Pol. J. Environ. Stud. Vol. 29, No.

1 (2020), 749-761
DOI: 10.15244/pjoes/104455 ONLINE PUBLICATION DATE: 2019-09-09

Original Research
Competitive Adsorption of Heavy Metal Ions
from Aqueous Solutions onto Activated Carbon
and Agricultural Waste Materials

Xiaofeng Liu1, Xin Xu2, Xiaoqiang Dong1*, Jounboum Park2**

College of Civil Engineering, Taiyuan University of Technology, Taiyuan, China

1

Department of Geotechnical and Geo-Environmental Engineering, Seoul National University, Seoul, South Korea
2

Received: 17 December 2018

Accepted: 17 February 2019

Abstract

Agricultural waste materials (peanut shell and sawdust) were used as replacements for activated
carbon to remove heavy metal ions from aqueous solution. Batch adsorption experiments were conducted
in single, and competitive systems. The adsorption efficiencies of different heavy metal ions were, in
descending order: lead, copper, cadmium. Activated carbon showed best adsorption efficiency (lead:
14.01 mg/g; copper: 13.1 mg/g; cadmium: 5.5 mg/g), followed by peanut shell (lead: 9.5 mg/g; copper:
49.1 mg/g; cadmium: 5.07 mg/g), and sawdust (lead: 5.5 mg/g; copper: 5.3 mg/g; cadmium: 3.99 mg/g),
which showed the worst efficiency. The amount of heavy metal ions adsorbed onto activated carbon,
peanut shell and sawdust increased with the increase of adsorption time and then reached equilibrium
values. As the initial concentration of heavy metal ions increased, the amount of heavy metal ions
adsorbed increased while the removal ratios thereof decreased. The adsorption processes in both single
and competitive systems followed a Langmuir isotherm model and pseudo second-order kinetic model.
The intraparticular diffusion process can be divided into two stages for the adsorption process of heavy
metal ions. There were antagonistic effects among three kinds of heavy metal ions in a competitive
system.

Keywords: lead, copper, cadmium, peanut shell, sawdust

Introduction application of chemical fertiliser, development of the

mining industry, the soil, water and atmosphere are
Heavy metal pollution is a pressing problem: owing severely polluted by heavy metal ions [1, 2]. Cadmium,
to the emission of industrial three waste gas, wastewater lead and copper are the most common pollutant elements
and waste residue, emission of automobile exhaust gas, in wastewater and can cause significant problems [3].
sewage irrigation, use of pesticides, use of herbicide, Heavy metal ions in wastewater cannot be biodegraded
but accumulate to either directly or indirectly threaten
living beings, including humans [4, 5]. Cadmium in the
human body can cause hypertension, cardiocerebral
*e-mail: 13333515050@126.com vascular diseases, destruction of bones, liver, kidney
**e-mail: junbpark@snu.ac.kr or renal failure [6]. Lead can directly injure the human
750 Liu X., et al.

brain cells and especially the nervous system of a foetus The object of this research is to investigate the
(causing congenital feeblemindedness) [7]. Copper is a competition adsorption characteristics for the field
necessary microelement for life, but excessive copper is application of peanut shell and sawdust in multiple heavy
harmful to humans, animals and plants [8]. metal-contaminated wastewater treatments. Agricultural
At present, the treatment technologies for heavy waste materials (peanut shell and sawdust) were selected
metal ions in wastewater mainly include adsorption, as adsorbents, and activated carbon was selected for
flocculation, precipitation, membrane separation, and comparison: batch adsorption experiments using single
biological methods [9]. Among these, adsorption is heavy metal ion solutions and mixed heavy metal ion
a commonly used method for wastewater treatment solutions were conducted to investigate the competitive
by using porous solid substances to adsorb pollutants adsorption characteristics. Adsorption equilibrium
from aqueous solution [10]. Activated carbon is a non- experiments were performed and adsorption kinetics
polar adsorbent and is widely used for the adsorption were investigated. Adsorption results under different
of heavy metal ions from wastewater. Owing to the initial pollutant concentrations were used to study the
special pore structure and high specific surface area, adsorption isotherms. The effect of interactions among
it has strong adsorption capacity and offers a high heavy metal ions in a competitive system was evaluated
removal rate for heavy metal ions; however, because of by evaluation ratio E.
its cost, its application is limited: it is thus necessary
to find alternative materials for use as adsorbents in
wastewater treatment [11, 12]. Some agricultural waste Methodology of Experiment
materials are potential adsorbents for heavy metal ion
removal since they are cheap and always include some Adsorbent Preparation
adsorptive constituents such as lignin and cellulose [13-
15]. China is an agricultural nation and thus generates Peanut shells and activated carbon were taken from
significant amounts of agricultural waste. There are Shanxi Province, China. Sawdust was obtained from
still 286 million tonnes of agricultural wastes that coconut trees in Hainan Province, China. All materials
remain unused annually [16]. These were always were washed with tap water three times to remove the
burned for heating or discarded without any industrial coloration and dirt, then they were washed with distilled
utilization [17, 18]. Sawdust is produced every year in water three times. They were then oven-dried at 70ºC
large quantities as a by-product of the woodworking for 48 h and pulverized. The pulverized materials were
process [17]. Total peanut shell production in China is sieved with 16-mesh and 20-mesh wire material sieves
also very large [19]. Therefore, the easy accessibility of to obtain the 0.85-1.18 mm size fraction. The adsorbents
peanut shells and sawdust may indicate a bright future were shaken for about 10 minutes in the sieves and then
for their application in the treatment of wastewater. stored in different bottles. The characteristics of the
Peanut shells and sawdust are cheap agricultural waste adsorbents are listed in Table 1.
materials that can be used as potential adsorbents for
heavy metal ion removal [20, 21]. Currently, many SEM and EDS of Adsorbents
researchers have shown that peanut shells and sawdust
exhibit good adsorption efficiency for heavy metal ions The morphology and chemical compositions
at a reasonable cost [22-27]. of adsorbents were analyzed by scanning electron
Usually, many kinds of heavy metal ions are present microscope (SEM) and consideration of their energy
in wastewater at one time. There are three types of dispersion spectrum (EDS) (Fig. 1). There are many
inter effects in the multicomponent system: synergism, pores in the surface of activated carbon, providing
antagonism and non-interaction [28, 29]. The adsorption high adsorption efficiency for heavy metal ions. Peanut
efficiency in a competitive system was always lower shells have a rough, textured structure and cavities or
than that in a single system because of antagonistic pores on their surface, thus peanut shells can be used for
interaction [30]. Researchers have tried to develop novel adsorption. Sawdust shows anisotropic characteristics
methods for multiple heavy metal removal; however, and has few pores, indicating the possibility of use in
scholars have seldom studied the competitive adsorption heavy metal adsorption. The main elements present
characteristics of heavy metal ions on peanut shells and therein are carbon and oxygen.
sawdust [31-34].

