Carbon dioxide sequestration by

phosphogypsum based 9
procedure
Luis Esquivias 1 , Victor Morales-Flo
rez 1 , Alberto Santos 2
1
Universidad de Sevilla, Sevilla, Spain; 2Universidad de C
adiz, C
adiz, Spain

9.1 Introduction
Phosphogypsum (PG) is an industrial waste generated from wet phosphate industry.
The “wet acid method” is widely used to produce phosphoric acid and calcium
sulfatedmainly in dihydrate form (CaSO4$2H2O). The wet process is economic but
generates a large amount of waste (USEPA, 2002) (5 t of PG/t of phosphoric acid pro-
duced). Every year, more than 200 million tons of PG are produced all over the world.
Most of this byproduct is disposed of without any treatment, usually by dumping in
large stockpiles. In some cases, these are located in coastal areas close to phosphoric
acid plants where they occupy large land areas, which causes environmental problems
and controversy and public rejection for its alleged implications for the health of the
local population (Parreira et al., 2003; Villa-Alfageme et al., 2009; Papageorgiou
et al., 2016; Pérez-L
opez et al., 2016; Corisco et al., 2017; Macias et al., 2017).
The PG is a collective term for a mixture comprising major solid and minor liquid
waste components. The PG waste is impregnated with the chemical reactants used.
Therefore, the products obtained in the industrial process contain high concentrations
of certain components, mainly phosphate, but also sulfate, fluoride, and often ammo-
nium (Lottermoser, 2010). Moreover, phosphate rocks also contain, as impurities,
metal and radionuclides that are released during the industrial process (IAEA, 2013)
and finally concentrated in the reaction products (Rutherford et al., 1994). Thus, all
these components are trapped in the interstices of PG particles, explaining its acidic
nature and the high contaminant release potential under leaching conditions (Pérez
L
opez et al., 2016). These impurities limit the commercial use of PG.
Only 15% of world PG production is recycled as building materials, including
cement retarder, building gypsum powder, gypsum board, filler in papermaking, fiber
plasterboard, mine filling agent, and roadbed material (Yang et al., 2013; Zhao et al.,
2015; Campos et al., 2017; Holanda et al., 2017; Mechi et al., 2017). It is also recycled
as agricultural fertilizers or soil stabilization amendments and as set controller in the
manufacture of Portland cement (Alcordo and Rechcigl, 1993; Domínguez et al.,
2001; Abril et al., 2009; Tayibi et al., 2009; Hentati et al., 2015; Smaoui-Jardak
et al., 2017). Therefore, the stacks of PG are realistically a significant problem in phos-
phoric acid industry. However, prospective processes for large-scale utilization of PG
are still under investigation. Additionally, these wastes could also contain high

Carbon Dioxide Sequestration in Cementitious Construction Materials

https://doi.org/10.1016/B978-0-08-102444-7.00009-5
Copyright © 2018 Elsevier Ltd. All rights reserved.
200 Carbon Dioxide Sequestration in Cementitious Construction Materials

concentrations of elements of economic interest. Some studies examine the potential

recovery of metals of economic interest in wastes generated by the fertilizer industry
(Canovas et al., 2017; Lambert et al., 2017).
Despite those drawbacks, environmentally friendly applications are already being
investigated. One of them is based on the use of PG as a calcium source for CO2 min-
eral sequestration in the framework of the mitigation of greenhouse gases emission
(C
ardenas-Escudero et al., 2011; Romero-Hermida et al., 2014; Contreras et al.,
2015; Mattila and Zevenhoven, 2015; Zhao et al., 2015; Msila et al., 2016; Xie
et al., 2016; Romero-Hermida et al., 2017; Zhao et al., 2017). Large efforts on carbon
sequestration strategies are focused on reducing these emissions. Nevertheless, it is un-
likely that any single strategy will achieve the necessary reduction in CO2 concentra-
tions, considering the colossal magnitude of global carbon dioxide emissions,
currently 38 Gt/year (Power et al., 2013). Moreover, it has been suggested that
one of the seven emission-reducing activities, or stabilization wedges (Pacala and
Socolow, 2004), such as geological CCS1, should include carbon mineralization
(Power et al., 2013) (also known as mineral sequestration), that is, any process that
sequesters CO2 as a solid carbonate phase, not only into geological formations, but
also on feedstocks other than natural minerals (Seifritz, 1990; Lackner et al., 1995;
Sipila et al., 2008; Bobicki et al., 2012; Olajire, 2013).
In fact, in the last years, the research of carbon mineralization is mainly focused on
three main aspects: reduction of energy requirements, enhancement of the slow chem-
ical kinetics, and look for alternative feedstock of sequestration agents (Romanov
et al., 2015). Nevertheless, it has been shown that carbon mineralization under atmo-
spheric conditions can achieve high mineralization kinetics and full efficiency (Santos
et al., 2009; Morales-Fl
orez et al., 2011) without significant energy costs thanks to the
high reactive surface area of the carbon sequestration agent. Besides, the potential for
carbonation of alkaline wastes to provide a sink for CO2 has only recently been recog-
nized (Renforth et al., 2011; Sanna et al., 2012; Kirchofer et al., 2013; Kuwahara and
Yamashita, 2013). Thus, one area of recent investigation, known as “accelerated
carbonation” (Fern
andez Bertos et al., 2004; Gunning et al., 2010) involves examining
substitute materials for the mineral feedstock for carbonation (Rendek et al., 2006).
Candidates as carbonation reactants (carbon sequestration agents) are industrial waste
streams containing significant quantities of Ca and Mg oxides. However, the amount
of available feedstock is much less than the necessary to capture the emitted CO2 but
the wastes proposed for reducing these energy requirements are typically produced
near point sources of CO2 (Huntzinger et al., 2009) eliminating transport costs. Be-
sides, the carbonation byproducts are carbonate minerals that could potentially be
sold for enhancing the economic viability of the process, and possibly a financial
advantage in the case of carbon taxes (Huntzinger et al., 2009; Hitch and Dipple,
2012; Teir et al., 2016). Even in certain industries, carbonation of industrial wastes
provides an opportunity to “close the loop” on CO2 emissions.

1
Carbon Capture and Storage.
Carbon dioxide sequestration by phosphogypsum based procedure 201

Recent alternative mineral feedstock for carbon sequestration has been found in the
PG byproduct stockpiles (C
ardenas-Escudero et al., 2011). In this case, the PG waste is
first transformed into a carbon sequestration agent (calcium hydroxide) and sodium
sulfate by alkaline dissolution with soda and then, this agent reacts rapidly and
completely with CO2 giving mineral carbonates. Other experimental studies propose
to convert PG into ammonium sulfate via PG carbonation with ammonia (Mattila
and Zevenhoven, 2015; Zhao et al., 2015). In summary, in the cited studies, the reuse
of PG and the valorization of the byproducts obtained are achieved since calcite and
sodium sulfate or ammonium sulfate are obtained. All these byproducts have different
industrial applications (fertilizers, filler material, and building materials). Thereby, be-
sides PG valorization, large amounts of CO2 are also fixed into carbonates contributing
to carbon emissions control strategies.
Other options for transforming the PG wastes may be those in which the alkaline
dissolutions themselves come from basic wastes (Romero-Hermida et al., 2014,
2017). One of these is the caustic liquid waste of the aluminum industry. Aluminum
anodizing plants produce different waste effluents mostly from the main sections:
anodizing and etching. Anodizing is usually performed in sulfuric acid and etching
is performed in sodium hydroxide solutions with concentrations ranging between 50
and 200 g/L. Typically, alkaline waste streams from the etching operation are treated
by mixing them with the acid wastewaters from the anodizing step, producing the so-
called anodizing mud. Nevertheless, this neutralization process requires the incorpora-
tion of an additional neutralizing agent (NaOH or lime) since the overall balance is


generally acid (Alvarez-Ayuso

and Nugteren, 2005; Alvarez-Ayuso, 2009).
Hence, the viability of the carbonation of PG by soda dissolution (reagent grade or
commercial soda) or caustic dissolution with liquid waste of the aluminum anodizing
industry has been tested. Also, the byproducts (Portlandite and katoite, respectively)
have been assayed as carbon sequestration agents by two different carbonation routes:
bubbling into aqueous media and weathering. In the case of Portlandite, its application
to the manufacture of mortars has been also considered but, in the case of the katoite
(member of the isomorphous hydrogrossular series; Passaglia and Rinaldi, 1984;
Geiger et al., 2012; Dinelsa et al., 2014), its own synthesis represents a novelty and
a new method to treat the waste streams of aluminum anodizing industry. Also, it is
a current research to explore the potentialities of the katoite carbonation reaction
and its application in the aluminum cement manufacturing industry (Taylor, 1997).

