Bioresource Technology 97 (2006) 994–1001

Low cost bio-sorbent
wheat bran for the removal of cadmium

from wastewater: Kinetic and equilibrium studies
K.K. Singh a, A.K. Singh b, S.H. Hasan a,*

a
Water Pollution Research Laboratory, Department of Applied Chemistry, Institute of Technology,
Banaras Hindu University, Varanasi 221 005, India
b
Department of Mining Engineering, Institute of Technology, Banaras Hindu University, Varanasi 221 005, India

Received 28 October 2003; received in revised form 29 April 2005; accepted 29 April 2005
Available online 1 July 2005

Abstract

Novel bio-sorbent wheat bran has been successfully utilized for the removal of cadmium(II) from wastewater. The maximum
removal of cadmium(II) was found to be 87.15% at pH 8.6, initial Cd(II) concentration of 12.5 mg l
1 and temperature of
20
C. The effect of different parameters such as contact time, adsorbate concentration, pH of the medium and temperature were
investigated. Dynamics of the sorption process were studied and the values of rate constant of adsorption, rate constant of intra-
particle diffusion and mass transfer coefficient were calculated. Different thermodynamic parameters viz., changes in standard free
energy, enthalpy and entropy have also been evaluated and it has been found that the reaction was spontaneous and exothermic in
nature. The applicability of Langmuir isotherm showed of monolayer coverage of the adsorbate on the surface of adsorbent. A gen-
eralized empirical model was proposed for the kinetics at different initial concentrations.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Adsorption; Wheat bran; Exothermic; Cadmium; Monolayer

1. Introduction age, emphysema, hypertension and testicular atrophy

A delicate balance exists between man and environ-
ment. Lately, this balance has been seriously disturbed
by mans direct as well as indirect activities. Thousands
of contaminants have found their way in to the environ-
ment. The presence of metal ions in natural or industrial
wastewater and their potential impact has been a subject
of research in environmental science for a long time.
Metal ions such as cadmium, chromium, copper, lead,
zinc and iron are commonly detected in both natural
and industrial effluents. Cadmium is one of them and
ingestion of Cd(II) above its permissible limit
(0.005 mg l
1) causes various types of acute and chronic
metabolic disorders such as itai-itai disease, renal dam-
*
Corresponding author. Tel.: +91 941 53 88 484.
E-mail address: kks_envir@yahoo.co.in (S.H. Hasan).
(Dara, 2002; Nagawa and Kido, 1991). Many physico-
chemical wastewater treatment processes viz., oxida-
tion–reduction, precipitation, ion exchange and liquid
membrane have used for Cd(II) removal. All these pro-
cesses have the limitations of technical and/or economi-
cal viability. However, adsorption is a simple and
attractive method for the removal of metal from the
effluents due to its high efficiency, easy handling and
economical feasibility.
The present work deals with the adsorption studies of
Cd(II) ion on wheat bran at different concentration,
temperature and pH. Some conventional chemisorbents
have been utilized for the removal of heavy metals.
However, these chemisorbents pose disposal problems.
Examining the literature reveals that many non-conven-
tional bio-sorbents viz., rice polish, wood saw dust,
Mangifera indica leaves, bamboo dust, peanut shell,

0960-8524/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2005.04.043
 K.K. Singh et al. / Bioresource Technology 97 (2006) 994–1001 995

Nomenclature

C0 initial adsorbate concentration DS 0 change in standard entropy

q amount adsorbed at time t (min) DH apparent heat of adsorption
qe amount of the adsorbed adsorbate at equilib- R gas constant
rium T temperature (K)
kad rate constant of adsorption Ce adsorbate concentration in the solution at
kid rate constant of intraparticle pore diffusion equilibrium

