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Journal of Environmental Chemical Engineering 2 (2014) 19121919

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Journal of Environmental Chemical Engineering


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

Biosorptive removal of Cu(II), Ni(II) and Pb(II) ions from aqueous


solutions using coconut dregs residue: Adsorption and characterisation
studies
Azlan Kamari a,b, *, Siti Najiah Mohd Yusoff a , Fadhilah Abdullah a , Wiwid Pranata Putra a
a
b

Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak, Malaysia
Nanotechnology Research Centre, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, Tanjung Malim, Perak, Malaysia

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 26 March 2014
Accepted 17 August 2014
Available online 21 August 2014

The efcacy of coconut dregs residue, a by-product from coconut milk production factory, to adsorb
Cu(II), Ni(II) and Pb(II) ions from aqueous solutions was investigated. The effects of experimental
parameters such as solution pH, contact time and initial metal concentration on adsorption process were
examined in batch experiments. The equilibrium data were best described by the Langmuir isotherm
model, while the dynamical data followed the pseudo-second order kinetic model. The Freundlich
constant (n) and separation factor (RL) values suggest that the metal ions were favourably adsorbed onto
biosorbent. The afnity of the biosorbent for metal ion was in the order of Pb(II) > Cu(II) > Ni(II), both in
single- and multi-metal systems. The characterisation studies were carried out using scanning electron
microscope (SEM), energy dispersive X-ray spectrometer (EDX) and Fourier transform infrared
spectrometer (FTIR). Complexation between metal ions and binding sites of the biosorbents was the
main adsorption mechanism. Coconut dregs residue removed Cu(II) better than bamboo derived
activated carbon, a commercial activated carbon, from electroplating efuent.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Adsorption
Characterisation
Equilibrium isotherm
Kinetics
Metal ions
Coconut dregs residue

Introduction
The release of industrial efuents containing excessive amount
of toxic metals to the environment have caused serious problems
with regards to water quality. Heavy metals such as Cr, Cu, Ni, Pb
and Zn can be found in the efuents of metal plating, battery
manufacturing, and leather nishing, mining and smelting
industries [1]. Heavy metals are non-biodegradable and carcinogenic contaminants. Therefore, their presence in the environment
can be harmful or nuisance to living organisms [2]. For example,
high intake of Cu can cause severe mucosal and central nervous
system irritation, kidney and liver dysfunction, anaemia and
gastrointestinal diseases [3]. According to Bahadori et al. [4], there
were 10 countries had serious water contamination issues in 2010.
The top 5 countries were Brazil, USA, China, Indonesia and Japan.
Due to rapid industrialisation, water pollution is becoming a

* Corresponding author at: Department of Chemistry, Faculty of Science and


Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak,
Malaysia. Tel.: +60 15 48117320; fax: +60 15 48117296.
E-mail addresses: azlan.kamari@fsmt.upsi.edu.my, azlkam@yahoo.co.uk
(A. Kamari).
http://dx.doi.org/10.1016/j.jece.2014.08.014
2213-3437/ 2014 Elsevier Ltd. All rights reserved.

serious environmental issue in Malaysia. Mohamed and Jahi [5]


studied the implication of manufacturing industries within Langat
Drainage Basin, Selangor. They reported that there were about
330 factories located in Langat Drainage Basin, ranging from the
manufacture of agricultural end products to high-tech products
such as consumer electronics. The electrical and electronic
industries were reported to predominate with 53 industries,
followed by factories manufacturing industrial and engineering
products, building materials, chemicals, textile and fabrics, and
furniture. They highlighted the rapid decline of the rivers water
quality, particularly metal concentration, beginning of 1991.
In order to maintain the quality of the water, several techniques
have been developed to purify industrial efuents before being
discharge to the main streams [6]. These techniques include
membrane ltration, solvent extraction, ion-exchange, chemical
precipitation, oxidation and electrodeposition [7,8]. However,
many of these techniques are not practical to implement due to
several drawbacks such as high operating cost, high energy
consumption, low selectivity and generate toxic slurries [9].
Therefore, physicochemical approach by using adsorption method
has been proposed to solve this problem.
Adsorption has been regarded as a promising and cost-effective
method for heavy metals removal. This technique does not