Table 1. Characteristics of adsorbents.

Fixed carbon content Ash content Volatile content Surface area Cost
Adsorbents pH
(%) (%) (%) (m2/g) (yuan/kg)
Peanut shell 9 27 29 2.8 6.7 0
Sawdust 6 25 31 1.01 5.1 5
Activated carbon 71 14 12 560 8.3 15
Competitive Adsorption of Heavy Metal Ions... 751

Fig. 1. SEM photographs and EDS spectra of adsorbents: a) activated carbon, b) peanut shell, c) sawdust.

FTIR of Adsorbents Fig. 2b) was FTIR spectra of peanut shell. The peak
around 3400 cm-1 can be attributed to O-H stretching
At present, Fourier transform infrared spectrometry vibrations of hydroxyl groups, which can present
(FTIR) has become one of most useful analytical cellulosic structure in peanut shells and are good for
means, it can be used to detect the functional groups in heavy metal ions adsorption. The peak around 2900
adsorbents. Fig. 2 showed the FTIR results of different cm-1 is assigned to C-H stretching vibrations of methyl
adsorbents, which can explain the difference between groups on the surface, which indicate the existence of
adsorbents. lignin structure [36]. The peak near 1400 cm-1 presents
Fig. 2a) was FTIR spectra of activated carbon. The the C-O stretching vibrations of the carboxyl group. The
broad band around 3425 cm-1 indicates the existence peak around 1300 cm-1 may be due to the C-O, C-H or
of hydroxyl groups with O-H stretching vibrations. C-C stretching vibrations. There are complex interacting
The peak at 2900 cm-1 is attributed to C-H stretching vibration systems below 1000 cm-1, thus they cannot be
vibrations. There are five peaks between 2000 and defined as a certain vibration. From Fig. 7b), it can be
1000 cm-1. The peak around 1800 cm-1 can be attributed concluded that there are many C-O groups and O-H
to C=O stretching vibration in carboxylic group. groups in peanut shells, and these ionizable groups can
The peak around 1600 cm-1 belongs to C=C stretching interact with heavy metal ions [37].
vibration absorption. The peak around 1400 belong The specific surface of sawdust is very small, thus
to COO- vibration. The peak around 1000 cm-1 is there are no high porous structures in sawdust. The
C-O stretching vibration of CH2-O-CH2. Surface functional groups of sawdust can react with heavy metal
functional groups containing oxygen play an important ions in solution and form some complex, and removed
role in the properties of activated carbon. The main heavy metal ions. The FTIR spectra of sawdust was
functional groups in activated carbon were carboxylic shown in Fig. 2c). The peak around 3446 cm-1 presents
group, hydroxyl group and so on, which can influence O-H stretching vibrations of hydroxyl groups. The peak
the adsorption characteristics of activated carbon around 2920 cm-1 means C-H stretching vibrations of
[35]. methylene groups. The peak around 1700 cm-1 is C=O
752 Liu X., et al.

water. In a single system, every kind of heavy metal

compound was separately used to obtain its single
solution. In a competitive system, three kinds of heavy
metal compounds were mixed together. The chemical
compounds were of analytical grade.

Batch Scale Experiments

A self-designed round stirrer was used for the batch

adsorption experiments. To investigate the adsorption
equilibrium characteristics of heavy metal ion adsorption
by activated carbon, peanut shell and sawdust, batch
adsorption experiments over different adsorption times
were performed with other conditions fixed (room
temperature: 25ºC; solution pH: 6.8; initial solution
concentration: 60 ppm; adsorbent amount: 0.4 g).
Adsorption experiments were performed using different
heavy metal concentrations ranging from 5 to 400 mg/L
with other conditions fixed (room temperature: 25ºC;
solution pH: 6.8; adsorption time: 5h; adsorbent amount:
0.4 g). Each experiment was conducted in triplicate.
The solutions, after adsorption, were filtered through
0.45 um membrane filters. Then the concentrations
of filtrate were measured using an atomic absorption
spectrophotometer (AAS), (Analytik Jena G, DE/novAA
300).
The amount of heavy metal ions adsorbed by per
unit mass of adsorbent was calculated by equation (1).
The removal ratio of heavy metal ions was calculated by
equation (2):

