Raman spectroscopy applied to
electrochemical scaling. Determination of the structure of vaterite, J. Raman
Spectrosc. 31 (2000) 497–501.
[237] A. Anderson, Group theoretical analysis of the v1 (CO32) vibration in crystalline
calcium carbonate, Spectrosc. Lett. 29 (1996) 819–825.
[238] J. Wang, U. Becker, Structure and carbonate orientation of vaterite (CaCO3), Am.
Mineral. 94 (2009) 380–386.
[239] B. Dickens, W.E. Brown, The crystal structure of calcium carbonate hexahydrate
at 120°, Inorg. Chem. 9 (1970) 480–486.
[240] I.P. Swainson, R.P. Hammond, Hydrogen bonding in ikaite, CaCO36H2O,
Mineral. Mag. 67 (2003) 555–562.
[241] W. Bao, H. Li, Synthesis of aragonite superstructure from steelmaking slag via
indirect CO2 mineral sequestration, World Acad. Sci. Eng. Technol. 6 (2012)
1084–1090.
[242] Q. Hu, J. Zhang, H. Teng, U. Becker, Growth process and crystallographic properties
of ammonia-induced vaterite, Am. Mineral. 97 (2012) 1437–1445.
[243] U.S. Department of Health and Human Services, Centers for Disease Control and
Prevention (CDC), Occupational Safety and Health Guideline for Calcium
Carbonate. www.cdc.gov/niosh/docs/81-123/pdfs/0090.pdf (accessed date April
2015).
[244] G. Hongxia, Q. Zhenping, Q. Peng, Y. Peng, C. Suping, W. Wei, Crystallization of
aragonite CaCO3 with complex structures, Adv. Powder Technol. 22 (2011)
777–783.
[245] S. Aouad, E. Saab, N. Nassrallah-Aboukaı̈s, E. Abi-Aad, A. Aboukaı̈s, The use of
vaterite as a trap for metallic ions in water study of copper/vaterite and manganese/
vaterite systems, Leban. Sci. J. 10 (2009) 101–111.
124 M.M.H. Al Omari et al.
[246] T.R. Martz, H.W. Jannasch, K.S. Johnson, Determination of carbonate ion con-
centration and inner sphere carbonate ion pairs in seawater by ultraviolet spectropho-
tometric titration, Mar. Chem. 115 (2009) 145–154.
[247] S. Ariponnammal, Spectroscopic analysis of Siddha medicine: Sirungi Parpam, Res. J.
Recent. Sci. 2 (2012) 106–109.
[248] A. Nangare, Simultaneous estimation of calcium carbonate and aspirin in tablet
dosage form by UV spectrophotometric method, Int. J. Pharm. Res. Dev. 6 (2014)
026–034.
[249] Y. Wang, Y.X. Moo, C. Chen, P. Gunawan, R. Xu, Fast precipitation of uniform
CaCO3 nanospheres and their transformation to hollow hydroxyapatite nanospheres,
J. Colloid Interface Sci. 352 (2010) 393–400.
[250] C. Linga Raju, K.V. Narasimhulu, N.O. Gopal, J.L. Rao, B.C.V. Reddy, Electron
paramagnetic resonance, optical and infrared spectral studies on the marine mussel Arca
burnesi shells, J. Mol. Struct. 608 (2002) 20–211.
[251] M.M. Tlili, M.B. Amor, C. Gabrielli, S. Joiret, G. Maurin, P. Rousseau, Character-
ization of CaCO3 hydrates by micro-Raman spectroscopy, J. Raman Spectrosc.
33 (2002) 10–16.
[252] M. Ni, B.D. Ratner, Differentiation of calcium carbonate polymorphs by surface
analysis techniques—an XPS and TOF-SIMS study, Surf. Interface Anal. 40 (2008)
1356–1361.
[253] A. Dandeu, B. Humbert, C. Carteret, H. Muhr, E. Plasari, J.-M. Bossoutrot, Raman
spectroscopy—a powerful tool for the quantitative determination of the composition
of polymorph mixtures: application to CaCO3 polymorph mixtures, Chem. Eng.
Technol. 29 (2006) 221–225.
[254] L.C. Prinsloo, Rock hyraces: a cause of San rock art deterioration? J. Raman Spectroc.
38 (2007) 496–503.
[255] S. Jacob, A.B. Nair, P.N. Patil, B.P. Panda, Solid state crystallinity, amorphous state,
and its implications in the pharmaceutical process, Int. J. Pharm. Sci. Res. 2 (2011)
472–482.
