Journal of Environmental Chemical Engineering 7 (2019) 103449

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

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

Adsorption behavior of Na-bentonite and nano cloisite Na+ in interaction T

with Pb(NO3)2 and Cu(NO3)2·3H2O contamination in landfill liners:
Optimization by response surface methodology
Parsa Mohajeria, Carol M.S. Smitha,⁎, Henry Wai Chaua, Niklas Lehtoa, Alvand Azimia,
Hossein Farrajib
a
Department of Soil and Physical Sciences, Faculty of Agriculture and Life Sciences, Lincoln University, New Zealand
b
School of Physical & Chemical Sciences, University of Canterbury, New Zealand

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

Keywords: Contamination of soils and water with Pb (II) and Cu (II) ions are very common in geo-environmental projects,
Geo-engineering but despite investigations of soil-contaminant interactions, the actual process of the interaction involving heavy
Adsorption metals and Nano-clays has not been extensively investigated. Lead can enter the food chain through con-
Bentonite taminated soil. Lead poisoning can affect the blood circulation, kidneys, and peripheral and central nervous
Heavy metal
systems especially in adults. Accumulation of Cu (II) in the human body causes brain, skin, pancreas and heart
Pb(II)
diseases.In this study, a wide range of the adsorbent / electrolyte and heavy metal concentration was considered
Cu (II)
Nano cloisite Na+ to compare the interaction process of Pb (II) and Cu (II) contaminants with Nano cloisite Na+ (NCNa) and
RSM bentonite. This classification of materials has a unique functionality which may have widespread applications,
due to their novel or significantly enhanced properties to use in the Geo-environmental projects. A series of
experiments was carried out using a range of Pb (II) and Cu (II) contaminant concentrations from 25 to 275 cmol
kg-soil−1, under a range of contaminant/absorbent ratios from 0.01 to 0.02. Response surface methodology
(RSM) was used to optimize the results. Generally, the results showed an increase in adsorption with increasing
the adsorbent / electrolyte ratio up to 0.015. Bentonite adsorbed up to %50 of the Pb (II) while the concentration
was 150 cmol/kg.soil. This amount was %40 for the NCNa in a constant ratio of adsorbent/electrolyte. Also the
behavior of bentonite clay adsorbents was likely to favor adsorption of Pb (II) rather than Cu (II), as indicated in
the previous research found.

1. Introduction
Heavy metals in general have a density greater than 5 g per cubic
centimetre and atomic weights between 63.5 and 200.6. Heavy metals
appear as a natural element in the environment at very low con-
centrations and to a small extent they enter our bodies via food,
drinking water and air. Certain heavy metals create essential compo-
nents which are required sustain life. As trace elements, heavy metals
(e.g. copper, cobalt, iron, manganese, vanadium, strontium, selenium
and zinc) are essential to maintain the metabolism of the human body.
Heavy metals are natural components of the Earth's crust and can enter
a water supply by industrial and consumer waste, or even from acidic
rain breaking down soils and releasing heavy metals into streams, lakes,
rivers, and groundwater.
Copper (Cu (II)) and lead (Pb (II)) are naturally occurring elements
within the earth's crusts - at natural levels they remain below 50 ppm.
But, anthropogenic activity often modify the amount and nature of their
constituents in the natural environment. Copper is a transitional metal
and occurs in nature in four oxidation states: elemental copper Cu (0)
(solid metal), Cu (I) cuprous ion, Cu (II) cupric ion, and rarely Cu (III).
Lead (Pb (II)) may exist as a free metal ion, complexed with inorganic
constituents, or may exist as organic ligands; alternatively it may be
adsorbed onto particle surfaces (e.g. biological material, organic
matter, and clay particles).
In recent years, copper and lead in wastewater pose a major pro-
blem, because of the high risks associated with ecosystems and human
health [1–3]. Exposure to small quantities are sufficient for biological
life cycles, problematically, every day they are discharged into the
environment by industrial and human activity, at large amounts where
they will be toxic to biota [4,5]. Unlike organic wastes, heavy metals

⁎
Corresponding author.
E-mail addresses: parsa.mohajeri@lincolnuni.ac.nz (P. Mohajeri), Carol.Smith@lincoln.ac.nz (C.M.S. Smith).

