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The main aim of this work was to assess the potential of in situ carbonation as a treatment to modify the properties of alkaline materials such as industrial soil in terms of leaching behaviour and mineralogy and to store the CO2 generated by specific treatments applied in the context of Brownfield regeneration. The process was investigated through lab-scale column carbonation experiments, in which 100% CO2 was fed through humidified stainless steel slag under ambient temperature and pressure for set reaction times. The reaction kinetics and the maximum CO2 uptake attained (5.5%), corresponding to a Ca conversion yield of 15.6%, after 4 h treatment proved slightly lower than those resulting from batch tests carried out on the same particle size fraction at enhanced operating conditions. The mineralogy of the material showed to be affected by column carbonation, exhibiting a higher calcite content and the decrease of Ca hydroxide and silicate phases. As a result of carbonation, the material showed a decrease in pH and Ca release as well as an increase in Si mobility. Furthermore, a reduction of Cr and Ba leaching, up to 63% and 96% respectively, was achieved after 2 h of reaction. However, carbonation was observed to lead to an increased leaching of V and Mo. The effects of carbonation on the leaching behaviour of the material were also investigated performing pH-dependence leaching tests and the results indicated that in situ carbonation appears to be a promising treatment to improve the properties of alkaline materials in view of their reuse on-site.
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Carbonation of stainless steel slag in the context of in situ Brownfield
remediation
Oriana Capobianco
a
, Giulia Costa
a
, Laurens Thuy
b
, Elisa Magliocco
a
, Niels Hartog
b,c
, Renato Baciocchi
a,
a
Laboratory of Environmental Engineering, Dept. Civil Engineering and Computer Science Engineering, University of Rome ‘‘Tor Vergata’’, Via del Politecnico 1, 00133 Rome, Italy
b
Dept. Earth Sciences, Utrecht University, Utrecht, The Netherlands
c
KWR Watercycle Research Institute, Nieuwegein, The Netherlands
article info
Article history:
Available online 3 December 2013
Keywords:
Brownfield
Carbonation
CO
2
uptake
Leaching
Mineralogy
Steel slag
abstract
The main aim of this work was to assess the potential of in situ carbonation as a treatment to modify the
properties of alkaline materials such as industrial soil in terms of leaching behaviour and mineralogy and
to store the CO
2
generated by specific treatments applied in the context of Brownfield regeneration. The
process was investigated through lab-scale column carbonation experiments, in which 100% CO
2
was fed
through humidified stainless steel slag under ambient temperature and pressure for set reaction times.
The reaction kinetics and the maximum CO
2
uptake attained (5.5%), corresponding to a Ca conversion
yield of 15.6%, after 4 h treatment proved slightly lower than those resulting from batch tests carried
out on the same particle size fraction at enhanced operating conditions. The mineralogy of the material
showed to be affected by column carbonation, exhibiting a higher calcite content and the decrease of Ca
hydroxide and silicate phases. As a result of carbonation, the material showed a decrease in pH and Ca
release as well as an increase in Si mobility. Furthermore, a reduction of Cr and Ba leaching, up to 63%
and 96% respectively, was achieved after 2 h of reaction. However, carbonation was observed to lead
to an increased leaching of V and Mo. The effects of carbonation on the leaching behaviour of the material
were also investigated performing pH-dependence leaching tests and the results indicated that in situ
carbonation appears to be a promising treatment to improve the properties of alkaline materials in view
of their reuse on-site.
Ó2013 Elsevier Ltd. All rights reserved.
1. Introduction
The modification of land use and the subsequent dismantling of
several industrial activities has led to the formation of a number of
derelict or underused sites, i.e. Brownfields, all across Europe (Oli-
ver et al., 2004) and worldwide (Marker et al., 2007) that are wait-
ing to be reintroduced within the so called Land Management
Cycle. One of the main factors that hinders the revitalization of
Brownfield sites, such as former metallurgical plants or mining
areas, is the need to address soil contamination issues, which
may arise from the past land activities as well as from the interim
uses of the site. Partly also as a consequence of the lack of a clear
requalification pathway, traditional remediation strategies, e.g.
excavation and landfilling, are generally applied for the manage-
ment of the contaminated soil, implying off-site transport and
leading to further land consumption. The poor acceptance of land-
filling and the environmental impact of this management practice,
together with its excessive costs in the case of large volumes of
material to be disposed of, drive the need of identifying alternative
integrated approaches for the management of contaminated soil
within a Brownfield regeneration framework. In this type of frame-
work, the approach to the Brownfield environmental problems
should shift from considering the individual contamination issue
towards a wider perspective accounting for integrated strategies
in the context of land management. The clean-up of the site, which
is mandatory for the reintroduction of a Brownfield within the land
cycle, should be fulfilled by (re)using material and exploiting re-
sources already present at the site and/or produced as a result of
the regeneration activities themselves (Baciocchi et al., 2012).
Namely, contaminated soil and industrial residues with specific
properties could be reused within the site as aggregates (Manso
et al., 2006; Scanferla et al., 2009), filling material (Scanferla
et al., 2009) or pozzolanic material for cement substitution (Pan
et al., 2008).
In a Brownfield regeneration context, soil is commonly referred
to as industrial soil, since it may be characterized by the presence
of material of anthropogenic origin arising from the historical use
of the site that may cause detrimental environmental effects re-
lated to the release of toxic metals and metalloids (Voglar and Leš-
tan, 2010). For instance, the profile of an industrial soil may be
characterized by the stratification or the heterogeneous mixture
0892-6875/$ - see front matter Ó2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.11.005
Corresponding author. Tel.: +39 0672597022; fax: +39 0672597021.
E-mail address: baciocchi@ing.uniroma2.it (R. Baciocchi).
Minerals Engineering 59 (2014) 91–100
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of native soil and industrial by-products, such as demolition waste
and slag from steel making processes (Renforth et al., 2009) for
which the leaching of specific elements may be significant, e.g.:
Cr from stainless steel slag (Shen et al., 2004). Furthermore, Ren-
forth et al. (2009) showed that some kinds of alkaline soils present
in Brownfield sites may act as carbon sinks by reacting with atmo-
spheric carbon dioxide. Namely, they found that the 20 cm-layer of
the industrial soil pertaining to a former steelmaking company was
characterized by a variable CaCO
3
content, ranging between 0% and
38% but presenting a poor correlation with sample depth. A step
forward aimed at employing this type of industrial soil as alkaline
source could be represented by the application of accelerated car-
bonation, using far more concentrated carbon dioxide sources than
atmospheric air. So far, accelerated carbonation, has been devel-
oped as an ex situ CO
2
storage option, by which a material rich
in alkaline earth metal oxides and/or silicates is contacted with
carbon dioxide at optimized operating conditions (i.e. temperature,
pressure and pH), thus leading to the formation of the correspond-
ing thermodynamically and chemically stable carbonate phases
(Lackner et al., 1995). Several reaction routes (e.g. indirect, direct
gas–solid or direct aqueous) have been investigated with the aim
of maximizing the CO
2
uptakes achievable by ex situ carbonation
of minerals and alkaline residues such as steel slag (see e.g. Doucet,
2010; Bobicki et al., 2012).
In addition, ex situ carbonation processes carried out in aque-
ous conditions, applying liquid to solid (L/S) ratios above 2 l/kg
(slurry phase route) or below 1 l/kg (wet route) and generally mild
operating conditions have been tested as treatment strategies to
reduce the release of metals and metalloids from alkaline indus-
trial residues, such as incineration bottom ash and steelmaking
slag (e.g. Van Gerven et al., 2005; Baciocchi et al., 2010a, 2010c;
van Zomeren et al., 2011). Furthermore, accelerated carbonation
has been tested in combination with cement as a stabilization
treatment for contaminated industrial soil (Antemir et al., 2010)
and also as a technique to increase the compressive strength of
compacts formed by residues rich in Ca silicates such as steel slag
(Johnson et al., 2003).