9.2 Materials and methods

9.2.1 Starting materials
Raw PG were supplied by Fertiberia (Huelva, Spain), collected at different depths from
bore-holes and carried out using a soil sampling auger from the PG stockpiles in
Huelva. The PG was homogenized, ground, and oven-dried at 40
C in order to pre-
serve the structural water of gypsum. Laser diffraction revealed a typical grain size
202 Carbon Dioxide Sequestration in Cementitious Construction Materials

Major element contents of the samples analyzed by X-ray

Table 9.1
fluorescence
Phosphogypsum Portlandite Na2SO4
Major elements (%)
SO3 50.2 4.28 55.8
CaO 44.7 89.4 1.04
F 1.56 1.61 n.d.a
Na2O 1.16 2.12 42.7
Cl 0.72 0.04 0.23
P2O5 0.67 1.21 n.d.
SiO2 0.43 0.64 0.16
Al2O3 0.24 0.27 n.d.
MgO 0.14 0.13 n.d.
Fe2O3 0.07 0.20 n.d.
SrO 0.07 0.06 0.02
Y2O3 0.02 0.04 n.d.
b
LOI 21.2 14.3 27.9

Weight percentages are normalized to the mass without loss-of-ignition (LOI) values.
a
n.d., not detected.
b
LOI, loss-of-ignition.
Reprinted with permission from C
ardenas-Escudero, C., Morales-Fl
orez, V., Pérez-L
opez, R., Santos, A., Esquivias, L.,
2011. Procedure to use phosphogypsum industrial waste for mineral CO2 sequestration. Journal of Hazardous Materials
196, 431e435.

of 40 mm with >90% below 110 mm. Major element concentrations determined by X-

ray fluorescence (XRF) appear in Table 9.1.
Raw PG composition is clearly dominated by S (50.2 wt.% as SO3) and Ca
(44.7 wt.% as CaO). However, the calcium content of the gypsum was slightly higher
than expected stoichiometrically, revealing the possibility of the existence of other
different calcium compounds. Other major impurities are F, Na, Cl, P, Si, Al, and
Mg, and to a lesser extent Fe, Sr, and Y. The presence of potentially toxic trace ele-
ments was analyzed by acid-digestion and inductively coupled plasma mass spec-
trometry (ICP-MS) (Table 9.2). The main trace elements identified were Cr, As, U,
Ni, V, Se, Cd, Pb, Zn, and Th, in the order of abundance. All trace elements were pre-
sent at 3.70 mg/kg. These values are close to the average values analyzed in surface
samples from the pile (Pérez-L
opez et al., 2010), supporting this sample as represen-
tative of the stack. The contents of trace elements are slightly inferior to those of PG
samples produced from other phosphate rock sources around the world (Tayibi et al.,
2009).
Carbon dioxide sequestration by phosphogypsum based procedure 203

Table 9.2 Contents of trace elements measured by analysis with ICP-

MS
Phosphogypsum Na2SO4 Portlandite Calcite
Trace elements (mg/kg)
Cr 3.70 <l.d. 7.59 8.17
As 3.58 <l.d. 8.57 9.32
U 3.48 0.07 7.84 8.05
Ni 2.49 <l.d. 4.76 5.21
V 2.10 <l.d. 4.76 4.79
Se 1.97 <l.d. 5.04 6.04
Cd 1.34 0.02 2.34 2.51
Pb 1.20 <l.d. 2.47 2.56
Zn 0.92 <l.d. 2.02 2.98
Th 0.69 <l.d. 1.62 1.71

l.d., limit of detection.

Reprinted with permission from C
ardenas-Escudero, C., Morales-Fl
orez, V., Pérez-L
opez, R., Santos, A., Esquivias, L.,
2011. Procedure to use phosphogypsum industrial waste for mineral CO2 sequestration. Journal of Hazardous Materials
196, 431e435.

Reaction grade and for domestic use soda, and a caustic liquid Na-Al rich industrial
waste, provided by Verinsur SA (Jerez de la Frontera, Spain), were employed as source
of soda. This waste was derived from the finishing process of the aluminum industry,
and, regarding the supplier, ca. 200 t are produced annually. It is a transparent solution
with pH z 14 and contains a small amount of reddish precipitate. This liquid waste
had a density of 1.32 g/cm3 and its chemical and elemental analyses show that it con-
tains [Na] ¼ 110  2 g/L (4.78  0.09 M) and [Al] ¼ 52  2 g/L (1.93  0.07 M)
(Romero-Hermida et al., 2014). XRF of the reddish precipitate indicated that its major
components are [Na2O] ¼ 80.24 wt.%, [Al2O3] ¼ 17.81 wt.%, [Cl] ¼ 1.23wt.%, and
[SiO2] ¼ 0.52 wt.%.

9.2.2 Synthesis of the carbon sequestration agent

The process begins by dissolving the raw PG in a solution of soda or caustic liquid Na-
Al rich liquid waste. In Fig. 9.1, the entire experimental procedures are sketched. In the
first case, raw PG was dispersed in high-purity water (mass ratio 1:4) by magnetic stir-
ring at room pressure and temperature. Immediately after, NaOH was added to reach
an OH/Ca molar ratio of 2. The mixture was kept at room temperature for 3 h under
constant stirring. The PG dissolution resulted in the precipitation of a primary whitish
204 Carbon Dioxide Sequestration in Cementitious Construction Materials

Phosphogypsum Phosphogypsum (PG)

+ +
NaOH(aq) Aluminium industry
(A(L))
Dissolution & separation caustic liquid waste

Alkaline PGA(L)
dissolution liquid
discarded
Liquid
Ca(OH)2
Na2SO4 PGA
solid phase
Carbonation Evaporation
(bubbling) Carbonation
Liquid Weathering Bubbling
(discarded) PGAB(L)
liquid
CaCO3 Na2SO4 discarded

PGAW PGAB
solid phase solid phase

Figure 9.1 Flowchart of the experimental methodology based on soda (left), and based on the
aluminum-rich liquid waste (right).
Reprinted with permission from Romero-Hermida et al. (2017).

solid phase (the carbon sequestration agent) and a supernatant liquid, in agreement to
the reaction:

CaSO4$2H2O þ 2Na(OH) 4 Ca(OH)2 þ Na2SO4 þ 2H2O (9.1)

Subsequent evaporation of the supernatant to dryness on a hot plate at 80
C yielded

a transparent salt, which was later characterized as a second solid phase.
In the second case, the process started by the addition of PG in Na-Al-rich liquid
waste (mass ratio 2:3) upon magnetic stirring in a closed beaker for 3 h under room
conditions, corresponding to a stoichiometric molar ratio of Ca:Al ¼ 1.5 (see Section
9.2.1 to check Ca and Al contents of the PG and the liquid waste)), targeting the
following chemical reaction:

3(CaSO4$2H2O) þ 6Naþ(aq) þ 12OH(aq) þ 2Al3þ(aq) 4

Ca3Al2(OH)12 þ 3Na2SO4 þ 6H2O (9.2)

During the process, the pH remained at 12.0. A precipitate was formed (called
“PGA,” the sequestration agent), which was separated by centrifugation. Then, it
was put inside a stove at 80
C to quickly dry the sample in order to avoid uncontrolled
carbonation by weathering or further hydration. Also, a supernatant resulted, labeled
“PGA(L).”
Carbon dioxide sequestration by phosphogypsum based procedure 205

9.2.3 Carbon sequestration procedures

Two procedures were considered to evaluate the carbon capture efficiency of the
sequestration agents: (1) bubbling pure CO2 into an aqueous suspension of the seques-
tration agent and (2) using the “weathering pools” (Morales-Fl
orez et al., 2011).

9.2.3.1 Bubbling
This procedure consists of subjecting a dispersion of the sequestration agent in distilled
water to a continuous pure CO2 flux under magnetic stirring and room conditions. The
expected carbonation reactions are:

Ca(OH)2 þ CO2 4 CaCO3 þ H2O (9.3)

Ca3Al2(OH)12 þ 3CO2 4 3CaCO3 þ 2Al(OH)3 þ 3H2O (9.4)

The carbonation capacity and efficiency of both solid phase precipitates were
assessed by a simple carbonation experimental set-up: the sequestration agent was
dispersed in high-purity water (mass ratio 1:20) under magnetic stirring into a reactor,
and a CO2 flux (1 bar, 20 cm3/s) was bubbled through the suspension (15 min for por-
tlandite and 90 min for PGA) at room pressure and temperature. Afterwards, the sam-
ple was left to rest overnight in the CO2-rich water.
This procedure resulted in new solid-liquid suspensions, which were separated by
centrifugation (3000 rpm, 5 min) into solid and liquid phases. The solid phases, ac-
cording to the (Eq. 9.3) (calcium carbonate) and (Eq. 9.4), were analyzed. The carbon-
ated sample from PGA sample was labeled as “PGAB.” The liquid phases were not
considered for carbon sequestration purposes.

