Polymer Bulletin

https://doi.org/10.1007/s00289-023-04792-8

ORIGINAL PAPER

Effective removal of Pb(II) and Cu(II) from aqueous

solutions using a hybrid composite of fuller’s earth,
aluminum silicate and chitosan

Heba Kandil1   · Shaimaa T. El‑Wakeel2

Received: 20 January 2023 / Revised: 28 March 2023 / Accepted: 29 March 2023

© The Author(s) 2023

Abstract
In this study, a highly effective hybrid adsorbent composite based on low-cost
fuller’s earth (FE), aluminum silicate (AS) and chitosan (CS) was prepared using
a facile method. The prepared composite was applied to adsorb lead ­(Pb2+) and cop-
per ­(Cu2+) ions from aqueous solutions. Several analyses such as Fourier transform
infrared spectroscopy (FTIR), Scanning electron microscopy (SEM) and X-ray dif-
fraction (XRD) were used to characterize the composite. The adsorption efficiency
of the prepared composite was investigated at different operating conditions. Moreo-
ver, the adsorption isotherm/kinetic models and adsorption thermodynamics of the
composite were examined. The results showed that the pseudo-second-order kinetic
model described well with the obtained data and the adsorption equilibrium can be
better described by Langmuir isotherm model with maximum adsorption capacities
of 305.5 and 284.2 mg/g for ­Pb2+ and ­Cu2+, respectively. The obtained data dem-
onstrated that the prepared composite is an efficient and kinetically fast metal ion
removal with high adsorption capacity and recovery efficiency.
Graphical abstract

Keywords  Hybrid composite · Adsorption · Metal ions · Kinetic models · Isotherm

models

Extended author information available on the last page of the article

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Introduction

The deterioration of water quality that causes water pollution occurs mainly
due to the recent rapid development of industrialization and urbanization [1–5].
Heavy metals are one of the toxic pollutants that primarily discharged to water
resources from fertilizers, mining, tanneries and battery industries [3, 6]. These
toxic metals are known to cause chronic poisoning and cancer risk due to their
bioaccumulation in organisms [7–10].
Lead is one of the human toxic metals that can enter the body through inhala-
tion and ingestion [11]. Lead accumulation in the bones, brain and kidney causes
anemia, damages the nervous system and even death with long-term of exposure
[12]. High concentrations of even necessary metals such as copper can also pose
a threat to the environment [13]; its high accumulation causes headache, vomiting
and respiratory problems, and excessive accumulation causes chronic liver injury
[14]. There are several methods used for heavy metal removal such as chemical
precipitation [15, 16], ion exchange [17], membrane separation [18], advanced
oxidation processes [19, 20] and adsorption [21]. Among these methods, adsorp-
tion is considered the most favorable technique used to remove heavy metals over
the other techniques because of its easy operation, simple design, low cost, high
adsorption capacity and accessibility of various types of adsorbed materials [3, 7,
22]. Additionally, the adsorbent materials can be regenerated and reused, while
the other methods have inherent limitations such as high energy consumption,
high cost, sensitive operating conditions and the production of a large amount of
sludge [23–25].
Many adsorbents have been used for heavy metal removal such as activated
carbon [26], silica gel [27] and magnetite nanocomposites [28]. Due to the high
cost of most of these materials, the need to study and develop low-cost adsorbent
materials has increased [29]. Hence, special attention has recently been diverted
toward the use of natural materials, agricultural waste and industrial waste as
promising alternative adsorbents for the removal of metal ions, either in their nat-
ural form or after subjecting them to some modification [30–38].
Particular interest here was given to fuller’s earth for its advantages over many
other available adsorbent materials which included its low cost, non-toxic nature,
high specific surface area and excellent adsorption properties [39, 40]. Fuller’s
earth is a naturally occurring sedimentary clay that consists of silicate, bentonite
and a small proportion of magnesium as well as sodium [41]. However, being soft
and easily crunching reduces its ability to be used as adsorbent [42]. Hence, it has
been combined with other polymeric materials to produce composite materials
that can be easily handled and separated within the adsorption process such as
the beads prepared by Hasan et  al. [42, 43] from combining fuller’s earth with
chitosan for use in removing cesium and strontium from waste stream and aque-
ous solutions, respectively. Kulkarni et  al. [41] also prepared beads from com-
bining fuller’s earth with alginate to be used as an adsorbent for the removal of
methylene blue (MB) dye from aqueous solutions. Hydrogel from fuller’s earth
(FE) was also prepared by Sharma et al. via incorporating FE into polyacrylamide

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(PAAm)/cellulose (CG) hydrogel. The produced hydrogel was used for adsorption
of MB dye [44]. In this study, fuller’s earth was combined with chitosan and alu-
minum silicate to produce a promising hybrid composite for use in heavy metal
ion removal. The hybrid composite was prepared using a facile method, charac-
terized and applied for the removal of Pb(II) and Cu(II) ions from aqueous water.
The kinetic/isotherm models of the composite were investigated to understand its
adsorption mechanism. Additionally, its adsorbent reusability was investigated to
determine its stability and potential recovery.

Materials and methods

Materials

Chitosan (CS; degree of deacetylation is greater than > 75% with average molecular

weight of 150 kDa) and acetic acid were provided from Sigma-Aldrich. Aluminum
silicate Qp (­Al2O3 · ­2SiO2 · ­2H2O) (AS) was supplied by Panreac Química SA.
Fuller’s earth LR (FE) was provided by Sd Fine Chem Limited Company. Sodium
hydroxide (NaOH; 99%) was obtained from laboratory chemicals (modern lab).
Lead nitrate and copper chloride of analytical grade were used for the preparation of
stock solution containing 1000 mg/l of Pb(II) and Cu(II) and by its dilution different
working solutions were prepared.

Preparation of hybrid fuller’s earth/aluminum silicate/chitosan composite (FE/AS/

CS)

To prepare the hybrid composite, fuller’s earth (FE) was first mixed with AS where
1 g of aluminum silicate (AS) was added into 2 g of FE dispersed in 10 ml of dis-
tilled water. Then, the mixture solution was allowed to stir for 1 h till a complete dis-
persion of AS within FE solution. After that, the mixture solution was slowly added
to a solution of 1 g of CS dissolved in 50 ml of 1% acetic acid solution. The obtained
mixture was continuously stirred for 2  h till it became a homogeneous solution.
After that, 100 ml of 2 M NaOH was slowly added to the solution as a white precipi-
tate began to form. The resulting precipitate was left in NaOH solution overnight,
then collected and washed with distilled water until the pH was neutral. Finally, the
obtained precipitate (FE/AS/CS composite) was dried under vacuum at 60  °C for
24 h. Scheme 1 shows the synthesis procedure of the hybrid FE/AS/CS composite.
For comparison, a control adsorbent from CS was prepared using the same process
for preparing the FE/AS/CS composite except for the step of adding AS and FE.

