Journal of African Earth Sciences 130 (2017) 238e251

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Journal of African Earth Sciences

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Production of silica gel from Tunisian sands and its adsorptive

properties
K. Lazaar a, W. Hajjaji b, c, *, R.C. Pullar d, J.A. Labrincha d, F. Rocha c, F. Jamoussi a
a
Georesources Laboratory, CERTE, 273, 8020 Soliman, Tunisia
b
Natural Water Treatment Laboratory, CERTE, 273, 8020 Soliman, Tunisia
c
Geobiotec, Geosciences Department, University of Aveiro, 3810-193 Aveiro, Portugal
d
Department of Materials and Ceramic Engineering/CICECO e Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal

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

Article history: Thanks to its highly absorbent character, silica gel is used in several applications, such as air moisture
Received 27 October 2016 removal, as a treatment agent for effluents. In this study, silica gels were synthesised from Tunisian
Received in revised form sands, collected from the Fortuna and Sidi Aich Formations in northern and central Tunisia. The collected
13 March 2017
quartz sand raw materials, as well as the prepared silica gels, were characterised by different techniques,
Accepted 17 March 2017
Available online 21 March 2017
such as X-ray diffraction (XRD), X-ray fluorescence (XRF) and scanning electron microscopy (SEM). XRD
patterns of quartz sands showed quartz as main phase (86.1e98%), with lower contents of potassic
feldspars, along with kaolinite and calcite. These quartz sands presented relatively small quantities of
Keywords:
Tunisian quartz sands
Fe2O3 (0.3%e0.5%) and TiO2 (0.1%e0.6%). The synthesised silica gels exhibited pore diameters exceeding
Silica gel 20 Å and surface areas up to 194 m2/g, comparable with those described in the literature and commercial
Retention silica gel. N2 adsorption isotherms showed that the silica gels prepared from Tunisian sands are meso-
Methylene blue porous materials with high adsorption capacities. To understand better their adsorbent properties and
Dye absorption applicability on an industrial scale, these gels were tested for methylene blue (MB) absorption. Maximum
decolourisation rates (up to 96% after a contact time of 180 min) occurred with products synthesised at
pH 3. The adsorption mechanism fitted better with a Langmuir model, revealing a monolayer coverage
process of MB molecules over the gel surface, and the adsorption kinetics of the dye on these materials is
well described by the second order model.
The corresponding equilibrium adsorption capacities obtained from experimental data (Qexp ¼ 292
e214 mg/g) were close to the estimated maximum adsorption capacities (Qe ¼ 333e250 mg/g), and to
that of an industrial silica gel (250 mg/g).
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Current global silica sand world production for industrial pur-
poses is around 140 Mt/year (Mansour, 2015), with the USA ac-
counting for 24%, the Netherlands for 20% and France for 5%. The
price of quartz sand varies as a function of its characteristics, such
as particle size and purity. In the case of Tunisia, this raw material is
essential to the economy, and various Tunisian manufacturers and
industries (glass, foundry sand …) are obliged to import huge
quantities from countries like Belgium, France, Germany, Italy,
Spain, the USA and Mexico, despite the obvious natural resources
* Corresponding author. Natural Water Treatment Laboratory, CERTE, 273, 8020
Soliman, Tunisia.
E-mail address: w.hajjaji@ua.pt (W. Hajjaji).
that Tunisia possesses of this material. This operation is costly (1.8
Million USD in 2000 to 5.2 Million USD in 2015, INS 2016) for the
state and the economy, while there exist abundant unstudied and
unexploited silica sand deposits from the Early Cretaceous to
Quaternary periods in the country (Jamoussi, 1991; Essid, 1997;
Aloui, 1999; Harrabi, 1999; Sdiri et al., 2010; Hajjaji et al., 2009;
Hajjaji, 2011). In addition, it has been shown that Tunisian sand is
a high purity material that can be used in many different industrial
areas, such as glass making (Hajjaji et al., 2009), cements (Aloui,
2010; Mechti et al., 2012), electro-metallurgy (Khalifa et al.,
2014), chemicals (Mansour, 2015), and especially as air and water
waste purifiers (Farrukh et al., 2014).
In this context, silica gel is an interesting amorphous material
(annual world production 25,000 t/year; Meljac, 2004) with a high
adsorption capacity (Go
mez et al., 2014), and is used as an