(C0 − Ce )V
Qe =
M ×1000 (1)

(C0 − Ce )
R= ×100%
C0 (2)
Fig. 2. FTIR spectra of adsorbents: a) activated carbon, b) peanut
shell, c) sawdust. …where Qe is the amount of heavy metal ions adsorbed
by per unit mass of adsorbent at equilibrium, mg/g;
R is removal ratio, %; C0 is the initial concentration
of heavy metal ions, mg/L; Ce is the concentration of
stretching vibration of carboxyl groups. The peaks heavy metal ions at equilibrium, mg/L; V is the volume
between 1500 cm-1 and 1300 cm-1 are caused by COO- of heavy metal solution, L; and M is the weight of the
stretching vibrations of carboxylate functional groups, adsorbent, g.
which present cellulose in sawdust. The peak between
1300 cm-1 and 1000 cm-1 can be attributed to C-O Adsorption Kinetic Models
stretching vibrations of carboxylic groups. The peak
around 900 cm-1 was an assignment of C-O bending. To Adsorption kinetics are important for the
sum up, sawdust includes some functional groups such understanding of adsorption processes. The relationships
as carboxylic, hydroxyl and methyl. These functional between heavy metal ion adsorption and adsorption
groups can form complex compounds with heavy metal time can be used to investigate the adsorption kinetics.
ions on the sawdust surface [38]. A pseudo first-order kinetic model, pseudo second-order
kinetic model and intraparticular diffusion model were
Heavy Metal Solution Preparation used to analyze the adsorption behaviour of heavy metal
ions by activated carbon, peanut shell, and sawdust in
Cadmium, lead, and copper ion solutions were both single and competitive systems. The linearized
obtained by dissolving the predefined amounts of pseudo first-order kinetic model and pseudo second-
CdCl2·5H2O; Pb (NO3)2; Cu(NO3)2·2H2O in distilled order kinetic model can be respectively expressed
Competitive Adsorption of Heavy Metal Ions... 753

as equations (3) and (4) [39-41]. The intraparticular Results and Discussion
diffusion model was expressed by equation (5) [42].
Adsorption Equilibrium
log(Qe − Qt ) = log Qe − k1t (3)
The relationship between heavy metal ions
t 1 1 adsorbed onto adsorbent and adsorption time can be
= 2
+ t used to investigate the adsorption equilibrium process.
Qt k 2Qe Qe Fig. 3 shows the effect of adsorption time on the
(4)
heavy metal ions amount adsorbed by activated carbon
Qt = k d t 1/ 2 + C (5)

…where t is adsorption time, min; Qt is the amount

of heavy metal ions adsorbed by per unit weight of
adsorbent at time t, mg/g; k1 is the rate constant of pseudo
first-order kinetic model, min-1; k2 is the rate constant of
pseudo second-order kinetic model, g/(mg·min); kd is
rate constant of intraparticular diffusion, mg/(L·min1/2);
and C is the y-intercept, mg/g.

Adsorption Isotherms

Adsorption isotherms can help us understand the

adsorption behavior: the Freundlich and Langmuir
isotherms are two models used to investigate adsorption
mechanisms [43]. The linear form of the Freundlich
model can be expressed as equation (6). The linear form
of the Langmuir model is presented as equation (7):

1
log Qe = log K F + log Ce
n (6)

(7)

…where K F is the Freundlich constant that is related to

adsorption capacity of heavy metal ions by adsorbent,
mg/g; n is Freundlich constant that can indicate the
adsorption process is favorable or unfavorable; b is
Langmuir constant that is related to the maximum
adsorption capacity of heavy metal ions by adsorbent,
mg/g; and K L is Langmuir constant that is related to
the change of adsorption energy in the adsorption
process, L/g.

Evaluation Ratio for Competition Adsorption

To investigate the interactive effect of three heavy

metal ions in a competitive system, an evaluation ratio
was introduced, as expressed by equation (8):

'
Q
E= e
Qe (8)

…where E is the evaluation ratio that is the ratio of Qe’ to Fig. 3. Effect of adsorption time on heavy metal ions adsorbed
Qe; Qe’ is the amount of heavy metal ions adsorbed in a by activated carbon, peanut shell and sawdust in single and
competition system, mg/g; and Qe is the amount of heavy competition systems: a) activated carbon, b) peanut shell, c)
metal ions adsorbed in single system, mg/g. sawdust.
754 Liu X., et al.