A. Kamari et al. / Journal of Environmental Chemical Engineering 2 (2014) 19121919

generate solid residues and suitable for a wide range of metal ion
concentrations [2,10]. Activated carbon has been widely used as an
adsorbent because it has large surface area and high adsorption
capacity [11]. In spite of its excellent ability to treat industrial
efuents, activated carbon is costly [12]. Therefore, alternative
adsorbents derived from natural materials, agricultural and
industrial wastes that are available in large quantities and cheap
need to be utilised [13,14].
Coconut dregs residue is the waste obtained from coconut milk
production and easily available at low-cost [15]. After extracting
most of the milk from the coconut, the remaining product is called
coconut dregs residue. This waste can be used to feed animal or just
let to decompose on the eld [15]. It was estimated that about
555,120 t of coconut have been produced in 2008 in Malaysia. From
this value, approximately 510,000 t of coconut has been used [16].
So, the application of coconut dregs residue for water clean-up can
offer a good solution for its disposal.
In this study, the potential of coconut dregs residue as a
biosorbent to sequester Cu(II), Ni(II) and Pb(II) ions from aqueous
solutions was evaluated. The effects of experimental parameters
such as solution pH, contact time and initial metal concentration
on metal ion adsorption were investigated. The equilibrium
adsorption data were tted with the Freundlich and Langmuir
isotherm models. The adsorption rates were determined using the
pseudo-rst order, pseudo-second order and intraparticle diffusion kinetic models. The characteristics of the biosorbents and
possible binding mechanism(s) involved were studied using SEM,
EDX and FTIR.
Materials and methods
Preparation of biosorbent
The coconut dregs residue was obtained from a coconut milk
production factory in Banting, Selangor. The residue was washed
thoroughly with deionised water and dried in an oven at 70  C for
7 days. The dried material was then ground and sieved through
150250 mm size fractions using an American Society for Testing
and Materials (ASTM) standard sieve. The ground material was
kept in self-sealing plastic bags to avoid moisture effects.
Preparation of stock solutions
The stock solutions of 1000 mg/L were prepared by dissolving
appropriate amount of Cu(NO3)22.5H2O (HmbG Reagent Chemicals), Ni(NO3)26H2O (Bendosen Laboratory Chemicals) and
Pb(NO3)2 (Bendosen Laboratory Chemicals) salts in 0.1 mol/L
KNO3. In this study, 0.1 mol/L KNO3 was used as an electrolyte
to control the ionic strength. The stock solutions were then diluted
to the required concentrations. Cu, Ni and Pb atomic absorption
spectrometer (AAS) standard calibration solutions were obtained
from Fisher Scientic. All reagents used were analytical reagent
grade, and deionised water was used throughout this study.
Characterisation studies
The surface area and pore diameter of coconut dregs residue
were determined using a Quantachrome Autosorb 1 Surface
Analyser. The surface area was determined according to the
BrunauerEmmettTeller (BET) multipoint technique [17], meanwhile the Barrett, Joyner and Halenda (BJH) technique was applied
for pore diameter analysis [18]. The surface area and pore diameter
of coconut dregs residue were measured as 0.38 m2/g and 1.83 nm,
respectively. According to the International Union of Pure and
Applied Chemistry (IUPAC) classication, the pore of the biosorbent corresponds to micropores (d < 2 nm).

1913

The presence of functional groups in the coconut dregs residue


was conrmed using a Thermo Nicolet 6700 FTIR Spectrometer. A
Hitachi SU 8020 UHR eld emission scanning electron microscope
(FESEM) was used to observe the surface morphology of coconut
dregs residue before and after interaction with metal ions. The
coconut dregs residue was rst coated with platinum to avoid
electron charging during analysis. The elemental composition in
the coconut dregs residue was examined using a Horiba energy
dispersive X-ray (EDX) spectrometer. The CHN analyses of the
biosorbent were determined using a Thermo Electron Flash EA
1112 Series CHNS/O Analyzer. The biosorbent contains 42.73% of C,
13.08% of H and 5.74% of N.
The pH of the zero point charge (pHzpc) of soya dregs was
determined by the acidbase titration approach outlined by Huang
and Ostovic [19] and Jha et al. [20]. The experiment was conducted in
the presence of 1.0, 0.1 and 0.01 mol/L NaCl electrolytes, and 0.1 mol/L
HCl and 0.1 mol/L NaOH solutions were used as the titrants.
Adsorption studies
Batch adsorption experiments were carried out in 250 mL
conical asks by adding approximately 0.5 g of biosorbent in 50 mL
of metal ion solution of the required concentration. The samples
were equilibrated by shaking at 120 rpm using a Protech orbital
shaker (model 720). The samples were then separated through
lter paper (Filtre Fioroni 601, 125 mm). The concentration of metal
ion in the supernatant was measured by using a PerkinElmer
AAnalyst 400 atomic absorption spectrometer.
The effect of solution pH was studied in the pH range of 3.07.0.
Appropriate amount of 0.1 mol/L of HCL or NaOH solution was used
to adjust the pH of 100 mg/L metal ion solutions. The pH readings
were measured using a Thermo Scientic, Orion 2-Star pH meter.
To study the effect of contact time, 10 sets of 100 mg/L of metal ion
solutions were equilibrated with biosorbents for a period of time
(between 15 and 240 min). The effect of initial metal concentration
was conducted by adding biosorbents in 50 mL of metal ion
solution ranging from 5 to 100 mg/L. The mixture was then
equilibrated for 60 min.
The competitive adsorption study was accomplished in multimetal system. The coconut dregs residue was added to 50 mL
solution containing 25 mg/L of Cu(II), Ni(II) and Pb(II). The
suspension was equilibrated for 4 h at a constant agitation speed.
The concentration of each metal ion in the supernatant was
measured using AAS, and the dried ltrate was characterised, as
discussed in Section Characterisation studies.
All experiments were run in triplicates and metal free blanks
were used as controls. The adsorption capacity at equilibrium was
calculated using Eq. (1):