[256] D. Wang, L.M. Hamm, R.J. Bodnar, P.M. Dove, Raman spectroscopic characteriza-
tion of the magnesium content in amorphous calcium carbonates, J. Raman Spectrosc.
43 (2012) 543–548.
[257] A. Shahar, W.A. Bassett, H.-K. Mao, I.-M. Chou, W. Mao, The stability and Raman
spectra of ikaite, CaCO36H2O, at high pressure and temperature, Am. Mineral.
90 (2005) 1835–1839.
[258] A. Mikkelsen, A.B. Andersen, S.B. Engelson, H.C.B. Hansen, O. Larsen, L. Skibsted,
Presence and dehydration of ikaite, calcium carbonate hexahydrate, in frozen shrimp
shell, J. Agric. Food Chem. 47 (1999) 911–917.
[259] H.N. Rutt, J.H. Nicola, Raman spectra of carbonates of calcite structure, J. Phys. C
Solid State Phys. 7 (1974) 4522–4528.
[260] D.A. Long, Raman Spectroscopy, McGraw-Hill, New York, 1977.
[261] F.M. Michel, J. MacDonald, J. Feng, B.L. Phillips, L. Ehm, C. Tarabrella, J.B. Parise,
R.J. Reeder, Structural characteristics of synthetic amorphous calcium carbonate,
Chem. Mater. 20 (2008) 4720–4728.
[262] United States Pharmacopeia Convention, United States Pharmacopeia 38/National
Formulary 33 (USP 38/NF 33), Calcium Carbonate Tablets, vol. 2, USP
Convention Inc., Maryland, 2015.
[263] B. Pharmacopoeia, Chewable Calcium Carbonate Tablets, Stationery Office, London,
UK, 2015.
[264] British Pharmacopoeia (BP), Calcium Carbonate and Heavy Magnesium Carbonate
Tablets, Stationery Office, London, UK, 2015.
Calcium Carbonate 125
[323] Y.S. Choi, L. Lvova, J.H. Shin, S.H. Oh, C.S. Lee, B.H. Kim, G.S. Cha, H. Nam,
Determination of oceanic carbon dioxide using a carbonate-selective electrode, Anal.
Chem. 15 (2002) 2435–2440.
[324] C.-R. Latha-Selvi, S. Christian, M. Michel, B. Sylvie, Calcium carbonate-hydrolyzed
soy protein complexation in the presence of citric acid, J. Colloid Interface Sci.
345 (2010) 88–95.
[325] M. Omar, G. Frederic, Determination of calcium-binding constants of caseins, pho-
sphoserine, citrate and pyrophosphate: a modeling approach using free calcium mea-
surement, Food Chem. 127 (2011) 676–682.
[326] F. Yang, C. Zhang, Q. Liu, C. Xu, Y.L. Xiong, Ca2+-selective electrode: a simple
method to measure the phytase-aided release of bound calcium in soymilk, J. Food
Compos. Anal. 39 (2015) 43–47.
[327] E. Francesco, R. Linfeng, Chemical speciation of uranium(VI) in marine environ-
ments: complexation of calcium and magnesium ions with [(UO2)(CO3)3](4) and
the effect on the extraction of uranium from seawater, Chemistry (Weinheim an
der Bergstrasse, Germany) 20 (2014) 14499–14506.
[328] C.N. Kotanen, A.W. Wilson, A.M. Wilson, K. Ishihara, A. Guiseppi-Elie, Biomi-
metic hydrogels gate transport of calcium ions across cell culture inserts, Biomed.
Microdevices 14 (2012) 549–558.
[329] B. Kabagambe, M.B. Garada, R. Ishimatsu, S. Amemiya, Subnanomolar detection
limit of stripping voltammetric Ca2+-selective electrode: effects of analyte charge
and sample contamination, Anal. Chem. (Washington, DC) 86 (2014) 7939–7946.
[330] D. Nanda, M.S. Oak, M.P. Kumar, Acrylic acid grafted PVC membrane based ion
selective electrode for calcium and hardness measurement of water, Indian J. Chem.
A 46A (2007) 258–262.
[331] P.C. Pandey, D.S. Chauhan, R. Prakash, Calcium ion-sensor based on polyindole-
camphorsulfonic acid composite, J. Appl. Polym. Sci. 125 (2012) 2993–2999.
[332] W. Li, F. Huang, J. Wang, A new calcium electrode based on the composite
thioacetamide/attapulgite as ionophore, Acta Chim. Sin. 70 (2012) 1963–1968.