http://dx.doi.org/10.1016/j.jafrearsci.2017.03.017
1464-343X/© 2017 Elsevier Ltd. All rights reserved.
 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251
adsorbent of moisture, or for the purification of effluents with its
hydrophilicity (the high moisture content trapped within the silica
structure creating the ideal environment to attract polar impu-
rities) (Armarego and Chai, 2013). This material has several ad-
vantages: for example, it is easy to regenerate, as when it has
become saturated with water the silica gel can be regenerated by
heating at 100e120  C until it returns to its original state (indicated
by a change in colour), the heating literally drives off the adsorbed
moisture. Silica gel is also chemically inert and non-toxic, with a
very high melting point, it is very much like quartz sand and thus
can safely be sent by any means of transport, has a long life, and has
low abrasion (the wear rates decreasing with increasing of the
porosity) (Trabelsi et al., 2009). In recent years, new studies are
underway into the use of this versatile amorphous material as
fillers (Lin et al., 2014), coatings (Liu et al., 2013), and hygroscopic
packaging for optical (Cha ^teau, 2013), electronics (Xu et al., 2010)
and pharmaceutical (Brown et al., 2014) products. Silica gel exhibits
superior adsorption and high surface area properties which paves
its way for use in water filtration, as growing environmental con-
cerns, coupled with the need to comply with stringent government
regulations concerning waste-water treatment, are driving the in-
dustry. The global water filtration market was valued over 17
million USD in 2012, and the transition towards the physical
treatment of water from conventional water-treatment methods is
expected to have an impact on the need for more silica gel (Grand
View Research Report). The Global Silica Gel market is forecast to
grow at a rate of 4% annually over the period 2014e2019 (Tech
Navio Report, 2015).
Dyes are widely used by textile industries to colour their
products, and one of the major problems concerning textile
wastewaters is the highly coloured effluent (Moursli and
Bengueddach, 2010), which can be difficult to decolourise. Over
15% of the textile dyes are lost in the wastewater stream during
dyeing operations, and so dye pollutants from the textile industry
are a significant source of environmental contamination. About half
of the global production of synthetic textile dyes (700,000 tons per
year) is classified as azo compounds that have the eN]Ne chro-
mophore unit in their molecular structure, such as methylene blue
(C16H18ClN3S). These azo dyes are known to be largely non-
biodegradable in aerobic conditions, and they reduced to form
more hazardous intermediates in anaerobic conditions. These re-
leases pose a real danger to humans and the environment because
of their stability and poor biodegradability (Sakr et al., 2015).
Several treatments have been used to reduce the harmful effect of
discharged effluents. Traditional methods such as biological pro-
cesses give unsatisfactory results, due to the composition of these
discharges toxic materials and dyes that are difficult biodegradable
(Sakr et al., 2015). Adsorption remains among the most used
techniques for dye removal, and is easy to implement. Removal of
dyes in aqueous solutions by adsorption on various solid materials,
especially on silica gel, has been the subject of many studies
(Kushwaha et al., 2010; Samiey and Toosi, 2010).
Methylene blue (MB) (3,7-bis(dimethylamino)-phenothiazin-5-
ium chloride trihydrate)is a cationic dye that is used in the dyeing
of cotton, wool, coating for paper stock and silk. The classification
provided by ECHA European Chemical Agency (2016) in CLP noti-
fications (EC/List no.: 615-731-6) showed that this substance is
harmful if swallowed, causes serious eye irritation, may cause
damage to organs through prolonged or repeated exposure, causes
skin irritation and may cause respiratory irritation (Karim et al.,
2010). It can cause chest pain, shortness of breath; an anxiety,
tremors, hypertension, and even skin coloration if the dose is high
(Kushwaha et al., 2014). Despite this, the toxicological data on the
use of MB in humans for many years have not yet indicated a
specific hazard in the use of this product, (Yi and Zhang, 2008), and
239
although MB is not classed as highly dangerous, it clearly has a
harmful effect on living organisms (Gobi et al., 2011) and waters
(Rafatullaha et al., 2010). Many synthetic dyes and pigments
generate harmful by-products, particularly when dumped directly
into the environment without any specific treatment of toxic con-
stituents (Saidi, 2013).
This work is aimed to promote local georesources (silica sands)
for the preparation of silica gel, and to investigate its decontami-
nation capacity for the treatment of synthetic dyes in solution.
2. Experimental details
2.1. Geological setting
In this study, three representative samples were collected from
different sites:
 Jebel Menchar (M): Fortuna formation (Burdigalian), Tunisian
Dorsal structural domain,
 Jebel SidiAïch (S) and Jebel Attaf (A): Sidi Aich formation (Bar-
remian), meridional Atlas.
The deposits of the Fortuna formation are located about 2 km
north east of the village of El Hammem Jedidi and 15 km south of
the city of Hammamet. It is an ENE/WSW anticlinal structure with
an Eocene level extending over 3.5 km long and 1.5 km wide. These
quartz sands appear in the channels interspersed with clayey ma-
terials, silt and rarely consolidated sandstone (Mejri, 2012). The Sidi
Aich formation (Central Tunisia) was deposited in a regressive
context in a field of passive margin. Of volcanic origin, the pre-
existing mother rock was eroded and transported from the area
of Dahar, south of the Saharian platform (M'Rabet, 1981; Gallala
et al., 2009). Central Tunisia is characterised by EeW and NWeSE
oriented faults, and ranges of NEeSW trending anticlines, sepa-
rated by large synclinal basins.
In this Central and north Tunisia, previous studies have been
carried out in sedimentology (Burollet, 1956; Burollet et al., 1983;
Ben Ferjani et al., 1990; Chekhma et al., 1990; Chaabani et al.,
1992; Ben Youssef, 1999; Chaabani and Razgallah, 2006; Gallala,
2010), tectonic studies (Bouaziz et al., 2002; Mejri, 2012; Said,
2011; Gharbi, 2013), paleogeography (Soussi, 2000; Abbe s, 2004)
and hydrocarbons prospection (Negra et al., 2009).
2.2. Methods
Mineralogical and major-minor chemical compositions were
determined for whole-rock samples. The mineralogy was deter-
mined in raw and gel materials using a Panalytical X'Pert PRO X-ray
diffractometer (CuKa, l ¼ 0.154056 nm). The collected data
(10e80 2q range, scan rate of 0.02 (2q)) were processed by Pan-
alytical X'Pert Highscore software. The existing phases were iden-
tified, and their relative amounts were estimated by measuring and
comparing the peak areas of the principal reflexion (Ali et al., 2016).
The chemical composition of these quartz sands was estimated, on
powdered samples, by X-ray fluorescence using a Panalytical Axios
Dispersive X-ray Fluorescence Spectrometer. The results are
expressed as percent concentrations of oxides of each element. The
obtained gels were characterised by scanning electronic micro-
scopy (SEM - Hitachi, SU 70) to observe the microstructural details.
The specific surface area and porosity parameters were determined
by B.E.T method based on the adsorption and desorption of nitro-
gen at 77 K. The sample with grain size <150 mm is degassed before
hand at 70  C under high vacuum for 72 h and then the cell was
plunged in a liquid nitrogen balloon (Brunauer et al., 1938). The
grain-size distribution was obtained via dry sieving in an AFNOR
240 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251