C0  Ce
qe
V
(1)
W
where qe is the amount of metal ion adsorbed by the biosorbent
(mg/g), C0 is the initial concentration of metal ion (mg/L), Ce is the
equilibrium concentration of metal ion (mg/L), W is the weight of
the biosorbent (g), and V is the volume of metal ion solution (L).
The percentage ion removal for the adsorption process was
estimated using Eq. (2):


C0  Ce
Removal%
 100
(2)
C0
Industrial efuent treatment
The effectiveness of coconut dregs residue to remediate metal
contaminated water was examined using an industrial efuent.
The industrial efuent sample was collected from an electroplating

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A. Kamari et al. / Journal of Environmental Chemical Engineering 2 (2014) 19121919

Results and discussion


Adsorption studies

Amount of metal ion adsorbed, qe (mg/g)

[(Fig._2)TD$IG]

factory in Bayan Lepas Industrial Zone, Penang. The industrial


efuent was rst ltered through a lter paper to remove dirt and
suspended solid. The metal concentration in the efuent sample
was then measured using AAS. The adsorption study was carried
out at optimum conditions and at adsorbent dosage of 1 g per
50 mL sample.

10

Effect of solution pH
The degree of ionisation of metal ions in aqueous solution and the
charge on the surface of adsorbents are greatly inuenced by the
solution pH [7]. The effects of solution pH on the adsorption of Cu(II),
Ni(II) and Pb(II) ions by coconut dregs residue were studied at an
initial pH ranged from 3.0 to 7.0 (Fig. 1). The adsorption studies were
performed within the pH range because it was observed that metal
ions formed insoluble hydroxide precipitates simultaneously at pH
value greater than 7.0. The removal of metal ions at pH value greater
than 7.0 was not solely by adsorption onto coconut dregs residue, but
due to hydroxide precipitation as well. This phenomenon leads to
inaccurate interpretation of adsorption process.
From Fig. 1, it is apparent that the amount of Cu(II), Ni(II) and
Pb(II) adsorbed by coconut dregs residue increased with increasing
the pH of the solution. This trend can be explained by the fact that
the concentration of H+ ions was high at low pH (acidic medium).
This scenario leads to competition and repulsion between H+ and
metal ions for active sites on the surface of biosorbent [8,21]. When
the pH increased, H+ ions were less available, and therefore more
metal ions can be bound to adsorption sites.
Cu(II) was the metal ion most affected by this effect, followed by
Pb(II). In contrast, Ni(II) adsorption was not really affected by
solution pH, whereby the amount of Ni(II) adsorbed was within
3.404.81 mg/g when the solution pH was adjusted from 3.0 to 7.0.
The behaviour and ability of a sorbent to adsorb contaminants from
aqueous environment can be described in terms of pH of the zero
point of charge (pHzpc). As discussed by Mall et al. [22], adsorption
of cations is favoured at pH greater than pHzpc, while adsorption of
anions is favoured at pH lesser than pHzpc. In this study, pHzpc
obtained for coconut dregs residue is 5.7. As can be seen from Fig. 1,
the maximum adsorption of Cu(II), Ni(II) and Pb(II) onto coconut
dregs residue was at pH 7.0 (higher than pHzpc value). Therefore,
pH 7.0 was chosen as the optimum pH for the adsorption process.
Effect of initial metal concentration and contact time
Fig. 2 presents the effect of initial metal concentration on the
adsorption of Cu(II), Ni(II) and Pb(II) ions by coconut dregs residue.