Hence, the application of accelerated carbonation in a Brown-
field regeneration context appears to be of particular interest since
it may allow the achievement of multiple benefits. In Brownfield
sites primary CO
2
sources, such as combustion or power plants
or other industrial processes, may be no longer available; however,
CO
2
emissions may result as a consequence of treatments aimed at
the remediation of groundwater contaminated by organic com-
pounds such as oxidation or CO
2
stripping (Nelson et al., 2009). Be-
sides, CO
2
may evolve from innovative treatments for the
improvement of the structural properties of the subsoil in view
of Brownfield sites redevelopment (Hartog et al., 2013). Therefore,
in these types of contexts, CO
2
upward flows through the subsoil
may be exploited to induce in situ carbonation reactions in existing
or specifically prepared layers of alkaline residues and/or industrial
soil to improve the environmental and technical properties of the
materials as well as to permanently store CO
2
. A schematic repre-
sentation of the proposed in situ carbonation process as a treat-
ment for industrial soil in Brownfield sites coupled with in situ
stripping of volatile organic contaminants (VOCs) from groundwa-
ter is depicted in Fig. 1. In this application the injected CO
2
can first
serve to strip VOCs from groundwater before stimulating the car-
bonation of the slag material in the overlying industrial soil. As
shown in Fig. 1, the reagents are injected into the subsurface,
resulting in the evolution of a CO
2
upward flow as well as the vol-
atilization of organic contaminants affecting groundwater quality.
Once the CO
2
reaches the layer of alkaline industrial soil, carbon-
ation occurs, resulting in the improvement of the environmental
properties of the carbonated material and CO
2
storage. Extraction
wells are also foreseen in order to collect the unreacted carbon
dioxide and the volatilized organic compounds to submit to proper
treatment.
The main aim of this work was to assess the feasibility of the
proposed in situ carbonation process by means of a column car-
bonation experimental method in terms of the effects exerted on
the environmental behaviour of the treated material as well as
on the achieved CO
2
uptakes. Specifically, this paper reports the re-
sults of laboratory scale column carbonation tests performed flow-
ing 100% CO
2
through stainless steel (SS) slag and applying
operating conditions expected at Brownfield sites. In addition, to
assess the reactivity of the material with CO
2
, accelerated carbon-
ation tests were also carried out under enhanced conditions in a
stainless steel batch reactor. All tests were performed on a mixture
of freshly produced slags provided by a stainless steelmaking plant.
Despite this sample may seem not adequately representative of
aged slags typically found in Brownfield sites, it is worth pointing
out that the effect of aging on the extent of carbonation is often
limited to the top layer of an industrial soil. For instance, Suer
et al. (2009) and Arm et al. (2011) reported upon weathering a
pH shift of steel slags sampled from a pile, whereas for instance
those buried beneath a road did not show remarkable changes of
pH. Similarly, also Renforth et al. (2009) found the extent of car-
bonation of an industrial soil collected in a former steelmaking
plant below a depth of 20 cm to be negligible. Therefore, this evi-
dence seems to suggest that the use of fresh slag samples adopted
in this paper may provide meaningful results also for slags present
in Brownfield sites. As for the effects of carbonation on the proper-
ties of the residues, the modifications occurring in the mineralogy,
acid neutralization capacity and release of major elements and
trace components from the material both at its native pH and as
a function of pH are analyzed.
2. Materials and methods
2.1. Materials
The slag sample tested in this study, provided from a stainless
steel production plant, is representative of the residues mix that
is sent out of the plant for disposal. As the main residues produced
by the plant are those generated from the Electric Arc Furnace
(EAF) and from the Argon Oxygen Decarburization (AOD) converter
units, the sample may be expected to be a mixture of these types of
slag. After determining its particle size distribution (ASTM D422),
the coarser fraction (d> 0.84 mm) was discarded as it was not con-
sidered suitable for performing reproducible lab-scale experi-
ments. The remaining material was divided into a fine
(d< 0.177 mm) and an intermediate (0.177–0.84 mm) fraction.
Both fractions were characterized in terms of their elemental com-
position and mineralogy.
The elemental composition was determined by alkali fusion of
the slag samples with Li
2
B
4
O
7
at 1050 °C followed by dissolution
with 10% HNO
3
of the molten material and analysis of the solutions
by inductively coupled plasma optical emission spectrometry (ICP–
OES). The mineralogy of the as received and carbonated slag was
evaluated by X-ray diffraction (XRD) analysis with Cu K
a
radiation
using a Philips Expert Pro diffractometer (equipped with a copper
tube operated at 40 kV and 40 mA) with an angular step of 0.02°
held for 2 s with 2hspanning from 5°to 85°.
The intermediate fraction was also characterized in terms of its
leaching behaviour before and after column carbonation tests, in
order to evaluate the influence of this treatment on the mobility
of major and trace elements. Specifically, the EN 12457-2 compli-
ance test and the CEN/TS 14429 pH-dependence leaching test were
applied both on as received and carbonated samples and the elu-
ates were analyzed by ICP–OES. For the latter type of test, in order
to span a wide pH range, acid additions were performed employing
92 O. Capobianco et al. /Minerals Engineering 59 (2014) 91–100
a 2 mol/l HNO
3
solution; while in order to increase the pH of the
eluates of the carbonated samples a 2 mol/l NaOH solution was
used. All chemical analyses, except the pH-dependence leaching
test were performed in triplicate.
2.2. Carbonation tests
Column carbonation experiments were performed in a glass
column with a height of 16 cm and a diameter of 2 cm, packed with
the intermediate particle size fraction of the slag, supported by a
3 cm layer of glass spheres to ensure homogeneous inlet gas distri-
bution. The coarser fraction of the slag was discarded as the parti-
cle size was too large with respect to the column diameter,
whereas the finest one was discarded as it was assumed that the
pressure drop through the column could become too high. Hence,
the selection of the intermediate grain size range was aimed at
obtaining a sufficient gas flow through the material as well as a sig-
nificant degree of carbonation, which is reported to vary greatly
with grain size (see e.g.: Baciocchi et al., 2009). Besides, the inter-
mediate fraction corresponded to a relevant portion of the as re-
ceived material.
In each experiment 40 g of dry material and 8 ml of distilled
water were mixed, following two different water addition meth-
ods. The first method (mixing) entailed the addition of the water
to the slag in a glass beaker until the material was homogeneously
wetted. In the second (percolation), the dry material was first
packed into the column in layers and then each layer was humid-
ified from the top with a standardized procedure so to possibly en-
sure uniform dispersion of the water throughout the slag. The
latter approach was adopted in order to more closely reproduce
the wetting of the material under a real application scenario,
whereas the former one was applied to obtain a homogeneously
wetted slag. In both cases, the material was placed into the column
from the top and compacted in subsequent layers to avoid the
presence of preferential flow pathways.