9.2.3.2 Weathering
The carbonation of the sample PGA was also studied using the atmospheric CO2 by the
weathering pools procedure (Morales-Fl
orez et al., 2011). Only the PGA sample was
studied using this type of carbonation. The weathering pools consist of very shallow,
flat ponds on which a thin layer (10e20 mm) of the sample is spread. Distilled water
was initially added, and the carbonation of the sample occurred during drying under
room conditions. Every 2 weeks extra distilled water was added to enhance the capture
performance. Typically, the complete process took up to 2 months. The final solid
obtained is hereafter referred to as “PGAW.”

9.3 Procedure based on soda reactions

9.3.1 Analysis of the sample prior to CO2 sequestration
The XRD of the raw PG sample is shown in Fig. 9.2. The diffraction pattern indicates
that the sample is composed mainly of gypsum (CaSO4$2H2O, Powder Diffraction
206 Carbon Dioxide Sequestration in Cementitious Construction Materials

Intensity (counts) CaSO4·2H2O + 2NaOH ↔ Ca(OH)2 + Na2SO4 + 2H2O

Portlandite

Thenardite

Gypsum

5 10 15 20 25 30 35 40 45 50 55 60 65

2θ (degrees)
Figure 9.2 Diffractograms of the raw phosphogypsum (CaSO4$2H2O) from Huelva (Spain), of
the solid filtered where portlandite (Ca(OH)2) can be clearly observed, and the solid phase
obtained from supernatant evaporation where the diffraction pattern of thenardite (Na2SO4) is
clearly matched. Diffractograms were shifted for clarity.
Reprinted with permission from C
ardenas-Escudero, C., Morales-Fl
orez, V., Pérez-L

opez, R.,
Santos, A., Esquivias, L., 2011. Procedure to use phosphogypsum industrial waste for mineral
CO2 sequestration. Journal of Hazardous Materials 196, 431e435.

File number: 99-101-0394), as expected. After the dispersion of this sample in water
and the addition of NaOH, the resulting whitish precipitate corresponded mostly to
portlandite (calcium hydroxide, Ca(OH)2, PDF number: 99-100-0115) (Fig. 9.2).
Finally, the diffractogram of the transparent salts precipitated by evaporation of the su-
pernatant liquid (Fig. 9.2) indicates that it is mostly composed of thenardite (Na2SO4,
PDF number: 99-100-4889), again as expected, regarding (Eq. 9.1). These results
confirm the efficiency of this reaction as a procedure to deal with the raw PG waste
and obtain roughly pure portlandite.
According to Table 9.1, portlandite is mainly composed of Ca (89 wt.% as CaO);
calcium content remains slightly higher than expected, possibly due to rest of the cal-
cium phosphate from original rock. Finally, the solid obtained from the supernatant
evaporation is characterized by high contents of S (55.8 wt.% as SO3) and Na
(42.7 wt.% as Na2O). Other major impurities of the starting PG are F, Na, Cl, P, Si,
Al, and Mg, and to a lesser extent Fe, Sr, and Y. Excepting some of Cl, Si, and Sr pre-
sent in the sodium sulfate, most of these impurities were also found in the resulting
portlandite.
Carbon dioxide sequestration by phosphogypsum based procedure 207

The contents of potentially toxic trace elements in the products from PG dissolu-
tion, that is, Portlandite and sodium sulfate, are shown in Table 9.2. Most of these trace
elements were below or near to the detection limit in the precipitated sodium sulfate.
Approximately, 100% of all trace elements are transferred from PG to the resulting
portlandite. Hence, no metals remained in the sodium sulfate solution resulting from
the PG dissolution.

9.3.2 Carbon dioxide capture efficiency

The XRD diffractogram of the carbonated portlandite (calcite) resulting from the
aqueous carbonation procedure is shown in Fig. 9.3. It clearly indicates that total con-
version of the original portlandite to calcite (CaCO3, PDF number: 99-101-2108) was
achieved.
This point was confirmed by thermogravimetric analyses of the original and calcite
samples. The analysis of the reference portlandite prior to the carbonation procedure
confirmed that the purity of the portlandite was close to 90%. The measured weight
loss due to dehydration was 22%, as estimated by XRF (see Table 9.1). The carbonated
portlandite showed a 38.4% weight loss due to the release of the CO2 at 700
C (almost

Ca(OH)2 + CO2 ↔ CaCO3 + H2O

Intensity (counts)

Calcite

Portlandite

5 10 15 20 25 30 35 40 45 50 55 60 65
2θ (degrees)
Figure 9.3 Diffractogram of the carbonated portlandite. No other phase than calcium carbonate
is observed. Portlandite diffractogram has been repeated for comparison purposes only.
Diffractograms were shifted for clarity.
Reprinted with permission from C
ardenas-Escudero, C., Morales-Fl
orez, V., Pérez-L

opez, R.,
Santos, A., Esquivias, L., 2011. Procedure to use phosphogypsum industrial waste for mineral
CO2 sequestration. Journal of Hazardous Materials 196, 431e435.
208 Carbon Dioxide Sequestration in Cementitious Construction Materials

40%, the maximum theoretical weight loss of pure calcite), indicating that all the cal-
cium present in the sample, whether from portlandite or from other minor calcium
compounds, was carbonated and revealed an extremely high carbonation efficiency
of these wastes.
During the aqueous carbonation process, toxic trace elements initially contained in
the portlandite are released into solution. The concentration of trace metals in the final
calcite implies a high transfer factor of around 100% for all elements (Table 9.2).

9.3.3 Fractionation and fluxes of toxic elements

The activity concentrations of natural radionuclides during the complete procedure
have been characterized (Contreras et al., 2015). Activity concentrations of the gamma
emitters were measured through the following energies: 210Pb (46.5 keV), 234Th
(63.3 keV), 226Ra (352 keV of 214Pb), and 40K (1460 keV). Detailed information about
the characterization techniques is available in the literature (Lozano et al., 2011).
To study the partitioning of elements during the dissolution and carbonation pro-
cesses, a transfer factor (h) was defined, which represents the fraction of each element
that remains in each one of the products in relation to the initial input of all the reac-
tants. Table 9.3 shows the transfer factor of major elements measured by XRF and
trace elements measured by ICP-MS in the products resulting from the overall process
based on soda.
The process of PG dissolution and carbonation can be traced to the major elements
Ca and S. According to the XRD and XRF data, 97% of Ca was transferred from the
PG to the portlandite and 95% from the portlandite to the calcite. On the other hand,
most of the S (>95%) in the PG was partitioned, along with Na from the sodium hy-
droxide, into the sodium sulfate. Other elements such as Al, Y, S, and P were also
completely transferred to the portlandite and on subsequent carbonation to the calcite.
And regarding the trace impurities initially contained in the PG, most of these elements
were completely transferred to the final calcite.
The dissolution of PG and precipitation of portlandite/calcite implies a loss of mass
and, therefore, an increased effect in the concentration of contaminants. Similarly, to
the precursor PG, the elements with higher concentrations than uncontaminated soils
in portlandite and calcite continue to be Sr, Y, Cd, Se, and La. On the other hand, in the
sodium sulfate and the solid residue from the evaporation of final liquid fraction after
carbonation (S2 and S4, respectively, in Table 9.3), most contaminants are in lower
concentrations compared with portlandite and calcite (S1 and S3, respectively, in
Table 9.3), with some values close to or even below the detection limit. It is worth
noting the relatively high transfer factors for Cr (40%), Zn (36%), Cu (29%), As
(28%), and Sr (25%) in portlandite, and Zn (14%) in final dry solid residue (S4 in
Table 9.3). However, Se is the only element the concentration of which is slightly
above that of uncontaminated soils in all the samples (Contreras et al., 2014). S4
showed negligible values.
Regarding the radionuclides, phosphate rock used in the factory of Huelva contains
U- and Th-series radionuclides in secular equilibrium (1600 and 15 Bq/kg of 238U and
Carbon dioxide sequestration by phosphogypsum based procedure 209

