See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/374031544

Stabilization of Chromium Waste by Solidification into Cement Composites

Article in Materials · September 2023

DOI: 10.3390/ma16186295

CITATIONS READS

0 81

6 authors, including:

Cherif Belebchouche Salah Eddine Bensebti

University of Constantine 1 University of Constantine 1
27 PUBLICATIONS 294 CITATIONS 9 PUBLICATIONS 26 CITATIONS

SEE PROFILE SEE PROFILE

Ouldsaid Chaima Karim Moussaceb

Algiers University Université de Béjaïa
8 PUBLICATIONS 13 CITATIONS 84 PUBLICATIONS 455 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Modeling of machining chips of steel parts for their recycling and reinforcement of cementitious matrix View project

Pale i fundamenty palowe View project

All content following this page was uploaded by Ouldsaid Chaima on 20 September 2023.

The user has requested enhancement of the downloaded file.

 materials
Article
Stabilization of Chromium Waste by Solidification into Cement
Composites
Cherif Belebchouche 1,2,3, * , Salah-Eddine Bensebti 1,2 , Chaima Ould-Said 4 , Karim Moussaceb 3 ,
Slawomir Czarnecki 5, * and Lukasz Sadowski 5
Citation: Belebchouche, C.; Bensebti,
S.-E.; Ould-Said, C.; Moussaceb, K.;
Czarnecki, S.; Sadowski, L.
Stabilization of Chromium Waste by
Solidification into Cement
Composites. Materials 2023, 16, 6295.
https://doi.org/10.3390/
ma16186295
Academic Editor: Yue Xiao
Received: 9 August 2023
Revised: 4 September 2023
Accepted: 13 September 2023
Published: 20 September 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Materials 2023, 16, 6295. https://doi.org/10.3390/ma16186295
1 Department of Civil Engineering, Faculty of Sciences of Technology, Frères Mentouri Constantine 1 University,
Constantine 25000, Algeria; s_bensebti@yahoo.fr
2 Materials and Durability of Constructions Laboratory, Faculty of Sciences of Technology,
Frères Mentouri Constantine 1 University, Constantine 25000, Algeria
3 Laboratory of Materials Technology and Process Engineering, Faculty of Technology, University of Bejaia,
Bejaia 06000, Algeria
4 Laboratory of Biology and Physiology of Organisms (LBPO), Faculty of Biological Sciences, USTHB,
BP 32 El-Alia, Bab Ezzouar 16111, Algeria; ouldsaidchaima93@gmail.com
5 Department of Materials Engineering and Construction Processes, Wroclaw University of Science and Technology,
Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland; lukasz.sadowski@pwr.edu.pl
* Correspondence: cherif.belebchouche@umc.edu.dz (C.B.); slawomir.czarnecki@pwr.edu.pl (S.C.)
Abstract: This article deals with the study of hazardous chromium leaching, stabilized/solidified
by cement CEM II after 28 days of curing, in an acidic environment. The mortars subjected to this
study were investigated by X-ray diffraction (XRD) characterization to evaluate the influence of
chromium waste on their mineralogical structure. In the study range (0.6–1.2%), increasing the mass
percentage of Cr2 O3 in the mortars indicates that chromium accelerates the hydration process and
setting of the mortar and increases the mechanical strength of the mortars compared to the control
sample. It was observed that the release of chromium during the Toxicity Characteristic Leaching
Procedure (TCLP) test and the efficiency of the stabilization/solidification process depended on
the initial Cr concentration and the leaching time. The use of XRD allowed the identification of
new crystallized phases in the cement matrices, namely, CaCrO4 ·2H2 O and chromium–ettringite
Ca6 Cr2 (SO4 )3 (OH)12 ·26H2 O, which confirms the immobilization of chromium and the efficiency
of the stabilization/solidification process. In this research, the release mechanism was found to be
primarily a surface phenomenon by modeling the experimental data (dissolution or precipitation).
Keywords: hazardous chromium wastes; acidic environment; cementitious materials; leaching
1. Introduction
Currently, more attention is being paid to protecting human health and the environ-
ment from the dangers of hazardous waste. One of these forms of hazardous waste is
chromium obtained from the production of cement [1], ceramic, stainless steel, and other
alloys from chromium plating [2–4]. Cr (VI) stands out among other chromium forms when
considering toxicity, solubility, and mobility [5,6]. Chromium is very dangerous for both
human health and the environment. When its concentration exceeds admissible values, it
causes the following problems: rashes, heart problems, disturbances of metabolism and
diabetes, upset stomach and ulcers, respiratory problems, weakened immune system, liver
and kidney damage, alteration of genetic material, lung cancer, birth defects, infertility,
formation of tumors, and death [7].
Therefore, the issue of environmental contamination by Cr (VI) is receiving increasing
attention due to its wide distribution worldwide, particularly in water [8] and soil [9].
This contamination is a result of both natural processes and human activities [10], includ-
ing mining, metal works, steel and metal alloy production, paint manufacturing, wood
https://www.mdpi.com/journal/materials
Materials 2023, 16, 6295 2 of 17

and paper processing, dyeing, and the discharge of chromium into wastewater [6,11,12].
Furthermore, the incineration of coal or municipal waste for energy generation and the
production of second-generation fertilizers contribute to the elevated levels of Cr (VI) in
soil and water through the deposition of ash [13]. Improper disposal of this heavy metal
can lead to severe environmental and ecological problems, as water serves as the primary
carrier of environmental pollutants. In Europe, the permissible concentration values for Cr
(VI) range from 0.05 to 2 mg/L, as determined by the environmental policies of countries
such as Norway, Poland (most precautionary value), and the Netherlands. In Algeria,
the permissible concentration values for Cr (VI) and Cr (III) are 5 mg/kg and 50 mg/kg,
respectively [14,15]. According to the latest statistical compendium on raw hides and skins
published by the Food and Agriculture Organization of the United Nations (FAO) [16], the
annual global production of bovine hides and skins amounts to approximately 6.5 million
metric tons (wet salted weight), with over 4.3 million metric tons being processed in devel-
oping countries. Sheepskins, lambskins, goatskins, and kidskins are processed globally for
approximately 750 thousand metric tons (dry weight). Therefore, based on rough estimates,
the tanning industry generates approximately 3.5–4.0 million metric tons of solid waste
annually, a significant portion of which (up to 30–35% [17]) may contain chromium.
All these threats have pushed researchers to find appropriate treatment solutions
for these heavy metals [18]. In the case of chromium, the powerful techniques are vitrifi-
cation [19,20] or solidification/stabilization (S/S). Solidification has especially shown its
effectiveness in reducing the polluting character of several types of hazardous wastes (by
rendering them inert), namely, heavy metal contaminated soil [21], marine sediment [22],
industrial waste [23], municipal solid waste incineration fly ash [7,24], and Cr (III) and
Cr (VI) from acid mine drainage (AMD) [25]. S/S treatment with cement is one of the
most widely used techniques due to its (1) very low cost and its ease of implementation
compared to the vitrification technique, which is commonly used for nuclear waste; (2) its
ability to render these heavy metals from toxic contaminants into a solid; and (3) the low
solubility of cement matrix with a reduced environmental impact [26].
Characterizing the products of stabilization/solidification by leaching tests and char-
acterization methods (e.g., XRD) has been used by many researchers throughout the world.
These scenarios have been proven to help determine these heavy metals’ released con-
centrations and crystallized phases [27,28]. Furthermore, the results of leaching tests and
characterization methods can be successfully used to confirm the mechanisms and reactions
of the immobilization of these metals within the cement matrix. Previous studies have been
conducted using cement, bentonite, coal fly ash, and metallurgical slag-based cementitious
material for the immobilization of Hg, Pb, As, Cr, and Cd [29–31], Pb and Zn [32], Ni [33],
Cr VI [25], and Pb, Zn, Cr, and Hg [34].
At present, and despite the advances made in the field of characterization of cement
pastes, researchers have been unable to identify and determine the morphology of hydrates.
Taking into account that these hydrates are formed in the presence of heavy metals and ce-
ment, an understanding of the mechanisms of immobilization is made more difficult [35,36].
In addition, it is difficult to identify all the phases formed during the hydration of cement in
the presence of chromium, to evaluate the degradation of cementitious materials containing
chromium, and to model the release of chromium from cementitious matrices. Moreover, it
is very rarely discussed in the literature. In this context, it would be advantageous to carry
out a deep experimental study to understand the phenomena that govern the process of
stabilization/solidification and the release of chromium from cementitious matrices.
Considering the above, the authors performed complex research to evaluate the possi-
bility of solidification/stabilization of chromium by cement CEM II. This complex research
contains multiscale analyses of chromium release from different cement matrices that vary
in the percentages of mass of the pure waste (Cr2 O3 ). These analyses were combined with
statistical criteria using the empirical Cote model. Furthermore, this study enables an evalua-
tion of the degradation of the stabilized/solidified mortars that are rarely studied to complete
previous works in the field of the solidification/stabilization of chromium.
 Materials 2023, 16, 6295 3 of 17