The carbonation experiments were carried out at ambient tem-
perature (T= 22–25 °C) and pressure (P= 1 bar) flowing 100% CO
2
through the column for reaction times of 1, 2, 4 and 8 h. We chose
to use 100% CO
2
as this composition is in keeping with that em-
ployed in in situ remediation of volatile organic contaminants from
groundwater using CO
2
-supersaturated water injection (Nelson
et al., 2009). The 100% CO
2
flow was first humidified with a bubbler
and then fed to the bottom section of the column with a flow rate
of around 10 ml/min. At the end of the experiment, slag samples
were collected from the top, middle and bottom level of the col-
umn with the aim of identifying potential differences in the extent
of carbonation. All of the collected samples were weighted and
then dried overnight at 105 °C, allowing to measure their moisture
content. A fraction of each sample was subsequently milled below
0.177 mm and analyzed to determine its Inorganic Carbon (IC) con-
tent with a solid sample module for total organic carbon analysis
(Shimadzu-5000A) through acidification of the sample with phos-
phoric acid at 200 °C and quantification of the evolved CO
2
by
infrared analysis (EN 13137). Selected milled samples were kept
for mineralogy evaluation, whereas representative unmilled sam-
ples obtained at different reaction times were collected for the
leaching tests.
Accelerated batch carbonation tests were performed on both
the fine and intermediate slag particle size fractions at the operat-
ing conditions (T=50°C, P= 10 bar, L/S= 0.4 l/kg) that showed to
enhance SS slag carbonation reaction in previous investigations
(Baciocchi et al., 2009). These tests were aimed at assessing the
maximum reactivity with CO
2
of the two grain size fractions. In
each test, performed in a pressurized stainless steel reactor follow-
ing the procedure described in previous works (Baciocchi et al.,
2010b), three 1 g samples, humidified at the set L/Sratio, were ex-
posed to a 100% CO
2
flow for different reaction times, ranging from
0.25 to 24 h. Batch tests were also carried out on the intermediate
fraction under similar conditions to those applied in the column
experiments (T=23°C, P= 1 bar, L/S= 0.2 l/kg). The aim of these
tests was to evaluate possible changes in the extent and kinetics
Fig. 1. Schematic overview of the in situ carbonation process proposed as a treatment option for alkaline industrial soils at Brownfield sites coupled with in situ stripping of
volatile organic contaminants (VOCs) from groundwater.
O. Capobianco et al. / Minerals Engineering 59 (2014) 91–100 93
of carbonation resulting from the different reaction mode adopted
(batch or column). The carbonated samples obtained from the
batch tests were analyzed to determine their IC content and min-
eralogy applying the same procedures as those adopted for the col-
umn experiments.
3. Results and discussion
3.1. Main properties of the tested slag
The stainless steel slag employed in this study was quite heter-
ogeneous in its grain size distribution and showed a large amount
(about 40 wt.%) of coarse particles (d> 0.84 mm). The two classes
selected for the carbonation experiments presented the following
weight distribution: 23.5% the fine fraction (D< 0.177 mm) and
36.8% the intermediate fraction.
The elemental composition of both grain size classes is reported
in Table 1. The major constituents of the slag included Ca, Si, Cr, Fe,
Al and Mg. Appreciable concentrations of Ni (0.05–0.14 wt.%) and V
(0.06–0.11 wt.%) were also observed. The Ca content (>30 wt.%)
proved to be comparable to the concentrations generally reported
for Electric Arc Furnace (EAF) slags (Shen et al., 2004; Baciocchi
et al., 2009, 2010b) but were lower than those exhibited by the res-
idues generated by steel refining processes, such as Argon Oxygen
Decarburization (AOD) (Shen et al., 2004; Baciocchi et al., 2010b).
Also Mg and Si contents resulted higher in the intermediate frac-
tion, showing average concentrations of 1.9 and 10.7 wt.%, respec-
tively. Significant concentrations of Fe and Cr were measured in the
intermediate fraction, the Cr content being rather high and compa-
rable to that reported for EAF slag between 3.2 (Shen et al., 2004)
and 3.7 wt.% (Baciocchi et al., 2009).
The XRD patterns resulting for the fine and intermediate frac-
tions are reported in Fig. 2. In both of the as received grain size
classes several silicate phases were detected, in agreement with
the results reported in previous studies on SS slag (Shen et al.,
2004; Baciocchi et al., 2009, 2010b). Moreover, some differences
between the two fractions were observed. In the fine fraction a
prevalence of dicalcium silicate (Ca
2
SiO
4
) was retrieved, while
aluminium calcium silicate (CaAl
2
SiO
6
) and melilite (Ca
2
(Mg
0.5
Al
0.5
)
(Si
1.5
Al
0.5
O
7
)) appeared to be the most abundant minerals in the
intermediate fraction. In both cases, some Fe phases, including iron
sulfide (FeS), iron oxide (Fe
2
O
3
) and calcium oxide (CaO) were
identified, together with calcite (CaCO
3
) and fluorite (CaF
2
). Despite
a peak corresponding to portlandite (Ca(OH)
2
) was also detected in
particular in the intermediate size class, the XRD results confirmed
that the analyzed residues were mainly characterized by Ca-bearing
reacting phases typical of EAF and AOD slags, i.e.: dicalcium silicate,
calcium–aluminium silicates and calcium–magnesium silicates (see
Baciocchi et al., 2010b).
The main results of the compliance leaching test carried out on
the intermediate fraction are reported in Fig. 3. For the elements
whose concentrations resulted lower than the instrumental quan-
tification limit, the corresponding limit of quantification (LOQ) is
reported and indicated in Fig. 3 with a star. The native pH of the
eluates was high, about 12.4, above the limits imposed by the Ital-
ian regulation for reuse as a filling material or for similar applica-
tions (5.5 < pH < 12). The composition of the leachates was
characterized by relevant concentrations of Ba and Ca, 4.6% and
2.5% of the available amount based on total elemental content,
respectively. Leaching of Mg, Mo and V was negligible, while Cr
concentrations (0.24 mg/l) resulted higher than the values re-
ported in previous studies for SS slag (Shen et al., 2004; Baciocchi
et al., 2009, 2010b) and significantly above the limits for reuse and
inert waste disposal (0.05 mg/l).
3.2. CO
2
uptake kinetics
The CO
2
uptake achieved after carbonation was determined as a
function of the CO
2
content after (CO
2
final) and before (CO
2
initial)
the treatment by applying Eq. (1). The CO
2
contents were derived
from the results of the inorganic carbon analysis; for the as re-
ceived slag a CO
2
content of 0.62 and 2.04 wt.% were obtained for
the intermediate and fine particle size fractions, respectively.
CO
2uptake
ð%Þ¼CO
2final
ð%ÞCO
2initial
ð%Þ
100CO
2final
ð%Þ
100CO
2initial
ð%Þ
100 CO
2final
ð%Þ100 ð1Þ
On the basis of the CO
2
uptake value, the corresponding calcium
conversion yield achieved may be directly calculated as the ratio
between the carbonated Ca, proportional to the measured CO
2
up-
take, and the amount of potentially reactive Ca phases, given by the
difference between the total Ca content and the initial carbonate
content (expressed as Ca) of the specific particle size fraction of
the slag (see Eq. (2)).
g
ð%Þ¼ CO
2uptake
ð%Þ
40
44
Ca
tot
ð%ÞCO
2initial
ð%Þ
40
44
100 ð2Þ
In Fig. 4a, the CO
2
uptake resulting for slag samples collected at
different column heights is reported as a function of reaction time.
As can be observed, significant differences in the values obtained at
different heights were evident only for the 1 h test for which the
upper layer presented a lower CaCO
3
content; for longer reaction
times the material appeared to react homogeneously with CO
2
,
with a maximum uptake of 5.5% achieved after 4 h, corresponding
to a Ca conversion yield of 15.6%. As can be observed in Fig. 4b, a
very similar evolution of CO
2
uptake over time resulted from the
carbonation tests carried out in batch mode applying the same
L/Sratio and operating conditions. It should be noted that the static
Table 1
Elemental composition of the fine (F) and intermediate (I) size fractions of the SS slag; the concentrations of major constituents are reported in wt.% while those of trace
constituents in mg/kg.