(a), peanut shell (b) and sawdust (c) – in both single was: lead > copper > cadmium. This preference of
and competition systems. With the adsorption time adsorbents for different kinds of heavy metal ion
increasing, the amount of heavy metal ions adsorbed adsorption can be related to many reasons, the heavy
increased rapidly at initial adsorption process and then metal ionic size, heavy metal ionic weight, and heavy
increased gradually. After the increasing period, the metal ionic charge, for example [32]. These different
maximum adsorption values were obtained and the adsorption capacities can be explained by the FTIR
adsorption process reached adsorption equilibrium. graphs of adsorbents.
This phenomenon can be explained by the adsorption From Fig. 3 we can see that heavy metal ions
sites of adsorbents. At the beginning of the adsorption adsorption equilibrium values in a competitive system
period there are enough adsorption sites on the were less than those in a single system. Competition
adsorbent that were available for the heavy metal ions’ between heavy metal ions affected adsorption efficiency
adsorption [44]. With the adsorption time increasing, the of every ion. The adsorption sites of the adsorbent
adsorption sites gradually become saturated, thus slopes will be replaced by other heavy metal ions in a
of curves in Fig. 3 decreased. Similar trends have been competitive system, thus the adsorption capacity for the
obtained by other researchers [39, 40, 43, 44]. same heavy metal ion decreased in a competitive system
By comparison, the adsorption capacity of three [30].
different adsorbents inferred that activated carbon
showed best adsorption efficiency, followed by peanut Adsorption Kinetics
shells, with sawdust showing the worst adsorption
efficiency for three heavy metal ions. In part this was The pseudo first-order kinetic model was based on
due to the high specific surface of activated carbon, solution concentration, it was always used for the initial
and peanut shells showed higher specific surface than adsorption process or the adsorption period closed
sawdust, even though it was not as good as activated to equilibrium [39, 40]. The pseudo second-order
carbon. In addition, the higher adsorption efficiency of kinetic model was based on the adsorption equilibrium
peanut shell can be attributed to the functional groups capacity, and it was assumed that there is a proportional
in peanut shell. relationship between the adsorption capacity and the
The ascending order of three heavy metal ions number of active sites on the surface of an adsorbent
adsorbed by activated carbon, peanut shell and sawdust [41].

Table 2. Fitting parameters of pseudo first-order and pseudo second-order adsorption kinetic models.
Adsorbent Pseudo-first-order Pseudo-second-order
Heavy metal Adsorption system
materials k1 Qe R2 k2 Qe R2
Singel 0.013 0.22 0.75 2.73 5.23 0.99
Lead
Competition 0.0024 0.49 0.84 0.18 3.52 0.99

Activated Singel 0.0061 2.75 0.91 0.088 5.27 0.99

Copper
carbon Competition 0.0048 4.03 0.96 0.017 4.09 0.99
Singel 0.0037 2.25 0.92 0.049 5.27 0.99
Cadmium
Competition 0.0062 2.82 0.96 0.023 3.43 0.99
Singel 0.028 0.11 0.98 1.39 5.15 0.99
Lead
Competition 0.0031 1.48 0.96 0.063 3.75 0.99
Singel 0.0034 0.32 0.94 0.46 4.47 0.99
Peanut shell Copper
Competition 0.0021 0.53 0.97 0.10 2.42 0.99
Singel 0.014 0.93 0.77 0.59 3.99 0.99
Cadmium
Competition 0.0029 1.07 0.96 0.045 2.26 0.99
Singel 0.0051 0.92 0.96 0.26 4.42 0.99
Lead
Competition 0.0019 0.99 0.98 0.056 2.94 0.99
Singel 0.0017 0.55 0.98 0.14 3.61 0.99
Sawdust Copper
Competition 0.0031 0.83 0.94 0.053 2.13 0.99
Singel 0.023 0.99 0.79 0.085 2.61 0.99
Cadmium
Competition 0.013 0.64 0.93 0.033 1.06 0.96
Competitive Adsorption of Heavy Metal Ions... 755

The fitting parameters of pseudo first-order and from the bulk solution to the external boundary layer
pseudo second-order adsorption kinetic models are film of liquid surrounding the outside of an adsorbent
listed in Table 2. As we can see, both kinetic models can particle; 2) adsorbate was attached to the surface of
help understand the adsorption process and all the fitting the adsorbent, this process was always rapid and the
degrees were in the range from 0.75 to 0.99. The fitting energy provided corresponded to the type of binding
degrees of the pseudo second-order kinetic model are all process (physical adsorption, chemical adsorption
more than 0.96 and very close to 1, which indicates that or both kinds of adsorption); and 3) adsorbate further
the heavy metal ions adsorption process fit the pseudo diffused into the inner adsorption sites of the adsorbent.
second-order kinetic model very well. The fitting plots The heavy metal ion adsorption process, with different
of the pseudo second-order kinetic model are shown in adsorbents, was mainly controlled by one or more
Fig. 4. steps of these three adsorption steps mentioned above
There were always three steps for the heavy metal [42].
ions adsorption process when the adsorbent was in Fig. 5 shows the plots of Qt versus t1/2 for the heavy
contact with the solution: 1) adsorbate transferred metal ions adsorption by activated carbon, peanut

Fig. 4. Plot of linearized pseudo second-order kinetic model Fig. 5. Plot of intraparticular diffusion kinetic model fitting for
fitting for heavy metal ions adsorption by activated carbon, heavy metal ion adsorption by activated carbon, peanut shell and
peanut shell and sawdust in single and competition systems: a) sawdust in single and competition systems: a) activated carbon,
activated carbon, b) peanut shell, c) sawdust. b) peanut shell, c) sawdust.
756 Liu X., et al.