Transfer factor (h) defined as the mass (g) of products for

Table 9.3
every gram of phosphogypsum that reacts during the carbonation
process
Alkaline dissolution Carbonation process
Raw materials (PG D NaOH / S1 D S2) (S1 D CO2 / S3 D S4)
PG D NaOH S1 D S2 S3 D S4
Major elements
CaO 100 <0.1 97.4 1.8 84.8 1.3
A12O3 100 <0.1 80.9 10.2 84.0 <0.1
SO3 100 <0.1 5.9 98.1 78.4 <0.1
P2O5 100 <0.1 98.8 <0.1 88.4 <0.1
K2O 68.0 32.0 33.3 79.9 102 5.6
Na2O 0.2 99.8 3.6 92.6 59.3 53.8
Trace elements
Sr 100 <0.1 68.2 24.8 96.5 3.4
Y 100 <0.1 93.7 <0.1 87.8 <0.1
Cd 100 <0.1 118.0 <0.1 99.9 <0.1
V 100 <0.1 75.6 <0.1 88.2 5.5
Cr 100 <0.1 104.2 39.9 77.6 1.7
Ag 100 <0.1 90.7 18.3 92.5 0.7
Se 100 <0.1 91.4 18.8 97.8 1.5
Zn 94.2 5.7 69.4 36.4 115.3 14.3
As 93.12 6.88 76.2 27.6 94.8 2.6
La 100 <0.1 120.2 0.5 117.3 <0.1
Pb 100 <0.1 115.0 <0.1 108.7 <0.1
Cu 100 <0.1 63.1 29.2 97.2 0.7

Phosphogypsum (PG), Portlandite (S1), Thenardite (S2), Calcite (S3), and solid residue from the evaporation of final liquid
fraction (S4).
Reprinted with permission from Contreras, M., Pérez-L
opez, R., G
azquez, M., Morales-Fl
orez, V., Santos, A., Esquivias,
L., Bolivar, J.P., 2015. Fractionation and fluxes of metals and radionuclides during the recycling process of phosphogypsum
wastes applied to mineral CO2 sequestration. Waste Management 45, 412e419.

232
Th series, respectively) (Bolivar et al., 1995, 1996), which is broken during the in-
dustrial process. These radionuclides are distributed between PG (U-series) and phos-
phoric acid, depending on their solubility and chemical affinity (Rutherford et al.,
1994; Abril et al., 2009).
210 Carbon Dioxide Sequestration in Cementitious Construction Materials

The homogenized PG sample used in the carbonation experiments contains

(6.7  0.4)  102 Bq/kg of 226Ra, which is in agreement with previous works (Mazzilli
et al., 2000; Carvalho, 2001). Similar conclusions were obtained for the rest of the
radionuclides (238U, 230Th, and 210Pbe210Po). Particularly striking is the behavior of
the 226Ra, with a concentration z700 Bq/kg (considered as NORM material), above
the upper limit set by the USEPA (370 Bq/kg) for use as a soil amendment (NES,
1992). Other radionuclides have activity concentrations slightly smaller than 226Ra,
such as 230Th ((5.0  0.4)  102 Bq/kg) and 210Pb ((5.5  0.3)  102 Bq/kg). On
the other hand, the concentrations of U-isotopes were very much lower than the rest
of the U-series radionuclides (68  8 Bq/kg of 238U). More than 85% remains in the
phosphoric acid fraction during the chemical industrial process as expected, because
of the high solubility of U in acidic media. Finally, Th-series radionuclides in PG are
generally near or below the detection limit (around 1 Bq/kg).
In general, the majority of the radionuclides initially present in PG accumulate in
portlandite and calcite (S1 and S3), in which the concentrations of U-isotopes, Ra-
isotopes, and Th-isotopes are twice as high as in the PG, being around 1100, 130,
1400, and 900 Bq/kg for 210Pbe210Po, 238U, 226Ra, and 230Th, respectively. Accord-
ing to the European Union regulation, S1 and S3 are NORM materials, and therefore
radiological control has to be applied during their commercial application. On the other
hand, the radionuclides’ concentrations in S2 (thenardite) are lower than in uncontam-
inated soils (Contreras et al., 2013).
The transfer factors involved during the complete process are also shown in
Table 9.3, and, as a general conclusion, it can be stated that 95% of the radionuclides’
activity was transferred during the dissolution reaction to the portlandite. Because of
the chemical affinity between Ca and Ra, these two elements have similar behavior
during the experimental run (Haridasan et al., 2001). Concentrations in S1 and S3 in-
crease up to twofold because impurities contained in the starting PG are transferred to
the products and only half of the weight of products is generated according to the stoi-
chiometry of both reactions. In the thenardite, the activity concentrations are near to
the detection limits, the same as in the dissolution and carbonation liquid phases. After
the carbonation process, the majority of the natural radioactivity contained in PG is
transferred to calcite (98%).

9.4 Procedures based on Al-rich wastes

9.4.1 Analysis of the samples prior to CO2 sequestration
Chemical analysis of the discarded liquid revealed the presence of Na ([Na] ¼
91  6 g/L), S ([S] ¼ 39.6  0.4 g/L), Al ([Al] ¼ 23  2 g/L), and a negligible
amount of Ca ([Ca] < 0.1 mg/L). The density of the supernatant was
1.34  0.1 g/cm3. The constituent crystalline phases of PGA were identified by
XRD (Fig. 9.4), and the two observed phases were hydrogrossularite (PDF: 00-002-
1124, Ca3Al2(OH)12, katoite) and thenardite (PDF: 01-074-2036, Na2SO4, sodium
sulfate). No residual gypsum was detected. In accordance with this, the chemical
Carbon dioxide sequestration by phosphogypsum based procedure 211

(+) Thenardite ( ) Katoite (G) Gypsum

PGA
Intensity (arb. un.) (washed)

PGA

G
G
PG G
GG G G GG G

10 20 30 40 50 60
2θ (°)
Figure 9.4 X-ray diffraction patterns of samples “PG” and “PGA,” as-synthesized and washed.
Adapted with permission from Romero-Hermida, I., Santos, A., Pérez-L
opez, R., García-
Tenorio, R., Esquivias, L., Morales-Fl
orez, V., 2017. New method for carbon dioxide miner-
alization based on phosphogypsum and aluminium-rich industrial wastes resulting in valuable
carbonated byproducts. Journal of CO2 Utilization 18, 15e22.

composition of PGA revealed Ca, Al, S, and Na as the major components, in relative
molar ratios Ca:Al and Na:S equal to those of the katoite (which was the target ratio of
the experimental procedure) and thenardite, respectively.
Katoite is included in a group of minerals known as hydrogarnet (Ca3(Al,Fe)2
(SiO4)y(OH)4(3y); 0 < y < 3), where the SiO4 4 tetrahedra are partially or
completely replaced by OH. The Al-containing hydrogarnet includes the hydrogros-
sular solid solution (Ca3Al2(SiO4)y(OH)4(3y), 0 < y < 3), katoite being the Si-free
end-member (C3AH6 in chemical notation2) (Pollmann, 2012; Dilnesa et al., 2014).
Thenardite is easily separated from the mixture of thenardite and katoite by gentle
rinsing with pure water (“PGA washed” in Fig. 9.4; Ca3Al2(OH)12) within a purity
of 95%, as estimated by XRF. TGA analysis (Romero-Hermida et al., 2017) confirmed
that the whole of the weight loss of 12 wt.% occurred in a two-step process (Rivas-
Mercury et al., 2008) between 250 and 400
C. The morphology of thenardite and
katoite present in PGA was observed by SEM. In Fig. 9.5, the micron-sized octahedral
habit of the katoite can be seen (Fogg et al., 2002; Kyritsis et al., 2009). Elongated
thenardite crystals can be readily observed.

2
Cement short-hand notation: C ¼ CaO, A ¼ Al2O3 and H ¼ H2O.
212 Carbon Dioxide Sequestration in Cementitious Construction Materials

Figure 9.5 SEM images of sample PGA, where z2-mm sized katoite octahedra (left and right)
and elongated thenardite crystals (right) were readily identified.

9.4.2 Carbonation experiments

The carbonation performance of the synthesized sequestration agent, PGA, was tested
by two different methods: bubbling CO2 into an aqueous suspension of PGA and
weathering.