Amount of metal ion adsorbed, qe (mg/g)

[(Fig._1)TD$IG]

20

40

60

80

100

120

Initial metal concentration (mg/L)


Cu(II)

Ni(II)

Pb(II)

Fig. 2. Effect of initial metal concentration on adsorption of metal ion by coconut


dregs residue.

From Fig. 2, it is clear that the amount of metal ion adsorbed by the
biosorbent increased when increasing the initial metal concentration. For example, the amount of Pb(II) adsorbed by coconut dregs
residue increased from 0.50 to 9.60 mg/g as the initial Pb(II)
concentration increased from 5 to 100 mg/L. High adsorption
capacity at high initial metal concentration can be related to two
main factors, namely high probability of collision between metal
ion and biosorbent, and high diffusion rate of metal ion into
biosorbent. As a result, it will increase the driving force and reduce
the mass transfer resistance [23].
In contrast to adsorption capacity, the removal percentage of
metal ion decreased signicantly when the initial metal concentration was increased (Table 1). For example, the removal
percentage of Cu(II) reduced from 86.58% to 26.64% when the
initial concentration was increased from 5 to 100 mg/L. This
observation can be explained by the fact that the ratio of metal ion
to active site was low at low initial metal concentrations and vice
versa. In other words, active sites were less available for metal ion
binding at high initial metal concentrations, reducing the
percentage of metal ion removal from aqueous solution.
The experimental data for metal ion binding by the biosorbent
with respect to contact time revealed that the adsorption process
consists of two stages. The rst stage showed a rapid adsorption
pattern, while the second stage exhibited a gradual pattern until
equilibrium has been reached. The high amount of metal ion
adsorbed at the initial stage of the adsorption process was due to
the number of active sites available on the bare surface of the
biosorbent. The actives sites were progressively occupied by
the metal ions and led to no great difference in the adsorption rate.
The adsorption of metal ions onto coconut dregs residue attained
equilibrium within 60 min.

12

Adsorption isotherms

10

The interaction and distribution of metal ions on the surface of


adsorbent can be explained by adsorption isotherm study [9,24].
The Langmuir and Freundlich isotherm models are commonly used
to discuss the behaviour of metal ions at equilibrium.

Table 1
Percentage of metal ion removal by coconut dregs residue.

Initial metal concentration (mg/L)

Removal (%)
Cu(II)

Ni(II)

Pb(II)

86.58
88.14
85.83
56.76
26.64

77.67
81.31
74.11
68.18
46.37

100
100
100
99.31
96.08

0
2

pH
Cu(II)

Ni(II)

Pb(II)

Fig. 1. Effect of solution pH on adsorption of metal ion by coconut dregs residue.

5
10
25
50
100

A. Kamari et al. / Journal of Environmental Chemical Engineering 2 (2014) 19121919

Langmuir isotherm is the simplest isotherm model and was


based on the assumption that the metal ions form a monolayer on
the surface of adsorbent. All the adsorbent active sites have equal
energy and when all are occupied, the maximum adsorption
occurred. Therefore, no more metal binding could take place. The
linear form of the Langmuir equation is given as [25]:
Ce Ce
1

qe
Q Qb

(3)

where Q is the maximum adsorption at monolayer (mg/g), Ce is the


equilibrium concentration of metal ion (mg/L), qe is the amount of
metal ion adsorbed per unit weight of adsorbent at equilibrium
concentration (mg/g), and b is the Langmuir constant related to the
afnity of binding sites (mL/mg) and is a measure of the energy of
adsorption. The Q and b can be determined from linear plot of Ce/qe
against Ce.
Freundlich isotherm model is usually used to describe
adsorption at multilayer heterogeneous surface [7]. During
adsorption process, the stronger binding sites will occupy rst.
As more sites occupied by metal ions, the binding strength
becomes weaker [26]. The linear form of the Freundlich equation
can be expressed as [27]:
log qe log K F