2. Materials and Methods

Materials 2023, 16, x FOR PEER REVIEW
2.1. Materials and Preparation of Mortar Mixes
The constituents used in formulations of the synthesized materials are Portland cement
(CEM II 42.5), from the Ain El Kebira cement factory in Algeria and synthetic waste com-
posed of standard sand, from the New Littoral Company in France, while pure pollutant
Cr2 O3 (CAS: 1308-38-9) is introduced in the form of pure laboratory products, to facilitate
the tracking and detection of this metal inside the cementitious matrix. Demineralized
water was used as mixing water to avoid any possible contamination by trace elements.
The chosen content of pollutant (Cr2 O3 ) of 0.6%, 0.96%, and 1.2% (mass) for pollution
levels is considered plausible [35]. The chemical composition of the synthesized
4 of 18 materials
developed is recorded in Table 1 and their grain size distributions are presented in Figure 1.

(a)

(b)
Figure 1. (a)Grain size distribution of cement and pure waste. (b)Grain size distribution of standard
Figure 1. (a) Grain size distribution of cement and pure waste. (b) Grain size distribution of standard
sand.
sand.
Table 1. Chemical composition of cement, pure waste, and standard sand.

Compound SiO2 Al2O3 Fe2O3 CaO MgO SO3 K2O + Na2O Cr2O3
Cement (%) 28.36 ± 0.04 6.82 ± 0.09 3.48 ± 0.07 58.57 ± 0.22 1.03 ± 0.02 1.52 ± 0.02 0.17 ± 0.01 n.d.
Pure waste
Materials 2023, 16, 6295 4 of 17

Table 1. Chemical composition of cement, pure waste, and standard sand.

Compound SiO2 Al2 O3 Fe2 O3 CaO MgO SO3 K2 O + Na2 O Cr2 O3

Cement (%) 28.36 ± 0.04 6.82 ± 0.09 3.48 ± 0.07 58.57 ± 0.22 1.03 ± 0.02 1.52 ± 0.02 0.17 ± 0.01 n.d.
Pure waste 1 99.94 ± 0.03
(%) n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Standard 98.05 ± 0.23 0.54 ± 0.05 0.07 ± 0.01 n.d. n.d. n.d. n.d. n.d.
sand (%)
1 n.d. Not detected.

Each mortar is formulated using a 3 kg mixer. Initially, sand and the pollutant are
blended at a moderate velocity to achieve a uniform mixture. Subsequently, cement and
demineralized water are introduced, and the entire blend is mixed for a brief duration.
It is then necessary to stop the agitation to scrape the bottom of the container with a
spatula so that the hydration occurs homogeneously. After mixing, the mortars are poured
into 4 × 4 × 16 cm3 and 7 × 7 × 28 cm3 molds and stored airtight at room temperature
(20 ± 3 ◦ C) for 28 days.
The rapid formation of a thin layer of surface calcite CaCO3 [36] by atmospheric
carbon dioxide can impede the surface porosity and have considerable repercussions on
the leaching rate, making carbonation of the surface a significant issue during sample
preparation. This leads us to obtain a sample preparation method designed to minimize
exposure to atmospheric conditions. We employed a water-to-cement ratio of 0.5 to pro-
mote effective diffusion [37], allowing us to obtain a constant capacity without needing a
“vibrating table”.
After 28 days of cure in a wet room, the specimens of dimension 4 × 4 × 16 cm3
underwent mechanical tests according to the standard CEN 196-1. Each sample was
tested in triplicate. On the other hand, the 7 × 7 × 28 cm3 specimens were dry-cut to
prepare 3 × 3 × 3 cm3 monoliths from their cores to run the TCLP test. XRD and infrared
spectrometry (FTIR) were then used to characterize the synthesized materials at different
times (before and after leaching). The diffractometer used in our study was of type X’Pert
PRO PANalytical. The samples were subjected to analysis in their powdered form, with
particle sizes smaller than 100 µm.
XRD patterns and FTIR spectra were treated using X’Pert High Score (version 2. 1b
2.1.2, 9 January 2005) and IR solution software (version 1.4, 12 October 2007), respectively.

2.2. Testing Methodology

2.2.1. Toxicity Characteristic Leaching Procedure (TCLP) Test
The TCLP test aims to characterize the behavior of the stabilized/solidified waste over
time. S/S materials are subjected to the standard TCLP protocol, except in this study, the
test duration is over 50 h [38] instead of 18 h. The leachant is a solution that is a mixture
of 63.4 mL of 1 N sodium hydroxide and 5.7 mL of 1 N acetic acid, adjusted with distilled
water to a 1 L solution. The pH of the leaching solution is 4.93. The liquid-to-surface
ratio (L/S) is maintained at 20 cm3 /cm2 under leaching conditions. The mortars made
up are crushed to a diameter less than 9.5 mm, then they are submitted in contact with
the leachant in 1 L containers, which are tightly closed to avoid, on the one hand, the
admission of air, thus the risk of carbonation, and, on the other hand, the evaporation of
the solution. In addition, agitation is ensured during the entire test. During the TCLP test,
six samples were taken after 2, 4, 18, 26, 42, and 50 h of leaching. They were filtered and
acidified to pH = 2 with 68% nitric acid (HNO3 ). They were then stored in airtight vials at
room temperature. It is important to highlight that prior to analysis using flame atomic
absorption spectrophotometry (FAAS) with the Aurora Instruments AI 1200, the samples
underwent centrifugation to convert the different chromium forms into total chromium.
To assess the degradation of S/S mortars, a solid block measuring 3 × 3 × 3 cm3 is
placed in contact with a fixed volume of leachant. The leachant used corresponds to that
employed in the Toxicity Characteristic Leaching Procedure (TCLP) test. The leachant is
replaced at intervals of 0.25, 0.75, 1, 2, 5, 7, 20, and 28 days, resulting in a total leaching
period of 64 days. This duration is equivalent to 96 years of continuous leaching under
 went centrifugation to convert the different chromium forms into total chromium.
To assess the degradation of S/S mortars, a solid block measuring 3×3×3 cm3 is placed
in contact with a fixed volume of leachant. The leachant used corresponds to that em-
ployed in the Toxicity Characteristic Leaching Procedure (TCLP) test. The leachant is re-
placed at intervals of 0.25, 0.75, 1, 2, 5, 7, 20, and 28 days, resulting in a total leaching
Materials 2023, 16, 6295 period of 64 days. This duration is equivalent to 96 years of continuous leaching under 5 of 17
experimental conditions. During each leachant replacement, the liquid-to-surface ratio
(L/S) is maintained at a constant value of 10 cm3/cm2, and the experiment is conducted at
room temperature
experimental (23 ± 1 During
conditions. °C). Theeach
setup is shielded
leachant from lightthe
replacement, and protected against
liquid-to-surface air
ratio
penetration
(L/S) (CO2). at a constant value of 10 cm3 /cm2 , and the experiment is conducted at
is maintained
roomUpon completing
temperature 1 ◦ test,
(23 ±the thesetup
C). The monolithic blocks
is shielded are light
from subjected to X-ray against
and protected diffraction
air
penetration (COto
(XRD) analysis 2 ). assess the extent of degradation in terms of peak intensities related to
Upon completing the test, the monolithic blocks are subjected to X-ray diffraction (XRD)
portlandite.
analysis
Thetoexperimental
assess the extent of degradation
program in terms
undertaken in thisofstudy
peak is
intensities related
summarized in to portlandite.
Figure 2.
The experimental program undertaken in this study is summarized in Figure 2.