Characterization

The functional groups of the prepared adsorbents were characterized using Fou-
rier transform infrared (FTIR) spectrophotometer (Shimadzu 8400, Japan) with
KBr disks. The morphologies of the prepared adsorbents were investigated using

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Scheme 1  Procedure for the synthesis of FE/AS/CS composite

scanning electronic microscopy (SEM, Quanta FEG-250). The phase composition

of the prepared adsorbents was studied using an X-ray diffractometer (XRD, Bruker
AXS D8 advance instrument) of 2θ between 5 and 80°.
The point of zero charge ­pHZPC was determined using pH drift method for the
prepared composite as follows: 0.15 g of adsorbent was added to solutions of 50 mL
of 0.01 mol/l sodium chloride (NaCl), with different pH values (between 2 and 12)
by adjusting with 0.1 mol/l hydrochloric acid (HCl) and 0.1 mol/l NaOH. Then, the
mixtures were shaken for 48 h at room temperature [33, 34, 45–47]. The final solu-
tion pH values were measured, and the obtained data were curved versus the initial
pH to obtain the point of intersection which expresses the ­pHPZC value.

Batch adsorption experiments

The metal adsorption was conducted in batch mode at room temperature in a 50-mL
conical flask containing the tested Pb(II) and Cu(II) ions. Based on the effects of
different process variables on Pb(II) and Cu(II) adsorption, the following parameters
were evaluated:

1. Contact time at different time intervals (5–150 min) using initial Pb(II) and Cu(II)
concentrations of 10 mg/l with 0.5 g/l of adsorbent dose.
2. Initial Pb(II) and Cu(II) concentrations at 5, 10 and 50 mg/l using and different
contact time intervals (5–150 min) with 0.5 g/l of adsorbent dose.
3. Initial pH values at the range of 2.0–6 for Pb(II) ions and 2.0–5 for Cu(II) ions
using metal concentrations of 10 mg/l at the optimum contact time.
4. Adsorbent doses which tested at the range of 0.05–2 g/l at the optimum contact
time and pH.

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5. Temperature range (313–353 K) was used to test metal ion removal at initial
concentration of 10 mg/l and the optimum contact time and pH.

Samples were filtered with a filter membrane of a pore size of 0.45  μm. Sam-
ples were analyzed for Pb(II) and Cd(II) concentrations using inductively coupled
plasma optical emission spectrometry (ICP-OES) (Agilent 5100).
The adsorption capacity (qe) of the metal on the adsorbent was estimated via
equation
Ci − Ce
qe = ×V (1)
m
where qe is the adsorption capacity in (mg/g), Ci and Ce (mg/l) are the initial and
final metal ion concentrations, respectively, V(l) is the volume of the solution taken
and m(g) is the mass of the adsorbent.

Adsorption kinetic and isotherm study

To understand the adsorption mechanism, adsorption kinetic was studied using dif-
ferent kinetic models [37, 48–53]. Pseudo-first-order (Eq. 2), pseudo-second-order
(Eq. 3), Elovich (Eq. 4) and intra-particle diffusion models (Eq. 5) have been tested
for the present adsorption systems. The equations are presented as follows:
( )
qt = qe − 1 − e(−K1 t) (2)

K2 q2e t
qt = (3)
1 + k2 qe t

1
qt = ln (1 + 𝛼𝛽t) (4)
𝛽

qt = kp t1∕2 + C (5)

where qt is the amount of adsorbed metal at equilibrium (mg/g) at time t, k1 ­(min−1)

and k2 (g/mg min) are the adsorption rate constants, C is the intercept and kp is the
­ in1/2). Values of β (g/mg) and α (mg/g
intra-particle diffusion rate constant (mg/g m
min) represent constants related to the surface coverage degree and chemisorption
rate, respectively.
Three replicate experiments were performed; then, the mean and standard devia-
tion of metal adsorption were calculated and fitted using Origin Pro 2016 version
9.3.226 software. In the applied Origin software, different statistical parameters such
as relation coefficient (R2), sum of squared estimate of errors (SSE) and Chi-square
(χ2) values were calculated and compared with the fitted models to find the best
model applying data precision.

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The basic adsorption isotherm models, Langmuir (Eq.  6), Freundlich (Eq.  7),
Dubinin–Radushkevich (D–R) (Eq.  8) and Redlich–Peterson (Eq.  9), have been
investigated to understand the adsorption behavior for metal ion removal at constant
temperature.

qe = KF Ce1∕n (6)

Ce
qe = qm KL (7)
1 + KL Ce

qe = qs e(−KDR 𝜀 ) (8)
2

KR Ce
qe = g (9)
1 + aR Ce

KL (l/mg) is the Langmuir equilibrium constant related to the affinity of adsorp-

tion sites and qm (mg/g) represents the maximum theoretical monolayer adsorption
capacity.
Ce (mg/l) is the equilibrium concentration. kF and n are the Freundlich adsorption
constants which are related to the bonding energy and determine the deviation from
the adsorption linearity. KL (l/mg) is the Langmuir equilibrium constant related to
the affinity of adsorption sites, and qm (mg/g) represents the maximum concentra-
tion of adsorbed layer corresponding to monolayer. KDR is a constant related to mean
free energy ­(mol2/kJ2), qs (mg/g) is related to the adsorption capacity and ε repre-
sents the Polanyi potential, which can be calculated from equation:
( )
1
𝜀 = RT ln 1 + (10)
Ce

In Redlich–Peterson model, kR (l/mg) is a constant related to the adsorption

capacity, ­aR (l/mg) is a constant related to the affinity of the binding sites and g
exponent is related to the adsorption intensity which lies between 0 and 1.

Thermodynamics studies

The effect of temperature on the adsorption was studied at three different tempera-
tures (303, 313 and 333 K). By this study, the change in Gibbs free energy (ΔG°),
entropy (ΔS°) and enthalpy (ΔH°) could be determined according to the following
equations:
ΔG◦ = −RT ln Kd (11)

ΔG◦ = ΔH ◦ − TΔS◦ (12)

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Desorption and regeneration study

To study the metal desorption and the prepared composite reusability for metal ion
adsorption, a number of adsorption–desorption cycles were performed. For metal
desorption experiments, the metal ion-loaded composite samples were collected
after adsorption experiment and then shaken with 0.1 M of H­ NO3 which is used as
an eluent to remove metal ions. The regenerated composite was rinsed with deion-
ized water (DI) and then reused after drying for another cycle of adsorption. The
concentrations of metal ions were measured at each step of process. To evaluate the
reusability of the adsorbents, the regenerated composite was used for three succes-
sive adsorption/desorption recycles.

