Journal of African Earth Sciences 139 (2018) 165e172

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Journal of African Earth Sciences

journal homepage: www.elsevier.com/locate/jafrearsci

Study of Zn-Pb ore tailings and their potential in cement technology

J. Nouairi a, W. Hajjaji b, *, C.S. Costa c, L. Senff d, C. Patinha c, E. Ferreira da Silva c,
J.A. Labrincha e, F. Rocha c, M. Medhioub a
a
Dept of Geology, Faculty of Sciences of Sfax, 3018, Sfax, Tunisia
b
LabTEN Natural Water Treatment Laboratory, CERTE, BP 273, 8020 Soliman, Tunisia
c
Geobiotec, Geosciences Dept, University of Aveiro, 3810-193, Aveiro, Portugal
d
Center of Mobility Engineering, Federal University of Santa Catarina (UFSC), Joinville, SC, Brazil
e
Department of Materials and Ceramic Engineering / CICECO, Aveiro Institute of Materials, University of Aveiro, Aveiro, 3810-193, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: This paper describes the synthesis of sulfobelite clinkers incorporating mining rejects. The targeted Zn-
Received 13 October 2016 Pb tailing wastes generated in the diapiric zone (NW Tunisia) were tested in clinker/cement composi-
Received in revised form tions to ensure the inertization of existing hazardous heavy metals. Mineralogical composition of the two
8 September 2017
selected samples revealed calcite, dolomite, quartz, kaolinite, galena, pyrite and gypsum as crystalline
Accepted 8 November 2017
phases. Vertical distributions of dominant heavy metals (Pb, Zn and Cu) in soil profiles show enrichment
Available online 9 November 2017
in the surface layers and decrease towards the depth. In sintered clinkers powders, the presence of the
targeted crystalline phases (trialuminate sulphate (C4A3S),
belite (C2S), and ferrite (C4AF)) are in the
Keywords:
Mining rejects
predicted desirable amounts.
Diapiric zone Heat flow generated during the hydration of different cement pastes showed a slower reaction for
Clinker clinkers with higher amounts of C4A3S
or constituted by coarser particles. After 28 days curing, the best
Heavy metal mechanical resistance (24.34 MPa under compression) was obtained for the clinker calcined at 1350
C
Immobilisation and showing a suitable particle size distribution. Concerning heavy metals, immobilisation of 75e85% of
Pb, Zn and Cu was assessed in the mortars formulated with the produced clinker/cement, posing no
hazardous risks to the environment.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Concrete based on Ordinary Portland Cements (OPC) is the most
widely used material in buildings throughout the world. Indeed, its
workability, mechanical behaviour and durability have contributed
to its extensive use (Li, 2011; Desmettre and Charron, 2013; Tang
et al., 2015). However, its synthesis demands large amount of en-
ergy and produces a lot of CO2, while consuming considerable
amounts of non-renewable raw materials. OPC production is
responsible for 6% of anthropogenic CO2 emissions which arose
from calcite decarbonation and fuel combustion (Aranda et al.,
2011; Damtoft et al., 2008; Telesca et al., 2016; Reddy et al., 2014;
Ke et al., 2012).
Over the years, more interest in developing alternative clinkers
and cements have been reported, aiming to decrease CO2 emissions
and using low-cost materials (Berger, 2009). Sulfobelite-based
* Corresponding author.
E-mail address: w.hajjaji@ua.pt (W. Hajjaji).
clinkers present low CO2 rate and sintering temperature (saving
energy) in comparison to commercial OPC products (Telesca et al.,
2016; Quillin, 2001; Senff et al., 2011). Therefore, up to 35% CO2
emission reduction (depending on the composition) can be
attained (Aranda et al., 2011).
Moreover, in the quest of low cost raw materials, some the
recent investigation had been focused on the recycling of different
wastes in the cement industry like Industrial By-Products (Telesca
et al., 2016); red mud (Senff et al., 2011), rubber (Idrissi, 2012);
phosphogypsum (Huang et al., 2016), fly ash (Ma et al., 2013), are
some examples.
This paper is aligned with that purpose, since describes the
synthesis of sulfobelite clinkers incorporating mining rejects.
Moreover, tested clinker and cements are being targeted also for
inertization or immobilisation of heavy metals containing wastes.
Currently, on the NW Tunisia (Siliana governorate), large
quantities of mine discharges containing high levels of Pb, Zn, Cd
occupy large dumping areas without any special precaution for
their harmful effects on humans and the environment (Boussen

