Anal. Methods Environ. Chem. J.

6 (3) (2023) 67-88

Research Article, Issue 3

Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir

AMECJ

Analytical study on lead elimination by anionic

clays: Characterization, adsorption kinetics, isotherm,
thermodynamic, mechanism and adsorption
Salah Bahaha,b,*
a
Department of Environmental Engineering, Faculty of Science and Technology,
University Bachir El Ibrahimi of Bordj Bou Arreridj, Algeria.
b
Laboratory of Chemical Processes Engineering (LGPC), Department of Process Engineering, Faculty of Technology,
University Ferhat Abbas Setif19000 ,1- Sétif, Algeria.

ARTICLE INFO: ABSTRACT

Received 20 May 2023 The co-precipitation method synthesized the synthetic anionicMg–Al
and Ni-Al clays with three molar ratios (Mg/Al, Ni/Al). The samples
Revised form 30 Jul 2023
were characterized by powder X-ray diffraction (XRD), Fourier
Accepted 19 Aug 2023 transform infrared spectroscopy (FTIR), and scanning electron
Available online 30 Sep 2023 microscopy (SEM). No other crystalline phases were detected in the
------------------------ powder XRD patterns of the co-precipitated samples. The infrared
spectra obtained all the functional groups that characterize these two
Keywords: types of anionic clays. SEM micrographs indicate the presence of
Anionic clays, particles and aggregates. The particles, or aggregates, are in the form
Lead, of plates, supported by particles of acceptable sizes. The optimal pH
Adsorption, for maximum lead adsorption is about 6.5 for both clays. The optimal
Co-precipitation, adsorbent masses for the maximum percentages of lead removal are
Functional groups 0.2 g for Mg3AlCO3 and 0.25 g for Ni3AlCO3. The Mg3AlCO3 has a
maximum adsorption capacity of lead, where qm=73.42 mg g-1. The
adsorbed amount increases with increasing temperature for both types
of clays studied. The equilibrium time of Pb2+ adsorption is reached
after 5 min for both clays. The most appropriate models to describe
the experimental data of adsorption kinetics and isotherms are
pseudo-second-order and Langmuir. The detection limit (LOD) was
0.272 mg L-1. The linearity range was 1 to 5 mg L-1; the correlation
coefficient in this range was 0.9997.
1. Introduction The structure of these clays consists of positively
Anionic clays, or Layered Double Hydroxides charged mixed metal hydroxide layers separated by
(LDHs), are mixed metal hydroxides that have a charge-balancing anions and water molecules [4].
general formula expressed as[(MII)1−x(MIII)x(OH)2] The cationic sheets containing M(OH)2 in octahedral
x+
(Am−x/m)·nH2O]. M2+is a divalent cation (typically surroundings are linked by three edges, as in the
Mg, Zn, Ni, Co), M3+is a trivalent metal cation brucite structure, between which compensating
(Al, Fe, Cr), An- is a charge anion, n/x is the molar layers of anions are found [5]. These compounds
ratio between di and trivalent cations, M2+/(M2+ + have been the subject of much interest and research
M3+), and m, the number of water molecules[1-3]. in recent years thanks to their interesting properties
of anionic exchange [6,7], adsorption and porosity,
*Corresponding Author: Salah Bahah
which make it possible to envisage the intercalation
Email: [email protected]
of a large variety of anions (organic or inorganic)
https://doi.org/10.24200/amecj.v6.i03.248
68 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