Result and discussion

Characterization of FE/AS/CS composite

Different analyses were used to characterize the FE/AS/CS composite such as FTIR,
SEM and XRD. The FTIR spectra of FE/AS/CS composite and CS (control) adsorbents
are shown in Fig. 1. By comparing the FTIR spectrum of CS with that of FE/AS/CS
composite, it was observed that the characteristic vibration bands for CS were observed
in both spectra besides the emergence of new bands in the spectrum of FE/AS/CS com-
posite. The main characteristic bands of CS that were observed in both spectra were
at 3393  ­cm−1  (for N–H and O–H stretching), 1573  ­cm−1  (due to N–H bending) and
1009 ­cm−1 (for C–O stretching) [54], while the new bands that were observed in the
spectrum of FE/AS/CS composite were at 3688 ­cm−1 (for O–H stretching of Al–OH
of FE and AS), 3619 ­cm−1 (for O–H stretching of structural hydroxyl groups of FE and
AS), 910 ­cm−1 (due to Al–OH stretching of AS and FE), 848 ­cm−1 (for –OH bending
of Al–Mg–OH of FE), 795 ­cm−1 (for Al–O stretching of FE and AS and Mg–O stretch-
ing of FE), and 529 and 461 ­cm−1 (for Si–O–Si and Si–O–Al bending of AS and FE)

Fig. 1  FTIR of a CS, b FE/AS/

CS composite and c, d FE/AS/
CS composite after Cu(II) and
Pb(II) adsorption, respectively

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Fig. 2  SEM images of CS and FE/AS/CS composite adsorbents

Intensity

(b)

(a)

0 10 20 30 40 50 60 70 80
2θ

Fig. 3  XRD patterns of a CS and b FE/AS/CS composite

[55]. Since the characteristic vibration bands for CS, AS and FE were observed in the
spectrum of FE/AS/CS composite, this indicates that the AS and FE were successfully
combined with CS matrix.
Figure  2 shows SEM images of CS and FE/AS/CS composite adsorbents. It was
found from the SEM image of FE/AS/CS composite that the surface morphology of
the composite showed a rougher surface with irregular pores compared with the SEM
image of the CS adsorbent. As a result of this roughness, this composite is expected to
have a high adsorption capacity. This is attributed to the fact that the roughness pro-
vides more active sites for contaminant adsorption [56, 57].
In XRD pattern, peaks of chitosan (CS) are observed at 2θ = 20.4 and 29.6◦ confirm-
ing the structure of CS (Fig. 3). In the prepared FE/AS/CS, the presence of FE, AS and
CS was verified via peaks in the range 2θ = 15–40°. Peaks at 26.6° indicate the pres-
ence of FE and aluminum silicate, while CS peaks seem to be little shifted to 24.8°,
suggesting that FE was well mixed with AS and CS.

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Batch adsorption experiments for metal ions

The equilibrium time for maximum adsorption of Pb(II) and Cu(II) ions, on both CS
and FE/AS/CS composite adsorbents, was investigated at different time intervals as
shown in Fig. 4.
By using FE/AS/CS composite, the adsorption of both ions increased with time
and was considered very rapid where the equilibrium was reached within 30 and
45  min with 98.5 and 97% removal for Pb(II) and Cu(II), respectively. Compared
with the prepared FE/AS/CS composite, the prepared CS showed lower adsorption
results for both metal ions showing removal (%) of 74 and 72% for Pb(II) and Cu(II)
ions, respectively, after an hour of experiments. This result demonstrates the signifi-
cant influence of ­fuller’s earth and silicate. The increase in metal adsorption at the
beginning of the adsorption is due to the presence of a large number of active sites
which increase the adsorption of metal ions. The adsorption rate slowly increased
until equilibrium was reached. After that, adsorption decreased. This decrease may
be associated with a decrease in active sites.
The efficiency of adsorption was tested at different initial metal ion concentra-
tions using 0.5 g/l of adsorbents at room temperature (Fig. 5). Metal ion adsorption
decreased with the increase in initial concentration of metal ions for both adsorbents
but no great difference in the removal was observed in the adsorption of metal ions
of 5 and 10  mg/l. The possible reason could be that the driving force may over-
come the resistance of adsorbate mass transfer from the bulk to the surface of the
adsorbent [58]. The prepared composite still has a large adsorption ability for both
tested metal ions using 50 mg/l of metal ions and the removal attained 92 and 90%
for Pb(II) and Cu(II) ions, respectively, which reveals the efficiency of the prepared
composite for metal ion adsorption at range of 5–50 mg/l.
Since the initial pH is one of the main factors affecting the adsorption process
of heavy metals as it affects the solubility of metal ions, different values of pH are
used to test metal ion removal. Using the prepared composite, it can be noticed that

Fig. 4  Removal of Pb(II) and Cu(II) ions at different time intervals (dose 0.5  g/L; metal concentration
10 mg/l; agitation speed 200 rpm) by CS and FE/AS/CS composite

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Fig. 5  Removal of P­ b2+ and ­Cu2+ ions by: a, c FE/AS/CS composite and b, d CS, respectively, at differ-
ent initial metal concentrations (amount of adsorbent 0.5 g/L; agitation speed 200 rpm)

with increasing pH, the removal of metal ions gradually increased and the maximum
removal occurred at pH 5.5 and 5 for Pb(II) and Cu(II) ions, respectively (Fig. 6).
Beyond pH values of 5.5 and 5 for Pb(II) and Cu(II), metal removal is a combination

Fig. 6  Removal of P ­ b2+ and

2+
­Cu ions by FE/AS/CS com-
posite at different pH values
(amount of adsorbent 0.5 g/L;
initial metal concentration
10 mg/l)

