Applied Clay Science 168 (2019) 87–95

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Applied Clay Science

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

Research paper

Wastewater treatment test by removal of the sulfamethoxazole antibiotic by T

a calcined layered double hydroxide
⁎
El Hassane Mourida, Mohamed Lakraimia, , Lhaj Benaziza, El Hassan Elkhattabia,
Ahmed Legrourib
a
Physical Chemistry of Materials Team, Cadi Ayyad University, Marrakech, Morocco
b
International University of Grand Bassam, Grand-Bassam, Côte d'Ivoire

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, we investigated the removal of the sulfamethoxazole drug (SMX) by calcined layered double
Calcined layered double hydroxide hydroxides (CLDHs) at 500 °C. The characterization of the fresh CLDH solids and after removal of SMX, by X-ray
Sulfamethoxazole diffraction, infrared spectroscopy and scanning electron microscopy, shows that the removal is carried out by
Antibiotic reconstruction of LDH phases intercalated by SMX via the memory effect of mixed oxides. The thermodynamic
Removal
parameters indicate that the adsorption is governed by physisorption.
Intercalation
Reconstruction
The removal capacity of SMX by CLDHs, under optimal conditions, reaches 4314 mg/g with an SMX/CLDH
mass ratio of 1.6 and the elimination rate reaches 93%. This result is a good sign for fighting the development of
bacterial resistance to such antibiotics because the quantity that may remain in natural environments is very
low. Recycling of the intercalated phases remains efficient after six cycles.

1. Introduction ampicillin, 43.9% to trimethoprim/sulfamethoxazole and 10.4% to

fluoroquinolones. The analysis of the evolution of these resistances
The presence of micropollutants in aquatic environments constitutes between 1999 and 2004 showed a significant increase in the resistance
a major problem for aquatic ecosystems, leading to an increase in the to ampicillin and fluoroquinolones, particularly in the 15 to 65 year-old
rate of waterborne diseases. The World Health Organization (WHO) persons. In contrast, the resistance to trimethoprim/sulfamethoxazole
reported that > 80% of these diseases in developing countries are did not show significant growth, compared to the IMS (Intercontinental
linked to poor water quality, resulting in about 30% mortality (Jensen, Medical Statistics) data, despite the high consumption of antibiotics.
2009). Emerging micropollutants include pharmaceuticals that have Different methods have been used in recent years to eliminate the
attracted the attention of the global scientific community for several pollutants (Sureshkumar and Namasivayam, 2008; Abaamrane et al.,
years. Many reports on the occurrence, effects and risks of these com- 2012; Alventosa-Delara et al., 2014; Ghaedi et al., 2015). Adsorption is
pounds have been exposed for sensitization to their toxicity (Kummerer, one of the most common treatment processes in water treatment and
2009). In addition, these potential pollutants are sometimes directly has become a method of choice because it is very effective and easy to
emitted into watercourses without effluent treatment. use (Crini, 2006; El Gaini et al., 2009; Yasin et al., 2010).
The sulfamethoxazole (SMX) belongs to the family of sulphonamide LDHs, also known as hydrotalcite-like compounds or anionic clays,
drugs. It is commonly used to treat digestive infections, typhoid fever and their calcined products (CLDHs), have been widely used as pollu-
and certain bronchopulmonary infections as well as urinary tract in- tants adsorbents (You et al., 2002; Li et al., 2005; Legrouri et al., 2005;
fections in humans and animals. It prevents the formation of dihy- Ni et al., 2007). These are layered materials with a net positive charge
drofolate acid, which is needed for bacteria to survive (Fernández et al., on the layer, due to partial substitution of divalent by trivalent cations.
2014), but some studies have shown a relatively high incidence of This charge is balanced by exchangeable charge compensating organic
bacterial resistance to this antibiotic (Trovo et al., 2009). or inorganic anions, which are present in the interlayer space with
According to a study carried out in 2009 in Morocco (El Bakkouri water molecules (Ni et al., 2007). The materials can be represented by
et al., 2009) on the resistance of uropathogenic Escherichia coli (E. coli) the general formula:
to antibiotics, 62.4% of the 799 strains of E. coli were resistant to
[MII1 − x MIII x (OH)2 ](An −) x/n . mH2 O