and the immobilization of various species, giving Spectroscopy (ICP-AES), sometimes named ICP-
these hybrid materials a particular reactivity [6,7]. optical emission spectrometry (ICP-AES), is a
Therefore, LDH is considered a promising material device that results from the coupling between a high-
[8]. Heavy metals are one of the main categories of frequency induced argon plasma and a spectrometer,
water pollution; these releases pose a real danger which is used to calculate the concentration of
to humans and their environment due to their metals in solid, liquid or gas samples. The LOD of
stability and low biodegradability [9-11]. The use the ICP-AES technique is lower than ICP-MS [19].
of the adsorption technique to remove heavy metals In addition, there are other lead dosage techniques
in aqueous solutions on different solid supports, without spectroscopic techniques, such as cyclic
especially on new materials such as anionic clays, voltammetry (CV). Riyanto et al. showed that the
has been the subject of much work [3, 5, 12]. electroanalysis method for lead determination in
Among the scientific results that use layered double wastewater is accurate, precise, reproducible and
hydroxides as adsorbents to remove lead are the inexpensive, with acceptable correlation [20].
studies of Yasin et al. (2014) [13]. The types of Compared with spectroscopic techniques, the LOD
LDHs used to remove lead (Pb) from the aqueous of electroanalysis (0.929 mg L-1) is higher than that
solution are MgAl-NO3 and Tartrate-MgAl. In of spectroscopic methods.
this study, the maximum lead adsorption capacity In this paper, lead removal from an aqueous
calculated by the Langmuir model is 8.4 and 3.2 mg solution was performed using two-layered double
g-1 for Tartrate-MgAl and MgAlNO3, respectively hydroxides, namely Mg3AlCO3 and Ni3AlCO3.
[13]. Yanming et al. (2017) [14] studied the removal The co-precipitation method prepared these two
of Pb2+ ions from an aqueous solution by glutamate adsorbents with a molar ratio of (Mg/Al) equal to
intercalated in layered double hydroxide. The 3. Ni3AlCO3 can be considered among the LDHs
maximum retention capacity of Pb2+ is 68.49 mg g-1 not used to eliminate heavy metals from aqueous
[14]. The concentration of Pb and other metal ions solution. The adsorption capacities of lead with
can be determined by several techniques, which can two anionic clays at room temperature in optimized
be grouped under atomic spectrometry. Graphite pH were compared and analyzed. We studied
furnace atomic absorption spectrophotometer the effect of different parameters such as the Ni/
(GF-AAS) is the best technique method. Several Al ratio, pH, contact time, dose of adsorbent and
research studies use this technique to determine temperature in the adsorption of Pb2+ ions from an
the lead concentration in the blood, like studies of aqueous solution. In addition, the mechanism and
Pacer et al. (2022) [15]. In addition, GF-AAS is an thermodynamic parameters were studied.
excellent method currently applied for trace lead
concentration with high accuracy and precision 2. Experimental
[15, 16]. Like GF-AAS, inductively coupled 2.1. Reagents and Materials
plasma mass spectrometry and ICP-MS is other The products of magnesium nitrate hexahydrate
assay technique with precise and accurate results. (Mg(NO3)2.6H2O; CAS 13446-18-9; Molecular
However, it is a simple and rapid method compared Weight 256.41), Aluminum nitrate nonahydrate
to ICP-MS [17]. The comparative study carried out (Al (NO3)3.9H2O; CAS Number: 7784-27-2;
by Trzcinka-Ochocka et al. for the determination of M. W.: 375.13) and Nickel nitrate hexahydrate
lead and cadmium shows that validation parameters (Ni(NO3)2.6H2O; CAS 13478-00-7; Molecular
for ICP-MS and GF-AAS were similar. However, Weight 290.79) used for the synthesis of MgAlCO3
ICP-MS for Pb determinations is better than GF- and NiAlCO3 were purchased from Sigma,
AAS. Also, the detection limits (LOD) of ICP-MS Germany. Sodium carbonates (NaCO3), Sodium
are better than GF-AAS for lead analysis [18]. hydroxide (NaOH) and Lead nitrate Pb(NO3)2 were
Inductively Coupled Plasma -Atomic Emission purchased from Merck.
 Study the elimination of lead by anionic clays Salah Bahah 69

2.2. Apparatus 2.4. Adsorption method

The absorption measurements were made with The study of the adsorption of lead was performed
AA-6200 Atomic Absorption Flame Emission by the batch method. The lead stock solution
Spectrophotometer SHIMADZU. Calibrating was prepared by dissolving Pb (NO3)2 in distilled
standard lead solutions were prepared by dilution water and diluting it to the desired concentration.
from the stock solution (1000 mg L-1). The linear Adsorption of Pb2+ on the selected clay was carried
working range was obtained between 1 to 5 mg L-1. out in a 50 ml conical flask by taking 50 ml of a
To estimate the sensitivity of the FAAS method, solution of the desired Pb2+ concentration to which
we calculated the limit of detection (LOD) and the 200 mg of the adsorbent was added. The adsorbate
limit of quantification (LOQ). The LOD and LOQ in the mixture was separated by centrifugation. An
values were achieved at 0.272 mg L-1 and 0.825 mg atomic absorption spectrophotometer determined the
L-1, respectively. residual Pb2+ in the filtrate. All experiments except
the pH variation study were performed at the stock
2.3. Synthesis method solution pH. In the case of pH variation studies, a
The LDHs studied are NiAlCO3 (R=2, 3 et 4) and variable concentration of diluted NaOH and HCl
MgAlCO3 (R=3). These clays were synthesized solutions was used to adjust the pH. Figure 1 presents
by the direct co-precipitation method, in which an the adsorption method.
aqueous solution containing appropriate amounts The adsorption of lead was calculated by Equation 1.
of nitrate elements (hydrated metal salts as sources)
was added dropwise into an alkaline solution of (Eq.1)
Na2C03 and NaOH at room temperature under
vigorous stirring. During the synthesis, the pH was Where qe= lead adsorbed (mgg-1); V = solution
adjusted to pH 10. The resulting suspension was volume (L); Ci = initial concentration (mg Pb2+L-1);
stirred for 18 hours at 65 °C. After cooling to room Ce (mgPb2+ L-1) =equilibrium concentration and
temperature, the precipitate was centrifuged and m adsorbent mass. % Removal of metal ions were
washed several times with bi-distilled water until calculated using Equation 2.
there was no trace of nitrate (AgNO3 test) and then
dried overnight in an oven at 100 °C. (Eq. 2)