1
logC e
n

(4)

where KF (mg/g) and n are the Freundlich constants related to


adsorption capacity and intensity, respectively. A linear plot of qe
against log Ce will give KF and n values.
The calculated Langmuir and Freundlich isotherm constants are
listed in Table 2. As presented in Table 2, the equilibrium data for
Cu(II), Ni(II) and Pb(II) adsorption by coconut dregs residue were
correlated well with the Langmuir isotherm model (R2 > 0.99). The
maximum adsorption capacities (Q) for Cu(II), Ni(II) and Pb(II) by
coconut dregs residue were 2.76, 5.86 and 9.74 mg/g, respectively.
From Table 2, it is found that coconut dregs residue had better
afnity towards Pb(II) ion than Cu(II) and Ni(II) ions. According to
Usman [28], the afnity of an adsorbent is mainly inuenced by
two aspects, namely ionic radius and atomic weight. Pb(II) has the
largest ionic radius (0.132 nm) and heaviest atomic weight
(207.2 g/mol) as compared to Cu(II) (0.072 nm and 63.5 g/mol)
and Ni(II) (0.069 nm and 58.7 g/mol), respectively [29]. These
characteristics cause the valence electron to polarise easily and less
attracted to the nucleus. As a consequence, Pb(II) ions had greater
opportunity to interact with active sites of the biosorbent.
The adsorption behaviour of metal ions onto coconut dregs
residue was further evaluated by dimensionless constant separation factor or equilibrium parameter (RL), which can be expressed
as [30]:
RL

1
1 bC 0

(5)

As described by Hall et al. [30],RL values indicate the shape of


isotherm process whether it is favourable (0 < RL < 1), unfavourable (RL > 1), linear (RL = 1) and irreversible (RL = 0). The RL values for
Cu(II), Ni(II) and Pb(II) adsorption by the biosorbent were in the
range of 01. This suggests that the adsorption of metal ions onto
coconut dregs residue was favourable. The 1/n values calculated

Table 2
Langmuir and Freundlich isotherm constants and correlation coefcients.

Table 3
Comparison of adsorption capacities of Cu(II), Ni(II) and Pb(II) on various
adsorbents (selected papers).
Adsorbents

Q (mg/g)

Coconut dregs residue


Rice hulls
Corn cobs
Eupatorium adenophorum
Jujube complex bead
Modied poplar tree sawdust
Cladoria furcata
Thuja oreintalis
Hazelnut shells
Almond shells
Black carrot residue

Cu(II)
Ni(II)
Pb(II)

Langmuir

Freundlich

Q (mg/g)

b (L/mg)

R2

KF (mg/g)

1/n

R2

2.76
5.86
9.74

0.4958
0.0732
13

0.9974
0.9917
0.9931

0.76
0.47
2.12

0.3595
0.6292
0.3833

0.801
0.9496
0.0777

Reference

Cu(II)

Ni(II)

Pb(II)

2.76
2.1
7.63

3.64
6.92

8.88

5.86
1.82
13.5

7.9
12.42
3.83
3.11
5.75

9.74
8.09
8.29
2.24
2.93

12.3

16.23
5.43

This study
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[38]
[39]

from the Freundlich isotherm model lie between 0 and 1 (Table 2).
This indicates that the metal ions were successfully separated from
the aqueous solutions.
The capacity of coconut dregs residue to bind Cu(II), Ni(II) and
Pb(II) ions was compared with various adsorbents (Table 3). It is
apparent that the adsorption capacity of coconut dregs residue
was comparable with other adsorbents. It is known that each
adsorbent own unique physical and chemical characteristics.
Therefore, they have different abilities to bind metal ions from
aqueous solutions.
Adsorption kinetics
From a system design viewpoint, adsorption equilibrium
studies provide insufcient information on adsorption reaction
pathways. In chemical engineering practice, kinetic study is crucial
and inevitable as it provides information on adsorption rate and
rate-limiting step during adsorbate uptake at the solid-phase
interface. In this study, the pseudo-rst order, pseudo-second
order and intraparticle diffusion kinetic models are used to
determine the rate constant and the controlling mechanism of
Cu(II), Ni(II) and Pb(II) adsorption onto coconut dregs residue. The
correlation coefcient (R2) was used to determine the best t
kinetic expression of this process.
The linear form of the pseudo-rst order equation is given as
[40]:
logqe  qt logqe 

k1
t
2:303

(6)

where qe and qt (mg/g) are the amount of metal ion adsorbed at


equilibrium and at time t (min), respectively and k1 is the rate
constant of pseudo-rst order equation (min1). The linear plot of
log (qe  qt) against t will give k1 value.
The linear form of the pseudo-second order equation is
described as [41]:
t
1
t

qt k2 q2e qe

(7)

where k2 is the rate constant of pseudo-second order equation


(g/(mg min)). The values of qe and k2 can be determined from linear
plot of t/qt against t.
The intraparticle diffusion equation is expressed as [42]:
qt kid t0:5