https://doi.org/10.1016/j.jafrearsci.2017.11.004
1464-343X/© 2017 Elsevier Ltd. All rights reserved.
166 J. Nouairi et al. / Journal of African Earth Sciences 139 (2018) 165e172

Fig. 2. Powder diffraction pattern of representative samples from the old tailings of
Lakhouat (T1) and Fej Lahdoum (T2): C ¼ Calcite, D ¼ Dolomite, Q ¼ Quartz,
Gy ¼ Gypsum, K ¼ Kaolinite, G ¼ Galena, Py ¼ Pyrite.

Fig. 1. Location of the study sites (ONM, modified).

and Zn and other heavy metals in these abandoned mine sites.

Northern Tunisia and in particular the Mejerda basin was the
et al., 2010, 2013; Ghorbel et al., 2010). In a sedimentary carbonated
most important mining region for the exploitation of base metals
context, as happens in Tunisia, the main risk of mining activities is
(Sainfeld, 1952). The most important sites were operated since the
the dispersion of tailings particles by prevaling winds and tailings
nineteenth century. This mining production fell from 1980, and
erosion and hazardous elements leaching during seasons of heavy
now the mines are closed for lack of reserves. Two abandoned
rains (Boussen et al., 2010; Ghorbel et al., 2010; Destrigneville et al.,
mining sites were selected for sampling: the Fej Lahdoum mine
2012).
(T2) located 139 km south of Tunis, which was mined several times
External inputs of trace metals in soils are mainly caused by
industrial and/or agricultural effluents (Kim et al., 2002). In general,
the concentration of a particular trace element measured in a soil
horizon results first from the inheritance from the parent rock Table 1
(local geochemical background), which is more or less modified by Formulations and compositions of studied clinkers (C2S ¼ 2CaO.SiO2;

¼ Ca4Al6(SO4)O12; C4AF ¼ 4CaO.Al2O3.Fe2O3).
C4A3S
the pedogenetic processes and possibly increased by the various
contributions related to human activities (Baize and Paquereau, CT1A CT1B CT2A CT2B
1997). Theoretical composition
C2S 30.0 50 30.0 50
C4A3S
60.0 40 60.0 40
2. Materials and methods C4AF 10.0 10 10.0 10
Batch formulations
2.1. Studied context and materials CaCO3 40 48 40 45.3
Al2O3 29 17.6 28.5 16.1
T1 70 55 0 0
The main deposits of Zn-Pb ores were located in the diapiric T2 0 0 50 50
zone: Fej Lahdoum (81.000 ton Pb and 150.000 ton Zn ores Rietveld quantification
extracted) and Lakhouat (until February 2004, 140 tons of PbS and C2S 33.8 42.6 32.7 45.2
C4A3S
64.5 44.9 62.6 41.4
350 tons of ZnS per month were extracted) (ONM, 2010; Babbou-
C4AF 1.7 10.7 4.7 13.4
Abdelmalek et al., 2011). Both mines have a well established
SO3 e 1.5 e e
infrastructure and have been operated until quite recently (Mseddi Refinement indices
et al., 2010; ONM, 2010). Nowadays, their mine tailings are prob- Rwp (%) 0.2283 0.1967 0.2291 0.1688
lematic due to the high concentration of lead and zinc sulphides. Rp (%) 0.1530 0.1344 0.1530 0.1175
Recent studies (Chakroun et al., 2010; Babbou-Abdelmalek et al., x2 7.232 5.705 8.157 3.729
R(F2) 0.2581 0.1887 0.2826 0.1033
2011; Sahraoui and Hachicha, 2016) have detected high levels of Pb
 J. Nouairi et al. / Journal of African Earth Sciences 139 (2018) 165e172 167