https://doi.org/10.1016/j.jece.2019.103449
Received 9 May 2019; Received in revised form 8 July 2019; Accepted 30 September 2019
Available online 03 October 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
P. Mohajeri, et al.
Table 1
Permissible limits of the toxic heavy metals.
Metal IS 10500 [31] WHO [32] USEPA [32,33] EU Standard [33]
Lead 0.010 0.010 0.015 0.010
Copper 0.050 2.000 1.300 2.000
Permissible limit for drinking water (mg L−1).
are non-biodegradable causing them to accumulate and reach con-
centrations toxic or harmful to the human physiology and other bio-
logical systems. Copper and Lead are some of the most toxic metals
which are stable and persist as environmental contaminants as they
cannot be degraded or destroyed [6]. Many diseases result from the
presence of lead, when it is more than 0.02 (mgL−1) in drinking water
(anemia, encephalopathy, diarrhea, hepatitis, and kidney nephritic
syndrome). While the accumulation of Cu (II) in the human body causes
brain, skin, pancreas and heart diseases [7].
Only small quantities of heavy metals are necessary for incorpora-
tion into the biological cycles. The bulk that is expelled every day into
the environment by human activities will add to the toxicity of these
elements. Lead and copper are among the few toxic heavy metals that
exist in the environment that are stable against the microbiological
degradation. But once heavy metals get into drinking water at threshold
exceeding levels, there are significant effects on human health, in-
cluding, anaemia, encephalopathy, diarrhoea, hepatitis, and nephritic
kidney syndrome (Tables 1 and 2).
In order to prevent pollution of soil and underground water from
hazardous leachates, clay barriers are a viable option. Geo-chemical
barriers are used in nuclear waste reservoirs and hazardous chemical
landfill sites. These linings use bentonite and in particular montmor-
illonite. The low cost, high specific surface and commercial availability
have made bentonite a valuable material for Geo-environmental pro-
jects [8]. Previous research has shown that bentonite is an ideal ad-
sorbent to solidify and stabilize heavy metal contaminants in great
concentrations [9,10]. Clay soils as a base liner of industrial and mu-
nicipal waste deposit are exposed to intensive physic-chemical attacks
by waste leachates; but due to the silicate structure, clays are able to
assimilate a significant portion of hazardous substances in the waste
solution [11]. Nano Cloisite® Na+ is a natural montmorillonite and an
additive for plastics to improve various plastic physical properties, such
as reinforcement, HDT, CLTE and barrier and it’s not been used as an
adsorbent.
The presence of heavy metals in waste leachate changes the pore
fluid characteristics and influences the double layer properties of clay
and Nano clay particles. The effective application of clay in any landfill
liners, slurry walls, and wastewater treatment requires knowledge of
the variety and changes of their environmental behaviour in terms of
adsorption capability, adsorption selectivity, and microstructure
changes. This process may cause a noticeable change in the environ-
mental behaviour of clays that depends strongly on physical-chemical
properties of pore fluid. A change in the clay fabric and clay particles of
soil may directly change the adsorption capacity of the adsorbent.
Every metal in solution possesses a hydrated layer which has a
characteristic thickness and degree of stability. It has been confirmed
that ions with large radii often show large rejections while smaller ions
are often favoured by exchangers. The metal ions having smaller hy-
drated ionic radius have easier ac- cess to the mineral’s surface and can
diffuse more easily inside its pores. On the other hand, the presence of
ions having a larger hydrated ionic radius results in a more rapid sa-
turation of the adsorption sites. Adsorption involves several processes:
chemical sedimentation, ion exchange, and solvent extraction which
will affect the choice of adsorbent. The choice of adsorbent in a landfill
and wastewater treatment project will also depend on cost, availability,
ease of use, and adaptability with the surroundings. Recently, re-
searchers have nominated a number of inorganic adsorbent such as fly
2
Journal of Environmental Chemical Engineering 7 (2019) 103449
MEP, China [33] CDW, Canada [34] NHMRC, Australia [35]
0.010 0.010 0.010
1.000 1.000 2.000
ash [12–14], zeolite [15,16], and agricultural by-products such as
onion skins [17,18], rice husks [19,20], clays [21,22], and activated
carbon [23,24]. Nowadays, a wide range of novel Nano-particles are
developed in order to the heavy metal adsorption [25–29]. Md. Rabiul
Awual et al. [26,28] proposed a highly selective mesoporous composite
adsorbent to remove the Cu (II) ions in natural waters. the adsorbent
exhibited high sorption capacity (182.15 mg/g) and extreme high se-
lectivity in high concentration ionic competition. The adsorbent ma-
terials had retaining their functionality in terms of Cu (II) detection and
recovery after multiple reuse cycles without deterioration in its sig-
nificant performances. Ahmed Shahat et al. [30] reported the feasibility
of the large-pore diameter nano-adsorbent for capturing low level Pb
(II) ions from aqueous solutions in a batch system, in order to comply
with the toxicity limit for discharging wastewaters. The adsorbent
displayed an excellent selectivity to Pb (II) ions compared to a range of
ions within multiple mixtures of metal species, the system achieved a
maximum sorption capacity was 169.34 mg/g. Still it’s hard to find
researches to use the nano particles (NCNa) as a soil liner media in the
landfills for the contamination adsorption and prevent the underground
from the contamination. This research aims at comparing the adsorp-
tion capacity of bentonite and NCNa at different lead and copper con-
centrations, for a range of adsorbent/electrolyte ratios and discuss
about the adsorption mechanisms and reusability of each adsorbent.
2. Materials and methods
2.1. Reagents and solutions
The bentonite soil was provided by "AMC, United States" and Nano
Cloisite® Na+ by "BYK, France". The Pb(NO3)2 and Cu(NO3)2.3H2O
powders were provided from "Merck company". Double distilled water
was used for all the experiment.
The bentonite was first washed with deionised water several times
in order to remove dust, unwanted materials and water- soluble im-
purities The sample was then oven dried at 110 °C for 48 h before being
used as an adsorbent. At this point, the grey bentonite was in fine form
passing mesh number 30. Until the next stage of preparation, it was
stored in a cool, shaded and dry environment. The NCNa was used as it
was received from the supplier.
Physical properties such as specific gravity, particle size distribu-
tion, Atterberg limits, organic content, and moisture content were de-
termined according to American Society for Testing and Materials
(ASTM) methods [40]. The cation exchange capacity (CEC) was de-
termined using the BaCl2 replacement method [41]. The X-ray powder
diffraction (XRD) analysis was performed based on the 77method by
Moore and Reynold [42]. The carbonate content was determined using
the titration method [43]. The specific surface area (SSA) was de-
termined according to the Brunauer–Emmett–Teller (BET) method
[44]. The pH was measured on the bentonite-water solution of 1:10
ratio by mass—i.e., one portion of bentonite for every 10 portions of
water.
For Geo-environmental analysis, the bentonite was air-dried and
sieved through #200 mesh while the Nano cloisite was used without
any preparation. The geo-environmental engineering analyses were
conducted in duplicate using the procedures described in (EPA) [45].
The Geo-environmental and physical characteristics of the bentonite
and NCNa are given in Table 5.
P. Mohajeri, et al. Journal of Environmental Chemical Engineering 7 (2019) 103449