9.4.2.1 Bubbling
The PGAB(L) presented a density of 1.00  0.1 g/cm3, and substantial S ([S] ¼
1.200  0.006 g/L) and Na ([Na] ¼ 0.763  0.008 g/L) contents by the dissolution
of the thenardite from the sample PGA, and low Al and Ca contents ([Al] ¼
6.2  0.3 mg/L; [Ca] ¼ 0.227  0.006 g/L). XRD analysis of the solid carbonated
precipitate, PGAB, is plotted in Fig. 9.6. The crystalline phases were almost exclu-
sively comprised of calcium carbonate (PDF: 01-083-1762, CaCO3, calcite),
although some impurities of quartz from the raw PG could be seen. Thenardite
was not present, confirming its complete dissolution during the carbonation process
(pH z 6.7). Nevertheless, XRF analysis (Table 9.3) revealed the presence of sub-
stantial contents of amorphous phases, containing mainly Al and S, and, to a lesser
extent, Na.

9.4.2.2 Weathering
Sample PGAW was obtained by the carbon sequestration experiments by the weath-
ering pools method (Morales-Fl
orez et al., 2011). The XRD analysis (Fig. 9.6)
revealed the presence of calcium carbonate (calcite), a substantial amount of remaining
thenardite, and aluminum hydroxide (PDF: 01-074-1119, Al(OH)3, bayerite). The re-
sults of TGA analysis of PGAW confirm that the weathering procedure achieved full
carbonation (100% efficiency) (Romero-Hermida et al., 2017). Considering the rele-
vance of specific surface area in the weathering kinetics (Morales-Fl
orez et al.,
2015), nitrogen physisorption analysis of the PGA sample revealed a very low specific
surface area (0.32 m2/g), which explains the extensive time required for full
Carbon dioxide sequestration by phosphogypsum based procedure 213

10 20 30 40 50 60
C (C) Calcite (Q) Quartz
(B) Bayerite (T) Thenardite

CC
Intensity (arb. un.)
C Q C C
PGAW B C B C
Q C B
(Washed) B
C T

T
TT TC
C
B C C T T C T
Q C B C
PGAW Q B T

C
Q C C C CC C
PGAB Q C Q Q

10 20 30 40 50 60
2θ (°)
Figure 9.6 XRD patterns of samples PGAB, PGAW, and PGAW (washed).
Reprinted with permission from Romero-Hermida, I., Santos, A., Pérez-L
opez, R., García-
Tenorio, R., Esquivias, L., Morales-Fl
orez, V., 2017. New method for carbon dioxide
mineralization based on phosphogypsum and aluminium-rich industrial wastes resulting in
valuable carbonated byproducts. Journal of CO2 Utilization 18, 15e22.

carbonation. Finally, the XRD pattern of sample PGAW (washed) shown in Fig. 9.6
reaffirmed that the thenardite present in PGAW could be readily removed.

9.4.3 Fractionation and fluxes and path of the toxic elements

In Table 9.4, mass balances and transfer factors are summarized; some estimation of
the discrepancies with respect to the expected values are also provided. In a typical
experiment, 12.50 g of PG was dissolved in 25 mL of alkaline waste (33.00 g,
density ¼ 1.32 g/cm3). The dissolution reaction yielded 17.0 g of PGA, containing
most of the Ca content of the system: 90% of the CaO was transferred from PG to
PGA, which was the ultimate objective of the process, as CaO is the chemically active
carbon sequestration species. Additionally, the Al2O3 was almost completely trans-
ferred to PGA.
Regarding the transfer of trace elements, as a general consideration, Cr, Sr, Cd, Ba,
Pb, and Th were fully transferred from PG to PGA, while a substantial part of the U
was transferred to the residual liquid phase PGA(L). The contents of V and As in
PGA were also raised by contributions from the liquid caustic Al-rich precursor (trans-
fer factors >100%).
The transfer of the trace elements through the carbonation reaction was expected to
be similar to previously reported procedures (C
ardenas-Escudero et al., 2011;
Contreras et al., 2015). The toxic trace elements present in the original PG were
214 Carbon Dioxide Sequestration in Cementitious Construction Materials

Mass balance and transfer factors (h) of the chemical

Table 9.4
species throughout the process
Mass of the
chemical
species Total
present in mass
the samples of the
(g) sample A12O3 Na2O SO3 CaO
Raw materials
PG 12.50 0.025  0.001 (1.25  0.01) 5.75  0.06 4.00  0.06
103
A(L) 33.00 2.44  0.06 3.960  0.005 e e
Total mass 45.50 2.47  0.06 3.961  0.005 5.75  0.06 4.00  0.06
involved
Dissolution
PGA 17.0 2.16  0.03 3.5  0.1 4.6  0.3 3.6  0.2
Transfer h ¼ 87% h ¼ 88% h ¼ 80% h ¼ 90%
factor
PGA(L) 26.80 0.88  0.02 2.44  0.04 1.98  0.01 103
Total mass 43.8 3.04  0.05 5.9  0.1 6.6  0.3 3.6  0.2
involved
Discrepancy 4% 23% 50% 14% 10%
Carbonation*
PGAB 9.8 1.43  0.03 0.22  0.01 1.42  0.09 3.1  0.2
Transfer h ¼ 66% h ¼ 6% h ¼ 31% h ¼ 86%
factor
PGAB(L) 297.12 (3.4  0.1)103 1.97  0.03 3.59  0.04 0.09  0.01
Total mass 306.9 1.43  0.03 2.19  0.04 5.0  0.1 3.2  0.2
involved
Discrepancy 14% 34% 38% 13% 11%

Uncertainties are given as standard deviation of the mean. “Discrepancy” stands for absolute values of discrepancy between
the total values. Discrepancies of carbonated species are only related to species contained in the PGA sample, given PGA(L)
was discarded. (*) Mass data of the carbonation experiments consider the addition of demineralized water (see Romero-
Hermida et al., 2017 for details). () No data. Digits in the first column are restricted to the minimum precision of each
sample series.
Reprinted with permission from Romero-Hermida, I., Santos, A., Pérez-L
opez, R., García-Tenorio, R., Esquivias, L.,
Morales-Fl
orez, V., 2017. New method for carbon dioxide mineralization based on phosphogypsum and aluminium-rich
industrial wastes resulting in valuable carbonated byproducts. Journal of CO2 Utilization 18, 15e22.
Carbon dioxide sequestration by phosphogypsum based procedure 215

generally transferred to the solid precipitated phases and finally trapped in the final car-
bonate, improving its fixation and avoiding its release to the environment through
dissolution or lixiviation, as it can occur in their current state within the PG stockpiles
(Pérez-L
opez et al., 2016). Thus, Sr, Cd, Ba, and Th were almost completely trans-
ferred, and Cr, Pb and U to a lesser extent, from PGA to the solid precipitate
PGAB. Only V and As were substantially shared between solid PGAB and liquid
phase PGAB(L). The trace elements from liquid caustic waste, V and As, were almost
equally distributed between solid and liquid phases.
The radiometric determination of several radionuclides of the uranium series asso-
ciated with the raw materials and different phases of the process are compiled in
Table 9.5. The U and Th radionuclides ratify the conclusions obtained from their
ICP-MS determinations (Romero-Hermida et al., 2017). Almost all the Th originally
associated with the raw PG was transferred into the final solid product, while the ma-
jority of U was also transferred to the same final product. A fraction of the U was trans-
ferred to the liquid phases but in concentrations low enough to affirm that no
radiological issues would be associated with their management. Based on the results
obtained for Sr by ICP-MS, and the similar chemical behavior of Sr and Ra (both

Summary of average activity concentrations of

Table 9.5
radionuclides
Concentration (mBq/g)
234 238 234
(Transfer factor,h) U U U/238U 230
Th
Raw materials
PG 69  4 67  4 1.03  0.08 534  19
A (L)
1.5  0.2 1.1  0.1 1.2  0.2 2.2  0.3
Dissolution
PGA 42  10 54  4 0.8  0.2 401  98
(78%) (102%) (101%)
PGA(L) 8.8  0.2 8.5  0.2 1.04  0.09 0.81  0.09
(26%) (26%) (0.3%)
Carbonation
PGAB 69  10 70  4 0.9  0.2 847  35
(95%) (75%) (122%)
PGAB (L)
0.16  0.05 0.14  0.04 1.1  0.4 0.15  0.05
(7%) (5%) (0.6%)

Uncertainties are given as standard deviation of the mean.