⁎
Corresponding author.
E-mail address: [email protected] (M. Lakraimi).

https://doi.org/10.1016/j.clay.2018.11.005
Received 20 June 2018; Received in revised form 18 September 2018; Accepted 5 November 2018
Available online 10 November 2018
0169-1317/ © 2018 Elsevier B.V. All rights reserved.
E.H. Mourid et al. Applied Clay Science 168 (2019) 87–95

where MII is a divalent cation, like Zn2+, Ni2+, …, MIII a trivalent

cation, like Al3+, Fe3+, …, An− an interlayer anion, such as Cl−, NO3−,
CO32–, … (Miyata, 1983; Constantino and Pinnavaia, 1995) and x the
metallic ratio MII/(MII + MIII).
CLDHs are well known for their memory effect. In fact, when ex-
posed to an aqueous solution containing anionic species, they re-
construct to produce their original layered structure. They have there-
fore a good efficiency for the removal of toxic anions from wastewater
(Das et al., 2006; Lv et al., 2006).
Our work is a contribution to the mitigation of wastewater con-
tamination by pharmaceutical drugs, such as antibiotics, and hence to
fighting the development of bacterial resistance to antibiotics.
Therefore, we have studied the removal of the SMX antibiotic from
water using a CLDH based on [Zn2-Al-CO3]. Our goal is to determine
the retention capacity of our material and the removal rate of the
pollutant while optimizing the experimental parameters, such as con-
tact time, solution pH and SMX/CLDH mass ratio. The results of X-ray
diffraction (XRD), infrared spectroscopy (IR) and scanning electron
microscopy (SEM) showed that the adsorption is accompanied by re-
construction of a hydrotalcite matrix intercalated by the SMX anti-
biotic. A comparative study allowed to evaluate the capacity of our
material against other products. In addition, we investigated the pos-
sibility of regeneration of our material by studying the variation of the
retention capacity in different recycling cycles.

2. Materials and methods

2.1. Preparation and characterization of [Zn2-Al-CO3]

The [Zn2-Al-CO3] material was synthesized by coprecipitation at a

constant pH of 10 and a ripening time of 72 h under agitation. The
starting solutions were 0.5 M ZnCl2, 0.5 M AlCl3.6H2O, 0.75 M Na2CO3
and 0.25 M NaOH. The Zn2+ and Al3+ solutions were added dropwise
to a 250 mL of distilled water and the pH was maintained constant by
addition of Na2CO3 and NaOH. After 72 h, the precipitate was filtered,
washed several times with distilled water and then dried at room
temperature (25 °C). The material was calcined at a 500 °C during 5 h
leading mainly to ZnO and ZnAl2O4 mixed oxides.

2.1.1. X-ray diffraction

The XRD of [Zn2-Al-CO3] (Fig. 1a) showed that the phase corre-
sponds to a pure LDH (Miyata, 1975; Fan et al., 2011). The material
consists of a well-crystallized single phase with large constituting
crystallites. The experimental metal ratio is comparable to the theore-
tical ratio, Zn/Al = 1.99. The lattice parameters, refined on the hex-
agonal setting with rhombohedral symmetry in R−3 m space group, are
given as follows:
a = 0.306 nm, c = 2.292 nm and d = 0.764 nm.