2.2. Sample preparation and experimental methods

Sea and salt lake aerosols, forest fires and

Wind-blown dust, decaying vegetation,

The equilibrium saturated mix test (EPA) was used in order to
monitor the interaction of the bentonite clay soil and NCNa with dif-

forest fires and sea spray [38]

ferent concentrations of Pb (II) and Cu (II). Firstly, 20 g bentonite clay
soil and NCNa was added to the transparent bottles with a 1.5-L vo-
volcanic eruptions [37]

lume. Then, 1 L of each concentration of Pb (II) and Cu (II) electrolyte

was added to the bottles. The suspension of soil + electrolyte was
Source (natural)

shaken for 3 h on the electric screed. To reach the equilibrium condi-

tion, all the shaken specimens were kept for 24 h. The suspensions were
shaken again for another 3 h with an electric screed. In the following,
the specimens were kept for 120 h to allow the system to become
completely homogenous and for cation exchange to occur. After this
step, the liquid phase of the specimens was separated from the solid
Lead acid batteries, paints, e-waste, smelting operations, coal-
based thermal power plants, ceramics, bangle industry [36]

phase by the means of centrifuge with 3000 rpm. Samples with high
heavy metal concentrations required less centrifuge time, compared
with low heavy metal concentrations. The amounts of heavy metal re-
maining in the supernatant were analyzed for Pb (II) and Cu (II) using
Mining, electroplating, smelting operations [38]

an atomic absorption spectrophotometer (A.A.S).

2.3. Desorption studies

In order to remove the bounded Pb (II) and Cu (II) ions adsorbed

unto the adsorbents. Distilled water and HCl as stripping agent were
used for the desorption experiment. The Pb (II) and Cu (II) loaded ad-
Source (industry)

sorbents were prepared. 0.1 g of dried heavy metal loaded medias was
mixed with 50 ml of different concentration of HCl (0.05–1.0 M) and
mixed for 1 h, then filtered and the concentration of eluted metal was
determined in the filtrate by the AAS. The target of the process was to
study the effect of different concentrations of HCL on desorption. The
percentage desorption was calculated by the equation:
Carcinogenic, anaemia, abdominal, muscle and joint pains,

% Desorption = 1001[CDVD]/qe*m (1)

Stomach ache, irritation of nose, mouth, and eyes,

where CD (mg/L) is the concentration of metal ions in the desorbed

kidney problems, and high blood pressure [32]

solution, VD (L) is the volume of desorbed solution, m(g) is the mass of

adsorbent used for desorption studies and qe (mg/g) is the adsorption
capacity of the adsorbent for metal ions. The time needed to complete
desorption was also estimated at different time intervals of (5–60 min)
using 0.1 M HCl. Three cycles of adsorption/desorption was performed
to determine the reusability of the adsorbents. The adsorption and
desorption experiments were performed under the same conditions as
above. After each cycle the adsorbents were washed with deionized
headaches [39]

water and dried in the oven.

Health effects

2.4. Experimental design

Car batteries, pigments, lead crystal glass, radiation

In this study, the response surface methodology (RSM) (software

transmission wires, copper alloys and coins [38]

(Stat-Ease, Inc)) and central composite design (CCD) are mathematical

Electrical wiring, stoves, portable CD players,

and statistical techniques, which are used for the modeling and analysis
Source and health effects of toxic heavy metals.

of Geo-environmental engineering problems. These techniques are able

to identify which responses of interest are influenced by the specific
variables, the statistical design of the experiments and the data analysis.
The experimental design included k2 factorial points completed by 2k
protection, architecture [36]

axial points and a center point, where k is the number of variables.

Thereupon, CCD and RSM were applied in order to evaluate the asso-
ciation between the variables; in this case, the Pb (II) and Cu (II) con-
centration and the ratio of adsorbent/electrolyte. In summary, the main
scope of this design was to adjust the operating variables to predict the
optimum response values.
The Pb (II) and Cu (II) retention was calculated using the RSM and
Use

CCD techniques; and the response is shown in Tables 3 and 4.

Copper
Table 2

The following equation explains the quadratic equation model for

Metal

Lead

estimating the optimum conditions:

3
P. Mohajeri, et al. Journal of Environmental Chemical Engineering 7 (2019) 103449

k k k k
Table 3
Experimental variables and results of Pb (II) retention. Y = β0 + ∑ βi Xi + ∑ βii X 2 + ∑ ∑ βij Xi Xj +…+e
i=1 i=1 ii < j j (2)
Variable Response
Bentonite NCNa where Y is the response; Xi and Xj are the variables; β0 is a constant
Run A: Pb (II) B: Adsorbent/ Pb (II) Pb (II) coefficient; β j, β jj, and β ij are the interaction coefficients of linear,
Concentration (cmol Electrolyte Retention Retention (cmol
kg-soil−1) (cmol kg-soil−1)
quadratic and second-order terms, respectively; k is the number of
kg-soil−1) studied factors; and e is the error.