Major elements (wt.%) F(d< 0.177 mm) I(0.177 < d< 0.84 mm) Trace elements (mg/kg) F(d< 0.177 mm) I(0.177 < d< 0.84 mm)
Al 1.73 2.57 As 21.5 20.5
Ca 31.04 32.99 Ba 297.1 359.2
Cr 2.99 4.79 Bi 25.7 30.8
Fe 1.99 4.08 Cu 305.6 157.3
K 0.08 1.21 Hg 11.2 5.5
Mg 1.64 1.89 Mo 31.8 64.9
Mn 0.90 1.34 Pb 20.9 22.2
Na 0.10 0.15 Sb 276.9 348.3
Ni 0.05 0.14 Sn 24.9 11.6
Si 9.16 10.77 Zn 80.5 105.8
V 0.06 0.11
94 O. Capobianco et al. /Minerals Engineering 59 (2014) 91–100
batch tests were carried out using a much lower amount of
material so to favour CO
2
diffusion and assess the maximum
reactivity of the material at set operating conditions.
The main results of the batch carbonation experiments carried
out at enhanced conditions with the aim of assessing the reactivity
of the examined type of residues in comparison to the data re-
ported in previous works on steel slag carbonation are reported
in Fig. 5. After a rapid increase, the carbonation kinetics resulting
for the fine fraction seemed to reach completion in almost 8 h with
aCO
2
uptake higher than 13% by weight, implying a Ca conversion
Fig. 2. XRD patterns of the as received SS slag as a function of particle size: (i) fine size fraction (D< 0.177 mm) and (ii) intermediate size fraction (0.177 < D< 0.84 mm).
(b) (c)
(a)
Fig. 3. Comparison of the results of the leaching test at native pH on the intermediate fraction (0.177 < D< 0.84 mm) of SS slag before and after column carbonation (2 h and
8hatT= 22–25 °C, P= 1 bar, L/S= 0.2 l/kg) in terms of: (a) pH, (b) major elements and (c) regulated elements.
(b)(a)
Fig. 4. Results of carbonation tests performed on the intermediate size fraction (0.177 < D< 0.84 mm) of the SS slag: (a) column experiments at different depths (T= 23–25 °C,
P= 1 bar, L/S= 0.2 l/kg, water added by mixing); (b) batch experiments (T=23°C, P= 1 bar, L/S= 0.2 l/kg).
O. Capobianco et al. / Minerals Engineering 59 (2014) 91–100 95
yield above 42%. These values appeared to be quite similar to those
found in previous batch tests carried out at similar conditions on
the fine fraction (d< 0.15 mm) of mixed SS slag (Baciocchi et al.,
2009) and on milled EAF slag (Baciocchi et al., 2010b). The interme-
diate fraction showed almost the same trend with time but halved
CO
2
uptakes compared to the fine fraction, reaching a maximum
value of 7.4% after 24 h, corresponding to a Ca conversion yield
of 20.8%, confirming the strong influence of particle size on the
reactivity of alkaline materials with CO
2
(Baciocchi et al., 2009).
The lower reactivity of the intermediate particle size fraction with
CO
2
may be mainly related to the lower specific surface of the
material, but also partly to the differences in the mineralogy of
the two types of fractions, since the fine one was characterized
by a higher content of dicalcium silicate (see Fig. 2), a phase that
has been reported to exhibit a significant reactivity with CO
2
at
the tested operating conditions (Johnson et al., 2003; Baciocchi
et al., 2010b).
Comparing the results of the experiments performed at ambient
conditions in either the column or batch set-up (see Fig. 4) with
those resulting for the intermediate size fraction in batch mode
at enhanced conditions (see Fig. 5), a slight decrease in the reaction
rate and CO
2
uptake values may be noted. This result may be as-
cribed mainly to the decrease in operating temperature, which is
a parameter that is known to enhance the dissolution of silicate
phases (Baciocchi et al., 2009, 2010b).
The influence of the amount of water (expressed as L/Sratio)
and type of water addition method adopted on the results of the
carbonation column tests is reported in Fig. 6a and b, respectively.
As can be observed in Fig. 6a, CO
2
uptakes and reaction kinetics
seemed not to be considerably affected by the applied L/Sratio in
the timeframe of our experiments, during which no significant
variations of the humidity of the samples was observed to occur.
The L/Sratios employed in these tests proved comparable to those
indicated as optimal in a previous study (Johnson et al., 2003) for
SS slag with a similar composition to that used in this work. The
CO
2
uptakes resulting at different sampling heights for the two
water addition methods tested are reported in Fig. 6b. The slightly
better performance of the ‘‘mixing’’ method, more evident after 2 h
reaction, was probably due to the more uniform distribution of
water in the material. On the contrary, the water percolation meth-
od probably produced preferential water flow routes and conse-
quently a less homogeneous reaction of the slag with CO
2
.
Nevertheless, the results achieved with the water percolation ap-
proach are satisfactory in view of a possible future field-scale
application of the process, where the wetting of the alkaline mate-
rial will take place through percolation of rainwater or by artificial
irrigation.
3.3. Effects of carbonation on slag properties
3.3.1. Effects on physical and chemical properties
The column carbonation experiments did not notably affect the
physical properties of the slags. The moisture content measured at
the end of the different experiments was quite in line with the ini-
tial one after water addition, with a maximum reduction of about
3.5% and 3% for the tests carried out at L/Sequal to 0.1 and 0.2 l/kg,
respectively. Besides, no hardening of the material was observed.
Consequently, also considering that the gas flow rate was constant
throughout the experiments, it seems reasonable to assume that
the pressure drop through the packed column did not notably
change as well over time. As far as the chemical properties are con-
cerned, the results obtained by XRD analysis of carbonated samples
of the intermediate size fraction of the slag are shown in Fig. 7.
Specifically, the diffraction patterns of the products obtained from
the column tests carried out at ambient conditions are reported in
Fig. 7i, while those resulting from the batch tests performed at en-
hanced operating conditions are reported in Fig. 7ii.
The two carbonated samples showed a very similar mineralogy
and indicated that the most considerable variation in slag mineral-
ogy compared to that of the as received material reported in
Fig. 2ii, was a significant reduction of portlandite peak intensities
and a slight decrease in Ca–Al silicates and melilite peaks. Appar-
ently this could suggest that the main reacting phase is portlandite.
Nevertheless, it should be noted that XRD results are qualitative
and that the peak intensity is not directly correlated to the concen-
tration of a given phase. This is also proven by the trend of the ANC
curve of the as received slag reported in Fig. 8 (discussed in Sec-
tion 3.3.2) that shows very limited buffering capacity at pH 12 typ-
ical of portlandite (i.e. around 2 meq/g corresponding to a Ca(OH)
2
content of 7.4 wt.%). Assuming the Ca(OH)
2
content deriving from
the ANC analysis and considering only portlandite as the reacting
Fig. 5. Results of the accelerated batch carbonation tests performed at enhanced
operating conditions (T=50°C, P= 10 bar, L/S= 0.4 l/kg) on the fine (D< 0.177 mm)
and intermediate (0.177 < D< 0.84 mm) size fractions of the SS slag.