D pore diffusion coefficient Q0 Langmuirs constants related to the capacity
DG 0 change in standard free energy of adsorbent
DH 0 change in standard enthalpy

waste tea leaves, soyabean hull, algae, fungi etc. (Singh
et al., 2003; Ahuja et al., 2001; Ariff et al., 1999;
Matheickal and Yu, 1999; Marin and Ayele, 2003; Red-
dad et al., 2003; Mohammad et al., 2003; Shukla and
Sakhardande, 1992; Singh et al., 1993; Coupal and
Lalancette, 1976; Raji and Anirudhan, 1997; Yan
and Viraraghavan, 2001; Yan et al., 2001; Saed and
Iqbal, 2003; Mamman and Salewu, 2001; Esposito
et al., 2001) have been utilized for the removal of heavy
metals. With this in mind, wheat bran was examined as a
bio-sorbent, which is low cost, bio-degradable and poses
no disposal problems.
2. Method
2.1. Physico-chemical analysis of adsorbent
Various physical properties of the adsorbent are
given in Table 1. Chemical analysis of the wheat bran
shows the presence of various oxides. X-ray diffraction
(values given in Table 2) and IR studies (values given
in Table 3) of wheat bran shows that major constituents
are carbon while quartz, carbon hexagonal, Fe–O, SiO2,
Mn–O, CaSiO3, Ca2SiO4, Ca–P, Co and alumina has
been found in traces.
2.2. Experimental procedure
In present investigation batch mode of operation was
selected in order to measure the progress of adsorption.
A similar approach was carried out by shaking 1.0 gm of
desired grade of adsorbent with 50 ml aqueous solu-
tion of adsorbate (cadmium chloride) of different con-
centrations (10.0, 12.5 and 15.0 mg l
1) at different

Wheat bran was collected from M/s S.K. Industries

(Flour mill), Narainpur, Mirzapur, Uttar Pradesh, India Table 1
and was used in experiments with double washing to re- Physical and chemical properties of biosorbent wheat bran
move soluble lighter materials and drying at 60
C in Surface area (m2 g
1) 403.00
oven and crushing and sieving to less than 178 lm. Bulk density (g cm
3) 0.2718
Particle size (lm) <178
The characterization of surface area of the adsorbent Porosity 0.33
was determined by a three point N2 gas adsorption
method using a Quantasorb Surface Area Analyzer; Proximate analysis (%)
Volatile matter 42.63
model Q5-7, Quanta chrome Corporation, USA. The Ash 7.02
bulk density of the adsorbent was determined by densi- Moisture 7.54
tometer model D8 K, NGRI, Hyderabad, India. Particle Fixed carbon 31.71
size of the adsorbent was determined by Sieve Analysis. Oxides of Al, Mn, Si, Fe, etc. 11.10
Porosity of the adsorbent was determined by porosito-
meter, model H: M7V, NGRI, Hyderabad, India.
X-ray diffraction of the adsorbent was obtained using
X-ray Diffractometer, model-ID-3000 W, Rich Siefert
Table 2
and Company, Ahrensburg, Germany. Infrared spectra X-ray diffraction data of wheat bran
of the adsorbent were recorded using infra red spectro-
Target: Cu Scanning: 10
–70

photometer; model FT/IR-5300, JASCO Corporation, Filter: Ni Current: 30 mA
Japan in the range 400–4000 cm
1. Percentage of vola- GM speed: 1
Voltage: 40 KV
tile matter, ash and Moisture were determined as given
Alumina, Mn–O, Ca2 SiO4, CaSiO3, Co, Si–O2, Fe–O, Carbon
in the ‘‘Vogels Textbook of Quantitative Chemical hexagonal
Analysis’’, 5th Edition, Bath Press Ltd., UK.
996 K.K. Singh et al. / Bioresource Technology 97 (2006) 994–1001

Table 3 0.6
IR bands of wheat bran alongwith their possible assignments
Band position (cm
1) Assignment 0.5

Amount Adsorbed (mg g-1)