1 25 0.015 25 25
2 25 0.015 25 25 3. Results and discussion
3 275 0.02 87 71
4 275 0.01 83 63 3.1. Adsorption capacity
5 150 0.01 75 54
6 150 0.02 78 60
7 275 0.015 85 65 Figs. 1 and 2 illustrate the comparison of Pb (II) adsorption between
8 275 0.015 83 66 bentonite and NCNa with different ratios of adsorbent/electrolyte
9 150 0.015 72 58 under various heavy metal concentrations. The results demonstrate that
10 150 0.015 69 59 bentonite is more effective in improving the adsorption capacity of a
11 150 0.015 73 61
12 150 0.015 70 58
clay liner as used in Geo-environmental projects. However, at low
13 150 0.015 72 59 concentrations of Pb (II), both the adsorbents had the same behavior.
14 150 0.015 73 58 When the Pb (II) concentration increased to ≥100 (cmol kg-soil−1),
15 25 0.02 25 25 bentonite had a greater adsorption capacity in comparison with NCNa,
16 25 0.01 25 25
otherwise, both the adsorbents had an increasing rate of adsorption up
17 150 0.015 71 60
18 150 0.015 74 62 to 200 (cmol kg-soil−1). When the Pb (II) concentration was more than
19 150 0.015 75 54 200 (cmol kg-soil−1) the adsorption trend was constant. At low Pb (II)
concentrations, the ratio of adsorbent/electrolyte had no effect on the
adsorption capacity of the system and the minimum ratio could adsorb
Table 4 100% of the contamination (Table 3). So, the minimum ratio could be
Experimental variables and results of Cu (II) retention. considered in the engineering designs to decrease project costs.
Variable Response Bentonite clay soil had 52% adsorption efficiency in the presence of
Bentonite NCNa 150 cmol kg-soil−1 Pb (II) while under the same experimental condi-
Run A: Cu (II) B: Adsorbent/ Cu (II) Cu (II) tions, NCNa adsorbed 40% of the Pb (II) contamination. This trend was
Concentration (cmol Electrolyte Retention Retention (cmol
also observed at high Pb (II) concentration. When the system was in
kg-soil−1) (cmol kg-soil−1)
kg-soil−1) contact with 250 cmol kg-soil−1Pb (II), bentonite had 5% more ad-
sorption capacity compared with NCNa.
1 25 0.015 25 24 The Cu (II) retention efficiency of bentonite and NCNa are shown in
2 25 0.015 25 24 Figs. 3 and 4. Bentonite appears to be more effective for Cu (II) ad-
3 275 0.02 76 67
4 275 0.01 73 59
sorption at all concentrations, but the adsorption capacity of both ad-
5 150 0.01 50 50 sorbents for Cu (II) were much less than that compared to Pb (II)
6 150 0.02 57 57 (Figs. 3 and 4; Table 4). In comparison, in all the other Cu (II) con-
7 275 0.015 75 62 centrations the bentonite’s adsorption efficiency was greater than
8 275 0.015 74 64
NCNa. In the highest adsorbent/electrolyte ratio, bentonite’s adsorption
9 150 0.015 61 52
10 150 0.015 59 55 capacity was 7% and 4% more than Nano cloisite’s adsorption capacity
11 150 0.015 63 54 in the presence of 150 and 275 Cu (II) cmol kg-soil−1 respectively
12 150 0.015 64 54 (Table 5). The highest adsorbent/electrolyte ratio was more effective at
13 150 0.015 63 53 the lowest Cu (II) concentration. The improvement of the adsorption
14 150 0.015 64 55
15 25 0.02 25 25
efficiency by the highest adsorbent/electrolyte ratio was 8% and 16%
16 25 0.01 23 21 for bentonite and NCNa in 25 Cu (II) cmol kg-soil−1 respectively, while
17 150 0.015 63 54 this amount was 5% for both in 150 Cu (II) cmol kg-soil−1 and 1% and
18 150 0.015 65 54 3% in 275 Cu (II) cmol kg-soil−1 (Table 5).
19 150 0.015 65 53

3.2. Adsorption mechanisms

Table 5
Physical and Geo-environmental engineering characteristics of adsorbents.
Properties
pH (1:10 ; soil : water)
Carbonate content (%)
Organic content (%)
Organic Modifier
Modifier Concentration
Surface area (m2/
kg*10−3)
CEC (cmol / kg soil)
Gs (Specific gravity)
Classification
Mineral composition
Bentonite is a montmorillonite-rich clay and it follows that the
NCNa Bentonite
properties of this clay will influence the geo-environmental behavior of
the system. The high cation exchange capacity (CEC) of montmor-
10.1 9.8 illonite clay mineral is the most notable part which is responsible for
0 8 ± 0.5 the favorable heavy metal retention capacity of the soil. Otherwise, the
6 1
– –
specific surface area (SSA) is the other component of bentonite behavior
– – which contributes to its ability to absorb heavy metals. Bentonite, by
548.8 ± 5 422.5 ± 5 means of the montmorillonite mineral can adsorb Pb (II) and Cu (II) via
two different mechanisms: (1) Cation exchange in the interlayers re-
51.16 65.23
sulting from the interactions between ions and negative permanent
2.88 2.73
CH (High plasticity) CH (High plasticity) charge and (2) Formation of inner-sphere complexes through SieO and
Montmorillonite Montmorillonite, Calcite, AleO groups at the clay particle edges. On the other hand, Nano cloisite
Quartz particles form strong ionic bonds within the product in which they are
being mixed. They have a high cation exchange capacity (CEC). This

4
P. Mohajeri, et al. Journal of Environmental Chemical Engineering 7 (2019) 103449

Fig. 1. Design-expert plot; response surface plot for Pb (II) removal by bentonite.

Fig. 2. Design-expert plot; response surface plot for Pb (II) removal by NCNa.

means the Nano clays alumina-silicate platelets form ionic bonds that
allow them to remain in suspension indefinitely, where other materials
would separate and sediment. This unique behavior makes the Nano
clays an appropriate material for heavy metal adsorbence.
Montmorillonite is a clay mineral with substantial isomorphic sub-
stitution. The negative charges which generated by isomorphic sub-
stitution balances by exchangeable cations in the 2:1 layers. In the
different environmental conditions such as pressure, temperature, pH,
and chemical and biological composition of the water, Bentonite ad-
sorbs the heavy metals in different types and concentrations. Cation
exchange reactions are a response to changes in the environmental
conditions of clay. This point is noteworthy that, the exchange reactions
lead to the changes in physical and physicochemical properties while
don’t affect the structure of clay particles directly. Totally three sources
of clay exchange capacity are known.
1 Isomorphous substitution: Mg2+ for Al3+ in the octahedral sheets
and Al3+ for Si4+ in the silica sheet are the most common iso-
morphous substitution in the Bentonite. This is the major source of
Bentonite exchange capacity.
2 Broken Bonds: The exchange sites along particle edges and on non-
cleavage surfaces just contribute up to 20 percent of the total

5
P. Mohajeri, et al. Journal of Environmental Chemical Engineering 7 (2019) 103449

Fig. 3. Design-expert plot; response surface plot for Cu (II) removal by bentonite.