Sphalerite
Quartz

Galena

Calcite
Galena

Fig. 3. SEM micrographs of T1 (A) and T2 (D) samples. EDS mapping of dominant heavy metals are shown also shown: B and C for T1; E and F for T2.

from 1992 to 2008 (ONM, 2010) and the Lakhouat mine (T1) (in the
Table 2 Siliana district, located just 120 km south of Tunis), where the
Chemical composition of T1 and T2 (wt.%). mining of the lead and zinc lasted almost a century since its dis-
T1 T2 covery in 1892 until the exhaustion of the ore reserves in 1992
(Fig. 1). The Fej Lahdoum abandoned mining site is located in the
SiO2 15.5 23.4
Al2O3 6.56 10.1
upstream part of the Medjerda River (the biggest supplier of fresh
CaO 19.9 27.6 water in Tunisia). This region is characterized by a semi-arid
P2O5 0.05 0.09 climate (see Fig. 2).
SO3 21.9 9.12
K2O 0.33 0.55
MgO 3.99 5.12 2.2. Characterization tests
TiO2 0.2 0.35
Fe2O3 5.91 4.1
Pb 1.54 0.46 The studied mining tailings, and products were analysed using
Zn 4.27 2.31 XRD by Rigaku Geiger flex diffractometer with a Cu Ka radiation
Sr 2.37 1.17 source in 10e800 2Ө, the scan rate of 0.02, 4s per step. The GSAS-
Ba 2.43 0.86 EXPGUI software was used for the phases' quantification of the
LOI 15.1 14.7
various phases following a Reference Intensity Ratio (RIR) and the
168 J. Nouairi et al. / Journal of African Earth Sciences 139 (2018) 165e172

Fig. 4. Studied soils P1 (N36
160 30.7300 E 09
140 48.2000 ) and P2 (N36
220 55.2400 E 09
060 26.7000 ) and metals distribution.

Rietveld refinement techniques. Up to 40 independent variables

were refined: scale-factors, zero-point, 15 coefficients of the shifted
Chebyshev function to fit the background, unit cell dimensions,
profile coefficients (1 Gaussian, GW, and 2 Lorentzian terms, LX and
LY). The agreement indices, as defined in GSAS, for the final least-
squares cycles of all refinements are represented by Rp (%), Rwp
(%), v2 and R(F2) (%). The raw wastes and the clinkers’ micro-
structure and chemical composition were determined using a SEM
- Hitachi, SU 70 coupled to EDS - EDAX detector Bruker AXS
(software: Quantax and by Link - Analytical electron microprobe).
Chemical analysis was carried out by x-ray fluorescence (XRF)
using an Axios Wavelength Dispersive XRF spectrometer. Loss on
ignition was estimated by measuring the difference in weight be-
tween a dried 10 g sample and that calcined at 1000
C. A Laser
Coulter LS320 was used to determine the particle size distribution.
The compressive strength was measured on a Shimadzu appa-
ratus (Model: AG-X/R Refresh). Moreover, the hydration tempera-
ture was estimated by the Langavant calorimeter.
The leaching test (Standard protocol NF EN 13656; Izquierdo
et al., 2009; Bowen, 1979) was conducted following microwave
assisted digestion method with hydrofluoric (HF), nitric (HNO3)
Fig. 5. X-Ray pattern of the clinker produced with T1 wastes. Phases; (1) C2S, (2)

and (3) C4AF. and hydrochloric (HCL) acid mixture. The solutions are produced by
C4A3S,
adding 1 g of sample to 6.66 ml of HCl (35% VWR supplier) (0 W),
2 ml of HF (Panreac) with 10 W output power during 10 min and
3.33 mL ml of HNO3 (60% VWR Rectapur) with 40 W output power
during 15 min. The obtained solution is filtered under

Fig. 6. SEM micrographs of the obtained CT1 and CT2 clinkers.