[333] J. Ping, Y. Wang, Y. Ying, J. Wu, Application of electrochemically reduced graphene
oxide on screen-printed ion-selective electrode, Anal. Chem. 84 (2012) 3473–3479.
[334] A. Vijayalakshmi, J.T. Selvi, Calcium ion selective electrode based on Schiff base as an
electro active material—its preparation and analytical applications, Int. J. Curr. Res.
5 (2013) 2176–2178.
[335] A. Vijayalakshmi, J.T. Selvi, Preparation of calcium ion selective electrode using
calcium lactate enzyme as an electroactive material, Orient. J. Chem. 29 (2013)
297–300.
[336] A. Vijayalakshmi, J.T. Selvi, A new simple ester ionophore based calcium ion selective
electrode—preparation and its analytical application, Res. J. Recent. Sci. 3 (2014)
362–365.
[337] A. Vijayalakshmi, J.T. Selvi, Vinyl acetic acid grafted PVC membrane based calcium
ion selective electrode—its preparation and analytical application, Pollut. Res.
33 (2014) 117–119.
[338] Y. Wang, H. Xu, X. Yang, Z. Luo, J. Zhang, G. Li, All-solid-state blood calcium sen-
sors based on screen-printed poly(3,4-ethylenedioxythiophene) as the solid contact,
Sens. Actuators B 173 (2012) 630–635.
[339] H. Xu, Y. Wang, Z. Luo, Y. Pan, A miniature all-solid-state calcium electrode applied
to in situ seawater measurement, Meas. Sci. Technol. 24 (2013) 125105/1–125105/6.
6 pp.
[340] C.M. Pereira, C.A. Neiverth, S. Maeda, M. Guiotoku, L. Franciscon, Complexometric
titration with potentiometric indicator to determination of calcium and magnesium in
soil extracts, Rev. Bras. Ciên. Solo 35 (2011) 1331–1336.
Calcium Carbonate 129
[341] R. Gao, H.P. van Leeuwen, H.J.F. van Valenberg, M.A.J.S. van Boekel, Accurate
determination of the Ca2+ activity in milk-based systems by Ca-ISE: effects of ionic
composition on the single Ca2+ activity coefficient and liquid junction potentials, Food
Chem. 129 (2011) 619–623.
[342] R. Stoodley, N. Rodriguez, R. Jose, T. Bartz, Field and in-lab determination of Ca2+
in seawater, J. Chem. Educ. 91 (2014) 1954–1957.
[343] K. Kuwamoto, Y. Iwamoto, T. Aomi, Pretreatment system and method before
measuring the calcium ion concentration in a sample solution, European Patent EP
2703805, 2014.
[344] G. Cohn, I.M. Kolthoff, Determination of calcium by precipitation with picrolonic
acid and polarographic measurement of the residual picrolonic acid, J. Biol. Chem.
147 (1943) 705–719.
[345] B. Breyer, J. McPhillips, The indirect polarographic determination of calcium by
chloranilic acid, Analyst 78 (1953) 666–669.
[346] B. Fleet, S. Win, T.S. West, Polarographic determination of calcium and magnesium,
Analyst 94 (1969) 269–274.
[347] H.W. Wharton, Calcium complexes determined by polarography, Talanta 27 (1980)
971–976.
[348] V. Mareček, Z. Samec, Determination of calcium, barium and strontium ions by
differential pulse stripping voltammetry at a hanging electrolyte drop electrode, Anal.
Chim. Acta 151 (1983) 265–269.
[349] J. Wang, P.A.M. Farias, J.S. Mahmoud, Trace measurements of calcium, magnesium,
strontium and barium, based on stripping voltammetry with adsorptive accumulation,
J. Electroanal. Chem. 195 (1985) 165–173.
[350] T.H. Kim, Voltammetric recognition of Ca2+ by calix[4]arene diquinone diacid, Bull.
Korean Chem. Soc. 31 (2010) 3115–3117.
[351] J.M.S. Almeida, R.M. Dornellas, S. Yotsumoto-Neto, M. Ghisi, J.G.C. Furtado,
E.P. Marques, R.Q. Aucelio, A.L.B. Marques, A simple electroanalytical procedure
for the determination of calcium in biodiesel, Fuel 115 (2014) 658–665.
[352] S.E. Martin, R. Reeve, A rapid manometric method for determining soil carbonate,
Soil Sci. 79 (1955) 187–197.
[353] A. Dreimanis, Quantitative gasometric determination of calcite and dolomite by using
Chittick apparatus, J. Sediment. Petrol. 32 (1962) 520–529.