2.1.2. Infrared spectroscopy

The IR spectrum of the intercalated phase by carbonate anions
(Fig. 1b) shows vibration bands of hydroxyl groups of the layers, ν(OH),
at 3470 cm−1, ν(H2O) at around 3000 cm−1 and the deformation vi-
bration of water, δ(H2O), at 1630 cm−1. The vibration of the carbonate
anions belongs to D3h symmetry group and only ν2, ν3 and ν4 vibrations
appear at 860, 1360 and 774 cm−1, respectively (Bhagavantam and Fig. 1. XRD pattern of LDH and CLDH (a), IR spectrum (b) and TG-DTG curves
Venkatarayudu, 1939; Nakamoto, 1963). The characteristic bands of of LDH (c).
the sheets correspond to the metal-oxygen vibrations for (ZneO) at
around 615 cm−1 and for (AleO) at around 554 cm−1 (Prikhodko et al., to differentiate and limit the different stages of decomposition.
2001). Up to 80 °C, there is a slight loss which can correspond to the
elimination of water weakly bound to the surface. On the other hand,
2.1.3. TG and DTG the loss which occurs between 80 °C and 190 °C, which is of the order of
It can be noted that the thermogram (Fig. 1c) of the [Zn2-Al-CO3] 13%, is due to the elimination of the interlamellar water. The decom-
phase has an almost continuous pace from the ambient, although the position of carbonate anions into CO2 occurs from 190 °C at the same
phenomenon only starts at around 80 °C, until the end of the decom- time as dehydroxylation.
position. For this we have drawn with the thermogram its derived curve

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Table 1
Characteristic properties of sulfamethoxazole.
Trade name Sulfamethoxazole (SMX)

Systematic name 4-amino-N-(5-methyl-1,2-oxazol-3-yl) benzenesulfonamide

Type Sulfonamide
Chemical structure

Formula C10H11N3O3S
Fig. 2. Chemical forms of SMX according to pH values.
Molecular weight 253.28 g/mol
pKa 1.7 ± 0.1 and 5.7 ± 0.1
log Kow 0.89 3. Results and discussions
Solubility in water 610 mg/L
Toxicity to Fish, 0.01 to 2 μg/L
CL50 3.1. Effect of pH
Class Antibiotic
The influence of solution pH on the LDH reconstruction and SMX
retention was examined using 30 mg of [Zn2-Al-CO3] calcined at 500 °C
The X-ray diffractogram of the [Zn2-Al-CO3] phase calcined at for 5 h and an initial concentration of SMX solution of 20 mg/L. The
500 °C (Fig. 1a) confirms the destruction of this LDH phase in favour of solutions were prepared with decarbonated water and adjusted to pH
the formation of mixed oxides which appear in amorphous form. values, between 4 and 11, by addition of a solution of a 0.1 M HCl or
0.1 M NaOH. Each time, the solution is stirred for 3 h with bubbling
2.2. Characteristics of the SMX pharmaceutical drug nitrogen. Given that SMX is an amphoteric compound that has two
ionisable functional groups, aniline amine and amide groups
The physical and chemical properties of SMX are presented in (pKa1 = 1.7 and pKa2 = 5.7), its speciation depends on the pH value. It
Table 1. may exist in form of cations, anions and/or neutral molecules (Hou
et al., 2013). Fig. 2 shows the three SMX forms according to the pH
2.3. Retention experiments range (Qi et al., 2014).
The results of SMX retention by CLDH at different pH values are
Experiments were carried out by the batch equilibrium technique at shown in Fig. 3. The low retention values observed in acidic solutions
room temperature, constant contact time (1 h) and constant pH, may be explained by partial dissolution of the solid by hydrolysis
maintained by addition of NaOH or 0.1 M HCl, under a stream of ni- (Boclair and Braterman, 1999; Kacha et al., 1997) and the neutral form
trogen in order to avoid, or at least minimize, the contamination by of SMX (Sharma et al., 2006), which can decrease its interaction with
atmospheric CO2. The experiments were carried out in different steps: CLDH. The maximum retention is obtained for a pH value between 7
dispersion of solid CLDH (10, 30 and 50 mg) in 100 mL SMX containing and 8. The low retention capacity of CLDH at higher pH values may
solutions at different concentrations, varying from 1 to 500 mg/L. After result from competition with the carbonate anions (CO32−), for which
filtration, the solids were dried at room temperature before being the LDH matrix has a very high affinity (Iyi et al., 2004; Yan et al.,
analysed by different techniques, such as XRD, IR and SEM. The su- 2016).
pernatants were recovered and their residual concentrations were de- The subsequent experiments, in this work, were performed at pH 7,
termined by UV–Vis spectroscopy. The absorbances were measured at which represents the pH of natural water.
285 nm on UV–Vis spectrophotometer. The capacity of adsorption was
calculated by the following equation:
Q = (Ci − Ce) V/m (1)
where, Q represents the quantity of SMX retained by mass of CLDH (m)
in the volume of solution (V), which is calculated as the difference
between initial (Ci) and equilibrium (Ce) concentrations of the phar-
maceutical in solution.