3436 W –OH str.
2910 W –C@C–H str. 0.4
1748 W –C@O str.
1552, 1520 S Aromatic ring 0.3
1490 W >N–H str.
775 M –C–H Def.
750 M Al–O 0.2 10.0 mg l-1
12.5 mg l-1
472 S Si–O–Ca bend 15.0 mg l-1
448 S Si–O bend 0.1
422 M Fe–O
0.0
0 25 50 75 100 125 150 175 200 225 250
Time (min.)
temperatures (20, 30 and 40
C) and different pH (4.0,
Fig. 1. Time variation plots for adsorption of Cd(II) on wheat bran at
6.4, 7.0, 8.6 and 10.0) in different glass bottles in a shak-
different adsorbate concentration conditions: concentration: 10.0, 12.5
ing thermostat at a constant speed of 125 rpm. The pH and 15.0 mg l
1; particle size: <178 lm; temperature: 30
C; pH: 8.6.
of the adsorbate solution was adjusted by adding HCl or
NaOH. The progress of adsorption was noted at differ-
ent time intervals till the attainment of saturation. At predict successfully the percentage removal of Cd(II)
the completion of predetermined time intervals, the by wheat bran at any initial concentrations. Percentage
adsorbate and adsorbent were separated by high speed removal of CdðIIÞ ¼ 0.2007C 00.236 .
centrifugation at 15,000 rpm and the supernatant liquid
was analyzed by the orion ion selective titrator plus 3.2. Adsorption dynamics
system, model no. 960, made by Thermo Orion (USA)
to determine the residual concentration of cadmium The rate constant kad (min
1) for cadmium adsorp-
ion. Blank solutions were run under similar conditions tion was determined by using the first order rate kinetic
of concentration, pH and temperature without the equation (Huang and Ostovic, 1978).
adsorbent in all the cases to correct for any adsorption k ad
on the internal surface of the bottles. logðqe
qÞ ¼ log qe
t ð1Þ
2.303
where q and qe are the amounts of adsorbate (mg g
1) at
time t (min) and at equilibrium, respectively. The linear
3. Results and discussion
plots of log (qe
q) versus t (Fig. 2) suggested the first
order kinetics of the uptake of Cd(II). The values of
3.1. Effect of contact time and concentration
kad at different temperatures were calculated from the
slopes of these curves and are represented in Table 4.
A series of experiments were performed at different
initial adsorbate concentrations viz., 10.0, 12.5 and
15.0 mg l
1 and time intervals and at a temperature of
0.0
30
C and pH 8.6. The percentage removal of Cd(II)
was found 86.80, 80.12 and 73.65, respectively. The
-0.5
results showed (Fig. 1) that the extent of adsorption
20 ºC
increased rapidly in the initial stages but slowed in the -1.0 30 ºC
later stages until the attainment of equilibrium and in
log (qe-q)

40 ºC
Fig. 1 it was also indicated that the extent of removal -1.5
was highly dependent on the concentration of the ad-
sorbate. The removal curves thus obtained are single -2.0
smooth and continuous suggesting the formation of
monolayer of adsorbate on the surface of the adsorbent -2.5
(Raji and Anirudhan, 1997; Huang and Wu, 1975).
Equilibrium time for the adsorption of Cd(II) on wheat -3.0
bran at various adsorbate concentrations was found to 0 20 40 60 80 100 120 140

be 110 min, which indicated that equilibrium time was Time (min.)
independent of initial adsorbate concentration. The fol- Fig. 2. Rate constant plot for adsorption of Cd(II) on wheat bran at
lowing correlation was developed between percentage different temperatures conditions: particle size: <78 lm; concentration
removal and initial adsorbate concentration (C0) to 12.5 mg l
1; pH: 8.6; temperature: 20, 30 and 40
C.
 K.K. Singh et al. / Bioresource Technology 97 (2006) 994–1001 997

Table 4
Adsorption rate constants for Cd(II) at different temperatures
Temperature (
C) kad (min
1) kid (mg g
1, min
1/2)  (cm2 s
1)
D b1Ss (cm min
1)

2
3
9
20 5.343 · 10 9.53 · 10 3.572 · 10 4.682 · 10
2
30 4.822 · 10
2 8.57 · 10
3 2.828 · 10
9 4.233 · 10
2
40 4.491 · 10
2 7.98 · 10
3 2.156 · 10
9 3.715 · 10
2