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of both adsorption and precipitation on the surface due to the formation of metal
hydroxides. At low pH levels, the removal of metal ions by the composite was found
to be low. This was due to the competition of hydrogen ions with the metal cations
which reduced the adsorption [59].
The ­pHPZC of the prepared composite was determined and found to be 4.2
(Fig.  7). It was shown that with increasing pH values above p­ HPZC, the metal ion
adsorption by the composite increased. This increase is because at pH > ­pHPZC the
adsorbent surface becomes negative resulting in the formation of electrostatic attrac-
tions with positively charged metal ions. Whereas, at pH < ­pHPZC, a decrease in the
adsorption of metal ions by the composite occurred. This decrease is due to the pres-
ence of repulsion forces between the positively charged surface of the composite as
a result of the richness of the solution with H + and the positively charged metal spe-
cies [49]. So it is concluded that the adsorption of both metal ions is a combination
of ion exchange. Similar findings were previously recorded for metal adsorption by
different adsorbents [45, 49].
The adsorption efficiency of FE/AS/CS for metal ions was studied at different
adsorbent doses of 0.05, 0.1, 0.5, 0.8, 1, 1.5 and 2 g/l at room temperature and initial
metal concentration of 10 mg/l.
The adsorption capacity increased with the adsorbent dose for both ions up to
0.5 g/l where the maximum adsorption capacity was attained using both adsorbents,
while there was a decrease in the adsorption capacity for both adsorbents, starting
from the use of 1 g/L, which may have occurred due to the agglomeration of adsor-
bent particles and the occurrence of saturation of the active sites.

Adsorption kinetics and isotherm

To determine the rate determining mechanism of metal adsorption by the prepared

composite, the adsorption kinetics were studied using the nonlinear fits of kinetic
models as shown in equations [2–5]. The kinetic parameters were determined from
models and the obtained data are summarized in Table 1.
By assuming the equilibrium conditions, the pseudo-first order (PFO) was applied
in the nonlinear fits. It can be noticed that the reaction for both metal ions cannot be

Fig. 7  pHPZC of the prepared

FE/AS/CS composite

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Table 1  Kinetic and isotherm parameters obtained for metal ion adsorption

Metal Pseudo-first order
qe,exp.(mg/g) qe,Cal (mg/g) K1 R2 χ2 RMSE

Pb(II) 19.7 1.1 0.05 0.90 2.55 1.8

Cu(II) 19.4 1.3 0.09 0.90 3.2 2.1
Metal Pseudo-second order
qe,Cal (mg/g) K2 (g/mg min) R2 χ2 RMSE

Pb(II) 20 0.125 0.99 0.01 1

Cu(II) 19.6 0.09 0.99 0.09 1.3
Metal Elovich
β (g/mg) α (mg/g min) R2 χ2 RMSE

Pb(II) 1.8 8.8 × ­1014 0.80 5.52 2.5

Cu(II) 1.4 4.4 × ­1010 0.82 8.03 2.9
Metal Langmuir isotherm parameters
qm (mg/g) KL (L/mg) R2 χ2 RMSE

Pb(II) 305.5 0.1 0.98 140.7 11.9

Cu(II) 284.2 0.09 0.98 114.7 10.7
Metal Freundlich isotherm parameters
1/n KF (L/mg) R2 χ2 RMSE

Pb(II) 0.27 75.9 0.97 265.5 16.3

Cu(II) 0.25 71.7 0.96 317.4 17.8
Metal D–R isotherm parameters
qK-D (mg/g) E (kJ/mol) R2 χ2 RMSE

Pb(II) 264.4 13.38 0.94 1688.2 41

Cu(II) 248.5 12.4 0.90 1093.03 33
Metal Redlich–Peterson parameters
KR (L/mg) aR (L/mg) g (g) R2 χ2 RMSE

Pb(II) 46.5 0.27 0.88 0.96 180.1 13

Cu(II) 34.2 0.18 0.91 0.96 199.6 14

described well with this model because of the small values of correlation coefficient
[R2(< 0.96)], besides that the values qe calculated using the model were not matched
to that determined experimentally.
On the other hand, the experimental data showed good fitting for the pseudo-sec-
ond-order model (PSO) where the values of R2 were larger (R2 > 0.96) and the calcu-
lated qe values using this model equation were matched to the experimental results
for lead and copper ions. The PSO model assumed the variation of sites available

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on the adsorbent surface with the adsorption rate, and by following the model, the
chemical nature of the adsorption process was confirmed.
Elovich model is used to describe the chemisorption of gas onto the adsorbent,
and this model assumes that the active adsorption sites of the adsorbent are hetero-
geneous [60]. Based on the obtained data (Table 1), it was found that R2 values of
Elovich model were lower than 0.96 and those of the pseudo-second-order equations
for both metal ions. It is suggested that active adsorption sites of the adsorbent are
homogeneous.
The adsorption model parameters and rate constants calculated from the plots are
shown in Table 1. For more analysis of the rate determining step of the adsorption,
the intra-particle diffusion model was applied to explain the transfer of metal ions
from the solution to the adsorbent surface. In the adsorption process, metal ions in
the boundary layer of adsorbent transfer to the surface of adsorbent (film diffusion).
On the other hand, metal ions in the solute may transfer to the adsorbent sites (inter-
nal diffusion) or interact with the active sites on the adsorbent forming adsorption,
precipitation or complexation. The model plot (Fig.  8) represents two adsorption
stages: The first stage reveals the diffusion of metal ions to the adsorbent surface
(film diffusion), while the second slow stage is attributed to the adsorption of ions
into the adsorbent pores (internal diffusion process).
As shown in Fig. 8, the plot did not pass the origin and the obtained values of two
intercepts C were not equal to zero which reveals that the intra-particle diffusion is
not the only rate-controlling step but also the film diffusion that contributes to the
sorption process.
The adsorption isotherm gives more information about the efficiency of the pre-
pared adsorbent for the adsorption.
The adsorption of metal ions on the prepared composite was tested at differ-
ent initial concentrations (25–250), and the obtained experimental data were fitted
by the different nonlinear isotherm models. The plots are shown in Fig. 9, and the
obtained parameters of the fitting are shown in Table 1.

Fig. 8  Intra-particle diffusion
model for the adsorption of
Pb(II) and Cu(II) by FE/AS/CS
composite

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Fig. 9  Adsorption isotherm models of Pb(II) and Cu(II) adsorption by FE/AS/CS composite

Fig. 10  Schematic diagram of the adsorption of Pb(II) and Cu(II) ions on the hybrid FE/AS/CS compos-
ite

The Freundlich model suggests the multilayer adsorption, while Langmuir

model suggests that all sites are identical.
The plot in Fig. 9 shows good fit (R2 = 0.98 and lowest Chi-square and RMSE
values) with applying Langmuir adsorption isotherm model for the experimental
data of both metal ions revealing the monolayer behavior of adsorption. In the
model, the maximum adsorption capacities (qm) were 312 and 294 mg/g for P ­ b2+
2+
and ­Cu , respectively.