2.4. Structural characterization techniques

The XRD equipment used was a Siemens D 501 diffractometer. The

samples of unoriented powder were exposed to copper Kα radiation
(λ = 0.15415 nm) and the measurement conditions were 2 h, 5–70°
range, 0.08–2 h step size, and 4 s step counting time. The data acqui-
sition was effected on a DACO-MP microcomputer and the unit cell
constants were calculated using a least squares refinement.
The IR spectra were obtained using a JASCO FT/IR-4600 Fourier
transform spectrometer. The samples were packaged in the form of
pellets consisting of the product diluted in KBr. The results are pre-
sented for wave numbers between 400 and 4000 cm−1 at a resolution of
4 cm−1 and a number of scans of 20.
SEM photographs of the material were taken on a Philips apparatus Fig. 3. Amount of SMX retained by CLDH as a function of pH (CSMX = 20 mg/L,
under a voltage of 10 kV. mCLDH = 30 mg).

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Fig. 4. Kinetics of retention of SMX by 30 mg of CLDH at different concentra-

Fig. 5. Pseudo-second order model for the adsorption kinetic of SMX onto
tions.
CLDH.

3.2. Kinetics study

Table 2
Parameters of the pseudo-second order model and the maximum adsorption
The evolution of the quantity of SMX retained by 30 mg of CLDH as amounts of SMX by CLDH.
a function of contact time (0 to 4 h) for three initial concentrations,
Ci (mg/L) Equation k2 (g/mg/ Qeth Qeexp R2
equal to 20, 50 and 200 mg/L, are represented in Fig. 4. The different
min) (mg/g) (mg/g)
solutions were kept under magnetic stirring at room temperature.
The results of Fig. 4 show that the retention rate of SMX is very fast 20 t/qt = 0.0263.t + 0.031 0.022 38 38 0.999
and the equilibrium is reached after one hour for the three initial SMX 50 t/qt = 0.010.t + 0.002 0.050 100 100 1
200 t/qt = 0.002.t + 0.002 0.002 500 488 0.999
concentrations. The maximum quantities retained, Qm, are of 38, 100
and 488 mg/g for 20, 50 and 200 mg/L, respectively.
The kinetics study is significant for a process of rapid elimination of
calculated from the following equation (Weber and Morris, 1963; Yang
the pharmaceutical pollutant by CLDH. The retention is likely to occur
et al., 2012):
by reconstruction of an LDH phase, through interaction of the SMX
anions with the sites between the reconstructed LDH sheets, and ad- Qt = kip t1/2 + C (4)
sorption on the surface sites. This reconstruction, which is carried out
by rehydration of the mixed oxides, is favoured by their memory effect where Qt is the capacity of adsorption (mg/g), kip is the intra-particle
(Yan et al., 2016). diffusion rate constant (mg/g/min1/2), and C is the vertical axis inter-
Several models have been established to describe the retention ki- cept.
netics; they include models of pseudo-first order, pseudo-second order The plot of the amount of adsorption as a function of the square root
and intra-particle diffusion. of time, according to the model proposed, led to a single linearity for
each SMX concentration (Fig. 6).
3.2.1. Pseudo-first and pseudo-second order models The constants for intra-particle diffusion are listed in Table 3. The
It is known that the adsorption kinetics is one of the most important kip rate constants are directly evaluated from the slopes of the regres-
characteristics that define the efficiency of adsorption. The experi- sion lines. The values of the intercept, C, provide information on the
mental data were fitted by the pseudo-first order Eq. (2) (Ho and
McKay, 2000) and the pseudo-second order Eq. (3) (Cheung et al.,
2007) as follows:
Log (Qe − Qt) = Log (Qe) − k1t (2)