During the batch mode of operation, there was a sion as the rate determining step. In this investigation,
possibility of intraparticle pore diffusion of adsorbate, the values of D  (Table 4) obtained was in order of
which is often the rate controlling step (Poots et al., 10
9 cm2 s
1 which was more than two order of magni-
1978; Huang and Oliver, 1989). The rate constants of tude higher, indicated that the intraparticle diffusion was
intraparticle diffusion (kid) at different temperatures not the only rate controlling step (Michelsen et al.,
were determined using the equation (Huang and Osto- 1975). It was concluded that both boundary layer and
vic, 1978) [q = kidt1/2] by plotting the amount of adsor- intraparticle diffusion might be involved in this removal
bate adsorbed (q) versus t1/2 (Fig. 3). The values of kid process.
were obtained from the slope of the respective plot at
later stages and are represented in Table 4. The double 3.3. Mass transfer analysis
nature of curves was obtained due to the varying extent
of adsorption in the initial and final stages of the exper- The mass transfer analysis for the adsorption of cad-
iment. This can be attributed to the fact that in the mium(II) ion was determined at various temperatures
initial stages, adsorption was due to the boundary layer (20, 30 and 40
C) using the following equation (Mckay
diffusion effect whereas, in the later stages (linear por- et al., 1981):
tion of the curve) was due to the intra-particle diffusion    
Ct 1 mK
effects. However, these plots indicated that the intra- ln
¼ ln
particle diffusion was not the only rate controlling C 0 1 þ mK 1 þ mK
 
step because it did not pass through the origin. This 1 þ mK

 b1  S s  t ð3Þ
was further supported by calculating the intraparticle mK
diffusion co-efficient (DÞ  using the following equation
where C0 is the initial adsorbate concentration, Ct is the
(Bhattacharya and Venkobachar, 1984).
adsorbate concentration after time t, m is the mass of the
2
 ¼ 0.03r
D ð2Þ
bio-sorbent per unit volume, K is the Langmuirs con-
t1=2 stant obtained by multiplying Q0 and b related to the
capacity and energy of the adsorption, respectively, b1
where r (cm) is the average radius of the adsorbent par-
is the mass transfer coefficient, Ss is the outer specific
ticle and t1/2 (min) is the time for half of the adsorption.
 value of the surface of the adsorbate per unit volume. The value of
According to (Michelsen et al., 1975) a D
m was constant and was 20 g L
1. The values of Ss were
order of 10
11 cm2 s
1 is indicative of intraparticle diffu-
determined by the following equation:
S s ¼ 6m=d p  qp ð1
ep Þ ð4Þ
0.7 where, dp is the particle diameter (cm), qp is the density
0.6
of the adsorbent (g l
1) and ep is the porosity of adsor-
bent particle.
Amount Adsorbed (mg g-1)

0.5 The mass transfer coefficient (b1) was determined from

the slopes and intercepts of the plots of ln(Ct/C0

0.4
1/1 + mK) versus t (Fig. 4). The values of rate parameter
0.3 20 ºC (b1 Æ Ss) were obtained by multiplying b1 and Ss, were sim-
30 ºC ilar to the adsorption rate constant (Kad) and given in Ta-
40 ºC
0.2 ble 4. However, it may be mentioned that the deviations
of some points from the linearity of the plots (Fig. 4) indi-
0.1
cated the varying extent of mass transfer at the initial and
0.0
final stages of the adsorption.
0 2 4 6 8 10 12
Time (min.1/2) 3.4. Effect of temperature
Fig. 3. Intraparticle diffusion plots for adsorption of Cd(II) on wheat
bran at different temperatures conditions: particle size: <178 lm; Experiments were also performed at different temper-
concentration: 12.5 mg l
1; pH: 8.6; temperature 20, 30 and 40
C. atures (20, 30 and 40
C). The percentage of adsorption
998 K.K. Singh et al. / Bioresource Technology 97 (2006) 994–1001

0 Table 5
Thermodynamic parameters for adsorption of Cd(II) on wheat bran at
20 ºC
different temperatures
30 ºC
40 ºC Temperature (
C)
DG 0
DH 0
DS 0
(k cal mol
1) (k cal mol
1) (cal mol
1 k
1)
ln (Ct/C0-1/1 + mK)