Reprinted with permission from Romero-Hermida, I., Santos, A., Pérez-L
opez, R., García-Tenorio, R., Esquivias, L.,
Morales-Fl
orez, V., 2017. New method for carbon dioxide mineralization based on phosphogypsum and aluminium-rich
industrial wastes resulting in valuable carbonated byproducts. Journal of CO2 Utilization 18, 15e22.
216 Carbon Dioxide Sequestration in Cementitious Construction Materials

elements from the column IIa in the periodic table), it could be expected that the ma-
jority of 226Ra (another member of the uranium series) would also be associated with
the final solid product. Finally, the 234U/238U ratio is close to unity, indicating that the
secular equilibrium present in the original phosphate rock was maintained during the
formation of the PG and subsequently along the carbon sequestration process.
Knowing the mass relation between the raw PG and the final carbonated phase
PGAB, it could also be affirmed that the concentrations of U, Th, and Ra in the solid
phases generated in the proposed sequestration processes would be similar to those
originally found in the PG. Consequently, from a radiological point of view, most
of the uses that have been recognized by the international community for the valoriza-
tion of PG (soil amendment, construction material, road basement, etc.) could be
considered for this new solid material (IAEA, 2013; Garcia-Tenorio et al., 2015;
Dweck et al., 2000). In this sense, at concentration levels found in the PG for the ra-
dionuclides of the uranium series (<1 Bq/g), it is now internationally recognized that
the valorization of PG can be performed safely without the need for radiological
regulation.

9.5 Future work: byproducts for construction materials

Preliminary studies for the application of the portlandite paste as construction material
have been carried out to evaluate the technological potentialities of one of the byprod-
ucts. Different mixtures of portlandite/sand and water/portlandite are being tested to
obtain a normal consistency, determined according to the procedure described in
UNE 83-811-92. For the preparation of the probes (4  4  4 cm3), portlandite/
sand ¼ 1:3 and water/portlandite ¼ 0.5, by weight, were used. Reference sand CEN
EN 196-1 of the Eduardo Torroja Institute was used as arid (SiO2 content, 99% by
mass). The preservation of the probes was followed according to the standard proced-
ure, that is, they were placed in a polyethylene bag for 5 days, then the molds were
removed and stored in the bag for 2 days. After this time they were kept in a humidity
chamber (RH 65  5%) for 21 days. Then, the compression tests were performed on
the flat faces of two of the probes. Other probes were left in contact with the atmo-
spheric CO2 or subjected to fast carbonation in a CO2-rich atmosphere (10% vol. of
CO2). Compressive strength test was performed on all the probes. The values of the
preliminary results of compressive and flexion strength tests are shown in Table 9.6.
They are within the values of other types of portlandite paste at these ages.
After fracture, the phenolphthalein test was carried out to check the mortar carbon-
ation degree (Fig. 9.7). From the outer to the inner of the mortar, it was observed that
the carbonation took place only in a thickness of few mm. Thus, the carbonation pro-
cess is incomplete and considerably higher mechanical strength could be expected for
longer aging times.
Also, a study of leaching of PG, intermediate phases, and mortars has to be carried
out to assess which of these materials encapsulate the toxic elements more reliably. It is
reasonable to expect that mortars give the best behavior since the concentrations of
Carbon dioxide sequestration by phosphogypsum based procedure 217

Table 9.6 Preliminary results of the mechanical properties of mortars

obtained from phosphogypsum reuses
Compression strength Flexure strength
Carbonation procedure (N/mm2) (N/mm2)

Natural carbonation
28 days 0.7  0.1 0.1
59 days 0.8
90 days 1.2 0.2
28 days natural carbonation D accelerated carbonation (time in chamber)
þ21 days 1.0 0.1
þ21 days acc. carb. þ 1 week nat. carb. 1.3  0.2 0.2

Acc. carb., accelerated carbonation; nat. carb., natural carbonation.

By courtesy of I. Romero-Hermida and V. Flores-Alés.

toxic elements decrease as a consequence of the added sand, as well as aging and
compaction lead to better encapsulation.
In cement chemistry, major attention has been paid to weathering processes of Port-
land cements (PC), which are based mainly upon lime-silica mineral phases. Transfor-
mation of portlandite into calcium carbonate occurs due to the action of CO2 on the
mineralogical compounds of PC. This causes the modification of the material micro-
structure and, consequently, of the mechanical and durability properties. Additionally,
today the use and production of PC face a number of problems, including the highly
polluting emissions (greenhouse gases, especially CO2 and NOx) generated during its
manufacture (Gartner, 2004) and certain technological limitations relating to concrete

High carbonation zone

Liesegang
pattern

Uncarbonated
zone

1 cm

Figure 9.7 Mortar probe carbonation revealed by the phenolphthalein test.

By courtesy of I. Romero-Hermida and V. Flores-Alés.
218 Carbon Dioxide Sequestration in Cementitious Construction Materials

durability (Metha, 1986). Hence, it is important to develop new cementitious materials

to replace PC in certain applications.
Calcium aluminate cements (CAC) are cements in which the main reactive phases
are lime-alumina compounds (Pastor et al., 2009). The katoite is the stable phase of the
calcium aluminate hydrates (C3AH6, also called hydrogarnet) that is formed during the
course of hydration of CAC (Taylor, 1997), the two meta-stable phases being CAH10
and C2AH8.
The properties of CAC include rapid strength development, good resistance to
sulfate attack as well as other forms of chemical attack, and, when used with refrac-
tory aggregates, effectiveness in refractory concretes (Fern
andez-Carrasco et al.,
2008). The reason for proposing the inclusion of CAC in alkaline concrete manu-
facture is that many alkaline materials, potentially susceptible to being alkali-
activated, lack sufficient aluminum to generate a product with the necessary
strength.
The synthesis of katoite by our experimental protocol has the advantage of being a
direct method to obtain the stable phase of aluminate hydrates, that is, it is not through
the metastable phase transformation reaction resulting from the hydration of CAC.
This transformation causes loss of porosity and cement strength. Hence, the direct syn-
thesis could be advantageous to obtain materials with great mechanical resistance and
also resistant to the attack of sulfates and others chemical elements. On the other hand,
the carbonation of katoite also implies an increase in mechanical strength, in addition,
to the production of durable and stable products, such as calcium carbonate and
aluminum hydroxide.
So, if we made building materials with katoite directly, will the effects associated
with such transformation reactions be reproduced? Accordingly, would the preparation
of such materials and such study be worthwhile? We are in the preliminary studies to
answer these questions.
Additionally, the PG wastes could also contain high concentrations of elements of
economic interest and some studies examine the potential recovery of metals of eco-
nomic interest in such wastes (Canovas et al., 2017). Particularly relevant would be
the presence of critical raw materials, those of high economic importance and at
risk of supply for European countries (European Commission, 2014).

Acknowledgments
The Spanish Government through the research project MAT2013-42934-R supported this work.
VM-F thanks the funding action of “V Plan Propio de la Universidad de Sevilla.” The technical
staff of the CITIUS-Universidad de Sevilla is acknowledged for their kind help with the analyses
of the samples. The authors also thank VERINSUR for supplying the aluminum industry waste,
and FERTIBERIA, for supplying phosphogypsum. The discussion and hints provided by Isa
Romero-Hermida and Vicente Flores from the University of Seville, Rafael Pérez-L
opez from
the University of Huelva, and Ron Zevenhoven from Åbo Akademi University were very valu-
able and appreciated.
Carbon dioxide sequestration by phosphogypsum based procedure 219

References
Abril, J.M., Garcia-Tenorio, R., Perianez, R., Enamorado, S.M., Andreu, L., Delgado, A., 2009.
Occupational dosimetric assessment (inhalation pathway) from the application of phos-
phogypsum in agriculture in South West Spain. Journal of Environmental Radioactivity
100, 29e34.


Alvarez-Ayuso, E., Nugteren, H., 2005. Synthesis of dawsonite: a method to treat the etching
waste streams of the aluminium anodising industry. Water Research 39, 2096e2104.