t/Qt = 1/(k2Qe2) + (1/Qe) t (3)

where Qe and Qt are the amounts of SMX adsorbed at equilibrium and

at time t, k1 and k2 are the rate constants of the pseudo-first and pseudo-
second order models of adsorption, respectively.
Fig. 5 shows that the kinetic of SMX adsorption onto CLDH is very
fast. The pseudo-second order model appears to fit well with the ex-
perimental data. The values of k2 and Qe calculated from the model are
listed in Table 2 along with the corresponding correlation coefficients.
The pseudo-first order model does not fit the experimental data given
that its correlation coefficient values are too far from unity.

3.2.2. Intra-particle diffusion

To investigate the contribution of intra-particle behaviour on the
adsorption process, the rate constant for intra-particle diffusion can be Fig. 6. Intra-particle diffusion kinetic for adsorption of SMX on CLDH.

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Table 3 The negative value of ΔS° suggests an order at the solid/solution

Parameters of the intra-particle diffusion model for the adsorption of SMX by interface when removing the SMX from the solution (Lv, 2007). The
CLDH. decrease in the retained amount of SMX is also observed when the
Ci (mg/L) kip (mg/g/min1/2) C (mg/g) R2 temperature increases from 298 to 333 K. This decrease can be due to
the thermal agitation which causes the release of adsorbed SMX mo-
20 0.267 33.05 0.982 lecules on sites of CLDH by relatively weak bonds (hydrogen or elec-
50 0.115 98.43 0.976
trostatic bonds).
200 1.866 460.48 0.965
The pseudo-second order rate constant of SMX adsorption is ex-
pressed as a function of temperature by the following Arrhenius type
thickness of the boundary layer and the resistance to external mass relationship:
transfer increases as the intercept increases (Santhi et al., 2010). The Ln k2 = Ln A − Ea /RT (8)
constant C increases from 33 to 460 mg/g when the SMX concentration
increases from 20 to 200 mg/L, respectively. This indicates an increase where Ea is the Arrhenius activation energy of adsorption and A, the
in the thickness of the boundary layer and a decrease in the chance of Arrhenius factor. The magnitude of activation energy gives an idea
external mass transfer, thus increasing the chance of internal mass about the mechanism of adsorption. Low activation energies (5–40 kJ/
transfer. The values of R2 are not all close to unity, which questions the mol) are characteristic of physisorption, whereas higher ones
applicability of this model alone. The linearity of the curves can de- (40–800 kJ/mol) suggest chemisorption (Özcan et al., 2006). The result
monstrate that intra-particle diffusion role in the retention of SMX by obtained is +33.443 kJ/mol (Table 4) indicating that the adsorption
CLDH. However, some authors have shown that if intra-particle diffu- has a low potential barrier and corresponding to a physisorption.
sion is the only rate-limiting step, it is essential that the Qt versus t1/2
curves pass through the origin (Ho, 2003; Prasad and Santhi, 2012), 3.4. Adsorption isotherms