Figure 2. Flowchart of the experimental program undertaken in this study.

Figure 2. Flowchart of the experimental program undertaken in this study.
2.2.2. Modeling and Simulation of Cr Leachate Release from Monoliths
By integrating the cumulative fraction expressions from three equations established in
the Cote model [39–41], we can formulate a semi-empirical expression for the cumulative
leached fractions of chromium in the following general format:

M(t) √
CLF (t) = = K 1 ( 1 − e − K2 t ) + K 3 t + K 4 t (1)
M0

where M(t) is the concentration of Cr in the leachate in (µmol/L); M0 is the initial con-
centration of Cr introduced into the sample in (µmol/L); and K1 , K2 , K3 , and K4 are the
parameters that were determined using the convergence of the Cote model by the simplex
method (using ORIGIN 6.0 MicroCal Software) on the experimental data of the released
chemical species.
The initial component of Equation (1) accounts for the influence of species whose
release kinetics are dictated by interactions between the sample surface and the leachant.
The subsequent term in Equation (1) represents the outcome of solving diffusion equations
(Fick’s laws), illustrating the impact arising from the release of species controlled primarily
by pure diffusional transport. Lastly, the third term, denoted as K4 t, encapsulates the
concept of species release governed by first-order dissolution kinetics.
Therefore, we shall conduct our predictive research utilizing the empirical model
of Cote, integrating surface phenomena with diffusion and chemical reactions. We use
four statistical criteria for validating the Cote model: the residual variance, the correlation
coefficient, the Student’s test, and the Fisher–Snedecor test.
Materials 2023, 16, 6295 6 of 17

R2 is the proportion of the variance of y explained by the explanatory variables. It is

used to test the goodness of fit of y by ŷ and is expressed by the following relationship:
n
2
∑ (ŷi − y)
i =1
R2 = n (2)
2
∑ ( yi − y )
i =1

The following quantity gives the part not explained by the regression and is called
residual variance:
1 n
Sr2 = ∑ (yi − ŷ)2 (3)
n i =1
The estimation of the influence of the regression coefficients is performed by the
Student’s t-test, which is based on statistics:

Cj
T= (4)
σ (Cj )

However, the overall validity of the model is assessed using the Fisher test, which
relies on the following statistical measure:
n
2
∑ (yi − y) /m − 1 R2
i =1 m −1
F= n = (5)
2 1− R2
∑ (yi − ŷ) /n − m n−m
i =1

3. Results and Discussion

3.1. Mechanical Tests
The results of the compressive strength (Rc) and flexural strength (Rf) tests are pre-
sented in Figure 3a,b and Table 2.

Table 2. Strength tests on S(Cr2 O3 , 0.6%, 0.96%, and 1.2%) and S(Control, 0%) mortars.

Designation Rc (MPa) Rf (MPa)

S (Control, 0%) 34.62 ± 1.22 6.34 ± 0.43
S(Cr2 O3 , 0.6%) 36.36 ± 0.87 6.47 ± 0.31
S(Cr2 O3 , 0.96%) 39.22 ± 1.65 6.69 ± 0.09
S(Cr2 O3 , 1.2%) 42.32 ± 0.54 7.20 ± 0.17

The results obtained show that the mechanical resistance values recorded for the S/S mate-
rials comply with those required by the X31-211 standard (strengths greater than 1 MPa) [42].
It was observed that increasing the amount of chromium in the mixtures increases the
mechanical strength of mortars. This is because chromium can precipitate in the form of
oxides, sulfates, and carbonates, as well as a substitute for calcium. In addition, it gives rise
to new compounds that accelerate the hydration of cement grains and the setting of the
material. The rapid precipitation of C-S-H and portlandite due to the addition of chromium
confers good mechanical strength to the hardened cementitious matrix. In summary, it can
be concluded that the mechanical strength of a material is distinguished by the nature of
the pollutant it contains [35].
 3. Results and Discussion
3.1. Mechanical Tests
Materials 2023, 16, 6295 The results of the compressive strength (Rc) and flexural strength (Rf) tests are7 ofpre-
17
sented in Figure 3a,b and Table 2.

(a)

(b)
Figure 3. (a)Figure
Compressive strengthstrength
3. (a) Compressive of studied mixes.mixes.
of studied (b) Flexural strength
(b) Flexural ofofstudied
strength studied mixes.
mixes.

3.2. TCLP Leaching Test

Table 2. Strength tests on S(Cr2O3, 0.6%, 0.96%, and 1.2%) and S(Control, 0%) mortars.
Chemical Properties
Designation
The chemical results of S(Cr2RcO3 ,(MPa)
0.6%, 0.96%, and 1.2%), namely, Rf pH,
(MPa)conductivity,
cumulative
S (Control, 0%)concentrations, and cumulative leached fractions (C.L.F.) of6.34
34.62 ± 1.22 monitored
± 0.43 chemical
species
S(Cr (Cr), are presented in Tables
2O3, 0.6%) 3–5.± 0.87
36.36 6.47 ± 0.31
S(Cr2O3, 0.96%) 39.22 ± 1.65 6.69 ± 0.09
S(Cr2O3, 1.2%) 42.32 ± 0.54 7.20 ± 0.17
Materials 2023, 16, 6295 8 of 17

Table 3. Chemical results of S(Cr2 O3 , 0.60%) after 50 h of leaching.

Conductivity Cumulative Time [Cr] (µmol/L) in the [Cr]0 (µmol/L)

Levy pH C.L.F.
(ms) (Hours) Leachate Initial
1 5.08 4.10 2 0.07499 2.901 × 10−7
2 5.18 4.10 4 0.25509 9.868 × 10−7
3 5.38 4.60 18 0.64860 2.509 × 10−6
258,500
4 5.46 4.60 26 0.66346 2.566 × 10−6
5 5.65 5.48 42 0.67115 2.559 × 10−6
6 5.80 5.00 50 0.67115 2.596 × 10−6

Table 4. Chemical results of S(Cr2 O3 , 0.96%) after 50 h of leaching.

Conductivity Cumulative [Cr] (µmol/L) in the

Levy pH [Cr]0 (µmol/L) Initial C.L.F.
(ms) Time (Hours) Leachate
1 5.15 4.30 2 0.13990 3.404 × 10−7
2 5.20 4.30 4 0.36661 8.820 × 10−7
3 5.44 5.21 18 1.09753 2.670 × 10−6
411,000
4 5.53 4.90 26 1.10189 2.681 × 10−6
5 5.68 6.18 42 1.10382 2.685 × 10−6
6 6.48 5.70 50 1.10164 2.680 × 10−6

Table 5. Chemical results of S(Cr2 O3 , 1.20%) after 50 h of leaching.