 J. Nouairi et al. / Journal of African Earth Sciences 139 (2018) 165e172
Fig. 7. Particle size distribution of the clinkers after milling.
centrifugation 3000 rpm during 10 min. The heavy metal solution
analysis was carried out by atomic absorption spectrometry (GBC
Avanta, SIGMA).
2.3. Samples preparation
The mine tailings (T1 and T2) were mixed with commercial raw
materials, calcite (Calcitec M1) and alumina (Alcoa CT3000), in
proportions adjusted to generate the desired phases on the clinkers
(C2S, C3A and C4AF) as shown in Table 1. The mixtures (CT1A, CT1B,
CT2A and CT2B) were milled for 1 h in a dry mixer and then
calcined in an electric furnace (Termolab). The firing cycle used was
as follows: (a) heating up to 1000
C at 15
C/min; (b) 45 min dwell
time at 1000
C, to ensure the decarbonation; (c) heating at 5
C/
CT1A
CT1B
Fig. 8. SEM micrographs for obtained cements.
169
min to maximum temperature 1400
C (CT1A and CT2A) and
1350
C (CT1B and CT2B); (f) rapid cooling by quenching in air.
A 5 wt% of calcium sulfate (gypsum) was added to tested clin-
kers to obtain desired cements and mixed with silica sand (the
main size ¼ 0.6 mm) and water (binder/aggregate and water/
binder ratio (in weight) were 1:2 and 0.5, respectively) to achieve
final desired mortars. Shaped mortars (30  45 mm diameter and
height) were cured in a climate chamber (66% relative humidity
and 22
C) up to 1, 14, 21 and 28 days.
3. Results and discussion
3.1. Tailing materials characterization
3.1.1. XRD, XRF and SEM
The XRD analysis of T1 and T2 raw samples revealed the pres-
ence of calcite, dolomite, quartz, kaolinite, galena, pyrite and gyp-
sum as the main crystalline phases. As confirmed by EDS mapping
and SEM micrographs (Fig. 3), galena (PbS) is the most abundant
crystalline phase in the samples. The Lakhouat (T1) and Fej Lah-
doum (T2) sulphide ores contain Pb (Fig. 3B) with an ore grade close
to 1%. Pyrite (FeS2) is also found in authigenic forms (Fig. 3A). It is
present in small crystals (1e10 microns) dispersed in the calcic
cement matrix of the T2 wastes, associated with other sulphides. In
T1, sphalerite (ZnS) is the most abundant sulphur-containing phase,
in the form of spherules dispersed in the carbonate matrix (Fig. 3D,
E and 3F).
Chemical analysis shows that SO3 is the main component of T1
wastes, while CaO is dominates in T2 samples (see Table 2). SiO2 is
also present in significant amounts in both mines wastes, mostly as
quartz according to the results of mineralogical analysis.
3.2. Trace elements and impact on soil
The studied tailings present a risk of metal contamination to the
surrounding water sources and soils due to their high load of the
following trace elements Pb, Zn, Cu and Cr. Neighboring soils are
mainly used for agriculture as a receptacle to eroded materials from
CT2A
CT2B
170 J. Nouairi et al. / Journal of African Earth Sciences 139 (2018) 165e172