Fig. 1. Adsorption of lead by a batch method

70 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

3. Results and Discussion layered double hydroxide materials (LDHs). Peaks

3.1. Characterization 003 and 006 are sharp, narrow, and symmetric;
A Bruker D8 diffractometer with CuKα radiation the baseline is low and stable, which indicates a
(λ= 0.15406 nm) was used to study the structural high degree of crystallinity and a typical structure
properties of the clay. A scanning electronic of anionic clays. These reflections correspond
microscopy instrument (S-4800), a Hitachi to the layer order along the c-axis [21]. Inter-
model (Japan), was utilized to study the surface reticular distances are 7.70 °A and 7.75 °A for Ni/
properties. Fourier transform infrared spectroscopy Al (R=3) and Mg/Al (R=3), respectively. These
(Perkin-Elmer model; USA) was applied to study values are in order of those reported in similar
the functional group of the adsorbent. Moreover, studies by Kristina Klemkaite et al. [22]and
this last technique was used to examine the effect Faour et al. [23]. The cell parameters of Ni3AlCO3
of the adsorption of Pb2+ on the different bands of and Mg3AlCO3, calculated as a = 2*d110 [24], are
the functional groups after adsorption. The infrared 3.04 and 3.06 °A, respectively. The constant c
spectra were carried out between 4000 cm-1 and calculated using the equation c=3*d003 [25] shows
400 cm-1. that the corresponding values for Ni3AlCO3
and Mg3AlCO3 are (23.10 °A) and (23.25 °A),
3.1.1.Characterization by XRD respectively. These values always agree with
The X-ray diffraction patterns of the prepared those of Kristina Klemkaite et al. [22] and Faour
phases (Fig. 2a and 2b) are characteristic of et al. [23].

Fig. 2a. XRD patterns of Mg3 Al–CO3

Fig. 2b. XRD patterns of Ni3Al–CO3.

 Study the elimination of lead by anionic clays Salah Bahah 71

Fig. 3a. The SEM micrograph of (a) Ni3Al–CO3 (R=3)

Fig. 3b. The SEM micrograph of Mg3Al–CO3(R=3).

3.1.2.Characterization by SEM are characterized by a rigid (compact) perimeter

The images characterizing the surfaces of the surrounding a highly porous surface.
different substrates are presented in Figure3a and
3b. The images at different magnifications show 3.2. Parameters of adsorption
surfaces with large porosities and different types In the following, we studied the effect of some
and sizes. The large inter-particle pores are occupied parameters on lead adsorption, such as the solution’s
by particles of smaller sizes for both clays, which initial pH, the adsorbent’s mass, contact time, molar
indicate the presence of inter-particle attraction ratio, and temperature. The concentration and
forces that form large aggregates. The particles, or volume of the aqueous lead solution were fixed at
aggregates, are in the form of plates, supported by 50 mgL-1 and 50 mL, respectively, and the stirring
particles of acceptable sizes. Mg3AlCO3 particles speed was set at 400 rpm.
72 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

3.2.1.Effect of pH slight decrease and then stability for lead removed

To find the optimal pH corresponding to the until pH 9. These results almost agree with those
maximum adsorption of lead in the aqueous found by Donglin Zhao et al., who used anionic clay
solution, we studied the effect of this factor on the based on Mg2Al-LDH to remove lead [26]. For the
retention of Pb2+ at different pHs (from pH 3 to pH anionic clay based on Ni3AlCO3, the characteristic
9). The results obtained are shown in Figure 4. The curve shows a remarkable decrease in the amount
amount retained as a function of the pH solution was of lead removed. At this pH range (pH ˃ 6.5),
determined from the concentration of Pb2+ remaining according to ZHAO, Donglin et al. (2011) [26],
in the solution after equilibrium by the atomic lead in the aqueous solution takes the forms of Pb
absorption technique. According to Figure 4, the (OH) and Pb (OH)2. Thus, the adsorption of Pb2+
curves can be divided as a function of pH into two on both LDHs occurred by precipitation reaction,
regions: the first one represents the domain of pH as explained by several authors in this pH range
lower than 6.5 in which the percentage removal of (pH ˃ 7) [26]. According to our results, it can be
Pb2+ retained on the selected anionic clays increases noted that the lead precipitation reaction is better
as the pH increases, reaching a maximum value catalyzed on the Mg3AlCO3 surface than that of
at pH 6.5. At this optimum pH, the lead removal Ni3AlCO3, where the amount adsorbed by Mg3Al
percentages are 95.4% and 81.34% for Mg3AlCO3 remains constant from pH 7.5 and higher compared
and Ni3AlCO3, respectively. The increase in Pb2+ to Ni3Al-based clays, where the amounts of lead are
adsorption on both types of LDHs with increasing decreased with the increase of pH (Figure 4).On the
pH can be explained by the decrease in H+ ion other hand, LIANG, Xuefeng et al. [25] conclude
concentration with increasing pH. Where the clay that the adsorption of Pb2+ on a clay-type Mg2Al-Cl
surface at low pH became positively charged LDH results mainly from the precipitation induced
due to the protonation reaction on the surfaces by the surface. At optimum pH (pH = 6.5), the
(formation of SOH2+) [25], which leads to repulsive results show that the order of the quantity of lead
forces between Pb2+ ions and SOH2+groups on the retained for the clays used becomes Equation 3.
adsorbent surface [26]. According to Donglin
Zhao, at pH values below 7, lead ions are present Qads (MgAlCO3(R=3) > Qads (NiAlCO3(R=3) (Eq. 3)
as Pb2+ in the solution. The adsorption reactions
are surface complexation reactions, including two Whereas, at pH˂5.5 (an acidic medium), the
surface reactions. The chemical bonding reaction percentage of Pb2+ removal by Ni3AlCO3 HDL is
occurs between the metal ions and the surface higher than that of Mg3AlCO3 HDL, conversely for
functional groups, forming surface complexes the pH ˃ 5.5 range. This can be explained by the
of the inner sphere. In the second region, an start of the lead precipitation reaction occurring in
electrostatic binding reaction occurs between metal parallel with the complexation reaction from pH
ions and oppositely charged surface functional 5.5 to the optimum pH of 6.5.
groups, forming surface complexes of the outer
sphere at some distance from the surface. The 3.2.2.Effect of adsorbent quantity
complex adsorption of lead on LDH samples can Different amounts of the adsorbent (0.05–0.3 g)
be described as follows [25,26]. were added to other conical flasks containing 50 mL
Sur-O- + Pb2+ → Sur-O--Pb+ + H+ of the aqueous solution of Pb2+ (pH 6.5). Figure 5
Chemical binding adsorption shows the variations of Pb2+ adsorbed amounts as
a function of adsorbent mass for the two anionic
Sur-O- + Pb2+ → Sur-O-----Pb2+ clays studied with a contact time of 2 hours. The
Electrostatic binding adsorption initial adsorbate concentration used is 50 mg L-1.
At pH greater than 6.5, for Mg3AlCO3, there is a Lead removal percentages increase as the adsorbent
 Study the elimination of lead by anionic clays Salah Bahah 73