(8)
0.5

Metal ion

1915

where kid (mg/(g min )) is the rate constant of intraparticle


diffusion equation.
The kinetic parameters of the adsorption by coconut dregs
residue are presented in Table 4. Based on the R2 values, the kinetic
data were best described by the pseudo-second order kinetic
model. A linear relationship between dynamical data and pseudo-

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A. Kamari et al. / Journal of Environmental Chemical Engineering 2 (2014) 19121919

Table 4
Kinetic parameters for metal ion adsorption onto coconut dregs residue.
Kinetic parameter

Cu(II)

Ni(II)

Pb(II)

qe(exp) (mg/g)

5.17

5.62

8.92

Pseudo-rst order
qe(calc) (mg/g)
k1 (min1)
R2

0.58
0.0092
0.9097

0.81
0.0023
0.3239

0.14
0.0005
0.0046

Pseudo-second order
qe(calc) (mg/g)
k2 (g/(mg min))
R2

5.18
0.0530
0.9995

5.42
0.0291
0.9927

8.86
0.1368
0.9997

Intraparticle diffusion
ki (mg/(g min0.5))
R2

0.0422
0.9477

0.0510
0.5112

0.0079
0.1003

reversible reaction with an equilibrium being established between


liquid and solid phases, whereas the pseudo-second order kinetic
model assumes that the rate-limiting step may be the adsorption
mechanism but not mass transport [45]. As discussed by Ho and
McKay [41], an adsorption process that follow pseudo-second
order kinetic model implies the chemical binding reaction is the
rate-limiting step.
Competitive adsorption study

[(Fig._3)TD$IG]
50

40

t/qt

30

20

10

0
0

50

100

150

200

250

t (min)
Cu(II)

Ni(II)

Pb(II)

Fig. 3. Test of pseudo-second order equation for adsorption of metal ion by coconut
dregs residue.

second order kinetic model is shown in Fig. 3. In addition, the


experimental equilibrium adsorption capacities (qe(exp)) determined from the contact time study were in good agreement with
the theoretical equilibrium adsorption capacities (qe(calc)) calculated using the pseudo-second-order kinetic model.
Several other metal ion adsorption studies using biosorbents
such as Syzygium cumini and Populous deltoids leaves [12],
watermelon shell [43] and Sphagnum peat [44] showed that the
adsorption process followed the pseudo-second order kinetic
model. The pseudo-rst order kinetic process has been used for

Table 5
Percentage of metal ion removal in multi-metal system.
Initial metal concentration (mg/L)

25

Removal (%)
Cu(II)

Ni(II)

Pb(II)

97.27

44.48

100

The potential of coconut dregs residue to remove metal ions


from aqueous solution was also evaluated in multi-metal system.
Table 5 presents the percentage removal of Cu(II), Ni(II) and Pb(II)
ions in multi-metal system at initial metal concentration of
25 mg/L. It is important to note that the percentage removal of
Pb(II) was 100% in both single- and multi-metal systems at initial
metal concentration of 25 mg/L (Tables 1 and 5). A different
observation was obtained for Cu(II) and Ni(II) ions. The percentage
removal of Cu(II) increased from 85.83% (single-metal system) to
97.27% (multi-metal system). On the contrary, the percentage
removal of Ni(II) decreased signicantly from 74.11% (single-metal
system) to 44.48% (multi-metal system). The afnity of coconut
dregs residue towards metal ions in multi-metal system was in the
order of Pb(II) > Cu(II) > Ni(II), in consistent with the afnity order
established for single-metal system (Tables 1 and 2). A similar
trend was reported by Miretzky et al. [46], for Cu(II), Ni(II) and
Pb(II) removal by three dead macrocytes.
As discussed earlier, adsorbents may have different preference to
bind metal ions. Tobacco dust was reported to adsorb Cu(II),
Ni(II) and Pb(II) ions in the order of Cu(II) > Pb(II) > Ni(II) [47]. Results
from competitive adsorption study suggest that the presence of
other metal ions in the solution may affect the removal efciency. A
pronounced effect was obtained for Cu(II) and Ni(II) removal. Pb(II)
adsorption onto the biosorbent was not affected by this effect.
Industrial efuent treatment
The feasibility of coconut dregs residue to remediate metal
contaminated water was further evaluated using an electroplating
efuent. The adsorption performance of coconut dregs residue was
compared with bamboo derived activated carbon (BDAC). BDAC is a
commercial adsorbent and has been widely used to treat industrial
efuents in Malaysia. The removal and recovery of Cu(II), Ni(II) and
Pb(II) from electroplating efuent are given in Table 6. It is apparent
that adsorption capacity of coconut dregs residue was comparable
with BDAC. In fact, the biosorbent was able to adsorb Cu(II) at a higher
capacity than BDAC under experimental conditions studied. Both
coconut dregs residue and BDAC were successfully reduced Cu(II)
concentration from 2.75 mg/L to 0.14 and 0.18 mg/L, respectively, and
thereby meeting the Malaysian Environmental Quality Act 1974 maximum limit of 0.20 mg/L for Cu in industrial efuent to be discharged
into inland surface water [48].