which is not the case in Fig. 6. It can be concluded that surface ad-
sorption and intra-particle diffusion function simultaneously during The study of adsorption isotherms makes it possible to determine
SMX and CLDH interaction. the adsorption capacity of SMX by CLDH. The study was carried out
The rapid adsorption process corresponds to a state of saturation with different initial SMX concentrations for three different doses of
that involves a very rapid reconstruction of the LDH phase. The inter- CLDH (10, 30 and 50 mg) during 1 h of stirring time at pH 7 and at
action between LDH and SMX is probably made through hydrogen room temperature. The results of SMX retention versus equilibrium
bonding between the hydroxyl group (OH) of the LDH sheet and the concentration for different CLDH masses are shown in Fig. 7.
amide group of the SMX (Qi et al., 2014). The isotherms obtained for the various CLDH masses are of S type,
which indicates the existence of a cooperative retention of SMX, fa-
3.3. Thermodynamic parameters of adsorption vouring thus the subsequent adsorption of other molecules (Foo and
Hameed, 2010; Olalekan et al., 2013). They tend therefore to be ad-
The effect of temperature is studied with the temperatures 298, 318 sorbed in groups.
and 333 K in a time interval of 15 to 60 min. The concentration of SMX The experimental data of the adsorption of SMX were linearized
is maintained at 50 mg/L and the mass of the calcined HDL is 30 mg. according to the three known models, which are Freundlich, Langmuir
Thermodynamic parameters, such as Gibbs free energy (ΔG°), and Elovich. The two latter models, gave negative values for the max-
enthalpy (ΔH°) and entropy (ΔS°) were calculated using the following imum quantities retained and for the affinities as well as correlation
equations (Akazdam et al., 2017): coefficients that are far from unity. This implies that these two models
are incompatible with our experimental results.
K c = Qe/Ce (5)
Only Freundlich model fits our experimental values of adsorption
Ln K c = ΔS°∕R − ΔH°∕RT (6) isotherms, which were linearized according to the Eq. (9) (Chen et al.,
2010):
ΔG° = −RT Ln K c (7)
Log (Qe) = Log (Kf ) + 1/n Log (Ce) (9)
With Qe is the adsorption capacity (mg/g), Kc the equilibrium
constant and Ce the concentration of the adsorbent at equilibrium (mg/
L). The values of ΔH° and ΔS° were determined from the slope and the
intercept of the plot of Ln Kc versus 1/T. The value of ΔG° was calcu-
lated from Eq. (7). The negative value of ΔH° indicates that this ad-
sorption is exothermic. The negative value of ΔG° confirms the spon-
taneous nature of the adsorption. The increase of ΔG° with temperature
indicates that the adsorption process is less favorable at high tem-
perature. The adsorption is governed by chemisorption when the value
of ΔH° is between 40 and 120 kJ/mol (Alkan et al., 2004; Zhao et al.,
2011). In our case, ΔH° equals −15.586 kJ/mol (Table 4) which in-
dicates that the adsorption of SMX by CLDH is a physisorption.