Fig. 4. Effect of initial pH on removal of Pb+2 ions onto Mg3AlCO3 and Ni3AlCO3.

Fig. 5. Effect of mass on the adsorption of Pb2+ onto Ni3Al-CO3 and Mg3Al-CO3

mass increases from 0.05 g to 0.2 g. Above 0.2 g According to Figure 5, the amount of Pb2+ was
for Mg3AlCO3 and 0.25 g for Ni3AlCO3, the amount adsorbed on the clays as Equation 4.
of Pb2+ retained remains almost constant regardless
of the adsorbent mass. The maximum capacities Qads (MgAlCO3(95.25%) ˃ Qads (NiAlCO3(83.665)
corresponding to these masses are 95.25 % and (Eq.4)
83.66 % for Mg3AlCO3 and Ni3AlCO3, respectively.
74 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

3.2.3.Effect of temperature Pb2+ in the solution is 50 mg Pb2+L-1, the stirring

The effect of temperature on lead adsorption was speed is 400 rpm, and the adsorption occurs at
studied at 20 °C, 30 °C, 40 °C, 50°C, and as well as ambient temperature. The equilibration time is an
pH of the solution. Figure 6 shows the percentage important parameter that allows the determination
of lead removal as a function of temperature for of the rate of lead elimination, whether it is fast or
Mg3AlCO3 and Ni3AlCO3. From the curves shown slow, as well as the evaluation of the effectiveness
in Figure 6, the adsorbed amount increases with of the absorbent. The shape of the curves shown
increasing temperature for both types of LDHs, in Figure 7 is typical of saturation curves with a
where the lead removal percentages reach 94.16 slight quantitative difference. The Pb2+ retention
% and 85.39 % for Mg3AlCO3 and Ni3AlCO3, kinetics consists of two distinct steps: an initial
respectively. The percentage of lead removal by fast step with a contact time of up to 5 minutes for
Mg3AlCO3 is higher than that of Ni3AlCO3 for all Mg3AlCO3 and Ni3AlCO3 and about 10 minutes
temperatures. This may indicate that the adsorption for Ni2AlCO3 and Ni4AlCO3, respectively, and a
of lead onto the active sites of LDHs studied is slower second step in which retention reaches a
endothermic [27]. The increase in temperature can plateau, indicating the achievement of balance.
be enlarged and activate the adsorbent surface, The equilibrium times for Ni2AlCO3 and Ni4AlCO3
which facilitates the mobility of lead ions from represent the double time required for equilibrium
the bulk solution to the adsorbent surfaces and compared to Mg3AlCO3 and Ni3AlCO3. This can
enhances the accessibility to the adsorbent active be explained by the crystalline factor in Mg3AlCO3
sites [27]. and Ni3AlCO3, which is good compared to
Ni2AlCO3 and Ni4AlCO3. The regular and repetitive
3.2.4.Effect of contact time and molar ratio distribution of atoms and functional groups bonded
The study of the contact effect was carried with these atoms, such as OH, facilitate the rapid
out using four LDHs of the types Mg3AlCO3, attachment of Pb2+ ions to these surface functional
Ni2AlCO3, Ni3AlCO3, and Ni4AlCO3 (to see the groups. It is known that the elimination of Pb2+ for
molar ratio effect, (R=2, 3, and 4). The mass of all adsorbents is done under the same conditions
the adsorbent used is 0.2 g, the concentration of (temperature, stirring speed).