-1
20 1.117 9.219 27.652
30 0.841 5.889 16.660
40 0.674

-2

(DS 0). These were calculated by using the following

equations;
-3 ðiÞ DG0 ¼ RT ln K c ð5Þ
0 20 40 60 80 100 120  
T 1T 2 Kc
Time (min.) ðiiÞ DH 0 ¼ R ln 2 ð6Þ
T2
T1 K c1
Fig. 4. Mass transfer plot for the adsorption of Cd(II) on wheat bran
at different temperatures conditions: concentration: 12.5 mg l
1; tem- DH 0
DG0
ðiiiÞ DS 0 ¼ ð7Þ
perature: 20, 30 and 40
C; particle size: <178 lm; pH: 8.6. T
where R is the gas constant, T is temperature on the
absolute scale and Kc, K c1 , and K c2 are the equilibrium
0.6 constants at temperature T, T1 and T2, respectively.
The values of these parameters were calculated and are
0.5 presented in Table 5. It is obvious from this table that
Amount Adsorbed (mg g-1)

the negative and small values of free energy change

0.4 (DG 0) was an indication of spontaneous nature of the
adsorption process. The negative values of standard en-
0.3 20 ºC thalpy change (DH 0) at different temperatures were indi-
30 ºC cating the exothermic nature of the adsorption process
0.2
40 ºC
and the negative values of (DS 0) suggested the probabil-
ity of a favourable adsorption.
0.1
3.5. Adsorption isotherm
0.0
0 25 50 75 100 125 150 175 200 225
Time (min.)
In the present investigation the data was found to fit
the Langmuir isotherm. The basic assumption of Lang-
Fig. 5. Time variation plot for adsorption of Cd(II) on wheat bran at muir adsorption isotherm is based on monolayer cover-
different temperatures conditions: concentration: 12.5 mg l
1; temper-
age of the adsorbate on the surface of adsorbent. The
ature: 20, 30 and 40
C; particle size: <178 lm; pH: 8.6.
saturated monolayer can be represented by the follow-
ing equation:

decreased from 87.15 to 74.65 with a rise of temperature Ce 1 Ce

from 20 to 40
C at concentration of 12.5 mg l
1 and pH
of 8.6 (Fig. 5). Equilibrium time for 20, 30 and 40
C
was found to be 110 min indicated that the equilibrium
time was independent of temperature. The above results
revealed the exothermic nature of the adsorption (Singh
et al., 2003; Sharma et al., 1991). The decrease in
adsorption with the rise of temperature may be due to
the weakening of adsorptive forces between the active
sites of the adsorbents and adsorbate species and also
between the adjacent molecules of the adsorbed phase
(Pandey et al., 1986).
The variation in the extent of adsorption with respect
to temperature has also been explained on the basis of
thermodynamic parameters viz., changes in standard
free energy (DG 0) and enthalpy (DH 0) and entropy
¼ 0 þ 0 ð8Þ
qe Q b Q
where Ce is the equilibrium concentration of the adsor-
bate, qe is the amount of the adsorbate adsorbed at equi-
librium, Q0 and b are Langmuirs constants related to
the capacity and energy of the adsorption, respectively.
The linear nature of the curve was found by plotting
Ce/qe versus. Ce at different temperatures (Fig. 6) sug-
gested the applicability of Langmuir isotherm for the
present system. The values of Q0 and b at different tem-
peratures were determined from the slopes and inter-
cepts of the respective plot and presented in Table 6.
From these results it was clear that the values of adsorp-
tion capacity (Q0) decreased with the rise of tempera-
ture. Further, it confirmed the fact that an exothermic
 K.K. Singh et al. / Bioresource Technology 97 (2006) 994–1001 999

14 0.6

12
0.5

Amount Adsorbed (mg g-1)

pH : 4.0
pH : 6.4
10
pH : 7.0
0.4
pH : 8.6
Ce/qe (g l-1)