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The application of D–R isotherm on the experimental data showed less values
of correlation coefficient (R2) for both metal ions for the model that is based on the
assumption of the filling adsorbent pores with solute.
The obtained E values were calculated as 13.3 and 12.2  kJ/mol for ­Pb2+ and
­Cu2+, respectively. Values of E in the range of 8–16 kJ/mol reveal that the process is
controlled by a chemical mechanism and occurs by ionic exchange or surface com-
plexation [61]. The Redlich–Peterson isotherm model showed lower R2 values than
the other models, and it is a combination of the Langmuir and Freundlich isotherm
models, applies inhomogeneous or heterogeneous surfaces and depends linearly on
the concentration. Values of g in this model are 0 = g ≤ 1; when its value equals to
1, the model equation reduces to the Langmuir model, and while values equal to 0,
it will reduce to Freundlich isotherm. As calculated from the study for g values, the
model may reduce to the Langmuir model which estimated before to be the well-
fitted model with the highest R2 values.

Mechanism of adsorption Pb(II) and Cu(II) ions on the hybrid FE/AS/CS composite

The adsorption mechanism of the adsorption of metal ions with the prepared com-
posite may be explained after the application of isotherm and kinetic models by that
the surface can form surface complexes with divalent metal ions with the release of
­H+ ions and the formation of ­AlO− and ­SiO− on the adsorbent surface.
The FTIR data obtained for the prepared composite confirmed the existence of
many functional groups. After Pb(II) and Cu(II) adsorption, the FTIR spectra of FE/
AS/CS (Fig.  1c, d) confirmed the interaction between heavy metal ions and com-
posite, where a chemical shift was observed in the absorption peaks of certain func-
tional groups as well as a clear reduction in their intensities as clearly seen in bands
at 3688, 3619, 3452, 910, 848, 529 and 461 ­cm−1. Figure 10 illustrates the proposed
mechanism of adsorption Pb(II) and Cu(II) ions by the composite.

Comparison with other chitosan adsorbents

Numerous reports on the adsorption of P ­ b2+ and ­Cu2+ have been made by various
materials based on chitosan. Hence, Table 2 presents a comparison of the qm of FE/
­ b2+
AS/CS with those of different adsorbents based on chitosan for the removal of P
2+
and ­Cu . The qm of FE/AS/CS was found to be higher than those listed in Table 2.
Therefore, it can be concluded that the FE/AS/CS is a promising adsorbent for the
removal of ­Pb2+ and ­Cu2+ from aqueous solutions.

Thermodynamic studies

Thermodynamic parameters ΔG°, ΔS° and ΔH° for the analysis of the adsorption
were determined from equations at 303, 313 and 333 K for both ions and the param-
eters value are listed in Table 3.
The estimated negative values of ΔG° revealed that the adsorption for Pb(II)
and Cu(II) ions onto the prepared composite was spontaneous. The positive

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 Polymer Bulletin

Table 2  Comparison with different chitosan-based adsorbents for the removal of ­Pb2+ and ­Cu2+
Adsorbent Metal ions qm (mg/g) References

Chitosan/montmorillonite composite aerogel Cu2+ 86.95 [62]

Chitosan-coated PVC beads Cu2+ 87.9 [63]
Chitosan-coated gasifier biochar (CGBC) Cu2+ 112 [64]
Acrylic acid–chitosan blend hydrogel Cu2+ 171 [65]
Polyethylenimine (PEI)-modified polystyrene/Fe3O4/chitosan mag- Cu2+ 204 [66]
netic composite (PS/Fe3O4/CS-PEI)
Carboxymethyl chitosan–kaolinite composite hydrogel Cu2+ 206 [67]
Potato starch-graft-polyamidoxime embedded in chitosan beads Cu2+ 238 [68]
FE/AS/CS composite Cu2+ 284.2 This study
Magnetic chitosan/graphene oxide composites Pb2+ 82.1 [69]
Magnetic chitosan/anaerobic granular sludge composite Pb2+ 97.97 [70]
Branched polyethylenimine-enhanced magnetic carboxymethyl Pb2+ 114.7 [71]
chitosan
Chitosan cross-linked with epichlorohydrin triphosphate Pb2+ 166.94 [72]
Acrylic acid–chitosan blend hydrogel Pb2+ 192 [65]
PEO/chitosan nanofiber membrane Pb2+ 237.2 [73]
FE/AS/CS composite Pb2+ 305.5 This study

Table 3  Thermodynamic Metal ions ΔG° (kJ/mol) ΔH° (kJ/mol) ΔS° (J/mol·K)

parameters for the adsorption of
Pb(II) and Cu(II) ions onto the 303 K 313 K 333 K
prepared composite
Pb(II)  − 13.3  − 15.5  − 21 64.8 285.5
Cu(II)  − 10.9  − 11.9  − 14.3 23.6 113.9

value of ΔH° reveals that the adsorption was endothermic. The positive value
of ΔS° reveals the randomness and disorganization between the solid and liq-
uid surface and that the composite surface is preferential for Pb(II) and Cu(II)
adsorption.

Reusability and regeneration

Adsorbents regeneration is important from the environmental and practical

points of view and used to evaluate the efficiency of an adsorbent.For desorbing
Pb(II) and Cu(II) ions, the H­ NO3 solution (0.1 mol/L) was used and the results
showed that the ions of Pb(II) and Cu(II) were recovered by 97 and 95.6%,
respectively, after the third cycle revealing the good desorption ability for the
tested metal ions. There was no obvious decline in the adsorption ability for

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Polymer Bulletin

Pb(II) and Cu(II) on the prepared composite after the third successive adsorp-
tion/desorption cycles.

Conclusion

A hybrid composite of FE, AS and CS was successfully prepared using a facile

method and was applied as adsorbent for heavy metal ions; P ­ b2+ and C­ u2+. Batch
adsorption studies showed that the prepared composite had excellent efficiency in
removing of ­Pb2+ and ­Cu2+ from aqueous solutions with maximum removals reach-
ing 98.5 and 97 % for ­Pb2+ and ­Cu2+, respectively. The adsorption process for both
metal ions was fitted well with the Langmuir isotherm model, indicating that the
chemical adsorption process was favorable and the rate determining step is not only
controlled by intra-particle diffusion by applying intra-particle diffusion model. The
reusability of the prepared composite indicated that it can keep its efficiency for the
adsorption after the third cycle of adsorption/desorption. It can be concluded that
the prepared composite can be used as an effective, eco-friendly, and low-cost adsor-
bent for lead and copper ions removal.

Author contributions The authors had equally contributed to conceptualization, methodology, formal

analysis, software, writing the original draft, and reviewing and editing.