Table 4
Thermodynamic parameters obtained from kinetic adsorption of SMX onto
CLDH.
T (K) Ea (kJ/ Ln Kc Qe (mg/g) ΔG° (kJ/ ΔH° (kJ/mol) ΔS° (J/mol/
mol) mol) K)

298 1.599 99.583 −3.962 −15.586 −38.827

318 33.443 1.279 86.458 −3.381
Fig. 7. Adsorption isotherms for SMX determined with three different doses of
333 0.927 71.875 −2.567
CLDH.

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Fig. 8. Linearization curves of Freundlich model with three different masses of Fig. 9. SMX retention rate versus SMX/CLDH mass ratio.
CLDH.
and sewage treatment effluents, or in river waters, the detected con-
Table 5 centrations of SMX vary between 4 ng/L and 12.8 μg/L (Lindberg et al.,
Parameter values of Freundlich adsorption isotherm model for SMX on CLDH. 2004; Carballa et al., 2008; Wahlberg et al., 2011; Oberlé et al., 2012;
Johnson et al., 2015; Al Qarni et al., 2016). The treatment of these
mCLDH (mg) Kf (mg/g) n R2
environments by CLDH may lead to the reduction of SMX concentra-
10 10.688 0.937 0.993 tions to values between 0.28 ng/L and 0.896 μg/L, respectively. These
30 4.826 0.940 0.983 remaining amounts in solution are well below tolerated thresholds for
50 2.362 0.883 0.981 humans (Cheng et al., 2009). They are even lower than the average
concentration of SMX responsible for the inhibition of the biological
and biochemical function of a bacterium, which is 0.256 mg/L (Al-
Qe is the equilibrium quantity of SMX retained by the unit mass of
Ahmad et al., 1999). It is worth mentioning that the attenuation of the
CLDH (mg/g); Ce is the equilibrium concentration of SMX (mg/L) and
SMX concentrations in different environments is such an important
Kf is the Freundlich isotherm constant, which represent the affinity of
result to cope with the development of bacterial resistance to currently
the adsorbate for the adsorbent. The factor n measures the deviation
used antibiotics (E. coli among others).
from linearity. The linear transformations of the Freundlich model for
three CLDH masses are exposed in Fig. 8 and the parameter values are
given in Table 5. 3.6. Study by X-ray diffraction
The affinity of SMX for CLDH, represented by Kf, increases when the
retention capacity increases. The heterogeneity factor of the surface is The XRD pattern of the solid compounds collected after intercation
represented by 1/n. When its value is higher than one, physisorption with SMX solutions are shown in Fig. 10. The CLDH phase presents
occurs and the adsorption surface is more heterogeneous (Sevim et al., broad ZnO lines indicating that the destruction of the layers leads to the
2011). According to the results exposed in Table 5, the adsorption sites amorphous form of the mixed oxides. The phase obtained after reten-
are heterogeneous (n < 1). This has been proven by the study of iso- tion of SMX displays a crystal structure similar to that of LDH phases.
therms that leads to cooperative adsorption (Olalekan et al., 2013). The
latter can be explained by the fixation of SMX anions by electrostatic
interactions with the LDH layers.
If n = 1, the adsorption is linear (linear curve); if the n > 1, the
adsorption is favorable (concave curve); if n < 1, the adsorption is
normal and cooperative (convex curve) (Mohan and Karthikeyan, 1997;
Voudrias et al., 2002; Foo and Hameed, 2010; Olalekan et al., 2013;
Akazdam et al., 2017). Such results have been reported by other re-
searchers (Ahmed et al., 2015) who have carried out work on the
elimination of several antibiotics from water (sulfamethazole, sulfa-
methoxazole, sulfamethazine, sulfapyridine, tetracycline …) by other
materials (activated carbon, bentonite).

3.5. Effect of SMX/CLDH mass ratio

To examine the effect of the adsorbate/adsorbent mass ratio on the

adsorption capacity of CLDH, the initial concentration of the adsorbate
was varied from 1 to 500 mg/L, while keeping the mass of CLDH equal
to 30 mg (Fig. 9).
It can be deduced that the maximum retention rate, equal to 93%, is
obtained for a mass ratio of 1.6. Fig. 10. XRD patterns of the phases [Zn2-Al-CO3] (a), CLDH (b) and [Zn2-Al-
In various surrounding environments, such as domestic, hospital SMX] (c).

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3.7. Study by infrared spectroscopy