Conductivity Cumulative Time [Cr] (µmol/L) in the [Cr]0 (µmol/L)

Levy pH C.L.F.
(ms) (Hours) Leachate Initial
1 5.19 4.20 2 0.15384 3.089 × 10−7
2 5.17 4.10 4 0.45250 9.086 × 10−7
3 5.43 4.70 18 1.40595 2.823 × 10−6
498,000
4 5.58 4.92 26 1.44230 2.896 × 10−6
5 5.73 5.10 42 1.45769 2.927 × 10−6
6 5.79 5.29 50 1.46154 2.934 × 10−6

Based on the findings presented in Tables 3–5, two distinct zones can be identified. In zone
1, characterized by pH values lower than 5.44 and time lower than 18 h, there is a significant
increase in cumulative chromium concentrations. This phenomenon is primarily attributed to
the pH-dependent solubilization of chromium, driven by concentration gradients between the
aggressive solution and the pore water within the cementitious matrix. This gradient induces
ion transfer through diffusion and the release of chromium present on the outer surface of the
mortar monoliths, akin to a water-washing phenomenon [43]. In contrast, in zone 2, where pH
levels exceed 5.36 and the time elapsed surpasses 18 h, there is a stabilization in the cumulative
chromium concentrations. This stabilization can be attributed to several factors:
(i). The dissolution of portlandite occurs when the pH is below 12.5 [44].
(ii). The decomposition of C-S-H and ettringite takes place, resulting in a silica gel residue,
when pH values are below 10.6 and 8.8, respectively [44].
(iii). Strongly soluble phases such as KOH and NaOH dissolve, neutralizing the leachant’s
acidity and aligning the pH with that of the strongly basic interstitial solution within the
cement mortar. Consequently, chromium release becomes significantly diminished [44].
Furthermore, it is worth noting that the concentrations of stabilized/solidified chromium
are substantially lower in comparison to the initial amount of Cr2 O3 introduced into the mixes.
This observation highlights that chromium has been effectively retained within the structure
of the cement matrices. This confirms the process used for the immobilization of chromium.
This shows that the process used in the context of our study is more efficient in terms of the
immobilization of Cr compared to the other processes cited in [26]. To better illustrate the
 lution within the cement mortar. Consequently, chromium release becomes signifi-
cantly diminished [44].
Furthermore, it is worth noting that the concentrations of stabilized/solidified
chromium are substantially lower in comparison to the initial amount of Cr2O3 intro-
duced into the mixes. This observation highlights that chromium has been effectively
retained within the structure of the cement matrices. This confirms the process used for
Materials 2023, 16, 6295 9 of 17
the immobilization of chromium. This shows that the process used in the context of our
study is more efficient in terms of the immobilization of Cr compared to the other pro-
cesses cited in [26]. To better illustrate the influence of Cr2O3 on the hydration product of
cement CEM II, influence of Cr2was
XRD analysis O3 on the hydration
performed product with
on the samples of cement CEM28II,days
Cr2O3 after XRDofanalysis was performed
hardening. on the samples with Cr2 O3 after 28 days of hardening.

3.3. X-ray
3.3. X-ray Diffraction Diffraction
(XRD) Analysis of(XRD) Analysis of S/S Mortars
S/S Mortars
Figure 4a–c and Table4a–c
Figure 6 show
andthe XRD6patterns
Table of XRD
show the the samples,
patternsdried 105 °C fordried at 105 ◦ C for 24 h,
at samples,
of the
24 h, crushed, crushed,
and sieved through
and sieveda through
100 μm sieve.
a 100 µm sieve.

Materials 2023, 16, x FOR PEER REVIEW 10 of 18

(a)

(b)

(c)
Figure 4. (a) XRD patterns
Figure of S(Cr
4. (a) XRD 2O3, 0.60%) before and after leaching. (b) XRD patterns of S(Cr2O3,
patterns of S(Cr2 O3 , 0.60%) before and after leaching. (b) XRD patterns of S(Cr2 O3 ,
0.96%) before and after leaching. (c) XRD patterns of S(Cr2O3, 1.20%) before and after leaching.
0.96%) before and after leaching. (c) XRD patterns of S(Cr2 O3 , 1.20%) before and after leaching.
Table 6. Mineralogical compounds detected by X’Pert High Score software (version 2. 1b 2.1.2, 9
January 2005).

Legend Compound Name Chemical Formula Reference Pattern

1 Calcium Chromium Oxide Hydrate CaCrO4.2H2O 00-038-1186
Materials 2023, 16, 6295 10 of 17

Table 6. Mineralogical compounds detected by X’Pert High Score software (version 2. 1b 2.1.2, 9
January 2005).

Legend Compound Name Chemical Formula Reference Pattern

1 Calcium Chromium Oxide Hydrate CaCrO4 ·2H2 O 00-038-1186
2 Portlandite Ca(OH)2 00-004-0733
3 Quartz SiO2 00-046-1045
4 Calcium Chromium Sulfate Hydroxide Hydrate Ca6 Cr2 (SO4 )3 (OH)12 ·26H2 O 00-033-0248
5 Ettringite Ca6 Al2 (SO4 )3 (OH)12 ·26H2 O 00-041-1451
6 Calcite CaCO3 00-005-0586

Based on XRD analyses, it can be seen that in all materials, the SiO2 was detected
due to presence of the standard sand. Moreover, the appearance of the chromium waste,
in all mixes S(Cr2 O3 0.60, 0.96, and 1.20%), have not blocked the hydration reactions,
which is confirmed by the presence of ettringite and portlandite Ca(OH)2 , which
Materials 2023, 16, x FOR PEER REVIEW 11 of are
18
these reactions’ products [45]. Furthermore, there is a visible increase in the formation
of ettringite while using chromium in the mortars mixtures; it is proved by the increased
number of ettringite peaks in the XRD patterns [46]. However, it is worth emphasizing that
that while
while usingusing chromium
chromium in mortar
in the the mortar mixtures,
mixtures, it proves
it proves thatthat
it is itpossible
is possible to obtain
to obtain two
two new crystallized phases, Calcium Chromium Oxide Hydrate CaCrO
new crystallized phases, Calcium Chromium Oxide Hydrate CaCrO4 ·2H2 O and Calcium 4.2H2O and Cal-

cium Chromium
SulfateSulfate Hydroxide HydrateCa 6Cr2(SO4)3(OH)12.26H2O, that were not
Chromium Hydroxide HydrateCa 6 Cr2 (SO4 )3 (OH)12 ·26H2 O, that were not detected
detected in previous works summarized in [47].
in previous works summarized in [47]. This is because Thischromium
is because chromium
substitutes thesubstitutes
aluminum
the aluminum in ettringite to form a new chromium–ettringite
in ettringite to form a new chromium–ettringite phase. phase.

3.4.
3.4.Infrared
InfraredAnalysis
Analysis(IR)
(IR)ofofS/S
S/SMortars
Mortars
FTIR
FTIR spectra
spectra of S(Cr
S(Cr22O33,, 0.60%, 0.96%,
0.96%,and
and1.20%)
1.20%)mortars
mortarsareare shown
shown in Figure
in Figure 5,
5, and
theirtheir
and vibration bands
vibration are presented
bands are presentedin Table 7. 7.
in Table

Figure
Figure5.5.FTIR
FTIRspectra
spectraofofS(Cr
S(Cr2O 3, 0.60%, 0.96%, and 1.20%) after 50 h of leaching.
2 O3 , 0.60%, 0.96%, and 1.20%) after 50 h of leaching.