series adopted by the French normalisation system. For the fraction of dye in mg absorbed per unit g of absorbent at equilibrium; V (ml)
inferior to 63 mm, the grain size distribution was determined by a is the volume of adsorbate; and W (g) is the mass of silica gel.
Micromeritics 5000 ET sedigraph. The adsorption isotherms of silica gel are often used for deter-
mining the maximum capacity of the binding of pollutants and
2.3. Silica gel preparation identification of the adsorption type. The results were treated by
Langmuir and Freundlich mathematical models, enabling us to
The preparation of silica gel based on these raw materials was calculate the maximum capacity of adsorption, as well as the pa-
carried out following three steps: rameters of adsorption (Meçabih et al., 2006).
The Langmuir equation is:
(i) The preparation of sodium silicates,
(ii) Their dissolution, and t 1 1
¼ þ (3)
(iii) The formation of the gel. qe qm KL qm Ce

The intermediate compound was obtained by heating at 1060  C
a mixture of sodium carbonate and Burdigalian or Barremian quartz
sand (molar ratio, n, of SiO2/Na2O equal to 1.5 or 3, Table 1). Pre-
vious researches reported optimal SiO2/Na2O ratio varying between
3.72 and 1 (Trabelsi et al., 2009; Brahmi et al., 2014). 10 g of pre-
pared amorphous silicate was dissolved in 500 ml of distilled water
(at 160  C) with stirring for 10 min to reach hydrated sodium sili-
cate (Trabelsi et al., 2009; Radian et al., 2015). The final product
(silica gel) was extracted after dropwise addition of 2 M hydro-
chloric acid solution, and washing to eliminate Clions (Marzouk
et al., 2004; Brahmi et al., 2014), and drying for 24 h at 60  C. In
this work, silica gels with different pH values 3, 6 and 10 were
prepared from silicates to see the effect of various media (acid,
medium and alkaline) in the gel synthesis (Table 1).
2.4. Adsorption tests
The study of adsorption tests was performed in batches with
varying contact time, initial MB dye concentration (5, 10, 15, 20,
25 ppm) and temperature (25, 30, 35, 40, 50  C). Preliminary trials
were carried out by introducing 0.01 g of adsorbent (silica gel) in
400 mL of dye solution. The solutions were vigorously mixed by
mechanical stirrer in the dark, and samples were taken at several
time intervals (0, 5, 10, 20, 40, 60, 90, 120, 180, 240 min). The su-
pernatant solution was analysed after centrifugation (3000 rpm for
15 min) using a Shimadzu UV3100 spectrometer by measuring the
absorbance at a wavelength of 665 nm. The dye removal efficiency
was calculated by the following equation:
Ci  Ce
Dye removal efficiencyð%Þ ¼ 100
Ci
Ci  Ce
qe ¼ V
W
where Ci (mg/L) is the initial concentration of MB dye; Ce (mg/L) is
the dye concentration at adsorption equilibrium; qe is the amount
where qm (mg/g) is the maximum capacity of adsorption; qe (mg/g)
is the capacity at adsorption equilibrium; KL (L/mg) is the Langmuir
constant and 1/KL is the slope of the plot. These values of qm and KL
are obtained, respectively, starting from the intersection with the
ordinate in the beginning and the slope of the right-hand side Ce/
qe ¼ f(Ce).
The Freundlich equation is
 