shell and sawdust in single and competitive systems. concentration increasing, the amount of heavy metal
The adsorption processes were divided into two stages: ions adsorbed increased, whereas the removal ratio
a fast adsorption stage wherein a large amount of decreased. Initial solution concentration can provide
heavy metals were transferred from bulk solution to a driving force for heavy metal ions in solution to
the external boundary layer film to be adsorbed. The transfer from solution to the surface of adsorbent.
intraparticular diffusion in this stage was rate limiting. With the increase of the initial solution concentration,
The second stage was an equilibrium stage in which the driving force is also enhanced, thus much heavier
most adsorption was saturated, and the adsorption metal ions can be attached onto the adsorption sites
rate was very slow and tended to be a stable state of adsorbent. However, the adsorption sites would
thereafter. The rate parameters of the intraparticular reach saturation state with the heavy metal ions
diffusion model for heavy metal ion adsorption by adsorbed increasing, the changing curves of heavy
activated carbon, peanut shell, and sawdust are listed in metal ion amounts would turn to being stable in
Table 3. The rate constants in the first stage were all the late stage of concentration growth [45]. For fixed
higher than those in the second stage, which indicated amount of adsorbents, the adsorption sites for heavy
that the intraparticular diffusion process was first rapid metal ions were limited, with the initial concentration
and then slow [42]. increasing, the total heavy metal ions in solution
also increased, corresponding to amounts of heavy
Effect of Initial Concentration on Adsorption metal ions that cannot be adsorbed by adsorbent
Efficiency also increased. As a result, the removal ratio declined
with the initial concentration increasing, although
Batch adsorption experiments were conducted the higher driving force can enhance the amount of
under different initial concentrations. The adsorption adsorbed heavy metal ions. It can be inferred that the
results of different heavy metal ions by different adsorption type is single-layer adsorption and this
adsorbents are shown in Fig. 6. As we can see, phenomenon can be further explained by adsorption
both in single and competition systems, with initial isotherms analysis.

Table 3. Fitting parameters of intraparticular diffusion kinetic model.

Intraparticle diffusion coefficiencies
Adsorbent Heavy metal Adsorption system First stage Second stage
Kd C R 2
Kd C R2
Singel 0.047 4.83 0.73 0.0026 5.19 0.87
Lead
Competition 0.055 2.79 0.99 0.063 2.50 0.93
Singel 0.35 1.47 0.98 0.11 3.48 0.99
Activated carbon Copper
Competition 0.21 0.19 0.93 0.013 3.43 0.75
Singel 0.28 1.21 0.94 0.0039 5.04 0.68
Cadmium
Competition 0.20 0.46 0.93 0.0045 3.14 0.66
Singel 0.43 4.76 0.99 0.011 1.97 0.86
Lead
Competition 0.13 1.82 0.93 0.046 2.69 0.96
Singel 0.06 3.84 0.92 0.029 4.01 0.89
Peanut shell Copper
Competition 0.087 1.37 0.69 0.033 0.74 0.99
Singel 0.089 3.17 0.93 0.025 3.61 0.76
Cadmium
Competition 0.12 0.70 0.98 0.052 1.27 0.78
Singel 0.076 3.34 0.90 0.0080 4.19 0.84
Lead
Competition 0.049 1.78 0.96 0.012 2.55 0.79
Singel 0.025 2.97 0.98 0.010 3.24 0.74
Sawdust Copper
Competition 0.043 1.24 0.97 0.0076 1.87 0.90
Singel 0.097 1.87 0.85 0.0054 2.46 0.83
Cadmium
Competition 0.061 0.53 0.99 0.0065 0.86 0.88
Competitive Adsorption of Heavy Metal Ions... 757

Fig. 6. Effect of initial concentrations on heavy metal ions adsorbed by activated carbon, peanut shell and sawdust in single and
competition systems: a) activated carbon, b) peanut shell, c) sawdust.

Adsorption Isotherms obtained from the Langmuir isotherm model were much
higher than those values obtained from the use of the
Adsorption results under different initial Freundlich isotherm model, thus it can be concluded
concentrations were used to fit the isotherm models. that the adsorption behaviour of heavy metal ions by
Freundlich isotherm is usually applied to characterize activated carbon, peanut shell, and sawdust follow the
heterogeneous adsorption on the adsorbent surface, Langmuir, which assumes single-layer adsorption and is
whereas the Langmuir isotherm was used to describe consistent with the above results (Fig. 7).
homogenous adsorption on the adsorbent surface,
it was also assumed that the adsorbent surface was Effect of Interactions among Heavy Metal Ions
covered with a monolayer of adsorbates [14]. The in a Competitive System
fitting parameters of these two isotherm models are
listed in Table 4. The adsorption behaviour exhibited a E can represent the type of interaction among heavy
good fit with both isotherm models. All the R2 values metal ions in a competitive system [46]. When E>1,
758 Liu X., et al.

Table 4. Fitting parameters of Freundlich and Langmuir isotherm models for heavy metal ions adsorption by activated carbon, peanut
shell and sawdust.
Freundlich isotherm Langmuir isotherm
Adsorbent Heavy metal Adsorption system
KF n R2 KL b R2
Single 3.95 4.08 0.93 0.19 13.70 0.99
Lead
Competition 2.10 3.69 0.98 0.048 11.35 0.98
Single 1.01 2.10 0.95 0.044 13.33 0.99
Activated carbon Copper
Competition 0.84 2.19 0.96 0.029 11.51 0.97
Single 1.72 4.46 0.87 0.31 5.32 0.99
Cadmium
Competition 0.93 3.76 0.94 0.067 4.40 0.99
Single 1.24 2.59 0.78 0.085 9.52 0.99
Lead
Competition 0.97 2.66 0.95 0.073 7.46 0.99
Single 0.67 2.19 0.94 0.027 9.26 0.94
Peanut shell Copper
Competition 0.60 2.61 0.98 0.017 7.04 0.90
Single 0.84 2.97 0.93 0.095 5.16 0.99
Cadmium
Competition 0.84 3.99 0.96 0.039 4.12 0.99
Single 1.15 3.55 0.93 0.83 5.65 0.99
Lead
Competition 1.26 4.37 0.98 0.12 4.47 0.99
Single 0.91 2.08 0.81 0.33 5.75 0.99
Sawdust Copper
Competition 1.06 4.27 0.98 0.067 4.32 0.99
Single 0.55 2.79 0.95 0.055 4.12 0.99
Cadmium
Competition 0.10 1.85 0.93 0.009 3.19 0.94

synergism with other heavy metal ions is generated, presence of another heavy metal ion would suppress the
the presence of other heavy metal ions can enhance adsorption of another.
adsorption of another heavy metal ion; when E = 1, no The values of E for the different heavy metal ion
interaction takes place in a competitive system, which adsorptions by activated carbon, peanut shell, and
means that the presence of other heavy metal ions would sawdust from aqueous solution with different initial
not influence the adsorption of another; each other’s solution concentrations are presented in Table 5. As
adsorption; and when E<1, antagonism prevails and the mentioned, these three adsorbents show their best