exchange capacity in the smectites. This source is the major source
for kaolinite mineral exchange capacity. Otherwise, the importance
of broken bond sites decrease with increasing the particle size.
3 Replacement: The hydrogen of an exposed hydroxyl is replaced by
another type of cations.
Additionally, the high specific surface area of Bentonite and surface
charge density are directly effect on the exchange capacity. Table. 6
presents the adsorption capacity of different Montmorillonite included
adsorbents in the presence of lead and copper.
The results of this research can be supported by the recent studies
around the application of novel composite material to adsorb the Pb (II)
and Cu (II) from the water. Novel composite material for selective
copper (II) detection and removal from aqueous media was developed
and the results showed that the high specific area can play the main role
in heavy metal adsorption [46]. In the other study a ligand anchoring
mesoporous conjucated adsorbent (CJA) was successfully fabricated to
remove the Pb (II) ions from the wastewater which the functional sites
on the surface was the main adsorption mechanism [47].

Fig. 4. Design-expert plot; response surface plot for Cu (II) removal by NCNa.

6
P. Mohajeri, et al. Journal of Environmental Chemical Engineering 7 (2019) 103449

A, first variable, contaminant concentration: cmol kg-soil−1; Adeq. P, adequate precision; Adj. R2, adjusted R2; B, second variable, adsorbent/electrolyte; cv, coefficient of variance; Press, predicted residual error sum of
3.3. Scanning Electron microscope (SEM)

151.20

141.27
78.22

24.61
Press

Fig. 5 illustrates the SEM micrographs of the blank bentonite and Pb

(II) loaded bentonite in 150 Pb (II) cmol kg-soil−1 concentration.
Fig. 5(a) represents the blank bentonite which demonstrates the het-
2.96
3.71
5.98
1.82
CV

erogeneous nature of the surface morphology of the clay sample.

Fig. 5(b) shows the morphology of the bentonite contaminated with Pb
(II) : the surface fabric is now flocculated after the adsorption process.
0.895

The morphology of Pb (II) loaded bentonite is shown by the agglom-

1.93
1.97
3.37
SD

erated and irregular fabric of bentonite following heavy metal adsorp-

tion.
Adec. P.

45.767
46.451
40.035
67.835

3.4. Statistical analysis

The response surface methodology (RSM) was used to analyze the

correlation between the variables: Pb (II) concentration; Cu (II) con-
Adj. R2

centration; adsorbent/electrolyte ratio; Pb (II) and Cu (II) retention.

0.9923
0.9807
0.9903
0.9954

Considerable model terms were preferred to achieve the best fit in a

particular model. CCD permitted the development of mathematical
equations where predicted results (Y) were evaluated as a function of
Pb (II) concentration (A), and adsorbent/electrolyte ratio (B). The re-
0.9953
0.9882
0.9941
0.9972

sults were computed as the sum of a constant, two first order effects
R2

(terms in A and B), interaction effect (AB), and two second-order effects
(A2 and B2), as shown in Eq. (1) and Tables 3 and 4.
In order to determine the accuracy of fit, the results were analyzed
< 0.0001
< 0.0001
< 0.0001
< 0.0001

by ANOVA statistical technique. Equations from the first ANOVA ana-

prob

lysis were adapted by neglecting the terms found statistically irrelevant.

The reduced quadratic models in terms of actual factors are illustrated
square; Prob. LOF, probability of lack of fit; prob., probability of error; R2, correlation coefficient; SD, standard deviation.

in Table 6. According to the probability values (less than 0.05), all

models were significant at the 5% confidence level. R2 values close to
+12.19050 + 0.360960*A+451.66667*B + 3.20000*A*B-8.03310E-004*A2-15500*B2

+5.69600 + 0.332720*A + 873.33333*B + 1.60000*A*B-6.62 10E-004*A2-16000*B2

one were favorable, and a high R2 coefficient ensured acceptable

−28.81800 + 0.392240*A + 5800*B + 0.40000*A*B-6.61E-004*A2-1.82E + 05*B2

modification of the quadratic model to the experimental data. The

correlation coefficient (R2) gave the proportion of total variation in the
+29.97 + 0.57640*A-2706.66667*B + 1.6*A*B-1.208E-003*A2 + 90000*B2

response predicted by the model, indicating the ratio of sum of squares

due to regression (SSR) to total sum of squares (SST). Adequate preci-
sion compared the range of the predicted values at the design points to
the mean prediction error [23]. Figs. 6 and 7 show the predicted versus
actual value plots of the response parameters for the COD and ammonia
removal. These plots signified a sufficient agreement between the real
data and the values achieved from the models.

3.5. Optimization of the system

Final equations in terms of actual factors

The final experimental results involving Pb (II) and Cu (II) retention

capacity with various adsorbent/electrolyte ratio and Pb (II) and Cu (II)
concentrations were analyzed using the (RSM) and (CCD) in order to
determine a specific design of the system that could lead to the op-
timum adsorbent/electrolyte ratio with high adsorption capacity [48].
The resulting responses from optimizing the Pb (II) and Cu (II) retention
are given in Table 7 and Figs. 8 and 9. Accordingly, the optimized
condition in the high concentration of contamination was the average
to high adsorbent/electrolyte ratio in most of the concentrations. In the
low heavy metal concentrations, the system could be designed with the
lowest adsorbent/electrolyte ratio.
ANOVA results for response parameters.