Table 7. IR vibration bands of S(Cr2O3, 0.60%, 0.96%, and 1.20%).

Wave Number cm−1

S(Cr2O3, 0.6%) S(Cr2O3, 0.96%) S(Cr2O3, 1.2%)
OH of portlandite 3460 3460 3460
H2O adsorbed 1617 1617 1600
C-S-H 1378 1378 1378
Materials 2023, 16, 6295 11 of 17

Table 7. IR vibration bands of S(Cr2 O3 , 0.60%, 0.96%, and 1.20%).

Wave Number cm−1

S(Cr2 O3 , 0.6%) S(Cr2 O3 , 0.96%) S(Cr2 O3 , 1.2%)
OH of portlandite 3460 3460 3460
H2 O adsorbed 1617 1617 1600
C-S-H 1378 1378 1378
M-O 1068 1075 1068
C-S-H 861 861 781
Si-O 686 686 622

The results presented in Table 7 and Figure 5 show that the characteristic bands of Si-O
can come from SiO2 of the C-S-H and/or the standard sand. We also note the appearance
of certain compounds, namely, the metal-oxygen (M-O) band [48], which confirms the
formation of bonds between chromium and cement hydrates. The band observed around
Materials 2023, 16, x FOR PEER REVIEW 12 of 18
1600 cm−1 corresponds to intermolecular water [49]. We also note the presence of the C-S-H
band, which is the result of hydration reactions. The detection of the band characteristic of
portlandite around 3460 cm−1 is confirmed by XRD.
3.5.
3.5. Modelling
Modelling and
and Simulation
Simulation
Cumulative
Cumulative leachedfractions
leached fractionswere
weremodeled
modeledusing
usinganan
empirical model
empirical developed
model by
developed
Cote
by Coteet al., and
et al., andthethemodeled
modeledandandsimulated
simulatedvalues
valuesshowed
showed remarkable
remarkable similarity,
similarity, as
as
demonstrated
demonstrated in in Figure
Figure 6.6. The
The validity
validity tests
tests of
of the
the selected
selected models
models and their parameters
and their parameters
are
are recorded
recorded inin Table
Table 8.8.

Figure 6. Experimental
Figure 6. Experimentaland
and simulated
simulated cumulative
cumulative leached
leached fractions
fractions of S(Crof S(Cr2O3, 0.60%, 0.96%,
2 O3 , 0.60%, 0.96%, and 1.20%).
and 1.20%).
The parameters recorded in Table 8 reveal that the surface phenomenon prevails
over The
the process. Moreover,
parameters recordedtheinminus
Tablesign of K3 that
8 reveal signifies the delay
the surface in leaching, prevails
phenomenon and the
infinitely
over small value
the process. of the constant
Moreover, the minusK4 sign
evaluates
of K3 the reaction
signifies thecomponent, indicating
delay in leaching, andthat
the
the phenomena
infinitely small of diffusion
value of theand chemical
constant K4 reaction
evaluatesarethe
lessreaction
significant.
component, indicating
that the phenomena of diffusion and chemical reaction are less significant.

Table 8. Simulated parameters and statistical tests of the proposed model for S(Cr2O3, 0.6%, 0.96%,
and 1.2%).

Chemical Reactions
Surface Phenomenon Diffusion (Dissolution or Precipi- Correlation Co-
Materials 2023, 16, 6295 12 of 17

Table 8. Simulated parameters and statistical tests of the proposed model for S(Cr2 O3 , 0.6%, 0.96%,
and 1.2%).

Chemical Reactions
Surface Phenomenon Diffusion
√ (Dissolution or Correlation
K1 (1−e−K2 t ) K3 t Precipitation) Coefficient
K4 t
Mechanisms Controlling the Release of Cr for S(Cr2 O3 , 0.6%)
K1 K2 K3 K4 R2
Coefficients
5.432 × 10−6 0.15622 −9.227 × 10−7 7.3955 × 10−8
Student’s t-test 51.98 - 29.69 31.16
T (n-m, α/2 = 4.514) 0.999
Fisher test (Ftabulated = 9.78) 11,879
Residual variance 2.167 × 10−16
Mechanisms controlling the release of Cr for S(Cr2 O3 , 0.96%)
K1 K2 K3 K4 R2
Coefficients
5.256 × 10−6 0.13359 −7.251 × 10−7 5.1065 × 10−8
Student’s t-test 18.32 - 9.16 8.85
T (n-m, α/2 = 4.514) 0.999
Fisher test (Ftabulated = 9.78) 1373
Residual variance 2.126 × 10-15
Mechanisms controlling the release of Cr for S(Cr2 O3 , 1.20%)
K1 K2 K3 K4 R2
Coefficients
5.679 × 10−6 0.12961 −7.957 × 10−7 5.7839 × 10−8
Student’s t-test 28.01 - 14.47 14.5
T (n-m, α/2 = 4.514) 0.999
Fisher test (Ftabulated = 9.78) 3254
Residual variance 1.101 × 10−15

In general, statistical evaluations of the chosen models led to:

- A residual variance of the order of zero;
- A closeness to one for the coefficients of determination;
- The models being integer-validated because the calculated values of the Fisher tests
are more significant than the tabulated values of the Fisher tests;
- Student’s t-test values demonstrating that all model coefficients are preserved apart
from the constant K3 , which is rejected by the delay in leaching;
- The release of chromium being controlled by surface phenomena, as indicated by the
simplex method and corroborated by statistical tests.
From the results of the modeling coupling the transfer of chromium by the surface
phenomenon, the diffusion, and the dissolution–precipitation reactions, it was observed that
the released flows obtained are theoretically very close to those determined experimentally.
This good agreement shows that it is possible to apply the present model to predict the
release of different heavy metals of previous research that did not take into account the
long-term prediction of the release of these toxic pollutants stabilized/solidified and subjected
to aggressive environments.

3.6. Degradation of Monolithic Cubes during the TCLP Test

To illustrate the degradation from the cumulative concentration released by the mono-
lithic cubes in the medium of study, the criterion of leached rate (percentage) has been used,
and is given by the mathematical expression illustrated in the fourth column of Table 9.
Based on the leached rate values, there is no significant degradation in the three
S/S mortars. The low leached concentrations of chromium are far below those required
by the TCLP test standard; this confirms that chromium is well fixed in the structure of
mortars, and consequently chromium becomes non-hazardous. It has also been proved by
the results presented in Figure 7. In the presented EDS spectrum of S(Cr2 O3 , 1.2%), the
Materials 2023, 16, 6295 13 of 17

presence of Ca, Si, O, Al, Fe, and Al was observed. These elements are the main components
of the materials used for the stabilization/solidification technique. It also confirms that the
presence of chromium is well fixed in the structure of mortars, and consequently chromium
becomes non-hazardous.

Table 9. Leached rates of chromium during the TCLP test.

Materials 2023, 16, x FOR PEER REVIEW 14 of 18

Initial Concentration of Cr (C0 ) en Cumulative Concentration
Designation Leached Rates (%)=(Ci ×100)/C0
µmol/L Leached (Ci ) en µmol/L
S(Cr2 O3 , 0.6%) 258,500 0.67 2.59 × 10−4
S(Cr2 O3 , 0.96%) confirms411,000
that the presence of chromium1.10
is well fixed in the structure −4
2.60 ×of10mortars, and
S(Cr2 O3 , 1.2%) 498,000chromium becomes non-hazardous.
consequently 1.46 2.93 × 10−4

Figure7.7.EDS
Figure EDSanalysis
analysisofofS(Cr
S(Cr2O3,,1.20%).
2O 3 1.20%).