1
log qe ¼ log Kf þ log Ce (4)
n
Were Kf is the Freundlich constant and 1/n is the intensity of
adsorption. The value of 1/n gives an indication on the validity of
the adsorption of the adsorbent - adsorbate system. When the
value of 1/n is between 0 and 1, the adsorption is favourable (Karim
et al., 2010).
In the case of Langmuir models, to know if favourable or
unfavourable adsorption is occurring, a factor of separation RL is
used (Hajjaji et al., 2013). This factor is defined by the following
relation (Asperger et al., 2014):
1
RL ¼ (5)
1 þ KL C0
where KL is the Langmuir constant (l mg1) and C0 is the initial
concentration of the dye (mg. L1).
The adsorption kinetics was evaluated following pseudo-first
and second order equations. The equation of the pseudo-second
order is often successfully used to describe the kinetics of the re-
action of fixing of the pollutants on the adsorbent (Ali et al., 2016).
(1)
The model of the pseudo-second order makes it possible to char-
acterise the kinetics of adsorption, by taking into account at the
same time both the case of a fast fixing of the aqueous solutions on
(2) the most reactive sites, and that of a slow fixing on the sites of weak
energy (Aarfane et al., 2014).
The pseudo-first order equation (Robalds et al., 2016) is given
by:

Table 1
Synthesis conditions and physical properties of prepared silica gels. G: Silica Gel, M: Menchar, S: Sidi Aich, A: Attaf, I: Industrial, pH ¼ 3, 6 or 10.

Sample pH Molar ratio SBET (m2/g) Pore volume (cm3/g) Pore diameter (Å)
SiO2/Na2O

GM3 3 1.5 194 0.53 111

GM6 6 3 91 0.23 79
GM10 10 1.5 33 0.12 129
GS3 3 3 133 0.46 127
GS6 6 1.5 58 0.14 85
GS10 10 3 24 0.06 22
GA3 3 1.5 178 0.50 107
GA6 6 1.5 86 0.20 83
GA10 10 3 31 0.09 115
GI 253 0.28 45
 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251 241

equilibrium rate constant (min1).

In this model, the speed of the adsorption process at the
moment “t” is proportional to the difference between the quantity
adsorbed at equilibrium, qe, and the quantity adsorbed at that
moment, qt, and this adsorption is reversible (Huston and Larson,
2015).
The pseudo-second order model (Robalds et al., 2016) is given
by:

t 1 t
¼ þ (7)
qt k2 q2e qe

were qe (mg/g) is the capacity at adsorption equilibrium, and k2

(g mol1 min1) is the constant speed of adsorption.

3. Results and discussions

3.1. Characterisation of studied sands

The XRD powder patterns are shown in Fig. 1. The studied sands
are mainly composed of quartz (71e98%) and feldspars (1e27%).
Minor proportions of kaolinite and calcite were also detected. The
dominance of quartz suggests that the depositional basins were
associated with a passive margin (Gallala et al., 2009). Where as the
presence of feldspar suggests that quartz sands could probably be
of magmatic origin, or even metamorphic, from the Hoggar Massif
(Hajjaji, 2011). Table 2 also gives the average chemical composition
of the tested sands by X-ray fluorescence. The high amount of SiO2
is ranged from 87.9% to 98%. Relatively low contents of Al2O3, K2O,
Fe2O3 and TiO2 were also identified. Al2O3 and K2O are associated
with the presence of potassic feldspars, while the other oxides are
coupled to non-depicted heavy metals (like TiO2 and Fe2O3 which
are usually considered undesirable elements in sands since they
induce colouring effects) (Hajjaji et al., 2009).
The “M” sand (Menchar) present a coarser granulometry (mean
size around to 400 mm) (Fig. 2). The particle size distribution of “S”
quartz sand (Sidi Aich) presents a mean size approximating 100 mm.

Fig. 1. XRD patterns of the collected quartz sand samples.

 
k1
logðqe  qt Þ ¼ log qe  t (6)
2:303

Were qe (mg/g) is the capacity at adsorption equilibrium, qt (mg/g)

is the quantity of adsorbent at the time t (min) and k1 is the

Table 2
Mineralogical and chemical quantification of studied silica sand samples (M: Men-
char, S: Sidi Aich, A: Attaf). LOI ¼ loss on ignition.