[354] R.H. Loeppert, D.L. Suarez, Carbonate and gypsum, in: D.L. Sparks (Ed.),
Methods of Soil Analysis, Part 3, third ed., SSSA Book Series 5, SSSA, Madison,
WI, 1996.
[355] L.A. Sherrod, G. Dunn, G.A. Peterson, R.L. Kolberg, Inorganic carbon analysis by
modified pressure-calcimeter method, Soil Sci. Soc. Am. J. 66 (2002) 299–305.
[356] S.W. Wagner, J.D. Hanson, A. Olness, W.B. Voorhees, A volumetric inorganic car-
bon analysis system, Soil Sci. Soc. Am. J. 62 (1998) 690–693.
[357] B. Paull, M. Macka, P.R. Haddad, Determination of calcium and magnesium in water
samples by high-performance liquid chromatography on a graphitic stationary phase
with a mobile phase containing o-cresolphthalein complexone, J. Chromatogr. A
789 (1997) 329–337.
[358] J.S. Fritz, H. Waki, Anion exchange separation of magnesium and calcium with
alcohol–nitric acid, Anal. Chem. 35 (1963) 1079–1083.
[359] J.S. Fritz, J.N. Story, Chromatographic separation of metal ions on low capacity,
macroreticular resins, Anal. Chem. 46 (1974) 825–829.
[360] M.D. Argiiello, J.S. Fntz, Ion-exchange separation and determination of calcium and
magnesium, Anal. Chem. 49 (1977) 1595–1597.
[361] J.R. Jezorek, H. Freiser, 4-(Pyridylazo)resorcinol-based continuous detection system
for trace levels of metal ions, Anal. Chem. 51 (1979) 373–376.
130 M.M.H. Al Omari et al.
[362] R.M. Cassidy, S. Elchuk, Trace enrichment methods for the determination of metal
ions by high performance liquid chromatography. Part II, J. Chromatogr. Sci.
19 (1981) 503–507.
[363] R.M. Cassidy, S. Elchuk, J.O. McHugh, Determination of metals in groundwaters by
trace enrichment and liquid chromatography, Anal. Chem. 54 (1982) 727–731.
[364] M.L. Dietz, The determination of calcium in dietary supplement tablets by ion-
exchange, J. Chem. Educ. 63 (1986) 177.
[365] R.G. Amundson, J. Trask, E. Pendall, A rapid method of soil carbonate analysis using
gas chromatography, Soil Sci. Soc. Am. J. 52 (1988) 880–883.
[366] C. Sp€ otl, T.W. Vennemann, Continuous-flow isotope ratio mass spectrometric anal-
ysis of carbonate minerals, Rapid Commun. Mass Spectrom. 17 (2003) 1004–1006.
[367] T. Ishimura, U. Tsunogai, T. Gamo, Stable carbon and oxygen isotopic determination
of sub-microgram quantities of CaCO3 to analyze individual foraminiferal shells,
Rapid Commun. Mass Spectrom. 18 (2004) 2883–2888.
[368] J. Fiebig, B.R. Sch€ one, W. Oschman, High-precision oxygen and carbon isotope anal-
ysis of very small (10–30 μg) amounts of carbonates using continuous flow isotope ratio
mass spectrometry, Rapid Commun. Mass Spectrom. 19 (2005) 2355–2358.
[369] G. Skrzypek, D. Paul, δ13C analyses of calcium carbonates: comparison between
Gasbench and elemental analyzer techniques, Rapid Commun. Mass Spectrom.
20 (2006) 2915–2920.
[370] T.A. Velivetskaya, A.V. Ignatiev, S.A. Gorbarenko, Carbon and oxygen isotope
microanalysis of carbonate, Rapid Commun. Mass Spectrom. 23 (2009) 2391–2397.
[371] X.-P. Zha, Y.Y. Zhao, Y.F. Zheng, An online method combining a Gasbench II with
continuous flow isotope ratio mass spectrometry to determine the content and isotopic
compositions of minor amounts of carbonate in silicate rocks, Rapid Commun. Mass
Spectrom. 24 (2010) 2217–2226.
[372] S.F.M. Breitenbach, S.M. Bernasconi, Carbon and oxygen isotope analysis of small
carbonate samples (20 to 100 μg) with a GasBench II preparation device, Rapid
Commun. Mass Spectrom. 25 (2011) 1910–1914.
[373] G.F. Taylor, The occurrence of monohydrocalcite in two small lakes in the southeast
of South Australia, Am. Mineral. 60 (1975) 690–697.