(a) (b)
Fig. 6. Results of the column carbonation tests (T= 22–25 °C, P= 1 bar) performed on the intermediate size fraction (0.177 < D< 0.84 mm) of the SS slag as a function of (a)
the L/Sratio applied (water added by mixing); (b) water addition method at different column depths (L/S= 0.2 l/kg, M= water added by mixing, P= water added by
percolation).
96 O. Capobianco et al. / Minerals Engineering 59 (2014) 91–100
phase would in fact result in Ca conversion yields higher than 100%
for reaction times above 1 h, therefore confirming that Ca-contain-
ing silicates must have participated in the reaction. Besides, if the
main reacting phase were portlandite, most probably the carbon-
ation rate would have been the same both at ambient and en-
hanced conditions, whereas the operating temperature was
shown to exert a positive effect on the carbonation rate (compare
Figs. 4 and 5); this finding can be explained if calcium silicates
were the main reacting phases, as the rate of silicate dissolution
may be actually affected by the operating temperature. Therefore,
the decrease of the CO
2
uptake rate over time observed in all the
carbonation kinetics trends (see Figs. 4–6), can be explained, rather
by the depletion of fast-reacting phases such as portlandite, by the
formation of a calcite and/or silica layer on the particle surface that
hinders the further dissolution of Ca-containing reactive phases.
The calcium carbonate content of the slag increased upon both
types of treatment, indicating that Ca-minerals partly converted
into calcite as a result of carbonation. Other carbonate phases be-
sides calcite were not detected, indicating that, at least under the
tested operating conditions, Mg and Fe oxides do not directly take
part in the carbonation reaction, as reported also in previous stud-
ies (Johnson et al., 2003; Huijgen and Comans, 2006; Baciocchi
et al., 2010b). The diffraction patterns of Fe-phases remained in
fact essentially unvaried.
3.3.2. Effects on leaching
Regarding the results of the compliance leaching test performed
on the carbonated samples obtained from the column experiments,
the pH of the eluates compared to the as received slag showed to
decrease progressively with reaction time, reaching values suitable
for reuse even after 2 h of treatment (see Fig. 3a). Ca concentrations
in the eluates of the carbonated slag (see Fig. 3b) were also found
to be lower than in the leachates of the as received slag, in agree-
ment with the findings of previous studies that were ascribed to
solubility control by less soluble phases caused by the changes in
the mineralogy of the treated material (Huijgen and Comans,
2006; Baciocchi et al., 2010b; van Zomeren et al., 2011). Con-
versely, Mg and Si leaching concentrations increased upon carbon-
ation; also these effects were reported in previous works and were
related for Mg to the pH reduction (Baciocchi et al., 2009) and for Si
to the conversion of the original silicate minerals into more soluble
phases (Huijgen and Comans, 2006).
The effect of carbonation on the leaching of regulated elements
is summarized in Fig. 3c. Ba release showed to decrease consider-
ably upon the reaction, as also reported in previous studies on steel
slag carbonation (van Zomeren et al., 2011). Regarding Cr release, a
decreasing trend with reaction time, leading to a 65% reduction
after 8 h, was observed, even though the leaching concentrations
still remained above the limit values set by Italian legislation for
both reuse and disposal. This result proved in good agreement with
the effects on Cr mobility reported for batch carbonation tests car-
ried out on SS slag at enhanced conditions, which were associated
mainly to the decrease in pH caused by the carbonation treatment
(Baciocchi et al., 2009). An opposite trend was found for Mo and V,
whose concentrations were found to rise with increasing reaction
times, but remained within the regulatory limits (see Fig. 3c).
In order to better analyze the effects of the tested column car-
bonation treatment on the leaching behaviour of the slag and to
identify the main mechanisms governing the release of major
and regulated elements in a long-term scenario, especially relevant
for the proposed application since the slag/industrial soil is ex-
pected to remain on site, the pH dependence test was performed.
On the basis of the amount of acid or base added in each sub-test
and the resulting pH of the leachate at equilibrium conditions, the
acid/base neutralization capacity of the slag before and after the
carbonation treatment, reported in Fig. 8, was evaluated.
As for the as received sample, the acid titration curve exhibited
a noticeable buffering capacity at alkaline pH values (between 8
and 12), consistent with the presence of calcium hydroxide and sil-
icate phases detected by XRD analysis. A second acid neutralization
plateau was observed in the pH range between 4 and 6 that may be
partly related to carbonate/bicarbonate buffering. As shown in
Fig. 8, the acid neutralization capacity of the slag was found to
change substantially upon carbonation. The buffering capacity of
the treated slag at pH higher than 7 was notably reduced, since a
rapid drop in the pH of the eluate was observed after the addition
of around 1 meq acid/g dry material. This behaviour was correlated
to the partial reaction of alkaline phases such as portlandite and
Fig. 7. XRD patterns for the intermediate (0.177 < D< 0.84 mm) size fraction of the column carbonated SS slag as a function of the reaction mode: (i) column experiments at
T= 23–25 °C, P= 1 bar, L/S= 0.2 l/kg, reaction time = 8 h; (ii) batch experiments at T=50°C, P= 10 bar, L/S= 0.4 l/kg, reaction time = 24 h.
Fig. 8. Acid/base neutralization capacity curves for the intermediate
(0.177 < D< 0.84 mm) size fraction of as received and column carbonated SS slag
(T= 23–25 °C; P= 1 bar; L/S= 0.2 l/kg; reaction time = 8 h); negative x-axis values
correspond to base additions.
O. Capobianco et al. / Minerals Engineering 59 (2014) 91–100 97
Ca-containing silicates with CO
2
. Conversely, the significant in-
crease of the buffering plateau observed in the pH range from 4
to 6.5 was related to the higher calcite content of the carbonated
slag. Besides a confirmation on the effects of the tested carbonation
treatment on the mineralogy of the material, these results provide
an indication on the pH value of the eluates that may be expected
in a long-term perspective upon contact with water under field
conditions. From these results it appears hence that the pH of
the leachate of the carbonated material may decrease to around
neutral values, whereas that of the as received slag may most prob-
ably remain quite alkaline (above 11), if substantial natural weath-
ering were not to occur.
The leaching curves of major elements as a function of pH, de-
rived from the pH-dependence test, are reported in Fig. 9, together
with the respective limits of quantification (LOQ). As can be ob-
served in Fig. 9, the shape of the Al leaching curve showed not to
be noticeably modified upon carbonation, except at pH values
above 12, for which a lower mobility was retrieved. Hence, the
reduction observed in Al release upon the compliance leaching test
may be related chiefly to the decrease in eluate pH. Regarding Mg,
its solubility curve seemed to remain unvaried throughout the en-
tire pH range, highlighting the negligible conversion of Mg into
carbonate phases, as also indicated by the results of XRD analysis.
This behaviour was consistent with the results of the EN 12457-2
test and confirmed that Mg release from the carbonated slag was
related to the decrease of the native pH of the slag upon carbon-
ation rather than to a change in mineralogy and solubility-control-
ling phases.
Conversely, the leaching curve of Ca showed to be notably af-
fected by carbonation, exhibiting a decrease in mobility at pH val-
ues higher than 6, proving the occurred conversion of the reactive
phases into calcite as a result of the reaction with CO
2
and, subse-
quently, a change in the solubility-controlling phases compared to
the as received slag (Huijgen and Comans, 2006; Baciocchi et al.,
2009; van Zomeren et al., 2011). Si leaching curves for the as re-
ceived and carbonated slag showed the same trend up to a pH va-
lue of around 10, from which the mobility of the as received slag
showed to decrease sharply with increasing pH, while the eluate
concentrations of the carbonated slag remained quite constant.