Table 6
Removal and recovery of Cu(II), Ni(II) and Pb(II) from electroplating efuent.
Adsorbent

Metal
ion

Concentration of metal ion (mg/L) Removal


(%)
Before
After
adsorption
adsorption

Concentration of metal ion desorbed with 0.5 mol/L EDTA


(mg/L)

Recovery
(%)

Coconut dregs residue

Pb(II)
Cu(II)
Ni(II)

5.33
2.75
1.86

0.32
0.14
0.61

93.9
94.9
67.2

0.63
0.42
0.39

12.6
16.1
31.2

Bamboo derived activated


carbon

Pb(II)
Cu(II)
Ni(II)

5.33
2.75
1.86

0.12
0.18
0.42

97.7
93.5
77.4

0.57
0.91
0.41

10.9
35.4
28.5

A. Kamari et al. / Journal of Environmental Chemical Engineering 2 (2014) 19121919

The recovery of metal ions was examined using 0.5 mol/L EDTA,
and the percentage of recovery was found to be in the range of
10.931.2% (Table 6). The recovery percentage obtained was rather
low, that is less than 40% of the amount of metal ion adsorbed on
the adsorbent. This suggests that the adsorption of metal ions onto
biosorbents was chemisorption, conrming results obtained from
kinetic study. Results also show that the biosorbent had a better
performance in removing Cu(II) from industrial efuent as
compared to commercial adsorbent, and therefore its application
in industrial efuent treatment is feasible.
Characterisation study
SEM analysis
SEM analysis was performed to observe the change in the
surface morphology of the biosorbent after interaction with metal
ions. The SEM images of coconut dregs residue before and after
metal ion adsorption at 5000 magnication are shown in Fig. 4.
The coconut dregs residue displayed a dense surface morphology with grooves texture (Fig. 4a). The grooves texture remained
following interaction with Cu(II) and Ni(II) (Fig. 4b and c).
However, this texture disappeared after Pb(II) adsorption (Fig. 4d).
Interaction with Cu(II) led to formation of tiny nodules on the
surface of coconut dregs residue (Fig. 4b). Bean- and lump-like
deposits were observed on the surface of the biosorbent following
adsorption of Ni(II) and Pb(II) ions (Fig. 4c and d).
EDX analysis
The elemental composition in the coconut dregs residue and
the presence of metal features after adsorption process were
examined by EDX analysis. The EDX spectrum of coconut dregs
residue exhibits the appearance of carbon, oxygen and potassium
features at energy values of 0.277, 0.523 and 3.313 keV, respectively. The feature of platinum can be detected at 2.048 and
9.441 keV. The samples were coated with platinum prior to