3.6. Desorption and adsorbent recycling

Cu (II) Retention
Cu (II) Retention
Pb (II) Retention
Pb (II) Retention

In the study of the s media regarding the heavy metal adsorption,

Response

It’s always essential to investigate the recovery and the desorption ca-
pacity of the adsorbent. In the geo-environmental projects, it’s the reuse
and recovery of the media can reduce the cost of the design sig-
nificantly. A well-develped media should have acceptable both ad-
sorption and desorption “recovery” capacity. The desorption of Pb (II)
Adsorbent

Bentonite

Bentonite

and Cu (II) ions using deionized water and HCl is presented in Fig. 10.
Table 6

NCNa

NCNa

This experiment was conducted to establish the appropriate con-

centration of desorbing agent to be utilized during desorption of metal

7
P. Mohajeri, et al. Journal of Environmental Chemical Engineering 7 (2019) 103449

Fig. 5. SEM micrographs of (a) blank bentonite, (b) Pb (II) loaded bentonite.

Fig. 6. Design-expert plot; predicted vs. actual values plot for Pb (II) removal.

ions from the loaded bentonite and Nano Cloisite Na. The optimum
concentration of HCl was 0.1 M and was considered as the stripping
agent for the desorption experiment. It could be concluded from the DW
that the physical adsorption was the main mechanism during the ad-
sorption process while more than %30 of the adsorbed heavy metals
desorbed by DW.
The time which was needed for a complete desorption process was
determined at time intervals of 1–60 min using 0.1 M HCl as desorbing
agent. The desorption of both metals from clay adsorbents was so rapid
in the first 5 min and it was increased slightly to the optimum deso-
rption which was 20 min for the all conditions (Fig. 11).
In order to study the reusability of the media, three cycles of the
adsorption desorption was performed as presented in Fig. 12. After the
first cycle, both the adsorbents showed the same behaviour as the initial
adsorption of heavy metals. The acid treatment (HCl) of the desorbing
agent during the desorption process can open the media pores and

8
P. Mohajeri, et al. Journal of Environmental Chemical Engineering 7 (2019) 103449

Fig. 7. Design-expert plot; predicted vs. actual values plot for Cu (II) removal.

Table 7 Cloisite Na showed a higher reusability potential. It’s because of the fine
The value of response at optimum conditions with desirability 1. particle sizes and smaller pore sizes [51].
Type Contaminant
concentrations (cmol 4. Conclusion
kg-soil−1)
50 100 150 200 250 In landfill disposal sites, Nanoclay can be used as a heavy metal
Bentonite/ 0.015 0.015 0.01 0.02 0.02
adsorbent material to prevent the contamination of surface and
Electrolyte groundwater resources. This is because the Nanoclay has a very high
Pb (II) Retention 35.92 56.92 73.5 85.23 88.63 surface area and consequently a greater possibility for interaction of
Nano/Electrolyte 0.02 0.01 0.015 0.015 0.015 clay particles with the liquid contaminant. However, industrial
Pb (II) Retention 34.20 46.22 58.58 64.84 67.08
Nanoclay materials are expensive, so their extensive use in geo-en-
Bentonite/ 0.015 0.02 0.015 0.015 0.02
Electrolyte vironmental projects would not be cost effective and their use would
Cu (II) Retention 33.89 52.34 62.24 70.25 76.67 therefore be limited. Addition of carbonate at 8% content plays a major
Nano/Electrolyte 0.02 0.01 0.01 0.01 0.015 role in heavy metal retention in bentonite as a buffer. The adsorption
Cu (II) Retention 33.42 41.22 50.36 56.15 62.57
characteristics Pb (II) and Cu (II) to bentonite and NCNa with different
adsorbent/electrolyte ratio and Pb (II) and Cu (II) concentrations are
summarized as follows:
causes the weight loss [49] as it was observed during the experiment.
From the first to the third cycle, the Pb (II) and Cu (II) removal de-
creased from %73.5 to %61.2 and from %62.3 to %55.4 for bentonite • The adsorption efficiency of Pb (II) and Cu (II) to bentonite and
NCNa decreases with the increase of heavy metal concentrations.
and from %58.6 to %51.5 and from %50.3 to %46.7 for the NCNa re-
Also, the adsorption capacity of the adsorbents increases with in-
spectively. The destructive effects of the desorbing agent and also
crease in adsorbent/electrolyte ratio.
•
weight loss of the media during the desorption process could be the
The adsorption efficiency of both adsorbent is more when the con-
main reason of the drop in adsorption capacity [50]. In general, it can
tamination is Pb (II). This result is in agreement with recent re-
be concluded that both the medias have the reusability while the Nano
search.

9
P. Mohajeri, et al. Journal of Environmental Chemical Engineering 7 (2019) 103449

Fig. 8. Design-expert plot; optimization of Pb (II) removal by Bentonite and NCNa.

Fig. 9. Design-expert plot; optimization of Cu (II) removal by Bentonite and NCNa.

• The presence of 8% carbonate content in the bentonite plays an
important role in the heavy metal retention and in improving the
adsorption capacity of the bentonite. Other factors affecting the
Geo-environmental behavior of the adsorbents are the cation ex-
change capacity (CEC) and Specific Surface Area (SSA).
• The adsorption efficiency follows the order of bentonite > NCNa at
the same Pb (II) concentration. Otherwise, at the most Pb (II) con-
centrations the ratio of adsorbent/electrolyte = 0.015 leads to the
optimum results.

10
P. Mohajeri, et al. Journal of Environmental Chemical Engineering 7 (2019) 103449

Fig. 10. Effect of distilled water (DW) and HCl concentration on desorption; (a) Bentonite, (b) Nano Cloisite Na.

Fig. 11. Effect of time on desorption; (a) Bentonite, (b) Nano Cloisite Na.

Fig. 12. Adsorption performance as a function of three operational cycles; (a) Bentonite, (b) Nano Cloisite Na.