Fig. 6. Effect of temperature on Pb2+ adsorption on Mg3AlCO3 and Ni3AlCO3

 Study the elimination of lead by anionic clays Salah Bahah 75

Qads (mg g-1)

Qads (mg g-1)
Qads (mg g-1)
76 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

Qads (mg g-1)

Fig. 7. Retention kinetics of Pb2+ on anionic clays studied

3.3. Kinetic models of adsorptions Where qe, qt, t, k1, k2, ki, and C are respectively the
To determine the most appropriate kinetic model, quantity of Pb2+ adsorbed at equilibrium (mg g-1),
we have chosen three models, the most used for the quantity of Pb2+ adsorbed at time t (mg g-1),
modelling adsorption kinetic data, which are: the the time (min), the rate constant of the pseudo-
pseudo-first-order (Equation 5), the second-order first-order kinetic equation in g/mg min-1, the
(Equation 6), and the intraparticle diffusion model rate constant of the pseudo-second-order kinetic
(Equation 7). The corresponding equations in linear equation in g/mg min-1, the rate constant mg/
forms are presented as follows [28, 29]. gmin0.5, and the boundary layer thickness.

(Eq.5) 3.3.1.Pseudo first-order model.

The calculated results of the pseudo-first-order
equation are presented in Table 1 and Figure 8. The
(Eq.6) values of the correlation coefficients are low, and the
values of qe acquired by this method are contrasted
with the experimental values. So, adsorption cannot
(Eq.7) be classified as pseudo-first order.

Table 1. Pseudo-first-order model parameters

Clay Parameters
qe (mg g-1) exp = 12.00
Mg3AlCO3 qe (mg g-1) cal = 0.048
K1 (mg g-1min-1) = 0.00057
R 2 = 0.00025
qe (mg g-1) exp = 11.96
Ni2AlCO3 qe (mg g-1) cal = 0.51
K1 (mg g-1min-1) = 0.06
R 2 = 0.13
qe (mg g-1) exp =11.86
Ni3AlCO3 qe (mg g-1) cal =0.44
K1 (mg g-1min-1) = 0.018
R 2 = 0.38
qe (mg g-1) exp =11.93
Ni4AlCO3 qe (mg g-1) cal = 0.11
K1 (mg g-1min-1) = 0.025
R 2 = 0.072
 Study the elimination of lead by anionic clays Salah Bahah 77

Fig. 8. Pseudo first-order model for anionic clays

3.3.2.Pseudo second-order model. by pseudo-second-order kinetics (Fig. 9). The

This model considers that the rate-limiting step in parameters of the two kinetic models are shown in
heavy metal adsorption is chemisorption and that Table 2. From these results and in contrast to the
chemisorptive bonds involving electron sharing or first-order model, the amount of Pb2+ adsorbed at
exchange between the absorbent and the adsorbent equilibrium determined experimentally is closer
have been applied [5]. According to the high values to that calculated using the second-order kinetic
of the regression constant R2 = 0.99 for all the model (Table 2).
studied clays, the evolution of t/qt vs. t is presented

Table 2. Parameters of the pseudo-second-order model.

Clay Parameters
qe (mg g-1) exp = 12.00
Mg3AlCO3 qe (mg g-1) cal =12.00
K1 (mg g-1min-1) =-9.29
R 2 =1
qe (mg g-1) exp = 11.96
Ni2AlCO3 qe (mg g-1) cal = 11.93
K2 (mg g-1min-1) = 0.487
R 2 = 0.99
qe (mg g-1) exp =11.86
Ni3AlCO3 qe (mg g-1) cal = 11.88
K2 (mg g-1min-1) = 1.59
R 2= 0.99
qe (mg g-1) exp =11.93
Ni4AlCO3 qe (mg g-1) cal = 11.94
K2 (mg g-1min-1) = 12.87
R 2 = 0.99
78 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

Fig. 9. Pseudo second-order model for anionic clays

3.3.3.Weber - Morris internal diffusion model adsorption does not follow only the mechanism
The Weber-Morris intra-particle diffusion of intra-particle diffusion and that several
model is the mos t used technique to identify processes affect the adsorption of Pb2+ and that
the mechanism involved in the adsorption intra-particle diffusion is not the limiting step for
process. Intra-particle diffusion plots (q t vs. the whole reaction. The values of the constant
t 0.5) (Fig. 10) were obtained from Equation 7. C, which presents the thickness of the boundary
All the parameters of this model are presented layer, are in the order CMg3AlCO3 ˃ CNi2AlCO3 ˃
in Table 3. Figure 10 indicates that straight lines CNi3AlCO3 ˃ CNi4AlCO3. The values of C determine
do not pass through the point of origin before the boundary layer effect; higher values indicate
reaching the equilibrium state; therefore, the a more significant impact [29].

Table 3. Parameters of the intra-particle diffusion model.