[374] K. Fukushi, T. Munemoto, M. Sakai, S. Yagi, Monohydrocalcite: a promising
remediation material for hazardous anions, Sci. Technol. Adv. Mater. 12 (2011).
12 pp.
[375] L.L.Y. Chang, R.A. Howie, J. Zussman, second ed., Rock-Forming Minerals, vol. 5,
Harlow: Longman, London, UK, 1996.
[376] C. Palache, H. Berman, C. Frondel, seventh ed., Dana’s System of Mineralogy, vol. 2,
Wiley/Chapman & Hall, New York/London, UK, 1951.
[377] S. Bentov, S. Weil, L. Glazer, A. Sagi, A. Berman, Stabilization of amorphous calcium
carbonate by phosphate rich organic matrix proteins and by single phosphoamino
acids, J. Struct. Biol. 171 (2010) 207–215.
[378] O.E. Meiron, E. Bar-David, E.D. Aflalo, A. Shechte, D. Stepensky, A. Berman,
A. Sagi1, Solubility and bioavailability of stabilized amorphous calcium carbonate, J.
Bone Miner. Res. 26 (2011) 364–372.
[379] N. Vaisman, G. Shaltiel, M. Daniely, O.E. Meiron, A. Shechter, S.A. Abrams, E. Niv,
Y. Shapira, A. Sagi, Increased calcium absorption from synthetic stable amorphous cal-
cium carbonate: double-blind randomized crossover clinical trial in postmenopausal
women, J. Bone Miner. Res. 29 (2014) 2203–2209.
[380] E. Suess, W. Balzer, K.F. Hesse, P.J. Mueller, C.A. Ungerer, G. Wefer, Calcium car-
bonate hexahydrate from organic-rich sediments of the Antarctic shelf; precursors of
glendonites, Science 216 (1982) 1128–1131.
Calcium Carbonate 131
[400] Food and Drug Administration (FDA), Drug Information Label for ACTONEL® with
CALCIUM (Risedronate Sodium Tablets with Calcium Carbonate Tablets, USP).
https://www.accessdata.fda.gov/scripts/cder/drugsatfda/index.cfm?
fuseaction¼Search.Label_ApprovalHistory#labelinfo (accessed date April 2015).
[401] J.A. Harvey, M.M. Zobitz, C.Y. Pak, Dose dependency of calcium absorption: a
comparison of calcium carbonate and calcium citrate, J. Bone Miner. Res. 3 (1988)
253–258.
[402] H.J. Heller, L.G. Greer, S.D. Haynes, J.R. Poindexter, C.Y. Pak, Pharmacokinetic
and pharmacodynamic comparison of two calcium supplements in postmenopausal
women, J. Clin. Pharmacol. 40 (2000) 1237–1244.
[403] P. Tondapu, D. Provost, B. Adams-Huet, T. Sims, C. Chang, K. Sakhaee,
Comparison of the absorption of calcium carbonate and calcium citrate after
Roux-en-Y gastric bypass, Obes. Surg. 19 (2009) 1256–1261.
[404] R.P. Hanzlik, S.C. Fowler, D.H. Fisher, Relative bioavailability of calcium from
calcium formate, calcium citrate, and calcium carbonate, J. Pharmacol. Exp. Ther.
313 (2005) 1217–1222.
[405] Y. Zhao, B.R. Martin, C.M. Weaver, Calcium bioavailability of calcium carbonate
fortified soymilk is equivalent to cow’s milk in young women, J. Nutr. 135 (2005)
2379–2382.
[406] M.A. Ayed, A.M. Thannoun, Calcium bioavailability of calcium carbonate based diets
for male growing rats, Mesopotamia, J. Agric. 34 (2006). 17 pp.
[407] G. Kressel, M. Wolters, A. Hahn, Bioavailability and solubility of different calcium-
salts as a basis for calcium enrichment of beverages, Food Nutr. Sci. 1 (2010) 53–58.
[408] E.A. Mueller, M. Seiberling, W. Kirch, A. Frentzel, S. Trapp, Pharmacokinetics and
pharmacodynamics of calcium–vitamin D3 chewable tablets: a single-blind, multiple-
dose study in postmenopausal women, Expert Opin. Drug Metab. Toxicol. 7 (2011)
785–791.
[409] Medscape, Tums-Calcium Carbonate (OTC). http://reference.medscape.com/drug/
tums-calcium-carbonate-341983#10 (accessed date April 2015).
[410] M.K. Picolos, P.R. Orlander, Calcium carbonate toxicity: the updated milk-alkali
syndrome; report of 3 cases and review of the literature, Endocr. Pract. 11 (2005)
272–280.