Declaration of Competing Interest from aqueous solutions, Process. Saf. Environ. Prot. 109 (2017) 97–105.
[3] M.E. Essington, Soil and Water Chemistry: an Integrative Approach, CRC press,
2015.
None. [4] A. Mojiri, H.A. Aziz, R.B.M. Tajuddin, S. Gavanji, A. Gholami, Heavy metals phy-
toremediation from Urban waste leachate by the Common reed (phragmites aus-
Acknowledgement tralis), Phytoremediation, Springer International Publishing, 2015, pp. 75–81.
[5] M. Oves, M. Saghir Khan, A. Huda Qari, M. Nadeen Felemban, T. Almeelbi, Heavy
metals: biological importance and detoxification strategies, J. Bioremediat.
This work was supported by Lincoln University, New Zealand, Biodegrad. 7 (2) (2016) 1–15.
3601/AGLS/45401/1130684. [6] B. Pourrut, M. Shahid, C. Dumat, P. Winterton, E. Pinelli, Lead uptake, toxicity, and
detoxification in plants, Reviews of Environmental Contamination and Toxicology
vol. 213, Springer, New York, 2011, pp. 113–136.
References [7] A. Gundogdu, D. Ozdes, C. Duran, V.N. Bulut, M. Soylak, H.B. Senturk, Biosorption
of Pb (II) ions from aqueous solution by pine bark (Pinus brutia Ten.), Chem. Eng. J.
153 (1) (2009) 62–69.
[1] M.G. Lines, Nanomaterials for practical functional uses, J. Alloys. Compd. 449 (1)
[8] P. Mohajeri, C. Smith, M. Selamat, H. Abdul Aziz, Enhancing the adsorption of lead
(2008) 242–245.
(II) by bentonite enriched with pH-Adjusted meranti sawdust, Water 10 (12) (2018)
[2] H.A. Sani, M.B. Ahmad, M.Z. Hussein, N.A. Ibrahim, A. Musa, T.A. Saleh,
1875.
Nanocomposite of ZnO with montmorillonite for removal of lead and copper ions