Fig. 9. Hydration temperatures of the CT1 and CT2 based cements.
Fig. 10. Compressive strength of CT1 and CT2 based mortars with 1, 14, 21 and 28 days
of curing time.
the mine dumps. To estimate the risk of contamination two soil
profiles were sampled 100 m each from the dumps (P1 from T1 and
P2 from T2 site) to follow the vertical distribution and infiltration of
metal pollutants.
For P1, the soil is occupied by large grain crops, the surface
horizon is highly porous, and the texture for the entire profile is
essentially sandy-loamy, bioturbated with centimetric roots. Con-
cerning P2, the soil is occupied by herbaceous plants; the surface
horizon is moderately porous, the profile texture is clayey loamy
with the presence of fine roots in low frequency. The vertical dis-
tribution of Pb, Zn, Cu and Cr in the studied soils showed enrich-
ment at the surface level and a decrease in depth (Fig. 4).
Compared to the geochemical background of the region and
standards allowed in soil environments, these values exceed the
normal concentrations (35 mg/kg, 90 mg/kg, 30 mg/kg for Pb, Zn,
and Cu, respectively) (Bowen, 1979; Tomgouani et al., 2007;
Kabata-Pendias and Pendias, 1992), defined by the French stan-
dard NF U44-041 (Baize and Paquereau, 1997). Only the Cr con-
centrations measured in this study are below the allowed standard
level (150 mg/kg). Distributions of Pb, Zn and Cu in both profiles
show vertical variations and higher enrichment at the surface due
to the infiltration of metal contaminated solutions. Even bellow
40 cm, the high levels of PTEs (Potentially Toxic Elements) occur, as
a result of the alluvial tailings transportation by rivers during flood
periods, and by particles migration from the external parts of the
profile during the prolonged dry periods through a turning-over
phenomenon (Boussen et al., 2010).
3.3. Clinker/cement characterization
3.3.1. XRD and SEM of clinkers
Fig. 5 presents a diffractogram of CT1A synthesised clinker. The
three main phases (Ye'elimnite C4A3S,
belite C2S and ferrite C4AF)
are identified (blue, pink and black dashes, respectively). C4A3S
is a
major phase formed. It appeared at a temperature between 1000
and 1250
C (Huang et al., 2016) via a solid state reaction between
mayenite (Ca12Al14O33) and anhydrite, or directly from the combi-
nation of anhydrite with calcium and aluminium oxides. The het-
erogeneous gas-solid reaction was also suggested by Strijac and
Majling (Strigac and Majling, 1997). Belite (C2S) is formed in the
same temperature range.
Depending on the initial formulations, the phases quantified by
Rietveld refinement are very close to those predicted from ….
(deviation inferior to 5%, see Table 1).
SEM micrographs of CT1 and CT2 clinkers (Fig. 6) are coincident
with XRD results since the three desired crystalline phases (C4A3S,