Clay Parameters
Kd = 0.135
Mg3AlCO3 C = 11.63
R 2 = 0.76
Kd = 1.54
Ni2AlCO3 C = 7.12
R 2 = 0.99
Kd = 0.68
Ni3AlCO3 C = 9.95
R 2 = 0.72
Kd = 0.32
Ni4AlCO3 C = 10.74
R 2 = 0.94
Study the elimination of lead by anionic clays Salah Bahah 79
80 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

Fig. 10. Internal diffusion curves at a time less than 10 min

3.4. Lead retention equilibrium studies Figure 11 shows the curves of adsorbed amounts
To determine the adsorption characteristics of versus equilibrium concentrations for Pb2+
Mg3AlCO3 and NiAlCO3 (R = 2, 3, and 4), a series adsorption isotherms on Mg3AlCO3, Ni2AlCO3,
of experiments are carried out in which solutions Ni3AlCO3, and Ni4AlCO3 clays. The adsorption
containing known concentrations of Pb2+ are in capacities of these clays are proportional to the
contact with the adsorbent. This study was carried metal concentrations. According to Giles et
out under the same conditions as the contact effect al., the allure of the isotherms is of type L [30].
parameter, except for the concentrations of the Pb2+ Furthermore, the results showed that Mg3AlCO3
solutions. After 24 hours, the solution concentration clay has a higher adsorption capacity than NiAlCO3
is measured when equilibrium has been established. (R = 2, 3, and 4).

Fig. 11. Adsorption isotherms of Pb2+ on anionic clays studied.

 Study the elimination of lead by anionic clays Salah Bahah 81

3.4.1. Characterization of adsorbents before and different concentrations. This shift, accompanied
after lead adsorption and mechanism by the decrease of free OH band area after
The infrared (IR) spectra of the raw Mg3AlCO3 adsorption, is explained by the reduction of free
and Ni3AlCO3 samples before and after the OH in the hydroxyl layer, which reacts with Pb2+
retention of lead at different concentrations are ions according to Equation 8.
shown in Figure 12. The spectra are subdivided
into three regions: between (1000 cm-1 and 400 M-OH + Pb2+ → M-O- - -Pb2+ + H+ (Eq. 8)
cm-1), (3000 cm-1 and 1000 cm-1), and (4500 cm-1
and 3000 cm-1). It can be noted that the IR spectra As Equation 8, M is a divalent or trivalent
corresponding to the second region (1000 cm-1 to cation (Mg or Al). For the adsorbent based on
3000 cm-1) indicate two essential bands between Ni3AlCO3, several bands were observed in the
(1650 cm-1 and 1660 cm-1) and (1350 cm-1 and low-frequency region of the spectrum (<600
1400 cm-1) for both adsorbents before and after cm−1) that characterize the lattice vibration
Pb2+ adsorption. These two bands are assigned to modes [32]. The spectra indicate a slight shift
H2O and CO32-vibration modes, respectively. with increasing peak intensity (sharp peak) at
In the low-frequency region between 1000 cm-1 about 418.56 cm-1 for all Ni/Al-based HDLs
and 400 cm-1, the infrared spectra after lead after Pb2+ adsorption (Figure 12a). This band
adsorption show intense vibration bands and can be attributed to the formation of Al-O-Pb or
are shifted compared to those of Mg3AlCO3 Pb-Al-OH [32]. The infrared spectra also show
and Ni3AlCO3 before adsorption, as shown in the shift of the vibration band peaks from about
Figure 12(a, b, c). For Mg3AlCO3, the vibration 560.28 cm-1 and 594.99 cm-1 before adsorption
bands observed at 446.49 cm-1 and 554.49 cm-1 to 562.25 cm-1 and 592.15 cm-1, respectively, for
are attributed to the AlOH and MgOH bands, all Ni3AlCO3 clays after lead adsorption. The
respectively [31]. After adsorption of the lead at band’s shift around 562 cm-1 has been assigned
different concentrations, the intensity of these to hydroxyl groups associated with mainly Al
bands increases and shifts slightly to high- [34], and bounds around 592 cm-1 have been
frequency regions (447.49 cm-1 and 555.50 given as hydroxyl groups associated with Al/
cm-1, respectively), which is explained by the Ni. The shift of these two bonds is assigned
fixation of Pb2+ ions on the lamellar layers to to the formation of M-O-Pb according to the
form bands of Pb-Al-OH and Pb-Mg-OH or reaction proposed above (case of Mg3AlCO3)
M-O-Pb [32]. The band observed at 668.28 cm-1 (M = Ni2+ or Al3+) [32]. Before the adsorption
for the Mg/Al-based clay before adsorption is of Pb2+, the strong and broad absorption band
assigned to the carbonate vibration mode [33]. centred on 3483.20 cm−1 corresponds to the
After adsorption of Pb2+, the spectrum does not O–H stretching vibration of the layer surface
show a remarkable shift of this band. The same and interlayer water molecules, and the band
remark was observed at the carbonate vibration in 1652.88 cm−1 is due to the O–H bending
band located at about 1357.79 cm-1 (Figure 12b) vibration of water molecules. After adsorption
(second region). For the high-frequency region of the lead, we notice the reduction and slight
between (4500-3000 cm-1), the vibration band shift of the bands, which are centred towards a
of free hydroxyl groups located around 3446.55 low frequency at 3482.53 cm-1, indicating that
cm-1 before adsorption is shifted to 3442 cm-1 the hydroxyl groups electrostatically attracted
for Mg3AlCO3 solids after lead adsorption for Pb2+ anions.
82 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