11
P. Mohajeri, et al.
[9] G.P.C. Rao, S. Satyaveni, A. Ramesh, K. Seshaiah, K.S.N. Murthy, N.V. Choudary,
Sorption of cadmium and zinc from aqueous solutions by zeolite 4A, zeolite 13X and
bentonite, J. Environ. Manage. 81 (3) (2006) 265–272.
[10] M. Yan, G. Zeng, X. Li, J. He, G. Chen, D. Huang, et al., Incentive effect of bentonite
and concrete admixtures on stabilization/solidification for heavy metal-polluted
sediments of Xiangjiang river, Environ. Sci. Pollut. Res. - Int. 24 (1) (2017)
892–901.
[11] V.R. Ouhadi, R.N. Yong, Impact of clay microstructure and mass absorption coef-
ficient on the quantitative mineral identification by XRD analysis, Appl. Clay Sci. 23
(1) (2003) 141–148.
[12] T.C. Nguyen, P. Loganathan, T.V. Nguyen, J. Kandasamy, R. Naidu, S. Vigneswaran,
Adsorptive removal of five heavy metals from water using blast furnace slag and fly
ash, Environ. Sci. Pollut. Res. - Int. 25 (21) (2018) 20430–20438.
[13] A. Mathur, S.K. Khare, D.C. Rupainwar, Removal of heavy metals from main sewer-
water of Varanasi city by adsorption on fly ash and blast furnace slag, J. Ind. Pollut.
Control 5 (1989) 52–57.
[14] Z.T. Yao, X.S. Ji, P.K. Sarker, J.H. Tang, L.Q. Ge, M.S. Xia, Y.Q. Xi, A comprehensive
review on the applications of coal fly ash, Earth. Rev. 141 (2015) 105–121.
[15] E. Zanin, J. Scapinello, M. de Oliveira, C.L. Rambo, F. Franscescon, L. Freitas, et al.,
Adsorption of heavy metals from wastewater graphic industry using clinoptilolite
zeolite as adsorbent, Process. Saf. Environ. Prot. 105 (2017) 194–200.
[16] M. Visa, Synthesis and characterization of new zeolite materials obtained from fly
ash for heavy metals removal in advanced wastewater treatment, Powder Technol.
294 (2016) 338–347.
[17] E.F. Olasehinde, A.V. Adegunloye, M.A. Adebayo, A.A. Oshodi, Sequestration of
aqueous lead (II) using modified and unmodified red onion skin, Anal. Lett. 51 (17)
(2018) 2710–2732.
[18] S.E. Agarry, O.O. Ogunleye, O.A. Ajani, Biosorptive removal of cadmium (II) ions
from aqueous solution by chemically modified onion skin: batch equilibrium, ki-
netic and thermodynamic studies, Chem. Eng. Commun. 202 (5) (2015) 655–673.
[19] F.A. Temel, N.G. Turan, O. Ozgonenel, Y. Ardalı, Heavy metal removal with pure
and biochar rice husks: modelling and optimisation using Box-Behnken design, Int.
J. Glob. Warm. 16 (1) (2018) 1–17.
[20] E. Agrafioti, D. Kalderis, E. Diamadopoulos, Arsenic and chromium removal from
water using biochars derived from rice husk, organic solid wastes and sewage
sludge, J. Environ. Manage. 133 (2014) 309–314.
[21] X.U. Yi, X. LIANG, X.U. Yingming, Q.I.N. Xu, Q. HUANG, W.A.N.G. Lin,
S.U.N. Yuebing, Remediation of heavy metal-polluted agricultural soils using clay
minerals: a review, Pedosphere 27 (2) (2017) 193–204.
[22] T.B. Musso, M.E. Parolo, G. Pettinari, F.M. Francisca, Cu (II) and Zn (II) adsorption
capacity of three different clay liner materials, J. Environ. Manage. 146 (2014)
50–58.
[23] A. Nayak, B. Bhushan, V. Gupta, P. Sharma, Chemically activated carbon from
lignocellulosic wastes for heavy metal wastewater remediation: effect of activation
conditions, J. Colloid Interface Sci. 493 (2017) 228–240.
[24] Z. Guo, J. Fan, J. Zhang, Y. Kang, H. Liu, L. Jiang, C. Zhang, Sorption heavy metal
ions by activated carbons with well-developed microporosity and amino groups
derived from phragmites australis by ammonium phosphates activation, J. Taiwan
Inst. Chem. Eng. 58 (2016) 290–296.
[25] M.R. Awual, Solid phase sensitive palladium (II) ions detection and recovery using
ligand based efficient conjugate nanomaterials, Chem. Eng. J. 300 (2016) 264–272.
[26] M.R. Awual, M.M. Hasan, M.A. Khaleque, M.C. Sheikh, Treatment of copper (II)
containing wastewater by a newly developed ligand based facial conjugate mate-
rials, Chem. Eng. J. 288 (2016) 368–376.
[27] A. Shahat, M.R. Awual, M. Naushad, Functional ligand anchored nanomaterial
based facial adsorbent for cobalt (II) detection and removal from water samples,
Chem. Eng. J. 271 (2015) 155–163.
[28] M.R. Awual, M. Ismael, T. Yaita, S.A. El-Safty, H. Shiwaku, Y. Okamoto, S. Suzuki,
Trace copper (II) ions detection and removal from water using novel ligand mod-
ified composite adsorbent, Chem. Eng. J. 222 (2013) 67–76.
12
Journal of Environmental Chemical Engineering 7 (2019) 103449
[29] M.R. Awual, M.M. Hasan, A. Islam, M.M. Rahman, A.M. Asiri, M.A. Khaleque,
M.C. Sheikh, Offering an innovative composited material for effective lead (II)
monitoring and removal from polluted water, J. Clean. Prod. 231 (2019) 214–223.
[30] M.R. Awual, Assessing of lead (III) capturing from contaminated wastewater using
ligand doped conjugate adsorbent, Chem. Eng. J. 289 (2016) 65–73.
[31] Drinking water [FAD 25: Drinking Water], Indian Standard Drinking Water- spe-
cification (Second Revision), ICS 13.060.20 IS 10500 (2012).
[32] M. Ahmaruzzaman, Industrial wastes as low-cost potential adsorbents for the
treatment of wastewater laden with heavy metals, Advanced Colloid Interface
Science 116 (2011) 36–59.
[33] Drinking Water Quality Standard, Wikipedia, viewed 01/04/2019. https://en.
wikipedia.org/wiki/Drinking_water_quality_standards..
[34] As per Canadian or B.C. Health Act Safe Drinking Water Regulation BC Reg 230/92,
& 390 Sch 120, 2001, Task Force of Canadian Council of Resource & Envir.
Ministers Guidelines for Canadian Drinking Water Quality, 1996, Amend. Health
Canada, 2006..
[35] NHMRC, Australian drinking Water guidelines, Paper 6 National Water Quality
Management Strategy, National Health and Medical Research Council, National
Resource Management Ministerial Council, Commonwealth of Australia, Canberra,
2011.
[36] Lead Properties, Royal Society of Chemistry, viewed 01/04/2019. http://www.rsc.
org/periodic-table/element/82/lead. .
[37] Hazardous Substance Data Bank (HSDB), U.S. Department of Health and Human
Services, National Toxicology Information Program. National Library of Medicine.
Bethesda, Maryland (CD ROM version), Micromedex, Denver, Colorado, 1995.
[38] Copper Properties, Royal Society of Chemistry, viewed 01/04/2019. http://www.
chemistryexplained.com/elements/C-K/Copper.html.
[39] Chemical properties of copper - Health effects of copper - Environmental effects of
copper, Lentech, viewed 01/04/2019. https://www.lenntech.com/periodic/
elements/cu.htm#ixzz5mWpfn1jv.
[40] American Society for Testing and Materials, ASTM, Annual Book of ASTM
Standards vol. 4, Philadelphia, 1992 08.
[41] W. Hendershot, M. Duquette, A simple barium chloride method for determining
cation exchange capacity and exchangeable cations, Soil Sci. Soc. Am. J. 50 (1986)
605–608.
[42] D. Moore, R. Reynolds, X-ray Diffraction and the Identification and Analysis of Clay
Minerals, Oxford University Press, Oxford, UK, 1989.
[43] P. Hesse, A Textbook of Soil Chemical Analysis, Cambridge University Press,
Cambridge, UK, 1971.
[44] G. Fagerlund, Determination of specific surface by the BET method, Matériaux
Constr. 6 (1973) 239–245.
[45] EPA, Process Design Manual, Land Application of Municipal Sludge, Municipal
Environmental Research Laboratory, 1983 EPA-625/1-83-016.
[46] M.R. Awual, M.M. Hasan, M.M. Rahman, A.M. Asiri, Novel composite material for
selective copper (II) detection and removal from aqueous media, J. Mol. Liq. 283
(2019) 772–780.
[47] M.R. Awual, Novel conjugated hybrid material for efficient lead (II) capturing from
contaminated wastewater, Mater. Sci. Eng. C 101 (2019) 686–695.
[48] S.Q. Aziz, H.A. Aziz, M.S. Yusoff, M.J. Bashir, Landfill leachate treatment using
powdered activated carbon augmented sequencing batch reactor (SBR) process:
optimization by response surface methodology, J. Hazard. Mater. 189 (1) (2011)
404–413.
[49] E. Igberase, P. Osifo, A. Ofomaja, The adsorption of copper (II) ions by polyaniline
graft chitosan beads from aqueous solution: equilibrium, kinetic and desorption
studies, J. Environ. Chem. Eng. 2 (1) (2014) 362–369.
[50] R.B. Nessim, A.R. Bassiouny, H.R. Zaki, M.N. Moawad, K.M. Kandeel, Biosorption of
lead and cadmium using marine algae, Chem. Ecol. 27 (6) (2011) 579–594.
[51] M.R. Awual, M.M. Hasan, Colorimetric detection and removal of copper (II) ions
from wastewater samples using tailor-made composite adsorbent, Sens. Actuators B
Chem. 206 (2015) 692–700.