C2S and C4AF) were identified. The crystallisation is higher in CT2
(angular morphology), due to the higher accuracy in composition/
stoichiometry that promotes the extended formation of desirable
phases.
Fig. 7 shows particle size distribution of different clinker after
milling. Finer granulometry was observed in CT2 (especially CT2B).
This plays an important role in the pozzolanic activity of the pre-
pared cements. On other hand, CT1B presents a better particle size
distribution.
3.3.2. Cements characterization
The SEM micrographs (Fig. 8) performed on cements shows the
presence of a product of the cement hydration; ettringite (needle
and columnar aspect). Associated with CeSeH, a dense amorphous
 J. Nouairi et al. / Journal of African Earth Sciences 139 (2018) 165e172 171

matrix has been developed. Nevertheless, the existence of C2S and enrichment at the surface and a decrease in depth of Pb, Zn, Cu and
hexagonal C4A3S
is still evident. Cr with values exceeding the normal\allowed heavy metal
According to Fig. 9, the first peak is attributed to the dehydration concentrations.
of gypsum (CSH
2) into anhydrite (CS)
and is similar for all the tested In clinker calcined at 1400
C and 1350
C, the targeted crys-
materials. This study shows that once mixed with water, ions such talline phases (C4A3S,
C2S and C4AF were formed with relative
þ
Ca2þ, SO2-4 , Na … are released as a result of a strong chemical re- amounts close to predicted compositions with a5 wt.% deviation.
action (Chenchen et al., 2016; Reddy et al., 2014). The heat flow When tested as cements, the workability and the compressive
generated upon hydration of different cement pastes showed a strength of …. showed different behaviour related to particle size
rapid reaction after initial mixing (3 h for CT1B, 4 h for CT2B, 5 h for and content of the C4A3S
phase. The mortars cured for 1, 14, 21 and
CT2A and 6 for CT1A). A better workability is observed in cements 28 days displayed good mechanical properties with strength values
based in clinkers calcined at 1450
C (CT1A and CT2A). This reaching ~25 Mpa.
behaviour could be related to the higher amount in C4A3S
and Finally, the concentrations of metal contaminants in the final
coarser clinker particles (Fig. 7). products were very low. Therefore they present no environmental
As illustrated in Fig. 10, differences in the compressive strength danger or threat to human health, especially that they are incor-
results were also observed. After 28 days curing, CT1B samples with porated into the cement matrix, and thus there is not risk of
clinker calcined at lower temperature 1350
C showed maximal leaching or transportation. Moreover, concentrations of leached
mechanical strength (24.34 MPa). In fact, cements made from sul- contaminants decreased in clinkers and mortars by 75e85%. This
fobelitic clinkers show higher mechanical strengths at early ages shows that this application can help in the immobilisation of Zn, Pb
(Cai and Zhao, 2016). In this case, this could be due to the good and Cu from similar mine tailings.
particle size distribution in the sample CT1B (Fig. 7). In the case of
CT2 based cements, clinker with a higher amount of C4A3S
gave
better compression resistance due to higher reactivity of this
compound. However, the compressive strength of CT2A with
clinker calcined at 1400
C decreases after 14 days due to the excess
of sulphur oxide.
Quillin (2001) reported that the hardening rate of sulfoalumi-
nate cements is intermediate between those of Portland and
aluminate cements, however being much faster than a Portland
cement. During the early hydration stages, the formation of
ettringite is responsible for hardening of sulfobelitic cement, while
strength gain in OPC is due to CeSeH formation. At later ages, the
strength development of sulfobelitic cements depends primarily on
CeSeH gel formation (Ma et al., 2013).
However, the variation in mechanical behaviour (Mechanical
strength CT1A < CT2A and CT2A > CT2B) observed between sam-
ples calcined at 1400
C (A) and 1350
C (B) should be the result of
the difference in the initial raw tailing compositions.
In order to track the leaching of heavy metals from the pro-
cessed cements and mortars, acid attack (with aqua regia) was
performed. For comparison, levels extracted from the tailings are
also given in Fig. 11. The dilution effect affecting the final leaching
data was neutralized by normalising the used T wastes amount in
all tested cements/mortars. Concentrations of leached contami-
nants decreased considerably in clinkers and mortars. Indeed, 75%
of Pb was immobilised in the mortars CT2B. Also, the concentra-
tions of Zn and Cu in CT2A sample decreases by approximately 85%
and 80%, respectively. The leached heavy metals values are in
accordance to Council Decision of 19 December 2002 establishing
criteria and procedures for the acceptance of waste at landfills
pursuant to Article 16 and Annex II to Directive 1999/31/EC (2003/
33/EC). Several recent investigations are focused on retention of
inorganic pollutants in soils through immobilisation in the cement
matrix at different pH range (Moon et al., 2013). Ettringite is sug-
gested to be a good candidate for fixing various divalent cations
such as Cu 2þ, Pb2þ and Zn2þ in substitution of existing Ca2þ(Moon
et al., 2013).