This behaviour confirmed that at least part of the Ca silicate con-
tent of the material was significantly affected by the carbonation
reaction. Similar results were also reported in previous studies
(Huijgen and Comans, 2006; Baciocchi et al., 2010c) and explained
by the fact that, during carbonation, a Ca-depleted silicate rim is
formed around the slag particles, which causes the solubility of
Si to be controlled by amorphous SiO
2
rather than Ca-silicate min-
erals (Huijgen and Comans, 2006).
The leaching of regulated elements as a function of pH is shown
in Fig. 10. In the same figure the limits imposed by the Italian leg-
islation for material reuse (Ministerial Decree 186/06) and inert
waste landfilling (Ministerial Decree 27/09/10) are also reported
for comparison. The concentrations of Ba in the leachates dropped
by several orders of magnitude upon carbonation with the most
relevant changes occurring at pH higher than 7. Similar results
were also found in a previous study carried out on steel slag car-
bonated in slurry phase under enhanced operating conditions
(Huijgen and Comans, 2006) and attributed to the possible forma-
tion of a Ba–Ca carbonate solid solution, resulting in the incorpora-
tion of Ba in a calcite structure and leading to a reduction of Ba
release. The solubility curves obtained for the metalloids Cr, Mo
and V appeared to be differently affected by carbonation. Cr leach-
ing both before and after carbonation exhibited an amphoteric
behaviour with a minimum solubility value between pH 6 and
10. The leaching behaviour of this element proved not to be consid-
erably altered by carbonation, probably due to solubility control by
Cr
3+
, as also reported in previous studies (Huijgen and Comans,
2006; Baciocchi et al., 2010c). For Mo, the leaching curves as a
function of pH indicated only a negligible influence of the tested
carbonation treatment on its release, with a slight decrease of
leaching concentrations between pH 9 and 11. The slight mobiliza-
tion effect of carbonation for Mo resulting from the batch compli-
ance test may be also in this case most probably related to the
variation in eluate pH; yet the shape of the leaching curves sug-
gests that a minor decrease in release may be obtained if more rel-
evant pH reductions were achieved upon carbonation. The shape of
the leaching curves of V as a function of pH suggested instead that
Fig. 9. Leaching of major elements as a function of pH for the intermediate (0.177 < D< 0.84 mm) size fraction of as received and column carbonated SS slag (T= 23–25 °C;
P= 1 bar; L/S= 0.2 l/kg; reaction time = 8 h). As a convention, data resulting below the LOQ are reported as half of the LOQ value.
98 O. Capobianco et al. / Minerals Engineering 59 (2014) 91–100
a change in solubility-controlling minerals occurred upon carbon-
ation for a pH value above 11 and between 4.5 and 6. Specifically,
in these pH ranges the as received slag exhibited an almost negli-
gible release of V, while the mobility of this element proved signif-
icantly higher (especially at pH values above 11) in the eluates of
the carbonated slag. A similar effect of carbonation on V leaching
at alkaline conditions was reported also in other studies (Huijgen
and Comans, 2006; van Zomeren et al., 2011) and attributed to
the incorporation of this element in Ca phases such as dicalcium
silicate that react during carbonation. However, observing the
shape of the V leaching curve resulting for the carbonated sample,
it may be expected that for long reaction times the pH of the trea-
ted sample could decrease further, approaching the leaching con-
centrations found for the as received slag at the same pH
conditions.
Hence, it may be concluded that notwithstanding the rather
mild operating conditions adopted in the carbonation column
experiments and quite limited resulting CO
2
uptakes, the effects
of the treatment on the leaching behaviour of the material proved
relevant even for short reaction times and quite similar to those re-
ported in studies carried out applying enhanced operating condi-
tions (Huijgen and Comans, 2006; Baciocchi et al., 2010c). In
addition, with regard to the behaviour of the material in the pro-
posed in situ application, observing the trends of the acid neutral-
ization capacity (Fig. 8) and of the leaching curves of the critical
contaminants as a function of pH (Fig. 10), it may be anticipated
that, due to the expected decrease in pH to neutral values, the
long-term release of the carbonated material in an application sce-
nario may result significantly improved in the case of Cr, improved
or at least similar to that of the as received slag (Ba and Mo), while
still higher than that of the as received slag with respect to V.
4. Conclusions
The feasibility of in situ carbonation as a treatment technique
aimed at improving the environmental behaviour of alkaline
industrial materials and to store the CO
2
generated from remedia-
tion/regeneration processes in a Brownfield site was investigated
through lab-scale carbonation column tests performed on stainless
steel slags at operating conditions expected for field-scale applica-
tion, i.e. ambient temperature and 1 bar CO
2
.
The results showed that, even at the mild operating conditions
tested, a significant degree of carbonation could be achieved.
Namely, an average CO
2
uptake of 6% was obtained for the inter-
mediate size fraction of the material (0.177–0.84 mm) after 8 h
of reaction. Despite this value being significantly lower than the
14% uptake achieved for the same reaction time by carbonation
of the fine size fraction (D< 0.177 mm) at enhanced operating con-
ditions (T=50°C, P= 10 bar), the tested column carbonation treat-
ment significantly affected the mineralogy and environmental
properties of the slag. The XRD patterns indicated a clear decrease
of portlandite and a slighter one of Ca–Al silicate and melilite
peaks, as a result of the carbonation reaction, that was confirmed
by the relevant increase of calcite peaks as well as by the results
of IC analysis of the treated samples.
As far as the leaching behaviour is concerned, the results of the
compliance test showed a decrease of the eluate pH well below the
limit for reuse set by the Italian national legislation. As to the
behaviour of regulated trace compounds, barium and chromium
leaching was improved after carbonation, although the eluate con-
centration was still above the limit for reuse for the latter element;
the opposite behaviour was observed for vanadium and molybde-
num, whose eluate concentration remained anyhow below the cor-
responding limits. Based on the results obtained from pH-
dependence tests, the behaviour observed for chromium and
molybdenum was explained by the reduction of eluate pH occur-
ring after carbonation, that of barium with the possible formation
of Ba–Ca carbonate solid solutions, whereas that of vanadium was
attributed to its incorporation in Ca phases, such as dicalcium sil-
icate, that react during carbonation.
The results of the acid neutralization test also showed that a
further reduction of the eluate pH to fairly neutral values could
be expected in a long-term perspective upon contact with water.
Fig. 10. Leaching of regulated elements as a function of pH for the intermediate (0.177 < D< 0.84 mm) size fraction of as received and column carbonated SS slag (T= 23–
25 °C; P= 1 bar; L/S= 0.2 l/kg; reaction time = 8 h) and comparison with Italian regulatory limits. As a convention, data resulting below the LOQ are reported as half of the LOQ
value.
O. Capobianco et al. / Minerals Engineering 59 (2014) 91–100 99
This suggests that in an application scenario Cr and Mo eluate con-
centrations could be reduced, thus making the reuse of the mate-
rial feasible from an environmental point of view. In order to
better investigate this point, up-flow column percolation tests
could be performed on the treated materials.
The results obtained in this work suggest that an in situ carbon-
ation process which exploits a CO
2
upward flow at mild operating
conditions may be a feasible option for the improvement of the
environmental properties of alkaline residues at Brownfield sites.
Further investigation will be needed with regard to the perfor-
mance of the process at larger scale and on industrial soil collected
at a Brownfield site, with the aim to possibly assess the effects of
the proposed carbonation process as a function of both material
characteristics (e.g. particle size distribution) and environmental
conditions (e.g. moisture exposure, wetting and drying cycles, aer-
ation, temperature). In addition, the effects of the above mentioned
parameters and of the in situ CO
2
flux on the overall CO
2
capture
efficiency during in situ carbonation also merit further analysis. Fi-
nally, the coupling of the process with other in situ techniques,
aimed to increase the environmental or mechanical characteristics
of the subsoil, should also be investigated at lab-scale, in view of a
possible pilot-scale field application.