Table 5. Calculated evaluation ratios.

Solution concentration 5 10 20 40 60 100 200 300 400
Adsorbent
Heavy metal Evaluation ratios
Cadmium 0.99 0.93 0.63 0.66 0.61 0.73 0.76 0.79 0.80
Activated carbon Copper 0.99 0.91 0.99 0.94 0.83 0.73 0.79 0.83 0.89
Lead 0.97 0.96 0.98 0.81 0.66 0.66 0.79 0.82 0.80
Cadmium 0.96 0.86 0.75 0.56 0.53 0.68 0.73 0.74 0.76
Peanut shell Copper 0.97 0.98 0.90 0.73 0.54 0.61 0.63 0.63 0.74
Lead 0.92 0.98 0.96 0.85 0.68 0.63 0.68 0.74 0.79
Cadmium 0.62 0.36 0.31 0.33 0.34 0.42 0.63 0.65 0.65
Sawdust Copper 0.87 0.83 0.87 0.63 0.65 0.61 0.78 0.78 0.81
Lead 0.93 0.98 0.83 0.69 0.61 0.62 0.79 0.79 0.81
Competitive Adsorption of Heavy Metal Ions... 759

[47]. In other research, heavy metal ion adsorption

decreased in multiple metal systems, which was similar
to the results of this study [45, 46].

Conclusions

The adsorption characteristics of heavy metal

ions by activated carbon, peanut shell, and sawdust
were investigated in single and competitive systems.
Adsorption efficiencies in descending order for different
kinds of heavy metal ions is: lead, copper, cadmium.
FTIR results indicate different functional groups
for different adsorbents, thus the adsorbents show
different adsorption capacities for heavy metal ions; the
adsorption efficiency of different adsorbents was ranked
(in descending order) as: activated carbon, peanut shell,
sawdust. The amount of heavy metal ions adsorbed
increased with increasing adsorption times; as the initial
concentration of heavy metal ions increased, the amount
of heavy metal ions adsorbed also increased, while the
removal ratio decreased; the adsorption process followed
the Langmuir isotherm model and pseudo second-order
kinetic model; there were antagonistic effects among the
three kinds of heavy metal ions in a competitive system,
as evinced by the adsorption results.
In conclusion, as an agricultural waste material,
peanut shell is a potential adsorbent for heavy metal
removal with good adsorption efficiency, however, there
are some limitations to this study: other factors that
can influence the adsorption efficiency should be taken
into consideration, including pH value and temperature;
and large-scale simulation experiments should be
conducted in order to improve understanding of their
adsorption efficiency of adsorbent in field application.

Acknowledgements

This study was financially supported by the National

Fig. 7. Plot of Langmuir isotherm model fitting for heavy metal
ions adsorption by activated carbon, peanut shell and sawdust in
Natural Science Foundation of China (51978438),
single and competition systems: a) activated carbon, b) peanut Shanxi Scholarship Council of China (2017-039),
shell, c) sawdust. Scientific Research Foundation of Shanxi Province of
China (201701D121121), Korea Ministry of Environment
as “The SEM(Subsurface Environment Management)
projects; 2019~”, China Scholarship Council.
adsorption efficiency for lead, then copper, and their
worst efficiency was that measured for cadmium in both
single and competitive systems. In a competitive system,
Conflict of Interest
each heavy metal ion’s adsorption can be suppressed by
other kinds of heavy metal ions. According to Table 5,
The authors declare no conflict of interest.
the sum of three heavy metal ion evaluation ratios in
the same competitive system was much greater than 1.
This can indicate that, although each heavy metal ion
References
was less well adsorbed in a competitive system, the total
heavy metal ion adsorption increased compared with 1. ZHOU G., LUO J., LIU C., CHU L., CRITTENDEN J.
that in a single system. Thus, the effect of mixing heavy Efficient heavy metal removal from industrial melting
metal ions in a competitive system was antagonistic, but effluent using fixed-bed process based on porous hydrogel
the degree of suppression therein was not very strong adsorbents. Water research, 131, 246. 2018.
760 Liu X., et al.