Also,
Also,the
thediffractograms
diffractogramsofofmonolithic
monolithicmortars
mortarsS(Cr 2O
S(Cr 3 ,3, 0.60%,
2O 0.60%,0.96%,
0.96%,and and1.20%)
1.20%)
presented
presentedinin Figure
Figure8 reveal that that
8 reveal the intensities of the peaks
the intensities of thebefore
peaksand afterand
before (core) leaching
after (core)
are of the same order of magnitude. On the other hand, a decrease
leaching are of the same order of magnitude. On the other hand, a decrease in peakin peak intensities after
in-
leaching
tensitiesisafter
recorded
leaching between the core
is recorded of the the
between matrix
coreand thematrix
of the side exposed
and the to theexposed
side acidic
medium during
to the acidic the TCLP
medium test. the
during ThisTCLP
shows a slight
test. This washing
shows a of the contact
slight washingsurface
of the due to
contact
dissolution
surface dueortoprecipitation
dissolution or reactions.
precipitation reactions.
The
Thedegradation
degradationofofmonolithic
monolithiccubescubesduring
duringthetheTCLP
TCLPtest
testwaswasevaluated
evaluatedfrom fromthethe
viewpoint of the intensities of portlandite peaks before and after leaching.
viewpoint of the intensities of portlandite peaks before and after leaching. This method This method
consists
consistsofof
measuring
measuring thethe
average
averageintensity of portlandite
intensity peaks peaks
of portlandite before before
and after
andleaching. It is
after leach-
used as a criterion for evaluating the degradation of monolithic cubes of mortars
ing. It is used as a criterion for evaluating the degradation of monolithic cubes of mor- [29,36,49].
tarsIn accordance with the trends observed in the average intensities of the portlandite
[29,36,49].
peaks, as shown in Figure 8, a slight reduction in the intensity of portlandite was observed
when comparing scans BL (Before Leaching), HAL (Heart After Leaching), and EIAF
(Exposed Interface After Leaching). This phenomenon can be attributed to the dissolution
of portlandite at interfaces exposed to the aggressive leachant.
When comparing different materials, it is evident that S(Cr2 O3 , 1.2%) exhibits lower
degradation compared to S(Cr2 O3 , 0.6%) and S(Cr2 O3 , 0.96%). This superior performance
can be attributed to its higher mechanical strength in comparison to S(Cr2 O3 , 0.6%) and
S(Cr2 O3 , 0.96%).
Materials 2023,16,
Materials2023, 16,6295
x FOR PEER REVIEW 14 of
15 of17
18

Figure8.8.Average
Figure Averagepeak
peakintensities
intensitiesofofportlandite
portlanditebefore
beforeand
andafter
afterleaching
leachingofofmonolithic
monolithiccubes
cubesofof
S(Cr 2O3, 0.6%, 0.96%, and 1.2%).
S(Cr2 O3 , 0.6%, 0.96%, and 1.2%).

In accordance
Based with the trends
on the degradation results,observed in the average
we recommend intensitiesand
that industrials of the portlandite
policymakers
peaks,
use as shown inwaste
chromium-rich Figure in 8, a slight reduction
cementitious materials in due
the to intensity of portlandite
the beneficial was ob-
contribution of
served when
chromium, comparing
which reacts withscans BL (Before
cement Leaching),
hydrates, increases HAL (Heart
their After Leaching),
mechanical strength, andand
EIAF (Exposed
enhances Interfacetowards
their durability After Leaching).
aggressive This phenomenon can be attributed to the dis-
environments.
solution of portlandite at interfaces exposed to the aggressive leachant.
4. Conclusions
When comparing different materials, it is evident that S(Cr2O3, 1.2%) exhibits lower
degradation compared
For a better to S(Cr2Oof
understanding 3, 0.6%) and S(Cr2Othat
the phenomena 3, 0.96%).
govern This
thesuperior
process performance
of stabiliza-
can be attributed to
tion/solidification anditsthe
higher mechanical
release of chromiumstrength in comparison
in mortars, to S(Cr
complex 2O3, 0.6%)
research and
was con-
S(Cr2O3This
ducted. , 0.96%).
research includes an evaluation of the chromium’s solidification/stabilization
process based
Based onontheanalyses performed
degradation using
results, XRD and statistical
we recommend analysesand
that industrials of the empirical
policymakers
Cote model.
use chromium-rich waste in cementitious materials due to the beneficial contribution of
It has been
chromium, proved
which thatwith
reacts it is cement
possiblehydrates,
to transform hazardous
increases theirwaste into non-hazardous
mechanical strength, and
material
enhances intheir
cementitious
durabilitycomposites by their synergistic
towards aggressive environments. use. The low leached concentra-
tions of chromium are far below those required by the TCLP test standard. This confirms
that chromium is well fixed in the structure of mortars, and consequently chromium be-
4. Conclusions
comesFor non-hazardous, which wasof
a better understanding confirmed by the results
the phenomena of SEM-EDX.
that govern It hasofalso
the process been
stabiliza-
noticed that the incorporation of chromium-rich waste into the cementitious
tion/solidification and the release of chromium in mortars, complex research was con- matrices in-
creases
ducted.theThismechanical
research strength and improves
includes the durability
an evaluation of theof these materials.
chromium’s In this
solidifica-
context, the use of this type of waste as an addition or partial replacement
tion/stabilization process based on analyses performed using XRD and statistical anal- of cement or
aggregate allows reducing the consumption of raw materials (preserves natural resources),
yses of the empirical Cote model.
reducing pollution, reducing energy use, reducing the volume of waste that must be treated
It has been proved that it is possible to transform hazardous waste into
and disposed of, and reducing CO2 emissions. It is beneficial to the cement industry,
non-hazardous material in cementitious composites by their synergistic use. The low
which is one of the most polluting sectors with a contribution of almost 7% of global CO2
leached concentrations of chromium are far below those required by the TCLP test
emissions [50].
standard. This confirms that chromium is well fixed in the structure of mortars, and
The simplicity of implementing the chromium stabilization/solidification process, the
consequently chromium becomes non-hazardous, which was confirmed by the results of
availability of hydraulic binders (cement), and their low cost compared to other techniques
SEM-EDX. It has also been noticed that the incorporation of chromium-rich waste into
(namely, vitrification, precipitation of waste by acids, decantation, adsorption, incineration,
the cementitious matrices increases the mechanical strength and improves the durability
and stabilization/solidification by geopolymer), high mechanical strength, great ability to
of these materials. In this context, the use of this type of waste as an addition or partial
chemically immobilize chromium inside the phases, low permeability, and relatively high
replacement of cement or aggregate allows reducing the consumption of raw materials
durability have made the process of stabilization/solidification by cement more reliable
(preserves
and adequate natural resources), reducing
for chromium-rich pollution,
waste treatment [26].reducing energy use, reducing the
volume of waste that must be treated and disposed of, and reducing CO2 emissions. It is
Materials 2023, 16, 6295 15 of 17

It was observed that chromium substitutes the aluminum in ettringite to form a new
chromium–ettringite phase, forming Calcium Chromium Oxide Hydrate CaCrO4 ·2H2 O
and Calcium Chromium Sulfate Hydroxide Hydrate Ca6 Cr2 (SO4 )3 (OH)12 ·26H2 O that
results in strengthening the materials.
XRD results explain the success of chromium immobilization within the cement
matrices of mortars, in the form of complex phases which were not detected in previous
works summarized in [46]. This is because chromium substitutes the aluminum in ettringite
to form a new chromium–ettringite phase. The formation of new phases due to the effect of
cement hydration and the various interactions between chemical elements considerably
reduce the polluting potential of chromium.
Based on the obtained results, we recommend industrials and policymakers use
chromium-rich waste in cementitious materials due to the beneficial contribution of
chromium, which reacts with cement hydrates, increases their mechanical strength, and
enhances their durability towards aggressive environments.
The main limitations of this study are the possibility of using the presented S/S method
for materials that are similar to those used during the experimental campaign. Further
research might need to be conducted to evaluate comparative analyses of different mixtures of
cementitious composites that may include other heavy metals. Performing experimental tests
similar to those used in this paper allows comparing the results and evaluating the presented
model and its suitability for other heavy metals. Moreover, from the cognitive point of view, it
might be beneficial to evaluate the effect of adding non-hazardous waste (such as limestone
filler, marble, glass, etc.) to cementitious materials on the release of heavy metals. In addition,
it would be advantageous to complete this research work by studying the possibility of using
chromium-rich waste as a raw material during the manufacture of cement.