Acknowledgements
The authors wish to acknowledge the support received by the
Seventh Framework programme of the European Commission
within the project Holistic Management of Brownfield Regenera-
tion (HOMBRE).
References
Antemir, A., Hills, C.D., Carey, P.J., Magnié, M.C., Polettini, A., 2010. Investigation of
4-year-old stabilised/solidified and accelerated carbonated contaminated soil.
Journal of Hazardous Materials 181 (1–3), 543–555.
Arm, A., Suer, P., Arvidsson, H., Lindqvist, J., 2011. Technical and environmental log-
term properties of industrial residues – summary of field and laboratory
investigations. Waste Management 31 (1), 101–107.
Baciocchi, R., Costa, G., Polettini, A., Pomi, R., 2009. Influence of particle size on the
carbonation of stainless steel slag for CO
2
storage. Energy Procedia 1 (1), 4859–
4866.
Baciocchi, R., Costa, G., Lategano, E., Marini, C., Polettini, A., Pomi, R., Postorino, P.,
Rocca, S., 2010a. Accelerated carbonation of different size fractions of bottom
ash from RDF incineration. Waste Management 30 (7), 1310–1317.
Baciocchi, R., Costa, G., Di Bartolomeo, E., Polettini, A., Pomi, R., 2010b. Carbonation
of stainless steel slag as a process for CO
2
storage and slag valorization. Waste
and Biomass Valorization 1 (4), 467–477.
Baciocchi, R, Costa, G., Polettini, A., Pomi, R., 2010c. The influence of carbonation on
major elements leaching from various types of stainless steel slag. In:
Proceedings of the. International Conference on Accelerated Carbonation for
Environmental and Materials Engineering (ACEME). Turku (Finland).
Baciocchi, R., Capobianco, O., Costa, G., 2012. Assessment of technology trains for
the treatment and reuse of excavated materials in the context of Brownfield
regeneration. In: Proceedings of the ISWA World Solid Waste Congress. Florence
(Italy), 17–19 September 2012.
Bobicki, E.R., Liu, Q., Xu, Z., Zeng, H., 2012. Carbon capture and storage using alkaline
industrial wastes. Progress in Energy and Combustion Science 38 (2), 302–320.
Doucet, F.J., 2010. Effective CO
2
-specific sequestration capacity of steel slags and
variability in their leaching behaviour in view of industrial mineral carbonation.
Minerals Engineering 23 (3), 262–269.
Hartog, N., den Hamer, D., Blauw, M., van der Star, W., Groot, H., 2013. ECOgrout: a
sustainable in situ carbonate-based grouting technology for use in brownfield
redevelopment. In: Proceedings of the 12th international UFZ-Deltares
Conference on Groundwater-Soil-Systems and Water Resource Management,
AquaConSoil 2013. Barcelona (Spain), 16–19 April 2013.
Huijgen, W.J.J., Comans, R.N.J., 2006. Carbonation of steel slag for CO
2
sequestration:
leaching of products and reactions mechanisms. Environmental Science &
Technology 40 (8), 2790–2796.
IT MD 186/06, Appendix 3, p. 10. <http://www.tuttocamere.it/files/camcom/
2006_186.pdf>.
IT MD 27/09/2010, p. 4, Table 2. <http://www.arpa.umbria.it/discariche/doc/norme/
DM%2027_09_2010.pdf>.
Johnson, D.C., Macleod, C.L., Hills, C.D., 2003. Solidification of stainless steel slag by
accelerated carbonation. Environmental Technology 24 (6), 671–678.
Lackner, K.S., Wendt, C.H., Butt, D.P., Joyce Jr., E.L., Sharp, D.H., 1995. Carbon dioxide
disposal in carbonate minerals. Energy 20 (11), 1153–1170.
Manso, J.M., Polanco, J.A., Losanez, M., Gonzales, J.J., 2006. Durability of concrete
made with EAF slag as aggregate. Cement & Concrete Composites 28 (6), 528–
534.
Marker, A, Nieters, A., Detlev U., 2007. Contaminated site management and
brownfield redevelopment in Latin America. In: Proceedings of the 2nd
International Conference on Managing Urban Land, Stuttgart (Germany), 25–
27 April 2007.
Nelson, L., Barker, J., Li, T., Thomson, N., Ioannidis, M., Chatzis, J., 2009. A field trial to
assess the performance of CO
2
-supersaturated water injection for residual
volatile LNAPL recovery. Journal of Contaminant Hydrology 109 (1–4), 82–90.
Oliver, L, Ferber, U, Grimski, D, Millar K, Nathanial P., 2004. The scale and nature of
European Brownfield. CABERNET (Concerted Action on Brownfield and
Economic Regeneration Network). <http://www.cabernet.org.uk/resourcefs/
417.pdf> (accessed May 2013).
Pan, J.R., Huang, C., Kuo, J., Lin, S., 2008. Recycling MSWI bottom and fly ash as raw
materials for Portland cement. Waste Management 28 (7), 1113–1118.
Renforth, P., Manning, D.A.C., Lopez-Capel, E., 2009. Carbonate precipitation in
artificial soils as a sink for atmospheric carbon dioxide. Applied Geochemistry
24 (9), 1757–1764.
Scanferla, P., Ferrari, G., Pellay, R., Volpi Ghirardini, A., Zanetto, G., Libralato, G.,
2009. An innovative stabilization/solidification treatment for contaminated soil
remediation: demonstration project results. Journal of Soils and Sediments 9
(3), 229–236.
Shen, H., Forssberg, E., Nordström, U., 2004. Physicochemical and mineralogical
properties of stainless steel slags oriented to metal recovery. Resources,
Conservation and Recycling 40 (3), 245–271.
Suer, P., Lindqvist, J., Arm, M., Frogner-Kockum, P., 2009. Reproducing ten years of
road aging – accelerated carbonation and leaching of EAF steel slag. Science of
the Total Environment 407 (18), 5110–5118.
Van Gerven, T., Van Keer, E., Arickx, S., Jaspers, M., Wauters, G., Vandecasteele, C.,
2005. Carbonation of MSWI-bottom ash to decrease heavy metal leaching, in
view of recycling. Waste Management 25 (3), 291–300.
van Zomeren, A., van der Laan, S.R., Kobesen, H.B.A., Huijgen, W.J.J., Comans, R.N.J.,
2011. Changes in mineralogical and leaching properties of converter steel slag
resulting from accelerated carbonation at low CO
2
pressure. Waste
Management 31 (11), 2236–2244.
Voglar, G.E., Leštan, D., 2010. Solidification/stabilisation of metals contaminated
industrial soil from former Zn smelter in Celje, Slovenia, using cement as a
hydraulic binder. Journal of Hazardous Materials 178 (1–3), 926–933.