Alvarez-Ayuso, E., 2009. Approaches for the treatment of waste streams of the aluminium
anodising industry. Journal of Hazardous Materials 164, 409e414.
Alcordo, I.S., Rechcigl, J.E., 1993. Phosphogypsum in agriculture. A review. Advances in
Agronomy 118, 49e55.
Bobicki, E., Liu, Q., Xu, Z., Zeng, H., 2012. Carbon capture and storage using alkaline industrial
wastes. Progress in Energy and Combustion Science 38, 302e320.
Bolívar, J.P., García-Tenorio, R., García-Le
on, M., 1995. Fluxes and distribution of natural
radionuclides in the production and use of fertilizers. Applied Radiation and Isotopes 46,
717e718.
Bolívar, J.P., García-Tenorio, R., García-Le
on, M., 1996. On the fractionation of natural
radioactivity in the production of phosphoric acid by the wet acid method. Journal of
Radioanalytical and Nuclear Chemistry 214, 77e78.
Campos, M.P., Costa, L.J.P., Nisti, M.B., Mazzilli, B.P., 2017. Phosphogypsum recycling in the
building materials industry: assessment of the radon exhalation rate. Journal of Environ-
mental Radioactivity 172, 232e236.
Canovas, C.R., Perez-Lopez, R., Macías, F., Chapron, S., Nieto, J.M., Pellet-Rostaing, S., 2017.
Exploration of fertilizer industry wastes as potential source of critical raw materials. Journal
of Cleaner Production 143, 497e505.
C
ardenas-Escudero, C., Morales-Fl
orez, V., Pérez-L
opez, R., Santos, A., Esquivias, L., 2011.
Procedure to use phosphogypsum industrial waste for mineral CO2 sequestration. Journal
of Hazardous Materials 196, 431e435.
Carvalho, F.P., 2001. Disposal of phosphogypsum waste containing enhanced levels of radio-
activity. In: International Conference on Management of Radioactive Waste from Non-
power Applications, Book of Extended Synopses. International Atomic Energy Agency
CN-87/6, pp. 67e68.
Contreras, M., G
azquez, M.J., García-Díaz, I., Alguacil, F.J., L
opez, F.A., Bolívar, J.P., 2013.
Valorisation of waste ilmenite mud in the manufacture of sulphur polymer cement. Journal
of Environmental Management 128, 625e630.
Contreras, M., Martín, M.I., G
azquez, M.J., Romero, M., Bolívar, J.P., 2014. Valorisation of
ilmenite mud waste in the manufacture of commercial ceramic. Construction and Building
Materials 72, 31e40.
Contreras, M., Pérez-L
opez, R., G
azquez, M., Morales-Fl
orez, V., Santos, A., Esquivias, L.,
Bolivar, J.P., 2015. Fractionation and fluxes of metals and radionuclides during the recy-
cling process of phosphogypsum wastes applied to mineral CO2 sequestration. Waste
Management 45, 412e419.
Corisco, J.A.G., Mihalik, J., Madruga, M.J., Prudencio, M.I., Marques, R., Santos, M., Reis, M.,
2017. Natural radionuclides, rare earths and heavy metals transferred to the wild vegetation
covering a phosphogypsum stockpile at Barreiro, Portugal. Water and Soil Pollution 228,
235.
220 Carbon Dioxide Sequestration in Cementitious Construction Materials

Dilnesa, B., Lothenbach, B., Renaudin, G., Wichser, A., Kulik, D., 2014. Synthesis and char-
acterization of hydrogarnet Ca3(AlxFe1x)2(SiO4)y(OH)4(3y). Cement and Concrete
Research 59, 96e111.
Domínguez, R., Del Campillo, M.C., Pe~na, F., Delgado, A., 2001. Effect of soil properties and
reclamation practices on phosphorus dynamics in reclaimed calcareous marsh soils from
the Guadalquivir Valley, SW Spain. Arid Land Research and Management 16, 203e221.
Dweck, J., Buchler, P.M., Vieira Coelho, A.C., Cartledge, F.K., 2000. Hydration of a Portland
cement blended with calcium carbonate. Thermochimica Acta 346, 105e113.
European Commission, 2014. Critical Raw Materials for the EU. Brussels (Belgium). http://ec.
europa.eu/growth/sectors/raw-materials/specific-interest/critical_es.
Fernandez-Bertos, M., Simons, S., Hills, C., Carey, P., 2004. A review of accelerated carbon-
ation technology in the treatment of cement-based materials and sequestration of CO2.
Journal of Hazardous Materials 112, 193e205.
Fern
andez-Carrasco, L., Rius, J., Miravitlles, C., 2008. Supercritical carbonation of calcium
aluminate cement. Cement and Concrete Research 38, 1033e1037.
Fogg, A., Freij, A., Oliveira, A., Rohl, A., Ogden, M., Parkinson, G., 2002. Morphological
control of Ca3Al2(OH)12. Journal of Crystal Growth 234, 255e262.
Garcia-Tenorio, R., Bolivar, J.P., Gazquez, M.J., 2015. Management of by-products generated
by NORM industries: towards their valorization and minimization of their environmental
radiological impact. Journal of Radioanalytical and Nuclear Chemistry 306, 641e648.
Gartner, E., 2004. Industrially interesting approaches to ‘low-CO2’ cements. Cement and
Concrete Research 34, 1489e1498.
Geiger, C., Dachs, E., Benisek, A., 2012. Thermodynamic behavior and properties of katoite
(hydrogrossular): a calorimetric study. American Mineralogist 97, 1252e1255.
Gunning, P.J., Hills, C.D., Carey, P.J., 2010. Accelerated carbonation treatment of industrial
wastes. Waste Management 30, 1081e1090.
Haridasan, P.P., Paul, A.C., Desai, M.V.M., 2001. Natural radionuclides in the aquatic envi-
ronment of a phosphogypsum disposal area. Journal of Environmental Radioactivity 53,
155e165.
Hentati, O., Abrantes, N., Caetano, A., Bouguerra, S., Goncalves, F., Roembke, J., Pereira, R.,
2015. Phosphogypsum as a soil fertilizer: ecotoxicity of amended soil and elutriates to
bacteria, invertebrates, algae and plants. Journal of Hazardous Materials 294, 80e89.
Hitch, M., Dipple, G., 2012. Economic feasibility and sensitivity analysis of integrating
industrial-scale mineral carbonation into mining operations. Minerals Engineering 39,
268e275.
Holanda, F.D., Schmidt, H., Quarcioni, V.A., 2017. Influence of phosphorus from phospho-
gypsum on the initial hydration of Portland cement in the presence of superplasticizers.
Cement and Concrete Composites 83, 384e393.
Huntzinger, D., Gierke, J., Sutter, L., Kawatra, S., Eisele, T., 2009. Mineral carbonation for
carbon sequestration in cement kiln dust from waste piles. Journal of Hazardous Materials
168, 31e37.
IAEA (Intetrnational Atomic Energy Agency), 2013. Radiation Protection and Management of
NORM Residues in the Phosphate Industry, Safety Report, 78.
Kirchofer, A., Becker, A., Brandt, A., Wilcox, J., 2013. CO2 mitigation potential of mineral
carbonation with industrial alkalinity sources in the United States. Environmental Science
and Technology 47, 7548e7554.
Kuwahara, Y., Yamashita, H., 2013. A new catalytic opportunity for waste materials: applica-
tion of waste slag based catalyst in CO2 fixation reaction. Journal of CO2 Utilization 1,
50e59.
Carbon dioxide sequestration by phosphogypsum based procedure 221