Author Contributions: Conceptualization, C.B. and K.M.; methodology, C.B. and K.M.; software, C.B.,
K.M., C.O.-S., S.-E.B. and S.C.; formal analysis, C.B. and S.-E.B.; investigation, C.B., K.M., C.O.-S., S.-E.B.,
L.S. and S.C.; resources, C.B., K.M. and S.C.; data curation, C.B., K.M. and S.C.; writing—original draft
preparation, C.B., L.S., S.C. and K.M.; writing—review and editing, C.B., K.M., C.O.-S., L.S. and S.C.;
supervision, C.B. and L.S. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are available on request.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Estokova, A.; Palascakova, L.; Kanuchova, M. Study on Cr(VI) Leaching from Cement and Cement Composites. Int. J. Environ.
Res. Public Health 2018, 15, 824. [CrossRef] [PubMed]
2. Tchounwou, P.B.; Yedjou, C.G.; Patlolla, A.K.; Sutton, D.J. Heavy metal toxicity and the environment. Mol. Clin. Environ. Toxicol.
2012, 101, 133–164. [CrossRef]
3. Varitis, S.; Kavouras, P.; Pavlidou, E.; Pantazopoulou, E.; Vourlias, G.; Chrissafis, K.; Zouboulis, A.; Karakostas, T.; Komninou,
P. Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization. Waste Manag. 2017, 59, 237–246.
[CrossRef]
4. Chakraborty, V.; Sengupta, S.; Chaudhuri, P.; Das, P. Assessment on removal efficiency of chromium by the isolated manglicolous
fungi from Indian Sundarban mangrove forest: Removal and optimization using response surface methodology. Environ. Technol.
Innov. 2018, 10, 335–344. [CrossRef]
5. Sharma, P.; Singh, S.P.; Parakh, S.K.; Tong, Y.W. Health hazards of hexavalent chromium (Cr (VI)) and its microbial reduction.
Bioengineered 2022, 13, 4923–4938. [CrossRef] [PubMed]
6. Liang, J.; Huang, X.; Yan, J.; Li, Y.; Zhao, Z.; Liu, Y.; Wei, Y. A review of the formation of Cr(VI) via Cr(III) oxidation in soils and
groundwater. Sci. Total Environ. 2021, 774, 145762. [CrossRef]
7. Achmad, R.T.; Budiawan; Auerkari, E.I. Effects of Chromium on Human Body. Annu. Res. Rev. Biol. 2017, 13, 1–8. [CrossRef]
8. Li, S.; Zhang, Y.; Feng, R.; Yu, H.; Pan, J.; Bian, J. Environmental Safety Analysis of Red Mud-Based Cemented Backfill on
Groundwater. Int. J. Environ. Res. Public Health 2021, 18, 8094. [CrossRef]
Materials 2023, 16, 6295 16 of 17

9. Ashraf, A.; Bibi, I.; Niazi, N.K.; Ok, Y.S.; Murtaza, G.; Shahid, M.; Kunhikrishnan, A.; Li, D.; Mahmood, T. Chromium(VI) sorption
efficiency of acid-activated banana peel over organo-montmorillonite in aqueous solutions. Int. J. Phytoremed. 2017, 19, 605–613.
[CrossRef]
10. Kazakis, N.; Kantiranis, N.; Kalaitzidou, K.; Kaprara, E.; Mitrakas, M.; Frei, R.; Vargemezis, G.; Tsourlos, P.; Zouboulis, A.;
Filippidis, A. Origin of hexavalent chromium in groundwater: The example of Sarigkiol Basin, Northern Greece. Sci. Total Environ.
2017, 593–594, 552–566. [CrossRef]
11. Jones, A.S.; Marini, J.; Solo-Gabriele, H.M.; Robey, N.M.; Townsend, T.G. Arsenic, copper, and chromium from treated wood
products in the U.S. disposal sector. Waste Manag. 2019, 87, 731–740. [CrossRef] [PubMed]
12. Pellerin, C.; Booker, S.M. Reflections on hexavalent chromium: Health hazards of an industrial heavyweight. Environ. Health
Perspect. 2000, 108, A402–A407. [CrossRef] [PubMed]
13. Yang, Y.; Ma, H.; Chen, X.; Zhu, C.; Li, X. Effect of incineration temperature on chromium speciation in real chromium-rich
tannery sludge under air atmosphere. Environ. Res. 2020, 183, 109159. [CrossRef] [PubMed]
14. Vaiopoulou, E.; Gikas, P. Regulations for chromium emissions to the aquatic environment in Europe and elsewhere. Chemosphere
2020, 254, 126876. [CrossRef]
15. Munn, S.J.; Allanou, R.; Aschberger, K.; Berthault, F.; Cosgrove, O.; Luotamo, M.; Pakalin, S.; Paya-Perez, A.; Pellegrini, G.;
Schwarz-Schulz, B.; et al. Chromium Trioxide, Sodium Chromate, Sodium Dichromate, Ammonium Dichromate, Potassium Dichromate,
EUR 21508 EN; European Union Risk Assessment Report; Office for Official Publications of the European Communities:
Luxembourg, 2005; Volume 53.
16. Food and Agriculture Organization of the United Nations. World Statistical Compendium for Raw Hides and Skins, Leather and
Leather Footwear 1999–2015; Food and Agriculture Organization of The United Nations: Rome, Italy, 2016; Available online:
http://www.fao.org/3/a-i5599e.pdf (accessed on 15 January 2020).
17. Joseph, A.M.; Snellings, R.; Van den Heede, P.; Matthys, S.; De Belie, N. The Use of Municipal Solid Waste Incineration Ash in
Various Building Materials: A Belgian Point of View. Materials 2018, 11, 141. [CrossRef]
18. European ICCP Bureau. Reference Document on Best Available Techniques for the Tanning of Hides and Skins; European ICCP Bureau:
Seville, Spain, 2013; Available online: http://eippcb.jrc.ec.europa.eu/reference/BREF/TAN_Published_def.pdf (accessed on 15
January 2020).
19. Ballesteros, S.; Rincón, J.; Rincón-Mora, B.; Jordán, M. Vitrification of urban soil contamination by hexavalent chromium. J.
Geochem. Explor. 2017, 174, 132–139. [CrossRef]
20. Rincón-Mora, B.; Jordan, M.; Rincón, J.M. Chromium oxide additions in lithium disilicate glass crystallization. Mater. Lett. 2016,
179, 138–141. [CrossRef]
21. Zha, F.S.; Xu, L.; Cui, K.R. Study on strength characteristics of heavy metal contaminated soils solidified/stabilized by cement.
Rock Soil Mech. 2012, 33, 652–656.
22. Zhou, Y.; Cai, G.; Cheeseman, C.; Li, J.; Poon, C.S. Sewage sludge ash-incorporated stabilisation/solidification for recycling and
remediation of marine sediments. J. Environ. Manag. 2022, 301, 113877. [CrossRef]
23. Xiong, X.; Zhang, Y.; Wang, L.; Tsang, D.C.W. Chapter 1—Overview of Hazardous Waste Treatment and Stabilization/Solidification
Technology, Low Carbon Stabilization and Solidification of Hazardous Wastes; Elsevier: Amsterdam, The Netherlands, 2022; pp. 1–14.
24. Shabalala, A.N.; Basitere, M. Interactive Relationship between Cementitious Materials and Acid Mine Drainage: Their Effects on
Chromium Cr(VI) Removal. Minerals 2020, 10, 932. [CrossRef]
25. Sanito, R.C.; Bernuy-Zumaeta, M.; You, S.-J.; Wang, Y.-F. A review on vitrification technologies of hazardous waste. J. Environ.
Manag. 2022, 316, 115243. [CrossRef] [PubMed]
26. Long, L.; Zhao, Y.; Lv, G.; Duan, Y.; Liu, X.; Jiang, X. Improving stabilization/solidification of MSWI fly ash with coal gangue
based geopolymer via increasing active calcium content. Sci. Total Environ. 2023, 854, 158594. [CrossRef]
27. Belebchouche, C.; Moussaceb, K.; Aït-Mokhtar, A. Evaluation of the encapsulation of nickel, chromium and lead-rich wastes in
cement matrices by TCLP test. Eur. J. Environ. Civ. Eng. 2015, 20, 711–724. [CrossRef]
28. Belebchouche, C.; Moussaceb, K.; Hammoudi, A. Influence of the Release Kinetics of Chemical Species on the Sus-tainability of
Stabilized/Solidified Materials with Hydraulic Binder Subjected to Chemically Aggressive Environments. Arab. J. Sci. Eng. 2019,
44, 9997–10015. [CrossRef]
29. Kim, H.T.; Lee, T.G. A simultaneous stabilization and solidification of the top five most toxic heavy metals (Hg, Pb, As, Cr, and
Cd). Chemosphere 2017, 178, 479. [CrossRef] [PubMed]
30. Li, Y.; Min, X.; Ke, Y.; Fei, J.; Liu, D.; Tang, C. Immobilization potential and immobilization mechanism of arsenic in cemented
paste backfill. Miner. Eng. 2019, 138, 101–107. [CrossRef]
31. Liu, M.; Zhao, Y.; Yu, Z.; Cao, Z. Impact of Ni(II) and Cd(II) on the hydration and microstructure of cement pastes for immo-
bilization: C-A-S-H composition and binding characteristic. Constr. Build. Mater. 2021, 310, 125284. [CrossRef]
32. Mao, Y.; Muhammad, F.; Yu, L.; Xia, M.; Huang, X.; Jiao, B.; Shiau, Y.; Li, D. The Solidification of Lead-Zinc Smelting Slag through
Bentonite Supported Alkali-Activated Slag Cementitious Material. Int. J. Environ. Res. Public Health 2019, 16, 1121. [CrossRef]
33. Deng, W.; Fu, P.; Fang, G.; Zhu, W.; Li, S.; Wang, X.; Xue, T.; Chen, Y. Solidification/Stabilization of MSWI Fly Ash Using a Novel
Metallurgical Slag-Based Cementitious Material. Minerals 2022, 12, 599. [CrossRef]
34. Gmira, A. Etude Structurale et Thermodynamique D’hydrates Modèle du Ciment. Ph.D. Thesis, Université d’Orléans, Orléans,
France, 2003.
Materials 2023, 16, 6295 17 of 17