Funding  Open access funding provided by The Science, Technology & Innovation Funding Authority
(STDF) in cooperation with The Egyptian Knowledge Bank (EKB).

Declarations 
Conflict of interest  The authors declare no competing interests.

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which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as
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ses/​by/4.​0/.

References
1. Kandil H, Abdelhamid AE, Moghazy RM, Amin A (2022) Functionalized PVA film with good
adsorption capacity for anionic dye. Polym Eng Sci 62:145–159
2. Fan Y, Fang C (2020) A comprehensive insight into water pollution and driving forces in Western
China—case study of Qinghai. J Clean Prod 274:123950
3. Afroze S, Sen TK (2018) A review on heavy metal ions and dye adsorption from water by agricul-
tural solid waste adsorbents. Water Air Soil Pollut 229:1–50

13
 Polymer Bulletin

4. Teng Y, Yang J, Zuo R, Wang J (2011) Impact of urbanization and industrialization upon surface
water quality: a pilot study of Panzhihua mining town. J Earth Sci 22(5):658–668
5. Mehdizadeh P, Jamdar M, Mahdi MA, Abdulsahib WK, Jasim LS, Yousefi SR, Salavati-Niasari M
(2023) Rapid microwave fabrication of new nanocomposites based on Tb-Co-O nanostructures and
their application as photocatalysts under UV/Visible light for removal of organic pollutants in water.
Arab J Chem 16:104579
6. Ali H, Khan E, Ilahi I (2019) Environmental chemistry and ecotoxicology of hazardous heavy met-
als: environmental persistence, toxicity, and bioaccumulation. J Chem 2019:1–14
7. Wang J, Huyan Y, Yang Z, Zhang H, Zhang A, Kou X, Zhang Q, Zhang B (2019) Preparation of
surface protein imprinted thermosensitive polymer monolithic column and its specific adsorption for
BSA. Talanta 200:526–536
8. Wen J, Fang Y, Zeng G (2018) Progress and prospect of adsorptive removal of heavy metal ions
from aqueous solution using metal–organic frameworks: a review of studies from the last decade.
Chemosphere 201:627–643
9. Yousefi SR, Alshamsi HA, Amiri O, Salavati-Niasari M (2021) Synthesis, characterization and
application of Co/Co3O4 nanocomposites as an effective photocatalyst for discoloration of organic
dye contaminants in wastewater and antibacterial properties. J Mol Liq 337:116405
10. Yousefi SR, Sobhani A, Alshamsi HA, Salavati-Niasari M (2021) Green sonochemical synthesis of
­BaDy2 ­NiO5/Dy2 ­O3 and ­BaDy2NiO5/NiO nanocomposites in the presence of core almond as a cap-
ping agent and their application as photocatalysts for the removal of organic dyes in water. RSC Adv
11(19):11500–11512
11. Jaishankar M, Tseten T, Anbalagan N, Mathew BB, Beeregowda KN (2014) Toxicity, mechanism
and health effects of some heavy metals. Interdiscip Toxicol 7:60
12. Kul AR, Koyuncu H (2010) Adsorption of Pb(II) ions from aqueous solution by native and activated
bentonite: Kinetic, equilibrium and thermodynamic study. J Hazard Mater 179:332–339
13. He S, Zhang F, Cheng S, Wang W (2016) Synthesis of sodium acrylate and acrylamide copoly-
mer/GO hydrogels and their effective adsorption for ­Pb2+ and ­Cd2+. ACS Sustain Chem Eng
4:3948–3959
14. Vardhan KH, Kumar PS, Panda RC (2019) A review on heavy metal pollution, toxicity and remedial
measures: current trends and future perspectives. J Mol Liq 290:111197
15. Saleh TA, Mustaqeem M, Khaled M (2022) Water treatment technologies in removing heavy metal
ions from wastewater: a review. Environ Nanotechnol Monit Manag 17:100617
16. Yousefi SR, Ghanbari M, Amiri O, Marzhoseyni Z, Mehdizadeh P, Hajizadeh-Oghaz M, Salavati-
Niasari M (2021) ­ Dy2BaCuO5/Ba4DyCu3O9.09 S-scheme heterojunction nanocomposite with
enhanced photocatalytic and antibacterial activities. J Am Ceram Soc 104:2952–2965
17. Vidu R, Matei E, Predescu AM, Alhalaili B, Pantilimon C, Tarcea C, Predescu C (2020) Removal
of heavy metals from wastewaters: a challenge from current treatment methods to nanotechnology
applications. Toxics 8(4):101
18. Qiu Y-R, Mao L-J (2013) Removal of heavy metal ions from aqueous solution by ultrafiltration
assisted with copolymer of maleic acid and acrylic acid. Desalination 329:78–85
19. Du J, Zhang B, Li J, Lai B (2020) Decontamination of heavy metal complexes by advanced oxida-
tion processes: a review. Chin Chem Lett 31(10):2575–2582
20. Yousefi SR, Ghanbari D, Salavati-Niasari M, Hassanpour M (2016) Photo-degradation of organic
dyes: simple chemical synthesis of Ni(OH)2 nanoparticles, Ni/Ni (OH)2 and Ni/NiO magnetic nano-
composites. J Mater Sci Mater Electron 27:1244–1253
21. Guo C, Wang Y, Wang F, Wang Y (2021) Adsorption performance of amino functionalized mag-
netic molecular sieve adsorbent for effective removal of lead ion from aqueous solution. Nanomate-
rials 11:2353
22. Abdelhamid AE, Kandil H (2022) Facile approach to synthesis super-adsorptive hydrogel based on
hyperbranched polymer for water remediation from methylene blue. React Funct Polym 177:105312
23. He J, Strezov V, Kumar R, Weldekidan H, Jahan S, Dastjerdi BH, Zhou X, Kan T (2019) Pyrolysis
of heavy metal contaminated Avicennia marina biomass from phytoremediation: characterisation of
biomass and pyrolysis products. J Clean Prod 234:1235–1245
24. Abu Taleb M, Halawani R, Neamtallah A, Kumar R, Barakat M (2022) Hybrid bioadsorbents for
heavy metal decontamination from wastewater: a review. Int J Eng Technol Innov 2(1):5–19
25. Sud D, Mahajan G, Kaur MP (2008) Agricultural waste material as potential adsorbent for seques-
tering heavy metal ions from aqueous solutions–a review. Bioresour Technol 99(14):6017–6027