2. DEMEY H., VINCENT T., GUIBAL E. A novel algal- 17. HAO L., ZHENG T., JIANG J., ZHANG G., WANG P.
based sorbent for heavy metal removal.  Chemical Removal of As (III) and As (V) from water using iron
Engineering Journal, 332, 582, 2018. doped amino functionalized sawdust: characterization,
3. BURAKOV A.E., GALUNIN E.V., BURAKOVA I.V., adsorptive performance and UF membrane
KUCHEROVA A.E., AGARWAL S., TKACHEV, A.G., separation.  Chemical Engineering Journal,  292, 163,
GUPTA, V.K. Adsorption of heavy metals on conventional 2016.
and nanostructured materials for wastewater treatment 18. BILIR M.H., ŞAKALAR N., ACEMIOĞLU B., BARAN
purposes: A review. Ecotoxicology and environmental E., ALMA M.H. Sorption of remazol brilliant blue r
safety, 148, 702, 2018. onto polyurethane-type foam prepared from peanut
4. JAISHANKAR M., TSETEN T., ANBALAGAN N., shell.  Journal of Applied Polymer Science,  127, 4340,
MATHEW B.B., BEEREGOWDA, K.N. Toxicity, 2013.
mechanism and health effects of some heavy 19. XU T., LIU X.Q. Peanut shell activated carbon:
metals. Interdisciplinary toxicology, 7 (2), 60, 2014. characterization, surface modification and adsorption of
5. LIU Y., XIAO T., BAVEYE P.C., ZHU J., NING Z., LI Pb2+ from aqueous solution.  Chinese Journal of Chemical
H. Potential health risk in areas with high naturally- Engineering, 16 (3), 401, 2008.
occurring cadmium background in southwestern 20. ÜNLÜ N., ERSOZ M. Adsorption characteristics of heavy
China. Ecotoxicology and environmental safety, 112, 122, metal ions onto a low cost biopolymeric sorbent from
2015. aqueous solutions.  Journal of Hazardous Materials,  136
6. LIU X., ZHONG L., MENG J., WANG F., ZHANG J., (2), 272-280, 2006.
ZHI Y., ZENG L., TANG X., XU J. A multi-medium chain 21. YU B., ZHANG Y., SHUKLA A., SHUKLA S.S.,
modeling approach to estimate the cumulative effects DORRIS K.L. The removal of heavy metal from aqueous
of cadmium pollution on human health.  Environmental solutions by sawdust adsorption-removal of copper. Journal
Pollution, 239, 308, 2018. of Hazardous Materials, 80 (1-3), 33, 2000.
7. WU W., WU P., YANG F., SUN D.L., ZHANG D.X., 22. GUPTA S., KUMAR D., GAUR J.P. Kinetic and isotherm
ZHOU Y.K. Assessment of heavy metal pollution modeling of lead (II) sorption onto some waste plant
and human health risks in urban soils around an materials.  Chemical Engineering Journal,  148 (2-3), 226,
electronics manufacturing facility.  Science of The Total 2009.
Environment, 630, 53, 2018. 23. WITEK-KROWIAK A., SZAFRAN R.G., MODELSKI S.
8. LU D., HUANG Q., DENG C., ZHENG Y. Biosorption of heavy metals from aqueous solutions onto
Phytoremediation of Copper Pollution by Eight Aquatic peanut shell as a low-cost biosorbent. Desalination, 265 (1-
Plants.  Polish Journal of Environmental Studies,  27 (1), 3), 126, 2011.
175, 2018. 24. BULUT Y., TEZ Z. Removal of heavy metals from aqueous
9. FU F., WANG Q. Removal of heavy metal ions from solution by sawdust adsorption. Journal of Environmental
wastewaters: a review. Journal of environmental Sciences(China), 19 (2), 160, 2007.
management, 92 (3), 407, 2011. 25. ŠĆIBAN M., RADETIĆ B., KEVREŠAN Ž., KLAŠNJA
10. ZHOU G., LUO J., LIU C., CHU L., CRITTENDEN M. Adsorption of heavy metals from electroplating
J. Efficient heavy metal removal from industrial wastewater by wood sawdust. Bioresource Technology, 98
melting effluent using fixed-bed process based on porous (2), 402, 2007.
hydrogel adsorbents. Water research, 131, 246, 2018. 26. YU L.J., SHUKLA S.S., DORRIS K.L., SHUKLA
11. LEGROURI K., KHOUYA E., HANNACHE H., EL A., MARGRAVE J.L. Adsorption of chromium from
HARTTI M., EZZINE M., NASLAIN R. Activated aqueous solutions by maple sawdust. Journal of hazardous
carbon from molasses efficiency for Cr (VI), Pb (II) materials, 100 (1-3), 53, 2003.
and Cu (II) adsorption: a mechanistic study.  Chemistry 27. BOŽIĆ D., STANKOVIĆ V., GORGIEVSKI M.,
International, 3 (3), 301, 2017. BOGDANOVIĆ G., KOVAČEVIĆ R. Adsorption of
12. CRINI G., LICHTFOUSE E., WILSON L. D., MORIN- heavy metal ions by sawdust of deciduous trees. Journal of
CRINI N. Adsorption-Oriented Processes Using hazardous materials, 171 (1-3), 684, 2009.
Conventional and Non-conventional Adsorbents for 28. BOHLI T., OUEDERNI A., FIOL N., VILLAESCUSA I.
Wastewater Treatment.  Green Adsorbents for Pollutant Evaluation of an activated carbon from olive stones used
Removal; Crini G, Lichtfouse E, Eds.,  Springer: Cham, as an adsorbent for heavy metal removal from aqueous
Volume 18, 23, 2018. phases. Comptes rendus chimie, 18 (1), 88, 2015.
13. ALI R.M., HAMAD H.A., HUSSEIN M.M., MALASH 29. WANG F., PAN Y., CAI P., GUO T., XIAO H. Single
G.F. Potential of using green adsorbent of heavy metal and binary adsorption of heavy metal ions from
removal from aqueous solutions: adsorption kinetics, aqueous solutions using sugarcane cellulose-based
isotherm, thermodynamic, mechanism and economic adsorbent. Bioresource technology, 241, 482, 2017.
analysis. Ecological Engineering, 91, 317, 2016. 30. PARK J.H., OK Y.S., KIM S.H., CHO J.S., HEO J.S.,
14. SADEEK S.A., NEGM N.A., HEFNI H.H., WAHAB DELAUNE R.D., SEO D.C. Competitive adsorption
M.M.A. Metal adsorption by agricultural biosorbents: of heavy metals onto sesame straw biochar in aqueous
Adsorption isotherm, kinetic and biosorbents solutions. Chemosphere, 142, 77, 2016.
chemical structures. International journal of biological 31. FANG L., LI L., QU Z., XU H., XU J., YAN N. (2018).
macromolecules, 81, 400, 2015. A novel method for the sequential removal and separation
15. DEMIRBAS A. Heavy metal adsorption onto agro- of multiple heavy metals from wastewater. Journal of
based waste materials: a review.  Journal of hazardous hazardous materials, 342, 617, 2018.
materials, 157 (2-3), 220, 2008. 32. LI Y.H., DING J., LUAN Z., DI Z., ZHU Y., XU C., WU
16. CUIPING L., CHUANGZHI W., HAITAO H. Study on the D., WEI B. Competitive adsorption of Pb2+, Cu2+ and
distribution and quantity of biomass residues resource in Cd 2+ ions from aqueous solutions by multiwalled carbon
China. Biomass and bioenergy, 27 (2), 111, 2004. nanotubes. Carbon, 41 (14), 2787, 2003.
Competitive Adsorption of Heavy Metal Ions... 761