4. Conclusions

In this study the recycling of Zn-Pb tailing rejects in sulfobelitic

clinkers was tested for …. These tainling samples are contaning
calcite, dolomite, quartz, kaolinite, galena, pyrite and gypsum as
crystalline phases. Due to this composition, high amounts in SO3
occur in the chemical analysis of mining rejects. The investigation Fig. 11. Histograms of Pb, Zn and Cu leached concentrations (in aqua regia) from ce-
of the surrounding soils showed a vertical distribution with ments and mortars processed with mine tailings T1 and T2.
172 J. Nouairi et al. / Journal of African Earth Sciences 139 (2018) 165e172
Acknowledgment
We would like to acknowledge the revision conducted by the
editor and the referees. This work was supported by UID/GEO/
04035/2013 project and the Tunisian Belgium Wallonie-Bruxelles
International WBI Research Project "Valorisation des Argiles tuni-
siennes". We thank R.C. Pullar for English review.
References
Aranda, M.A.G., Cuberos, A.J.M., Cuesta, A., Alvarez-Pinazo, G., De la Torre, A.G.,
Schollbach, K., Po €llmann, H., 2011. Hydrating behaviour of activated belite-
sulfoaluminate cements. In: Proceeding of the XIII International Congress on
the Chemistry of Cements, Madrid, p. 197.
Babbou-Abdelmalek, C., Sebei, A., Chaabani, F., 2011. Incurred environmental risks
and potential contamination sources in an abandoned mine site. Afr. J. Environ.
Sci. Technol. 5, 894e991.
Baize, D., Paquereau, H., 1997. Teneurs totales en e le
ments traces dans les sols
agricoles de Seine-et-Marne. Etude Gestion des sols 4, 77e94.
Berger, S., 2009. Etude des potentialite s des ciments sulfo-alumineux be litiques
pour le conditionnement du zinc De l'hydratation a la durabilite . Universite des
Sciences et Technologie de Lille, Lille I.
Boussen, S., Sebei, A., Soubrand-Colin, M., Bril, H.F., Chaabani, A., Abdeljaouad, S.,
2010. Mobilization of lead-zinc rich particles from mine tailings in northern
Tunisia by aeolian and run-off processes. Bull. la Soc. Geol. Fr. 181, 371e379.
Boussen, S., Soubrand, M., Bril, H., Ouerfelli, k., Abdeljaouad, S., 2013. Transfer of
lead, zinc and cadmium from mine tailings to wheat (Triticumaestivum)
incarbonated Mediterranean (Northern Tunisia) soils. Geoderma 192, 227e236.
Bowen, H.J.M., 1979. Environmental Chemistry of Elements. Academic Press,
London.
Cai, G., Zhao, J., 2016. Application of sulphoaluminate cement to repair deteriorated
concrete members in chloride ion rich environment-A basic experimental
investigation of durability properties. KSCE J. Civ. Eng. 1e10.
Chakroun, H.K., Souissi, F., Bouchardon, J.L., Souissi, R., Moutte, J., Faure, O.,
Remon, E., Abdeljaoued, S., 2010. Transfer and accumulation of lead, zinc,
cadmium and copper in plants growing in abandoned mining district area. Afr.
J. Environnemental Sci. Technol. 4, 651e659.
Chenchen, G., Jibao, X., Shoude, W., Lingcha, L., 2016. Hydrating characteristcs of
modified Portland with Ba-brearing sulphoaluminate minerals. Ceram-Silik aty
60, 12e18.
Damtoft, J.S., Lukasik, J., Herfort, D., Sorrentino, D., Gartner, E.M., 2008. Sustainable
development and climate change initiatives. Cem. Concr. Res. 38, 115e127.
Desmettre, C., Charron, J.P., 2013. Water permeability of reinforced concrete sub-
jected to cyclic tensile loading. ACI Mater. J. 110, 67e78.
Destrigneville, C., Castet, S., Munoz, M., Courjault-Rade , P., Ghorbel, M., Souissi, R.,
Souissi, F., Ben Mammou, A., Abdeljaouad, S., September 2012. Are abandoned
mine tailings of Northern Tunisia a source of metal contamination in surface
water? In: Wolkersdorfer, C. (Ed.), Proceedings International Mine Water As-
sociation Symposium: Mine Water and Innovative Thinking September 2010
Sydney, Nova Scotia, Canada, 2012. Curran Associates Inc., pp. 579e582
EUR-Lex - 32003D0033 e EN 2003/33/EC Council Decision of 19 December 2002