M S A

Quartz 98 71 98
Feldspars 1 27 2
Calcite 1 1 0
Kaolinite 0 1 0
SiO2 98 87.9 97
K2O 0.2 4.64 0.5
Al2O3 1.1 5.95 1.1
Fe2O3 0.3 0.33 0.4
Cr2O3 0.1 e e
TiO2 0.1 0.19 0.6
MnO e e e
CaO 0.1 0.25 e
LOI 0.5 0.9 0.3
Fig. 2. Granulometric distribution of the quartz sand samples.
242 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251
The morphological analysis confirms the bimodal grain distribution
of the M and A quartz sands (Fig. 3), with the presence of coarse and
fine grains (below 15 mm for the S samples). The differences in
granulometry between the S, A and M sands is related in the
variation of paleo-environmental conditions between Barremian
and Burdigalian periods. S and A type detrital deposits (Barremian
sands) are probably attributed to lower energy conditions during
the Cretaceous Period (Gallala et al., 2009; Hajjaji, 2011). On other
hand, M sands, with coarser particle mean size, are high energy
fluvial materials. Concerning the gel synthesis, finer particle size
means a higher surface area (Laabd et al., 2015). Also, in the
microscopic images (Fig. 3) the presence of heavy minerals
(ilmenite, iron inclusion, rutile, diopside) confirm the contribution
of igneous source rocks (Carr, 2003; Hajjaji et al., 2009).
3.2. Characterisation of the silica gel
The XRD patterns of the silica gels are reported in Fig. 4. They
show a partial non-crystalline structure at different pH values,
characterised by a large amorphous hump centred around 2q ¼ 23 ,
which indicates that the obtained gels are mostly amorphous.
Fig. 3. Microscopic observations of quartz sands of Menchar (M), Sidi Aich (S) and Attaf (A).
However, a significant amount of crystalline quartz is present, and
due to the incomplete alkali fusion, some residual non-dissolved
feldspars are also depicted (2q ¼ 28 ).
The microscopic observations of the silica gels is reported in
Fig. 5. According to these micrographs, the analysed silica gels all
had similar structures, with presence of some large pores. The gel
appears to consist of very finely aggregated particles of silica with
large pores (average sizes from 1.14 to 5.45 mm); as observed in SEM
images (Fig. 5). This variation is due to the aggregation of silica gel
particles, and contributed to inter-particle porosity. The size of
these silica gel particles is similar to the commercial silica gel
(average size ranged from 0.5 to 8 mm) studied by Farrukh et al.
(2014). Similar results for the size of silica gel particles were
found by Brahmi et al. (2014), who studied the preparation of
amorphous silica gel from Algerian siliceous sands. The wide
porous texture suggests that the obtained silica gels are good ma-
terials for adsorption.
The observations in SEM images was further confirmed by the
pore sizes and pore volumes of the silica gels (Table 1). The mate-
rials prepared present a pore volume ranging from 0.06 cm3/g to
0.53 cm3/g, with a pore diameter ranging from 22 Å to 120 Å.Along
 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251 243

Fig. 4. X-ray Diffractogram of silica gel: Qz: quartz, Fd: Feldspar.