35. Belebchouche, C.; Moussaceb, K.; Hammoudi, A.; Amouri, C. Modeling and evaluation of the performance of the stabiliza-
tion/solidification process of hazardous compound PbO by toxicity characteristic leaching procedure test. Rev. Romana Mater.
2018, 48, 260–267.
36. Van Gerven, T.; Cornelis, G.; Vandoren, E.; Vandecasteele, C. Effects of carbonation and leaching on porosity in cement-bound
waste. Waste Manag. 2007, 27, 977–985. [CrossRef] [PubMed]
37. Imyim, A. Méthodologie D’évaluation Environnementale Des Déchets Stabilisés/Solidifiés par Liants Hydrauliques. Ph.D. Thesis,
Institut National des Sciences Appliquées de Lyon, Lyon, France, 2000.
38. Environmental Protection Agency. METHOD 1311:1992 Test methods for evaluating solid wastes. In Physical/Chemical Methods:
Toxicity Characteristic Leaching Procedure; Environmental Protection Agency: Washington, DC, USA, 1992.
39. Richardson, G.L. The phantom dissolution leach model. Nucl. Chem. Waste Manag. 1981, 2, 237–241. [CrossRef]
40. Cote, P.L. Contaminant Leaching from Cement-Based Waste Forms under Acidic Conditions. Ph.D. Thesis, McMaster University
at Hamilton, Hamilton, ON, Canada, 1986.
41. Gilliam, T.M.; Wiles, C.C. Stabilization and Solidification of Hazardous, Radioactive, and Mixed Wastes; American Society for Testing
and Materials: Conshohocken, PA, USA, 1992.
42. NF X31-211:2012; Caractérisation des Déchets. Essai de Lixiviation D’un Déchet Solide Initialement Massif ou Généré par un
Procédé de Solidification. AFNOR: La Plaine Saint-Denis, France, 2012.
43. Shakir, S.; de Hemptinne, J.-C. The effect of diffusion on the modeling of the water-washing phenomenon. J. Pet. Sci. Eng. 2007,
58, 403–412. [CrossRef]
44. Alexander, M.; Bertron, A.; De-Belie, N. Performance of Cement-Based Materials in Aggressive Aqueous Environments: State-of-the-Art
Report; RILEM TC 211—PAE; Springer: Dordrecht, The Netherlands, 2013.
45. Deschamps, T.; Benzaazoua, M.; Bussière, B.; Belem, T.; Mbonimpa, M. Mécanismes de Rétention des Métaux Lourds en Phase Solide:
Cas de la Stabilisation Des Sols Contaminés et Des Déchets Industriels; Vertigo 7: Article numéro 2; Vertigo: Rome, Italy, 2006.
46. Liu, J.; Wu, D.; Tan, X.; Yu, P.; Xu, L. Review of the Interactions between Conventional Cementitious Materials and Heavy Metal
Ions in Stabilization/Solidification Processing. Materials 2023, 16, 3444. [CrossRef]
47. Dana, G. Constantes des Specters Infrarouges. Les Techniques de L’ingénieur K 1010; Techniques de l’ingenieur: Saint-denis, France, 1999.
48. Fantozzi-Merle, C. Etude de Matériaux à Base de Liant Hydraulique Contenant des Pollutants Organiques Modèles: Pro-
Priétésstructurales et de Transfert. Ph.D. Thesis, Institut National des Sciences Appliquées de Lyon, Lyon, France, 2003.
49. Planel, D. Les Effets Couplés de la Precipitation D’espèces Secondaires sur le Comportement Mécanique et la Dégradation des
Bétons. Ph.D. Thesis, Université Paris-East Marne-la-Vallée, Paris, France, 2002.
50. Sheheryar, M.; Rehan, R.; Nehdi, M.L. Estimating CO2 Emission Savings from Ultrahigh Performance Concrete: A System
Dynamics Approach. Materials 2021, 14, 995. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.

View publication stats