establishing criteria and procedures for acceptance of waste at landfills pur-
suant to Article 16 Annex II Directive 1999/31/EC Official Journal L 11, 2003, p
27-49. http://eur-lex.europa.eu/legal-content/EN/TXT/?uri¼uriserv:OJ.L_.2003.
011.01.0027.01.ENG&toc¼OJ: L:2003:011:TOC.
Ghorbel, M., Munoz, M., Courjault-Rade , P., Destrigneville, C., De Parseval, P.,
Souissi, R., Souissi, F., Ben Mammou, A., Abdeljaouad, S., 2010. Health risk
assessment for human exposure by direct ingestion of Pb, Cd, Zn bearing dust in
the former miner's village of Jebel Ressas, NE Tunisia. Eur. J. Mineralogy 22,
639e649.
Huang, Y., Qian, J., Liang, J., Li, N., Li, F., Shen, Y., 2016. Characterization and calo-
rimetric study of early-age hydration behaviors of synthetic ye’elimite doped
with the impurities in phosphogypsum. J. Therm. Analysis Calorim. 123,
1545e1553.
Idrissi, M., 2012. The se de doctorat, Etude de l’inclusion du Fer dans les ciments
Sulfo-alumineux et valorisation du caoutchouc dans leurs mortiers. Universite 
Mohamed V- Agdal, Faculte  des sciences, Rabat.
Izquierdo, M., Querol, X., Davidovits, J., Antenucci, D., Nugteren, H., Fernandez-
Pereira, C., 2009. Coal fly ash-slag-based geopolymers: microstructure and
metal leaching. J. Hazard. Mater. 166, 561e566.
Kabata-Pendias, A., Pendias, H., 1992. Trace Elements in Soils and Plants, second ed.
C.R.C. Press.
Ke, J., Zheng, N., Fridley, D., Price, L., Zhou, N., 2012. Potential energy savings and
CO2 emissions reduction of China's cement industry. Energy Policy 45, 739e751.
Kim, S.O., Kim, K.W., Stüben, D., 2002. Evaluation of electrokinetic removal of heavy
metals from tailing soils. J. Environ. Eng. 128, 705e715.
Li, Z.J., 2011. Advanced Concrete Technology. John Wiley & Sons.
Hoboken, Ma, B., Li, X., Mao, Y., Shen, X., 2013. Synthesis and characterization of
high belitesulfoaluminate cement through rich alumina fly ash and desulfur-
ization gypsum. Ceram-Silik aty 57, 7e13.
Moon, D., Park, J., Cheong, K., Hyun, S., Koutsospyros, A., Park, J., Ok, Y., 2013. Sta-
bilization of lead and copper contaminated firing range soil using calcined
oyster shells and fly ash. Environ. Geochem. Health 35, 705e714.
Mseddi, H., Ben Mammou, A., Oueslati, W., 2010. Methodology for the extraction of
carbonate-bound trace metals from carbonate-rich soils: application to
Lakhouat soils, Tunis, Tunisia. Chem. Speciat. Bioavailab. 22, 165e170.
Office National des Mines (2010) http://www.onm.nat.tn.
Quillin, K., 2001. Performance of belite-sulfoaluminate cements. Cem. Concr. Res. 31,
1341e1349.
Reddy, K., Srimurali, M., Bhaskar, M., 2014. Characterization of calcium sulfoalu-
minate cement. Int. J. ChemTech Res. 6, 1696e1698.
Sahraoui, H., Hachicha, M., 2016. Caracte risation de la contamination spatiale par le
Pb, Zn et Cd de l’ancienne mine de Lakhouat (Siliana-Tunisie). Journal of new
sciences. Agric. Biotechnol. IABC 9, 1255e1262.
Sainfeld, P., 1952. Les gîtes plombozincife res de la Tunisie. Off. Natl. Des. Mines 9,
252.
Senff, L., Castela, A., Hajjaji, W., Hotza, D., Labrincha, J.A., 2011. Formulations of
sulfobelite cement through design of experiments. Constr. Build. Mater. 25,
3410e3416.
Strigac, J., Majling, J., 1997. Phase composition development of calcium sulfoalu-
minate belite cement in the SOx atmoxphere. World Cem. 28, 82e86.
Tang, S.W., Yao, Y., Andrade, C., Li, Z., 2015. Recent durability studies on concrete
structure. Cem. Concr. Res. 78, 143e154.
Telesca, A., Marroccoli, M., Tomasulo, M., Lorenzo Valenti, G., Dieter, H.,
Montagnaro, F., 2016. Low-CO2 cements from fluidized bed process wastes and
other industrial by-products. Combust. Sci. Technol. 188, 492e503.
Tomgouani, K., Khalid, E.M., Abderrahim, B., 2007. Evaluation de la pollution
me tallique dans les sols agricoles irrigue s par les eaux use
es de la ville de Settat
(Maroc). Bull. l’Institut Sci. Rabat, Sect. Sci. la Vie 29, 89e92.