13
Polymer Bulletin

26. Sharma G, Naushad M (2020) Adsorptive removal of noxious cadmium ions from aqueous medium
using activated carbon/zirconium oxide composite: isotherm and kinetic modelling. J Mol Liq
310:113025
27. Tzvetkova P, Nickolov R (2012) Modified and unmodified silica gel used for heavy metal ions
removal from aqueous solutions. J Chem Technol Metall 47(5):498–504
28. Zhu Y, He X, Xu J, Fu Z, Wu S, Ni J, Hu B (2021) Insight into efficient removal of Cr (VI) by
magnetite immobilized with Lysinibacillus sp. JLT12: mechanism and performance. Chemosphere
262:127901
29. Unuabonah EI, Günter C, Weber J, Lubahn S, Taubert A (2013) Hybrid clay: a new highly efficient
adsorbent for water treatment. ACS Sustain Chem Eng 1(8):966–973
30. Sulyman M, Namiesnik J, Gierak A (2017) Low-cost adsorbents derived from agricultural by-
products/wastes for enhancing contaminant uptakes from wastewater: a review. Pol J Environ Stud
26(3):479–510
31. Chowdhury IR, Chowdhury S, Mazumder MAJ, Al-Ahmed A (2022) Removal of lead ions (­Pb2+)
from water and wastewater: a review on the low-cost adsorbents. Appl Water Sci 12(8):185
32. Khera RA, Iqbal M, Ahmad A, Hassan SM, Nazir A, Kausar A, Khan MI (2020) Kinetics and equi-
librium studies of copper, zinc, and nickel ions adsorptive removal on to Archontophoenix alexan-
drae: conditions optimization by RSM. Desalin Water Treat 201:289–300
33. Kuncoro EP, Soedarti T, Putranto TWC, Darmokoesoemo H, Abadi NR, Kusuma HS (2018) Char-
acterization of a mixture of algae waste-bentonite used as adsorbent for the removal of ­Pb2+ from
aqueous solution. Data Brief 16:908–913
34. Kuncoro EP, Isnadina DRM, Darmokoesoemo H, Fauziah OR, Kusuma HS (2018) Characterization,
kinetic, and isotherm data for adsorption of Pb2+ from aqueous solution by adsorbent from mixture of
bagasse-bentonite. Data Brief 16:622–629
35. Bhatnagar A, Minocha AK (2006) Conventional and non-conventional adsorbents for removal of pol-
lutants from water–a review. IJCT 13:203–217
36. Chaemiso TD, Nefo T (2019) Removal methods of heavy metals from laboratory wastewater. J Nat Sci
Res 9(2):36–42
37. Naat JN, Neolaka YA, Lapailaka T, Tj RT, Sabarudin A, Darmokoesoemo H, Kusuma HS (2021)
Adsorption of Cu (II) and Pb (II) using silica@ mercapto (hs@ m) hybrid adsorbent synthesized from
silica of Takari sand: optimization of parameters and kinetics. Rasayan J Chem 14(1):550–560
38. Neolaka YA, Riwu AA, Aigbe UO, Ukhurebor KE, Onyancha RB, Darmokoesoemo H, Kusuma HS
(2022) Potential of activated carbon from various sources as a low-cost adsorbent to remove heavy met-
als and synthetic dyes. Results Chem 5:100711
39. Uddin MK (2017) A review on the adsorption of heavy metals by clay minerals, with special focus on
the past decade. Chem Eng J 308:438–462
40. Zhang T, Wang W, Zhao Y, Bai H, Wen T, Kang S, Komarneni S (2021) Removal of heavy metals
and dyes by clay-based adsorbents: from natural clays to 1D and 2D nano-composites. Chem Eng J
420:127574
41. Kulkarni P, Watwe V, Doltade T, Kulkarni S (2021) Fractal kinetics for sorption of methylene blue dye
at the interface of Alginate Fullers earth composite beads. J Mol Liq 336:116225
42. Hasan S, Ghosh TK, Viswanath DS, Loyalka SK, Sengupta B (2007) Preparation and evaluation of
fullers earth beads for removal of cesium from waste streams. Sep Sci Technol 42:717–738
43. Hasan S, Iasir ARM, Ghosh TK, Sen Gupta B, Prelas MA (2019) Characterization and adsorption
behavior of strontium from aqueous solutions onto chitosan-fuller’s earth beads. Healthcare 7:52
44. Sharma A, Pande PP, Khare P, Kumar K (2022) Synthesis and application of polyacrylamide/cellulose
gel/fuller’s earth composite for removal of methylene blue from water. Iran J Chem Chem Eng 41:3580
45. Neolaka YA, Supriyanto G, Darmokoesoemo H, Kusuma HS (2018) Characterization, isotherm, and
thermodynamic data for selective adsorption of Cr (VI) from aqueous solution by Indonesia (Ende-
Flores) natural zeolite Cr (VI)-imprinted-poly (4-VP-co-EGDMA)-ANZ (IIP-ANZ). Data Brief
17:1020–1029
46. Neolaka YA, Lawa Y, Naat J, Riwu AA, Lindu YE, Darmokoesoemo H, Widyaningrum BA, Iqbal
M, Kusuma HS (2021) Evaluation of magnetic material IIP@ GO-Fe3O4 based on Kesambi wood
(Schleichera oleosa) as a potential adsorbent for the removal of Cr (VI) from aqueous solutions. React
Funct Polym 166:105000
47. Neolaka YA, Lawa Y, Naat J, Riwu AA, Mango AW, Darmokoesoemo H, Widyaningrum BA, Iqbal M,
Kusuma HS (2022) Efficiency of activated natural zeolite-based magnetic composite (ANZ-Fe3O4) as a
novel adsorbent for removal of Cr (VI) from wastewater. J Mater Res Technol 18:2896–2909