Kyritsis, K., Meller, N., Hall, C., 2009. Chemistry and morphology of hydrogarnets formed in
cement-based CASH hydroceramics cured at 200e350
C. Journal of the American
Ceramic Society 92, 1105e1111.
Lackner, K.S., Wendt, C.H., Butt, D.P., Joyce, E.L., Sharp, D.H., 1995. Carbon dioxide disposal
in carbonate minerals. Energy 20, 1153e1170.
Lambert, A., Tam, J., Azimi, G., 2017. Microwave treatment for extraction of rare earth elements
from phosphogypsum. Rare Metal Technology 2017, 47e53.
Lottermoser, B.G., 2010. Mine Wastes: Characterization, Treatment, Environmental Impacts.
Springer, Berlin Heidelberg.
Lozano, R.L., Bolívar, J.P., San Miguel, E.G., García-Tenorio, R., G
azquez, M.J., 2011. An
accurate method to measure alpha-emitting natural radionuclides in atmospheric filters:
application in two NORM industries. Nuclear Instruments and Methods in Physics Section
A 659, 557e568.
Macias, F., Canovas, C.R., Cruz-Hernandez, P., Carrero, S., Asta, M.P., Nieto, J.M., Perez-
Lopez, R., 2017. An anomalous metal-rich phosphogypsum: characterization and classi-
fication according to international regulations. Journal of Hazardous Materials 331,
99e108.
Mattila, H.P., Zevenhoven, R., 2015. Mineral carbonation of phosphogypsum waste for pro-
duction of useful carbonate and sulfate salts. Frontiers in Energy Research 48.
Mazzilli, B., Palmiro, V., Saueia, C., Nisti, M.B., 2000. Radiochemical characterization of
Brazilian phosphogypsum. Journal of Environmental Radioactivity 49, 113e122.
Mechi, N., Khiari, R., Ammar, M., Elaloui, E., Belgacem, M.N., 2017. Preparation and appli-
cation of Tunisian phosphogypsum as fillers in papermaking made from Prunus amygdalus
and Tamarisk sp. Powder Technology 312, 287e293.
Metha, P.K., 1986. Concrete: Structure, Properties and Materials. Prentice-Hall, Englewood
Cliffs, New York.
Morales-Fl
orez, V., Santos, A., Lemus, A., Esquivias, L., 2011. Artificial weathering pools of
calcium-rich industrial waste for CO2 sequestration. Chemical Engineering Journal 166,
132e137.
Morales-Fl
orez, V., Santos, A., Romero-Hermida, I., Esquivias, L., 2015. Hydration and
carbonation reactions of calcium oxide by weathering: kinetics and changes in the nano-
structure. Chemical Engineering Journal 265, 194e200.
Msila, X., Billing, D., David, G., Barnard, W., 2016. Capture and storage of CO2 into waste
phosphogypsum: the modified Merseburg process. Clean Technologies and Environmental
Policy 18, 2709e2715.
NES, 1992. “National emission standards for hazardous air pollutants, national emission stan-
dards for radon emissions from phosphogypsum stacks”, 40 CFR Part 61. Federal Register,
USA 57 (107), 23305e23320.
Olajire, A., 2013. A review of mineral carbonation technology in sequestration of CO2. Energy
Procedia 37, 6999e7005.
Pacala, S., Socolow, R., 2004. Stabilization wedges: solving the climate problem for the next 50
years with current technologies. Science 305, 968e972.
Papageorgiou, F., Godelitsas, A., Mertzimekis, T.J., Xanthos, S., Voulgaris, N., Katsantonis, G.,
2016. Environmental impact of phosphogypsum stockpile in remediated Schistos waste site
(Piraeus, Greece) using a combination of gamma-ray spectrometry with geographic in-
formation systems. Environmental Monitoring and Assessment 188, 3.
Passaglia, E., Rinaldi, R., 1984. Katoite, a new member of the Ca3Al2(SiO4)3-Ca3Al2(OH)12
series and a new nomenclature for the hydrogrossular group of minerals. Bulletin de
Mineralogie 107, 605e618.
222 Carbon Dioxide Sequestration in Cementitious Construction Materials

Parreira, A.B., Kobayashi Jr., A.R.K., Silvestre, O.B., 2003. Influence of Portland cement type
on unconfined compressive strength and linear expansion of cement-stabilized phospho-
gypsum. Journal of Environmental Engineering 129, 956e960.
Pastor, C., Fern
andez-Jiménez, A., V
azquez, T., Palomo, A., 2009. Calcium aluminate cement
hydration in a high alkalinity environment. Materiales de Construcci
on 59 (293), 21e34.
Pérez-L
opez, R., Nieto, J.M., L
opez-Coto, I., Aguado, J.L., Bolívar, J.P., Santisteban, M., 2010.
Dynamics of contaminants in phosphogypsum of the fertilizer industry of Huelva (SW
Spain): from phosphate rock ore to the environment. Applied Geochemistry 25, 705e715.
Pérez-L
opez, R., Macías, F., C
anovas, C.R., Sarmiento, A.M., Pérez-Moreno, S.M., 2016.
Pollutant flows from a phosphogypsum disposal area to an estuarine environment: an
insight from geochemical signatures. The Science of the Total Environment 553, 42e51.
Pollmann, H., 2012. Calcium aluminate cements e raw materials, differences, hydration and
properties. Reviews in Mineralogy and Geochemistry 74.
Power, I.M., Harrison, A.L., Dipple, G.M., Wilson, S.A., Kelemen, P.B., Hitch, M.,
Southam, G., 2013. Carbon mineralization: from natural analogues to engineered systems.
Reviews in Mineralogy and Geochemistry 77, 305e360.
Rendek, E., Ducom, G., Germain, P., 2006. Carbon dioxide sequestration in municipal solid
waste incinerator (MSWI) bottom ash. Journal of Hazardous Materials 128, 73e79.
Renforth, P., Washbourne, C., Taylder, J., Manning, D., 2011. Silicate production and avail-
ability for mineral carbonation. Environmental Science and Technology 45, 2035e2041.
Rivas-Mercury, J.M., Pena, P., De Aza, A.H., Turrillas, X., 2008. Dehydration of
Ca3Al2(SiO4)y(OH)4(3y) (0 < y < 0.176) studied by neutron thermodiffractometry.
Journal of the European Ceramic Society 28, 1737e1748.
Romanov, V., Soong, Y., Carney, C., Rush, G., Nielsen, B., O’Connor, W., 2015. Minerali-
zation of carbon dioxide: a literature review. ChemBioEng Reviews 2, 231e256.
Romero-Hermida, I., Morales-Fl
orez, V., Santos, A., Villena, A., Esquivias, L., 2014. Tech-
nological proposals for recycling industrial wastes for environmental applications. Minerals
4, 746e757.
Romero-Hermida, I., Santos, A., Pérez-L
opez, R., García-Tenorio, R., Esquivias, L., Morales-
Fl
orez, V., 2017. New method for carb
on dioxide mineralization base don phosphogyp-
sum and aluminium-rich industrial wastes resulting in valuable carbonated by-products.
Journal of CO2 Utilization 18, 15e22.
Rutherford, P.M., Dudas, M.J., Samek, R.A., 1994. Environmental impacts of phosphogypsum.
The Science of the Total Environment 149, 1e38.
Sanna, A., Dri, M., Hall, M., Maroto-Valer, M., 2012. Waste materials for carbon capture and
storage by mineralisation (CCSM) e a UK perspective. Applied Energy 99, 545e554.
Santos, A., Ajbary, M., Morales-Fl
orez, V., Kherbeche, A., Pi~ nero, M., Esquivias, L., 2009.
Larnite powders and larnite/silica aerogel composites as effective agents for CO2 seques-
tration by carbonation. Journal of Hazardous Materials 168, 1397e1403.
Seifritz, W., 1990. CO2 disposal by means of silicates. Nature 345, 486.
Sipila, J., Teir, S., Zevenhoven, R., 2008. Carbon Dioxide Sequestration by Mineral Carbon-
ation: Literature Review Update 2005e2007. Abo Akademi University, Turku, Finland.
Smaoui-Jardak, M., Kriaa, W., Maalej, M., Zouari, M., Kamoun, L., Trabelsi, W., Ben
Abdallah, F., Elloumi, N., 2017. Effect of the phosphogypsum amendment of saline and
agricultural soils on growth, productivity and antioxidant enzyme activities of tomato
(Solanum lycopersicum L.). Ecotoxicology 26, 1089e1104.
Tayibi, H., Choura, M., Lopez, F.A., Alguacil, F.J., Lopez-Delgado, A., 2009. Environmental
impact and management of phosphogypsum. Journal of Environmental Management 90,
2377e2386.
Carbon dioxide sequestration by phosphogypsum based procedure 223

Taylor, H.F.W., 1997. Cement Chemisty. Thomas Telford, London.

Teir, S., Kotiranta, T., Pakarinen, J., Mattila, H., 2016. Case study for production of calcium
carbonate from carbon dioxide in flue gases and steelmaking slag. Journal of CO2 Utili-
zation 14, 37e46.
USEPA (US Environmental Protection Agency), 2002. National Emission Standards for Haz-
ardous Air Pollutants (USA).
Villa-Alfageme, M., Mosqueda, F., Hurtado, S., Mantero, J., Manj
on, G., Peria~
nez, R., Vaca, F.,
García-Tenorio, R., 2009. Contamination and restoration of an estuary affected by phos-
phogypsum releases. The Science of the Total Environment 408, 69e77.
Xie, H.P., Wang, J.L., Hou, Z.M., Wang, Y.F., Liu, T., Tang, L., Jiang, W., 2016. CO2
sequestration through mineral carbonation of waste phosphogypsum using the technique of
membrane electrolysis. Environmental Earth Sciences 75, 1216.
Yang, L., Yan, Y., Hu, Z., 2013. Utilization of phosphogypsum for the preparation of non-
autoclaved aerated concrete. Construction and Building Materials 44, 600e606.
Zhao, H., Li, H., Bao, W., Wang, C., Li, S., Lin, W., 2015. Experimental study of enhanced
phosphogypsum carbonation with ammonia under increased CO2 pressure. Journal of CO2
Utilization 11, 10e19.
Zhao, S., Ma, L., Yang, J., Zheng, D., Liu, H., Yang, J., 2017. Mechanism of CO2 capture
technology based on the phosphogypsum reduction thermal decomposition process. En-
ergy & Fuels 31, 9824e9832.