80 80
Mg3AlCO3
70 a 31.25 ppm
56.25 ppm
70
Ni3AlCO3
18.75 ppm
43.75 ppm
56.25 ppm
156.25 ppm 93.75 ppm
60 200 ppm 60 156.25 ppm
226.95 ppm
50 50

40 40

30 30

20 20

10 10

0 0
1000 900 800 700 600
-1
500 400 1000 900 800 700 600 500 400
Wavenumber (cm )
Wavenumber (cm-1)
80 80

70
b 70

60 60

50 50

40 40

30 Mg3AlCO3 30 Ni3AlCO3
18.75 ppm
31.25 ppm 43.75 ppm
56.25 ppm 56.25 ppm
20 156.25 ppm 20 93.75 ppm
156.25 ppm
200 ppm
226.95 ppm
10 10

0 0

3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 300029002800270026002500240023002200210020001900180017001600150014001300120011001000
Wavenumber (cm-1) Wavenumber (cm-1)

80 80

70
c Mg3AlCO3 70
31.25 ppm
56.25 ppm
60 60
156.25 ppm
200 ppm
226.95 ppm 50
50

40 40

30 30 Ni3AlCO3
18.75 ppm
43.75 ppm
56.25 ppm
20 20 93.75 ppm
156.25 ppm

10 10

0 0

4400 4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 4500440043004200410040003900380037003600350034003300320031003000
Wavenumber (cm-1) Wavenumber (cm-1)

Fig. 12. FT-IR spectra of Mg3AlCO3 and Ni3AlCO3 before and after uptake of lead at different concentrations.
(a) region to 1000 cm-1 to 400 cm-1, (b) region to 3000 cm-1 at 1000 cm-1, and (c) region to 4500 cm-1 to 3000 cm-1

3.4.2.Model of adsorption isotherms

Modelling adsorption isotherm data is essential (Eq. 9)
for predicting and comparing adsorption
performance. Lead (Pb) adsorption was modelled
using Langmuir, Freundlich, and Temkin (Eq. 10)
models. The linear equations that correspond to
the three models are presented in Equations 9,
10, and 11 [28, 35]. (Eq. 11)
 Study the elimination of lead by anionic clays Salah Bahah 83

Where Ce, qe, and qm (mg g-1) are the equilibrium

concentration of lead (mg g-1), the quantity of Pb2+ (Eq. 12)
adsorbed at equilibrium (mg g-1), and the maximum
monolayer adsorption capacity of adsorbent (mg B is a constant related to the heat of adsorption, which
g-1), respectively. n and KF are the Freundlich equals B = RT/b. R, T, and b are the gas constant
adsorption constants. KL is the Langmuir adsorption (8.314 J.mol-1 K-1), the absolute temperature (K), and
constant (Lmg-1). This last parameter is used to the Temkin constant (J mol-1). Typical adsorption
calculate the dimensionless equilibrium parameter isotherms for Pb2+ on all selected anionic clays are
(RL) that explains the favorability of the adsorption shown in Figures 13, 14 and 15, respectively, for the
process; RL is calculated from Equation 12 [35]. Langmuir, Freundlich, and Temkin models.

Fig. 13. Langmuir isotherm model of the studied anionic clays

Fig. 14. Freundlich isotherm model of the studied anionic clays

84 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

Fig. 15. Temkin isotherm model of the studied anionic clays

According to Figures (12 and 14) and the regression The lead adsorption capacity values (Qm) found
coefficients found and shown in Table 4, the Pb2+ from the Langmuir model show that Mg3AlCO3 has
adsorption data on all the anionic clays followed a large adsorption capacity (73.42 mg g-1). For Ni/
the Langmuir and Temkin models. The values of Al-based clays, the Pb2+ ions adsorption capacity
the equilibrium parameter without dimension RL are increases with the increase of the molar ratio, and
between 0 and 1 for all the studied clays, showing Ni4AlCO3 has a Pb2+ adsorption capacity close to
that the adsorption of lead is favourable (Table 4). Mg3AlCO3.

Table 4. Parameters of Pb2+ adsorption isotherm models on selected anionic clays

Langmuir qmax (mg g-1) b (L mg-1) RL R2

Mg3AlCO3 73.42 0.33 0.04 0.73

Ni2AlCO3 35.71 0.44 0.05 0.98

Ni3AlCO3 43.47 0.44 0.05 0.95
Ni4 AlCO3 72.51 0.17 0.07 0.66
Freundlich Kf (n) R2

Mg3AlCO3 19.29 1.67 0.52

Ni2AlCO3 11.14 3.37 0.60

Ni3AlCO3 2.15 0.72

12.05
Ni4 AlCO3 12.08 1.62 0.95
Temkin K1(L mg ) -1
b BT (j mol )
-1
R2
Mg3AlCO3 1.00 155.14 16.13 0.66
Ni2AlCO3 16.96 527.95 4.74 0.85
Ni3AlCO3 6.35 309.33 8.09 0.89
Ni4 AlCO3 2.24 176.35 14.19 0.85
 Study the elimination of lead by anionic clays Salah Bahah 85