with type II adsorption isotherms (Fig. 6) for GM, GS and GA gel
samples (Witoon et al., 2011), these results confirm the mesoporous
character of the synthesised silica gels (pore diameter exceeding
20 Å) (Webb and Orr, 1988). In this case, the desorption isotherm
coincides with adsorption at relatively low pressures (Fig. 6) (Sdiri
et al., 2010). When the relative pressure approaches one, there is a
sudden elevation showing the condensation of the gas molecules.
In the isotherm for adsorption/desorption, mesoporous materials
create a wide hysteresis, indicating the filling of the pores by
capillary condensation (Webb and Orr, 1988; Daiguji et al., 2015).
The values of the specific surface area (SSA) of different silica
gels obtained from the Tunisian quartz sands (M, S and A) are re-
ported in Table 1. The silica gel synthesised at pH3 had a higher SSA,
reaching 194 m2/g in the case of GM3. This value is considered very
close to that of the industrial silica gel, GI (253 m2/g). The other two
products, deriving from S and A quartz sands (GA3 and GS3), pre-
sent SSA values of 178 and 133 m2/g, respectively. The silica gel GS3
displays a lower surface area (133 m2/g), probably due to the larger
244 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251
Fig. 5. Micrographs of Tunisian quartz sand based silica gels.
Fig. 6. Nitrogen adsorption isotherms for silica gels.
particle size and the presence of fluxing agents (feldspars) in the
raw material (A) (Mamery, 2013). Based on Brunauer's classification
(Brahmi et al., 2014), the silica gels prepared at pH 3 (GM3, GA3 and
GS3) show a larger uptake close to the saturation pressure, denoted
by the stronger hysteresis loop. The isotherms of the synthesised
silica gel show an H-2 type hysteresis loop, indicating the existence
of spherical pores (Brahmi et al., 2014). The H-2 type loop is broad,
with the desorption branch being much steeper than the adsorp-
tion branch. Type H-2 can be found in many porous adsorbents, and
is believed to occur in systems where the distribution of pore sizes
and pore shapes are broad (reference). For the silica gel prepared at
pH 6, desorption is slow at the beginning, and this may be due to
the interconnected pores of different shapes. In this case, the
adsorptionedesorption isotherm has a wider shape for relative
pressures (P/P0) of 0.6. The kinetics of adsorption and desorption
processes is no longer reversible. For the silica gel prepared at pH
10, the adsorption and desorption isotherms are substantially of the
same type as that at pH 6. This shows that the shape and pore
distributions obtained at pH 6 and 10 are similar. However, the
isothermal curves for pH 10 do not show a plateau for relative
pressure (P/P0) values approaching 1. This type of hysteresis is
typical of aggregates.
In case of the silica gels synthesised at pH6 and 10, it was
observed clearly that the SSA of silica gel decreased with increasing
pH, which is in a good agreement with previous results in the
literature (Brahmi et al., 2014). This can be explained by the
increasing solubility of silica with the solution pH accelerating the
phenomenon of dissolution/reprecipitation. During dissolution/
reprecipitation the average size of dense particles increases, the
granular network consolidates (bridge formation by aggregation),
and small pores are eliminated (densification). The shift of the pore
size distribution to larger sizes observed after drying induces an
increase in the permeability and the pore network, and a decrease
in SSA (Tognonvi, 2009). The three products deriving from M, S and
A sands (GM6, GA6 and GS6) at pH 6 have SSA values reaching 91,
86and 58 m2/g for GM6, GA6 and GS6, respectively. By increasing
the pH of 6e10, the values of the SSA decreased even further, to
24 m2/g in the case of GS10, due to dissolution/condensation
enhancement with increasing pH (Tognonvi, 2009). For this reason,
the MB absorption tests with time were carried out with the silica
gels produced at pH 3, which show the highest SSA.
3.3. Adsorption tests
3.3.1. Effect of contact time
The study of the MB adsorption vs contact time on silica gels
GM3, GA3 and GS3, obtained from Tunisian silica sands at pH 3, is
reported in Fig. 7. After 240 min reaction time, the decolourisation
rate exceeded 81%, 74% and 73% for GM3, GA3 and GS3, respec-
tively. These values are all similar, and are close to the industrial
product (GI) retention rate, which had the quickest uptake of 83% in
90 min. Fig. 8 illustrates the discolouration of MB solution by GM3.
3.3.2. Effect of pH
The effect of pH in the synthesis of the gels (pH 3, 6 and 10) on
the adsorption of MB was studied, and the results are summarised
 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251 245

Fig. 7. Adsorption kinetics of silica gels (GM3, GA3, GS3 and GI) of MB (madsorbent ¼ 0.01 g, Ci ¼ 10 ppm, T ¼ 25  C, Time ¼ 240 min).

Fig. 8. Photo of decolouration of dye solution (MB) by the Menchar silica gel (GM) in function of time (madsorbent ¼ 0.01 g, Ci ¼ 10 ppm, T ¼ 25  C, final time ¼ 240 min).

in Fig. 9. For neutral and alkaline synthesis pH (6 and 10), a lower
discolouration rate was assessed. In the case of Menchar based
silica gel (GM), the uptake decreased to 66 and 49% using GM6 and
GM10, respectively. In the same analytical conditions, GM3 adsor-
bed 81% after 240 min reaction time. Practically, the same response
was observed for Sidi Aich and Attaf based silica gels (GS6, GS10,
GA6 and GA10). As reported in Table 1, the difference in the specific
surface area of the adsorbents is behind this variation in the
adsorption capacities of the adsorbents at different synthesis pH.
For alkaline medium synthesis, the lower progressive discoloura-
tion is related to the minor specific surface developed by gels ob-
tained at pH 10 (Sakr et al., 2015).
As pH decreases to 3, higher discolouring efficiencies are ob-
tained. This behaviour is due to the higher surface areas (194, 178
and 133 m2/g for GM3, GA3 and GS3, respectively). At acidic pH, the
electrostatic attraction is developed between negatively charged
dyes and positively charged adsorbent as the binding capacity of a
dye by an adsorbent is dependent on the adsorbent surface charge
(Boukraa and Messemmeche, 2016).
3.3.3. Effect adsorbent amount
When 0.05 g of adsorbent (GM3) was used, the observed
maximum uptake reached 96% after 240 min of contact time
(Fig. 10). This MB adsorption rate decreased to 66%
with0.005 g.Indeed, the increase in the adsorbent amount en-
hances the availability of fixation sites, which facilitates the inter-
action of MB molecules and the adsorbent particles, therefore
increase the amount adsorbed (Makhlouf et al., 2013). However, a
10-fold decrease in the concentration of the absorbent only led to a
1/3 decrease in the amount of MB absorbed, interestingly. The
246 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251

Fig. 9. Adsorption kinetics: effect of pH of silica gel synthesis on subsequent adsorption of MB (Ci ¼ 10 ppm; T ¼ 25  C; pH ¼ 3, 6 or 10; madsorbent ¼ 0.01 g; total time ¼ 240 min).

minor difference of the adsorption between 0.03 and 0.05 g should 100%) and agglomeration of silica particle. A higher adsorbent
be related to the silica gel particle saturation (adsorption close to amount of (0.05 g) creates saturation in silica particles, resulting in
 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251 247

Fig. 10. Adsorption kinetics: effect of amount adsorbent (GM3) on adsorption of MB (Ci ¼ 10 ppm, T ¼ 25  C, pH ¼ 3, final time ¼ 240 min).