1917

analysis to avoid electron charging (see Section Characterisation


studies).
Following interaction with metal ions, the features of Cu, Ni and
Pb can be observed in each EDX spectrum of the biosorbent. The
EDX spectrum after exposure with Pb(II) is shown in Fig. 5, as an
example. The Pb features can be observed at energy values of
2.342 and 10.550 keV. The interaction of biosorbent with Cu(II) has
resulted in the appearance of Cu features at 0.930 and 8.040 keV
(data not shown). The peaks observed at 0.851 and 7.477 keV after
Ni adsorption can be assigned to Ni features (data not shown). The
disappearance of K features after metal ion adsorption may be due
to ion-exchange mechanism. Overall, the appearance of Cu, Ni and
Pb features on the surface of biosorbent indicates that the
biosorbent studied was able to bind metal ions.
FTIR analysis
The functional groups present in the biosorbent as well the
possible binding mechanism(s) involved in the interaction with
metal ion was conrmed by FTIR analysis. The FTIR spectra of
coconut dregs residue before and after adsorption of Cu(II), Ni(II)
and Pb(II) ions are presented in Fig. 6.
Based on Fig. 6, a broad and strong absorption band observed at
3370 cm1 corresponds to the stretching vibration of O
H and the
extension vibration of NH. The presence of two discernible bands
at wave numbers 2923 and 2854 cm1 are due to alkyl groups. The
absorption bands observed at 1744 and 1711 cm1 can be assigned
to CQO stretching vibration. The N
H bending vibration of amine
group can be observed at 1646 cm1. The weak bands at 1459 and
1377 cm1 are the characteristic of CH2 and CH3 deformation. The
absorption bands at 1240 and 1150 cm1 represent the C
N
stretching vibration. The prominent bands at 1065 and 1032 cm1
can be attributed to C
O stretching vibration [49].
There were signicant changes on FTIR spectrum of coconut
dregs residue following Cu(II), Ni(II) and Pb(II) adsorption
(Fig. 6bd). For example, adsorption of metal ions onto biosorbent

[(Fig._4)TD$IG]

Fig. 4. SEM images of coconut dregs residue at 5000 magnication before adsorption of metal ion (a), and after adsorption of Cu(II) (b), Ni(II) (c), and Pb(II) (d).

1918

A. Kamari et al. / Journal of Environmental Chemical Engineering 2 (2014) 19121919

[(Fig._5)TD$IG]

Fig. 5. EDX spectrum of coconut dregs residue after interaction with Pb(II).

[(Fig._6)TD$IG]
(a)
!

1646
1377

1711
3370

%T

(b)

2854
174
4

2923!

1457.10

1459

1065
1032

1584
1646

3365

1377
2852
1743

1711
1241
1149

2923

1064

3500

124
0
1150

3000

2500

2000

1500

1033

1000

Wavenumber (cm-1)

Fig. 6. FTIR spectra of coconut dregs residue before (a) and after adsorption of (b)
Cu(II), (c) Ni(II) and (d) Pb(II).

led to a shift in wave number from 3370 cm1 to 3365, 3378 and
3364 cm1 for OH stretching vibration. Furthermore, new
absorption bands were observed at wave numbers 1584 and
1514 cm1 after interaction with Cu(II) and Pb(II) ions (Fig. 6b and
d). These bands are related to N
H bending vibration of amine
group [50]. The absorption intensity of carbonyl group at
1742 cm1 decreased signicantly after exposure with Ni(II)
(Fig. 6c). Furthermore, the bands at 1646 and 1240 cm1 which
attributed to amine and carbonyl groups shifted to 1651 and
1246 cm1 after adsorption of Pb(II) and Ni(II), respectively
(Fig. 6c and d).
Apparently, the formation of new absorption bands, the change
in absorption intensity and the shift in wave number of the
functional groups could be due to interaction of metal ions with
active sites of coconut dregs residue through complexation. The
electron donor atoms (N and O) are involved in the binding
mechanism. It can be concluded that the main adsorption sites for
coconut dregs residue are hydroxyl, carbonyl and amine groups.
Conclusions
This study highlights the potential of coconut dregs residue, a
low-cost material, as an alternative biosorbent to treat industrial
efuent. It consists of amino, hydroxyl and carbonyl groups that
favour metal ion binding through complexation mechanism. The
selectivity of the biosorbent was in the order of Pb(II) > Cu(II) >
Ni(II), which was consistent in both single- and multi-metal
systems. Several fundamental aspects of chemical engineering

were assessed. This include adsorption equilibrium and isotherm,


adsorption kinetic and rate, and separation parameter. The
adsorption process was dependent on several experimental
parameters such solution pH, contact time and initial metal
concentration. Coconut dregs residue exhibited a greater capacity
than a commercial activated carbon for Cu(II) removal from
electroplating efuent. Coconut dregs residue is abundantly
available at low economic value in many countries, particularly
in Asian countries like Malaysia, Indonesia, Thailand and India.
Therefore, its utilisation for remediation of metal contaminated
would provide a solution to its disposal.
Acknowledgements
This work was supported by the Universiti Pendidikan Sultan
Idris Malaysia under research grants GPU 2011-0112-102-01 and
2013-0120-102-01, and Ministry of Education Malaysia under
research grant RACE 2012-0150-108-62. We thank Mr. Mohd Zurin
Mahmud, Miss Siti Noor Farina Mohd Fuad Ooi and Mr. Mohd
Hashimi Maani for their assistance.
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