According to the correlation coefficients of the The thermodynamic parameters are presented in
Freundlich model, the total experimental data on Table 5. The positive values of enthalpy suggested
lead adsorption on anionic clays do not follow the the endothermic nature of the adsorption. They
Freundlich model (Table 4). The n value in the range reflected the affinity of the adsorbent for Pb2+
of 1.62–3.37 indicates a favourable adsorption ions [36]. The low H values for both adsorbents
process. The correlation coefficients for the Temkin are 17.39 KJ mol-1 for Mg3AlCO3 and 4.97 for
model of all the clays studied show that this last Ni3AlCO3, which are less than 40 KJ mol-1. It
model adequately represents the experimental data shows a physical adsorption between Pb2+ ions
on lead adsorption. The Temkin constant (BT) and these clays [37]. Positive entropy values
values presented in Table 4, related to the heat of showed that the randomness at the solute-solution
sorption of Pb2+, increase with the increase of the interface increases with the adsorption of Pb2+ in
molar ratio of Ni/Al. the adsorption process. Negative free energy values
indicate a spontaneous process of the adsorption of
3.5. Thermodynamic parameters Pb2+ by Mg3AlCO3 and Ni3AlCO3. These results
To describe the thermodynamic behaviour of the obtained for Mg3AlCO3 agree with those found by
absorption of Pb2+ ions in the aqueous solution, we Ayawei et al. [38].
use the following Equation13 and 14 [35, 36].
4. Conclusion
As part of the study of layered double hydroxides
(Eq.13) and the possibility of using them as adsorbents to
remove lead from water, we have synthesized in
our laboratory two types of anionic clays by the
ΔG= -RT ln KD (Eq.14) direct co-precipitation method, namely Mg3AlCO3
and Ni3AlCO3. The analysis techniques used to
where ΔH, ΔS, ΔG and T are the enthalpy, entropy, characterize the LDHs show that the synthesized
Gibbs free energy, and absolute temperature, clays are materials from the family of layered
respectively, and R is the gas constant (8.314 J k-1. double hydroxides. They have the same properties
mol-1), KD = (qe/Ce), which depends on temperature. as the anionic clays of the Mg3AlCO3 and Ni3AlCO3
The thermodynamic parameters are determined types. The pH, adsorbent mass, temperature, contact
starting from the lines of ln (kD) vs. (1/T) in the time, and molar ratio show that the adsorption
linear domain of temperature, corresponding to the capacity of Pb2+ by Mg3AlCO3 is higher than that
adsorption of lead, i.e., between 20°C and 50°C. of Ni3AlCO3. According to the Langmuir model,

Table 5. Thermodynamic parameters for the adsorption of Pb2+by Mg3AlCO3 and Ni3AlCO3 at various temperatures
Temperature
Adsorbent ΔS (KJ.K-1.mol-1) ΔH (KJ.mol-1)
298 K 303 K 313K 323 K
Kd
2.32 2.90 2.72 4.02
Mg3AlCO3
0.065 17.39 ΔG (KJ.mol ) -1

-2,08 -2.68 -3.42 -3.74

Kd
1.261 1.265 1.363 1.461
Ni3AlCO3 0.018 4.97
ΔG (KJ.mol-1)
-0.576 -0.594 -0.80 - 0.102
86 Anal. Methods Environ. Chem. J. 6 (3) (2023) 67-88

Ni4AlCO3 and Mg3AlCO3 clays have a high lead Sorption study of an acid dye from an
adsorption capacity, and the maximum adsorption aqueous solution on modified Mg–Al layered
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increasing temperature for both types of LDHs, Preparation and evaluation of hydrotalcite-iron
where the lead removal percentages reach 94.16 oxide magnetic organocomposite intercalated
% and 85.39 % for Mg3AlCO3 and Ni3AlCO3, with surfactants for cationic methylene blue
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The results showed that at pH below 6.5, the [4] R. Shi, P. Yangn, Y. Yin, X. Dong, J. Li.
removal of Pb2+ may be achieved by complexation Fabrication of porous microspheres and network
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The experimental data on lead adsorption kinetics on Al substrate via facile hydrothermal method,
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5. Acknowledgements reactions of layered double hydroxides:
The authors would like to thank the MESRS and interplay between coulombic and H-bonding
DGRSDT (Ministère de l’Enseignement Supérieur interactions, Ind. Eng. Chem. Res., 48 (2009)
et de la Recherche Scientifique et la Direction 6315-6320. http://doi.org/10.1021/ie9004332
Générale de la Recherche Scientifique et du [7] A. V. Radha, P. V. Kamath, C. Shivakumara,
Développement Technologique- Algérie) for their Mechanism of the anion exchange reactions
Financial support. of the layered double hydroxides (LDHs)
of Ca and Mg with Al, Solid State Sci., 7
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