13
 Polymer Bulletin

48. Neolaka YA, Lawa Y, Naat J, Lalang AC, Widyaningrum BA, Ngasu GF, Niga KA, Darmokoesoemo
H, Iqbal M, Kusuma HS (2023) Adsorption of methyl red from aqueous solution using Bali cow bones
(Bos javanicus domesticus) hydrochar powder. RINENG 17:100824
49. Neolaka YA, Supriyanto G, Kusuma HS (2018) Adsorption performance of Cr (VI)-imprinted poly
(4-VP-co-MMA) supported on activated Indonesia (Ende-Flores) natural zeolite structure for Cr (VI)
removal from aqueous solution. J Environ Chem Eng 6:3436–3443
50. Neolaka YA, Lawa Y, Naat JN, Riwu AAP, Darmokoesoemo H, Supriyanto G, Holdsworth CI, Amena-
ghawon AN, Kusuma HS (2020) A Cr (VI)-imprinted-poly (4-VP-co-EGDMA) sorbent prepared using
precipitation polymerization and its application for selective adsorptive removal and solid phase extrac-
tion of Cr (VI) ions from electroplating industrial wastewater. React Funct Polym 147:104451
51. Neolaka YA, Lawa Y, Naat JN, Riwu AA, Iqbal M, Darmokoesoemo H, Kusuma HS (2020) The
adsorption of Cr (VI) from water samples using graphene oxide-magnetic (GO-Fe3O4) synthesized
from natural cellulose-based graphite (kusambi wood or Schleichera oleosa): study of kinetics, iso-
therms and thermodynamics. J Mater Res Technol 9:6544–6556
52. Budiana IGMN, Jasman J, Neolaka YA, Riwu AA, Elmsellem H, Darmokoesoemo H, Kusuma HS
(2021) Synthesis, characterization and application of cinnamoyl C-phenylcalix [4] resorcinarene
(CCPCR) for removal of Cr (III) ion from the aquatic environment. J Mol Liq 324:114776
53. Mahreni M, Ramadhan RR, Pramadhana MF, Permatasari AP, Kurniawati D, Kusuma HS (2022) Syn-
thesis of metal organic framework (MOF) based Ca-Alginate for adsorption of malachite green dye.
Polym Bull 79:11301–11315
54. Kandil H, Ali H (2023) Simultaneous removal of cationic crystal violet and anionic reactive yellow dyes
using eco-friendly chitosan functionalized by Talc and Cloisite 30B. J Polym Environ 31:1456–1477
55. Madejová JJ (2003) FTIR techniques in clay mineral studies. Vib Spectrosc 31(1):1
56. Kakavandi B, Raofi A, Peyghambarzadeh SM, Ramavandi B, Niri MH, Ahmadi M (2018) Efficient
adsorption of cobalt on chemical modified activated carbon: characterization, optimization and mod-
eling studies. Desalin Water Treat 111:310–321
57. Che H, Che G, Zhou P, Liu C, Dong H (2019) Yeast-derived carbon sphere as a bridge of charge car-
riers towards to enhanced photocatalytic activity of 2D/2D C ­ u2WS4/g-C3N4 heterojunction. J Colloid
Interface Sci 546:262–275
58. Kandil H, Moghazy RM, Amin A (2023) Enhancing the adsorption affinity of cellulose acetate film
toward cationic dye by incorporating Cloisite 30B grafted with polyacrylic acid. Polym Eng Sci
63:769–781
59. Gao X, Guo C, Hao J, Zhao Z, Long H, Li M (2020) Adsorption of heavy metal ions by sodium algi-
nate based adsorbent-a review and new perspectives. Int J Biol Macromol 164:4423–4434
60. Li X, Wen B, Li Y (2017) Adsorption of the malachite green by magnetic clam shell powder. Pol J
Environ Stud 30:717–726
61. Dada A, Olalekan A, Olatunya A, Dada O (2012) Langmuir, Freundlich, Temkin and Dubinin-Radu-
shkevich isotherms studies of equilibrium sorption of ­Zn2+ unto phosphoric acid modified rice husk.
IOSR-JAC 3:38–45
62. Ye X, Shang S, Zhao Y, Cui S, Zhong Y, Huang L (2021) Ultra-efficient copper ions adsorption of
chitosan-montmorillonite composite aerogel for wastewater treatment. Cellulose 28:7201–7212
63. Popuri SR, Vijaya Y, Boddu VM, Abburi K (2009) Adsorptive removal of copper and nickel ions from
water using chitosan coated PVC beads. Bioresour Technol 100:194–199
64. Burk GA, Herath A, Crisler GB, Bridges D, Patel S, Pittman CU Jr, Mlsna T (2020) Cadmium and cop-
per removal from aqueous solutions using chitosan-coated gasifier biochar. Front Environ Sci 8:541203
65. Marjub MM, Rahman N, Dafader NC, Tuhen FS, Sultana S, Ahmed FT (2019) Acrylic acid-chitosan
blend hydrogel: a novel polymer adsorbent for adsorption of lead (II) and copper (II) ions from waste-
water. J Polym Eng 39:883–891
66. Xiao C, Liu X, Mao S, Zhang L, Lu J (2017) Sub-micron-sized polyethylenimine-modified polystyrene/
Fe3O4/chitosan magnetic composites for the efficient and recyclable adsorption of Cu (II) ions. Appl
Surf Sci 394:378–385
67. He G, Wang C, Cao J, Fan L, Zhao S, Chai Y (2019) Carboxymethyl chitosan-kaolinite composite
hydrogel for efficient copper ions trapping. J Environ Chem Eng 7:102953
68. Dragan ES, Apopei Loghin DF, Cocarta AI (2014) Efficient sorption of ­Cu2+ by composite chelating
sorbents based on potato starch-graft-polyamidoxime embedded in chitosan beads. ACS Appl Mater
Interfaces 6:16577–16592
69. Fan L, Luo C, Sun M, Li X, Qiu H (2013) Highly selective adsorption of lead ions by water-dispersible
magnetic chitosan/graphene oxide composites. Colloids Surf B Biointerfaces 103:523–529

13
Polymer Bulletin

70. Liu T, Han X, Wang Y, Yan L, Du B, Wei Q, Wei D (2017) Magnetic chitosan/anaerobic granular
sludge composite: synthesis, characterization and application in heavy metal ions removal. J Colloid
Interface Sci 508:405–414
71. Wang Y, Wu D, Wei Q, Wei D, Yan T, Yan L, Hu L, Du B (2017) Rapid removal of Pb (II) from aque-
ous solution using branched polyethylenimine enhanced magnetic carboxymethyl chitosan optimized
with response surface methodology. Sci Rep 7:1–11
72. Laus R, Costa TG, Szpoganicz B, Fávere VT (2010) Adsorption and desorption of Cu (II), Cd (II) and
Pb (II) ions using chitosan crosslinked with epichlorohydrin-triphosphate as the adsorbent. J Hazard
Mater 183:233–241
73. Aliabadi M, Irani M, Ismaeili J, Piri H, Parnian MJ (2013) Electrospun nanofiber membrane of PEO/
Chitosan for the adsorption of nickel, cadmium, lead and copper ions from aqueous solution. Chem Eng
J 220:237–243

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Authors and Affiliations

Heba Kandil1   · Shaimaa T. El‑Wakeel2

* Heba Kandil
[email protected]
1
Polymers and Pigments Department, National Research Centre, 33 El Buhouth St., Dokki,
Giza 12622, Egypt
2
Water Pollution Research Department, National Research Centre, 33 El Buhouth St, Dokki,
Giza 12622, Egypt

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