Fig. 11. Adsorption kinetics: effect of initial concentration of MB in dye solution on adsorption of MB (Ci ¼ 5, 10, 15, 20, 25 ppm, T ¼ 25  C, pH ¼ 3, m adsorbent ¼ 0.01 g, Time of
equilibrium ¼ 180 min).

a reduction of the total surface adsorption and therefore, a decrease
in the amount of adsorbate per unit mass of adsorbent (Karim et al.,
2010).
3.3.4. Effect of initial dye concentration
The effect of the initial concentration of MB is shown in Fig. 11.
These tests were applied to GA synthesised at pH 3. The results
show that the MB adsorption capacity increases with the decrease
in the initial concentration of dye, as would be expected. The
adsorption rate of the GA3 exceeded 83% even after 180 min re-
action time using just 5 ppm (Fig. 11). When this initial concen-
tration dye was elevated to 25 ppm, the adsorption rate of the
adsorbent GA3 decreased to 30% due to the saturation of the active
sites in the adsorbent (Errais et al., 2011). Even if the adsorption is
248 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251

Fig. 12. Adsorption kinetics: effect of temperature in dye solution on adsorption of MB (Ci ¼ 10 ppm, T ¼ 25; 30; 35; 40; 50  C, pH ¼ 3, m adsorbent ¼ 0.01 g, Time ¼ 180 min).

Fig. 13. Fitting with the linear Langmuir (a) and Freundlich (b) models for MB adsorption on GM3 (Ci ¼ 10 ppm, T ¼ 25  C, pH ¼ 3, m adsorbent ¼ 0.01 g, Time ¼ 180 min).

supposed to follow a multilayer mechanism, high competition be-
tween the MB molecules is occurring at elevated dye concentra-
tions (superior to 5 ppm). However, it should be noted that in
400 ml of 25 ppm MB solution, the mass of MB present (0.01 g) was
equivalent to the amount of silica gel used, so it is a very efficient
absorbent material.
3.3.5. Effect of temperature
Fig. 12illustrates the temperature influence on MB dyes
adsorption. The heating slightly affected MB fixation in the silica
gel, especially withGM3. Generally, higher energy input overcomes
the repulsive forces localised at the interfaces of the liquid/solid
media (Baghriche et al., 2008; Laabd et al., 2015). Nevertheless, this
variation (not exceeding 2%) is not significant and is simply hin-
dered by the temperature. This behaviour can be justified by the
increase in mobility of the dye molecules which favors their
penetration within the pores of the support (Laabd et al., 2015).
3.4. Adsorption isotherms
The investigation of adsorption process kinetics was performed
by determining the equilibrium parameters, and the fitting with
Langmuir and Freundlich models calculated by linear regression
(Fig. 13 and Table 3). The values of the regression coefficients
indicate that the process of MB retention using the silica gel fitted
better with the Langmuir model, indicating that the adsorption
process corresponds to monolayer coverage of MB molecules over
the surface of the four samples analysed. The results indicated that
higher adsorption capacity (qm) was achieved by GM3 (125 mg/g)
compared than those obtained by GA (100 mg/g) and GS (83 mg/g),
 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251 249

Table 3 (qecal) is very close to the values obtained experimentally (qeexp)

Langmuir and Freundlich parameters for MB adsorption. (Table 4). These results suggest a chemisorption mechanism,
Materials Langmuir Freundlich involving covalent forces through sharing or exchange of electrons
qm (mg/g) KL (L/mg) RL R2 Kf (L/g) n R2
between sorbent and sorbate. This model is in good agreement
with MB adsorption on silica gel (or clays and active carbon) re-
GM3 125 1000 0.00091 0.993 112.72 1.03 0.988
ported in recent works. Values for qe are close to those reported by
GA3 100 1111 0.00085 0.995 136.46 1.84 0.790
GS3 83.33 2000 0.00046 0.987 129.12 1.91 0.734 Gaikwad and Misal (2010) and Norman et al. (2015) in studies on
GI 111.11 900 0.00010 0.998 104.23 1.06 0.994 the kinetics of MB adsorption by silica gel.