100 O. Capobianco et al. / Minerals Engineering 59 (2014) 91–100
Corrigendum
Corrigendum to ‘‘Carbonation of stainless steel slag in the context of
in situ Brownfield remediation’’ [Minerals Eng. 59 (2014) 91–100]
Oriana Capobianco
a
, Giulia Costa
a
, Laurens Thuy
b
, Elisa Magliocco
a
, Niels Hartog
b,c
, Renato Baciocchi
a,
a
Laboratory of Environmental Engineering, Dept. Civil Engineering and Computer Science Engineering, University of Rome ‘‘Tor Vergata’’, Via del Politecnico 1, 00133 Rome, Italy
b
Dept. Earth Sciences, Utrecht University, Utrecht, The Netherlands
c
KWR Watercycle Research Institute, Nieuwegein, The Netherlands
The authors regret Fig. 2. XRD patterns of the as received SS slag
as a function of particle size: (i) fine size fraction (D< 0.177 mm)
and (ii) intermediate size fraction (0.177 < D< 0.84 mm). Legend:
(a) calcium aluminum silicate (CaAl
2
SiO
6
); (c) calcite (CaCO
3
); (f)
fluorite (CaF
2
); (i) iron sulfide (FeS); (m) melilite (Ca
2
(Mg
0.5
Al
0.5
)
(Si
1.5
Al
0.5
O
7
)); (o) calcium oxide (CaO); (p) portlandite (Ca(OH)
2
);
(s) dicalcium silicate (Ca
2
SiO
4
); (x) iron oxide (Fe
2
O
3
).
Fig. 7. XRD patterns for the intermediate (0.177 < D< 0.84 mm)
size fraction of the column carbonated SS slag as a function of the
reaction mode: (i) Column experiments at T= 23–25 °C, P= 1 bar,
L/S= 0.2 l/kg, reaction time = 8 h; (ii) batch experiments at
T=50°C, P= 10 bar, L/S= 0.4 l/kg, reaction time = 24 h. Legend:
(a) calcium aluminum silicate (CaAl
2
SiO
6
); (c) calcite (CaCO
3
); (f)
fluorite (CaF
2
); (i) iron sulfide (FeS); (m) melilite (Ca
2
(Mg
0.5
Al
0.5
)
(Si
1.5
Al
0.5
O
7
)); (o) calcium oxide (CaO); (p) portlandite (Ca(OH)
2
);
(s) dicalcium silicate (Ca
2
SiO
4
); (x) iron oxide (Fe
2
O
3
).
The authors would like to apologise for any inconvenience
caused.
http://dx.doi.org/10.1016/j.mineng.2014.05.003
0892-6875/Ó2014 Elsevier Ltd. All rights reserved.
DOI of original article: http://dx.doi.org/10.1016/j.mineng.2013.11.005
Corresponding author. Tel.: +39 0672597022; fax: +39 0672597021.
E-mail address: baciocchi@ing.uniroma2.it (R. Baciocchi).
Minerals Engineering xxx (2014) xxx–xxx
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Please cite this article in press as: Capobianco, O., et al. Corrigendum to ‘‘Carbonation of stainless steel slag in the context of in situ Brownfield remedi-
ation’’ [Minerals Eng. 59 (2014) 91–100]. Miner. Eng. (2014), http://dx.doi.org/10.1016/j.mineng.2014.05.003
... Many studies have been reported on the immobilization and stabilization of heavy metals with various kinds of binders such as cement, slag, lime and apatite [14][15][16][17][18][19]. Lee et al. [17] reported the good stabilization efficiency of Cd-, Pb-and Zn-contaminated soils with the furnace slag, decreasing the bioavailability of the heavy metals. ...
... Kim et al. [16] reported that pH in carbonated slag paste can decrease, and the solubility of some heavy metals can increase. Conversely, Capobianco et al. [15] reported that the increase of the buffering capacity was observed with the high calcite content of the carbonated slag. Liu et al. [18] reported that the carbonation improved the immobilization efficiencies of heavy metals. ...
... The V release from the original sample A, but even more significantly from original sample B, increased below pH 11. This led to the assumption that during aging and carbonation of the slag samples, which leads to a pH decrease of the leachates [37,38], more V was leached from the original sample compared to the conditioned slag samples. The formation of less soluble calcium silicate phases due to the quartz sand addition is represented by the pH-dependent release of Ca and Si ( Figure 5). ...
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Chapter
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Mineral carbonation is a carbon utilisation technology in which an alkaline material reacts with carbon dioxide forming stable carbonates that can have different further uses, for instance as construction material. The alkaline material can be a residue from industrial activities (e.g. metallurgic slags) while CO2 can be recovered from industrial flue gasses. Mineral carbonation presents several potential environmental advantages: (i) industrial residues valorisation, (ii) CO2 sequestration and (iii) substitution of conventional concrete based on Portland cement (PC). However, both the carbonation and the CO2 recovery processes require energy. To understand the trade-off between the environmental benefits and drawbacks of CO2 recovery and mineral carbonation, this study presents a life cycle assessment (LCA) of carbonated construction blocks from mineral carbonation of stainless steel slags. The carbonated blocks are compared to traditional PC-based concrete blocks with similar properties. The results of the LCA analysis show that the carbonated blocks present lower environmental impacts in most of the analysed impact categories. The key finding is that the carbonated blocks present a negative carbon footprint. Nonetheless, the energy required represents the main environmental hotspot. An increase in the energy efficiency of the mineral carbonation process and a CO2 valorisation network are among the suggestions to further lower the environmental impacts of carbonated blocks production. Finally, the LCA results can promote the development of policy recommendations to support the implementation of mineral carbonation technology. Further research should enable the use of mineral carbonation on a broader range and large volume of alkaline residues.
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Article
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Article
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Article
This paper examines the main results of an accelerated carbonation treatment applied to different types and size fractions of stainless steel slag. The objectives of this work were essentially to assess the CO2 uptake achievable by each type of slag under mild operating conditions and to investigate the effects of carbonation on the mineralogy and leaching behaviour of the residues. The following types of materials were tested: different size fractions of commingled slag, milled electric arc furnace (EAF) slag and argon oxygen decarburization (AOD) slag. Each material was thoroughly characterized in terms of elemental composition, mineralogy and leaching behaviour. Accelerated carbonation batch experiments were performed exposing humidified (with liquid to solid ratios <0.6l/kg) slag to 100% CO2 for operating times between 0.5 and 24h, at controlled temperature and pressure. Maximum CO2 uptakes of 130, 180 and 300g CO2/kg slag were achieved (at 50°C and 3bar) for the finest fraction of the mixture, the milled EAF slag and the AOD slag, respectively. The mineralogy of each type of residue showed to be affected by the treatment, exhibiting an increase in calcite concentration and a decrease in the content of specific silicate and oxide phases. The leaching behaviour of all types of carbonated slag was also modified, exhibiting a reduction by 1–2 units of the natural pH of the materials, accompanied by a decrease of Ca release and an increase of Si leaching, as a result of modified leaching-controlling phases. In conclusion, at the tested operating conditions, AOD slag was the most reactive material with CO2. Milling, however, proved effective in increasing the carbonation yield of the EAF slag compared to that measured for the different size fractions of the commingled slag mixture. KeywordsStainless steel slag-Particle size-Mineral carbonation-CO2 uptake-Mineralogy-Leaching
Article
We introduce a safe and permanent method of CO2 disposal based on combining CO2 chemically with abundant raw materials to form stable carbonate minerals. Substantial heat is liberated in the overall chemical reaction so that cost will be determined by the simplicity and speed of the reaction rather than the cost of energy. Preliminary investigations have been conducted on two types of processes, involving either direct carbonation of minerals at high temperature or processing in aqueous solution. Promising raw materials are identified in both cases. For aqueous processing, a chemical cycle employing well-known reactions is proposed for digesting and carbonating the raw material. Cost estimates, based on comparison with standard industrial and mining practice, are encouraging. Necessary raw materials are surveyed and vast quantities are found to be easily accessible. Amounts are sufficient to allow utilization of the large known fossil-fuel reserves while avoiding build-up of atmospheric CO2.