33. PRELOT B., ARAÏSSI M., GRAS P., MARCHANDEAU 40. WANG J., JI B., SHU Y., CHEN W., ZHU L., CHEN, F.
F., ZAJAC J. Contribution of calorimetry to the Cr (VI) Removal from Aqueous Solution Using Starch
understanding of competitive adsorption of calcium, and Sodium Carboxymethyl Cellulose-Coated Fe and
strontium, barium, and cadmium onto 4A type zeolite Fe/Ni Nanoparticles.  Polish Journal of Environmental
from two-metal aqueous solutions. Thermochimica Acta, Studies, 27 (6), 2785, 2018.
664, 39, 2018. 41. HO Y.S., MCKAY G. Pseudo-second order model for
34. HE S., LI Y., WENG L., WANG J., HE J., LIU Y., sorption processes.  Process biochemistry,  34 (5), 451,
ZHANG K., WU Q., ZHANG Y., ZHANG Z. Competitive 1999.
adsorption of Cd 2+, Pb2+ and Ni2+ onto Fe3+-modified 42. ZAMRI M.F.M.A., KAMARUDDIN M.A., YUSOFF
argillaceous limestone: Influence of pH, ionic strength M.S., AZIZ H.A., FOO K.Y. Semi-aerobic stabilized
and natural organic matters.  Science of The Total landfill leachate treatment by ion exchange resin: isotherm
Environment, 637, 69, 2018. and kinetic study. Applied Water Science, 7 (2), 581, 2017.
35. SHEN J., HUANG G., AN C., XIN X., HUANG C., 43. GHASEMI M., NAUSHAD M., GHASEMI N.,
ROSENDAHL S. Removal of Tetrabromobisphenol A KHOSRAVI-FARD Y. Adsorption of Pb (II) from aqueous
by adsorption on pinecone-derived activated charcoals: solution using new adsorbents prepared from agricultural
Synchrotron FTIR, kinetics and surface functionality waste: adsorption isotherm and kinetic studies. Journal of
analyses. Bioresource Technology, 247, 812, 2018. Industrial and Engineering Chemistry, 20 (4), 2193, 2014.
36. KHAN M.A., KHAN S., DING X., KHAN A., ALAM 44. YI Z.J., YAO J., CHEN H.L., WANG F., YUAN Z.M.,
M. The effects of biochar and rice husk on adsorption and LIU X. Uranium biosorption from aqueous solution
desorption of cadmium on to soils with different water onto Eichhornia crassipes. Journal of environmental
conditions (upland and saturated).  Chemosphere,  193, radioactivity, 154, 43, 2016.
1120, 2018. 45. IQBAL M., KHERA R.A. Adsorption of copper and lead
37. SONG J., ZOU W., BIAN Y., SU F., HAN R. Adsorption in single and binary metal system onto Fumaria indica
characteristics of methylene blue by peanut husk in batch biomass. Chemistry International, 1 (3), 157, 2015.
and column modes. Desalination, 265 (1-3), 119, 2018. 46. MAHAMADI C., NHARINGO T. Competitive adsorption
38. WAHAB M.A., JELLALI S., JEDIDI N. Ammonium of Pb2+, Cd 2+ and Zn2+ ions onto Eichhornia crassipes in
biosorption onto sawdust: FTIR analysis, kinetics binary and ternary systems.  Bioresource Technology,  101
and adsorption isotherms modeling. Bioresource (3), 859, 2010.
Technology, 101 (14), 5070, 2010. 47. AGARWAL B., BALOMAJUMDER C., THAKUR
39. SOGUT E.G., CALISKAN N. Iisotherm and kinetic P.K. Simultaneous co-adsorptive removal of phenol and
studies of Pb (ii) adsorption on raw and modified diatomite cyanide from binary solution using granular activated
by using non-linear regression method. Fresenius carbon. Chemical engineering journal, 228, 655, 2013.
environmental bulletin, 26 (4), 2720, 2017.