The IR spectrum of the CLDH (Fig. 11b) gives the vibration bands of
the OH groups at around 3430 cm−1, the AleO bands at 486 and
765 cm−1 and the ZneO band at 685 cm−1 (Alvarez et al., 2010). The
bands corresponding to the vibration of carbonate ions diminished
significantly due to the loss of carbonates (Abderrazek et al., 2015) or to
residual bulk polydentate carbonates (Starukh et al., 2016). Compared
to Fig. 11a, we see the disappearance of the characteristic band of the
layers around 400 cm−1, which confirm that the crystal structure
layered is destroyed after calcination of LDH at 500 °C in agreement
with the results of DRX (Fig. 10). The IR spectrum of the SMX drug
(Fig. 11c) shows the characteristic bands of its different functional
groups (Yang and Guillory, 1972; Rambaud et al., 1983).
The IR spectrum of [Zn2-Al-SMX] (Fig. 11d) presents a large and
intense band around 3430 cm−1 corresponding to the valence vibra-
tions of the hydroxyl group OH. Two bands appear in the
1500–1645 cm−1 region, the first one reflecting the ν(CH) valence vi-
bration of the aromatic nucleus and the second one the δ(NH2) de-
formation. A band with a slight shoulder at around 1365 cm−1 may be
assigned to ν(CO32−) associated with a δ(NH) deformation band (Novak
et al., 1966). The characteristic deformation band δ(CN) is localized at
around 1330 cm−1.
The valence bands characteristic of the sulphonate group appear in
two modes, the νas(SO2) antisymmetric mode in the form of a doublet at
1300 cm−1 and the νs(SO2) symmetric mode at 1200 cm−1. The δ(CH)
and δ(SO2) deformation bands appear at around 850 cm−1 and
545–700 cm−1, respectively (Maury et al., 1985). Finally, we also note
the presence of metal‑oxygen vibrations with a band at 554 cm−1 for
AleO and a band at 615 cm−1 for ZneO (Alvarez et al., 2010). The
bands at around 400 cm−1, for O-MeO, are characteristic of re-
constructed LDH sheets.
Fig. 11. IR spectra of LDH (a), CLDH (b), SMX (c) and [Zn2-Al-SMX] (d). It can be concluded, from these results, that the calcined LDH ma-
terial has retained the pharmaceutical product (SMX).
This confirms the reconstruction of an LDH phase by the memory effect
of the mixed oxides obtained by LDH calcination.
The intercalation of SMX anions between the LDH sheets leads to a 3.8. Analysis by scanning electron microscopy
shift of the (003) line towards the low values of 2θ, which corresponds
to an increase in the interlayer distance to reach 1.10 nm (0.764 nm for The SEM micrograph of [Zn2-Al-CO3] (Fig. 12a) confirms the
[Zn2-Al-CO3]). The lines around 60° of 2θ correspond to the (110) line, layered structure of the compound by the presence of crystallites that
which is typical of LDH phases. The lattice parameters of [Zn2-Al-SMX] are homogeneously distributed in the form of a sand rose. The micro-
are: a = 0.306 nm, c = 3.300 nm and the interlayer distance graph of the CLDH phase (Fig. 12b) shows the absence of the layered
d = 1.10 nm. We note that the phase is contaminated by the carbonate character due to the destruction of LDH sheets and the appearance of
ions, coming from atmospheric CO2, for which LDHs are known to have mixed oxide aggregates.
great affinity (Miyata, 1975). The SEM image of [Zn2-Al-SMX] (Fig. 12c) displays aggregates of
different sizes, which measure up to 1.33 μm. The layered aspect of the
solids is manifest, proving thus the reconstruction of a LDH phase from
the mixed oxides by memory effect (Newman and Jones, 1998).

Fig. 12. SEM photographs of LDH (a), CLDH (b) and [Zn2-Al-SMX] (c).

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works on the retention efficiency was carried out (Table 6). It is clear
that the removal rate of SMX by CLDH, which is of 93%, is greater than
that obtained with other materials. With a value of up to 4314 mg/g,
CLDH can be considered as having a relatively high retention capacity.
This makes of calcined LDHs promising materials for the elimination of
this potential pollutant.

4. Conclusion

The aim of this work was to eliminate the SMX pharmaceutical drug
from wastewater using a calcined LDH material, which has shown high
retention capacity.
The kinetics of SMX retention by calcined LDH is rapid and follows
the pseudo-second order model. The values of activation energy Ea
(+33.443 kJ/mol) and enthalpy ΔH° (−15.586 kJ/mol) indicates that
the adsorption is governed by a physisorption mechanism. The iso-
therms are in agreement with the Freundlich model and are of S type,
which implies a cooperative adsorption. The elimination of SMX is
maximal for an SMX/CLDH mass ratio of 1.6, with a quantity exceeding
Fig. 13. Recycling efficiency of CLDH after retention of SMX for an SMX/CLDH 4314 mg/g. The retention rate reaches 93% and the quantities that may
mass ratio of 1.6. remain in various natural environments are encouraging for the fight of
possible development of bacterial resistance to such antibiotics.
Table 6 The results of the three complementary techniques used confirm the
Maximum adsorption capacity and removal rate of SMX on different materials. retention of SMX by adsorption on the surface and intercalation into the
Materials Qm Removal References reconstructed LDH phase. Our calcined material has shown its better
(mg/g) rate (%) efficiency and capacity compared to other adsorbents for the removal of
such pollutants with the possibility of its recycling.
Calcined LDH 4314 93 This work
Zeolitic Imidazolate 21.9 - Ahmed et al., 2018
Frameworks-8
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