GM3 also having the higher specific surface area (Table). Further-
more, the high coefficients of determination (R2 up to 0.99 for GM,
GA, and GS) further confirmed that our experimental data fit better
to the Langmuir model. This is indicative of the homogenous silica
gel surface as supported by KL values (KLequal to 1000, 1111 and
2000 L/mg) respectively for GM3, GA3 and GS3. Our results indi-
cated that RL ranged between 0 and 1 for the adsorption of MB on
GM3, GA3 and GS3, indicating a favourable adsorption. These
values are close to those reported for the industrial silica gel GI
(qm ¼ 111 mg/g; R2 ¼ 0.998; KL ¼ 900 L/mg and RL between 0 and
1).
For the Freundlich model, the measured parameters are sum-
marised in Table 3 and in Fig. 13b. A lower affinity for interaction
between the adsorbateeadsorbent was revealed by the small-
erR2regression coefficient. The above fact shows a monolayer
adsorption with a heterogeneous energetic distribution of active
sites, accompanied by interactions between the adsorbed
molecules.
3.5. Adsorption kinetics
Two models were applied to describe the adsorption kinetics
mechanism: the pseudo-first-order and pseudo-second-order
(Fig. 14a and b). From the obtained results, it is deduced that the
MB adsorption on the silica gel is better described by the pseudo-
second-order equation. All of the R2 correlation coefficients are
higher than 0.99 (GM3, GA3, GS3 and GI). Moreover, the adsorption
capacity calculated directly by the pseudo-second-order equation
4. Conclusions
This work was undertaken to exploit the potential of local
Tunisian quartz sands for the preparation of silica gels, and to study
their potential retention of a cationic dye (methylene blue, MB). It
was concluded that the quartz sands consisted mostly of silica and
feldspars more than 88% silica, and the specific surface areas of the
silica gels reached values as high as194 m2/g. For MB adsorption, it
was clear that silica gel GM3 shows the highest adsorption capacity
(81%) due to the larger surface area associated with fine particle
size, and the absence of feldspar minerals in the starting material.
The other two samples, GA3 and GS3, presented lower adsorption
capacity than GM3, not exceeding 75%. The adsorption capacity of
these silica gel materials increased to 83% when reducing the
concentration MB to 5 ppm. The percentage of discolouration was
influenced by the change in pH. The discolouration of the dye was
up graded to 49, 47 and 45%,respectively for the GM3, GA3 and GS3,
at pH 10. At lower pH value high dye removal efficiency were ob-
tained (between 73 and 81% removal after 240 min). The high dye
removal efficiency at low pH is due to the electrostatic attraction
between the negatively charged dye and the positively charged
adsorbent surface. When varying the batch temperature from 25 to
50  C, the adsorption capacity of silica gel was increased slightly.
Experimental results showed that the temperature positively af-
fects the adsorption phenomenon as the high energy input over-
comes the repulsive forces localised at the interfaces of the liquid
and solid media. The isotherms of the adsorption of the MB dye on
silica gel by the Langmuir isotherm model parameters was very
favourable (R2up to 0.99), and this reveals that adsorption process

Fig. 14. Kinetics by the pseudo-first-order (a) and pseudo-second-order (b) models for MB adsorption on GM3 (Ci ¼ 10 ppm, T ¼ 25  C, pH ¼ 3, m adsorbent ¼ 0.01 g, time ¼ 180 min).

Table 4
Pseudo-first and second order parameters for MB adsorption.

Materials Pseudo-first-order qe (exp) Pseudo-second-order

k1 (min1) qe (mg/g) R2 k2 (g/mg.min) qe (mg/g) R2

GM3 0.018 142.4 0.858 239.6 0.00038 250.0 0.990

GA3 0.015 141.6 0.799 291.8 0.00026 333,3 0.994
GS3 0.006 7.61 0.779 214.0 0.00038 250.0 0.991
GI 0.079 80.2 0.743 241.2 0.016 250.0 0.999
250 K. Lazaar et al. / Journal of African Earth Sciences 130 (2017) 238e251
corresponds to monolayer coverage of MB molecules over the
surface of the silica gel samples. The pseudo-second order
expression (R2 equals to 0.99) is better fitted to describe the
adsorption kinetics of all analysed samples. The MB discolouration
rates obtained by using the Tunisian sands based silica gels were
close to tested industrial silica gel.
Acknowledgements
We would like to thank the reviewer for their detailed com-
ments and suggestions for the manuscript. We believe that the
comments have identified important areas which required
improvement. This work was supported by FCT-Grant SFRH/BPD/
72398/2010 and by UID/GEO/04035/2013 project. This study was
supported by funding from MEDYNA: “FP7-Marie Curie Action
funded under Grant Agreement PIRSES-GA- 2013-612572”, and the
Tunisian Belgium Wallonie-Bruxelles International WBI Research
Project "Valorisation des Argilestunisiennes". Robert C. Pullar ac-
knowledges the support of FCT grant SFRH/BPD/97115/2013.
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