8 pH : 10.0
20 ºC 0.3
6 30 ºC
40 ºC
4 0.2

2
0.1

0
0 1 2 3 4 5
Ce (mg l-1)
Fig. 6. Langmuir isotherm plot for the adsorption of Cd(II) on wheat
bran at different temperatures conditions: particle size: <178 lm; pH:
8.6; temperature: 20, 30 and 40
C.
Table 6
Values of Langmuir constants and RL for Cd(II)
Temperature (
C) Q0 (mg g
1) b (mg l
1)
20 0.703 28.12
30 0.667 18.74
40 0.625 11.26
process took place in this adsorption system (Singh
et al., 1998, 2003; Sharma et al., 1991).
Heat of adsorption (DH) of the Cd(II) on wheat bran
was determined using the following equation:
ln b ¼ ln b0
DH =RT

1
where b (mg l ) is the Langmuirs constant related to
the energy of adsorption, b 0 is the constant and R and
T (
K) are gas constant and temperature, respectively.
Thus from ln b versus 1/T plot, the DH was calculated
and found to be
8.267 k cal mol
1. A negative value
of DH confirmed the exothermic nature of the process.
The equilibrium parameter RL which is defined as
RL = 1/(1 + bCi) in the range 0 < RL < 1 which reflects
the favorable adsorption process (Manju et al., 1999).
In the present investigation the values of equilibrium
parameter was found in the range 0 < RL < 1 and given
in Table 6 indicated that the adsorption process was
very favorable and the adsorbent employed exhibited
an optimum potential (Manju et al., 1999).
6 7 8 9 0.0
0 25 50 75 100 125 150 175 200 225 250
Time (min.)
Fig. 7. Time variation plots for the adsorption of Cd(II) on wheat
bran at different pH values conditions: concentration: 12.5 mg l
1;
particle size: <178 lm; temperature: 30
C; pH: 4.0, 6.4, 7.0, 8.6 and
10.0.
RL explained on the basis of the nature of sorbent used

2
2.315 · 10 which contained several metal oxides. These oxides
3.435 · 10
2 when mixed up with adsorbate solution undergo surface
5.589 · 10
2 hydroxylations and form hydroxyl compounds on the
surface which ultimately gives positively or negatively
charged surface as a result of subsequent acid base dis-
sociation (Pandey et al., 1984). It was clear from Fig.
7 that the adsorption of cadmium was higher in alkaline
pH. However, the removal was less in the acidic range
and reached a maximum at approximately pH 8.6. In
ð9Þ addition to this effect, the adsorbent surface was highly
protonated in acidic medium, which was not favourable
for cadmium uptake. This was because in this medium,
Cd++ was the dominant ion (Huang and Ostovic, 1978).
As a result the adsorption of cadmium was hindered
due to electrical repulsion. As pH increased the degree
of protonation of surface gradually reduced and ap-
proached zero at pH 7.0 resulting in a gradual increase
in the adsorption. Above pH 7.0 where Cd++ and
CdOH+ species were present in the solution (Huang
and Ostovic, 1978), the adsorbent surface began acquir-
ing a net negative charge making the situation electro-
statically favourable for a higher uptake of cadmium.
Above pH 8.6 removal of cadmium began to decrease
possibly due to soluble hydroxy complexes of cadmium
hydroxides (Leckie and James, 1974).

3.6. Effect of pH 3.7. Empirical model

Experiments were performed at different pH (4.0, 6.4,
7.0, 8.6 and 10.0). The removal increased from 30.85%
to 80.16% with increase of pH from 4.0 to 8.6 and there-
after removal decreased from 80.16% to 12.62% with an
increase of pH from 8.6 to 10.0 at 30
C and concentra-
tion of 12.5 mg l
1 (Fig. 7). The optimum pH for the
removal of Cd(II) by wheat bran was 8.6. It could be
In order to determine the removal rate of Cd(II) from
wastewater by wheat bran, the following empirical
mathematical model was developed between contact
time (min) and initial and remaining concentration C0
and Ct (both in mg l
1) of Cd(II), respectively.
A
logðt þ 1Þ ¼ KðC 0 C t Þ ð10Þ
1000 K.K. Singh et al. / Bioresource Technology 97 (2006) 994–1001

12 afterwards; it was also confirmed by mass transfer stud-

ies. Intraparticle studies indicated both boundary layer
10 and pore diffusion were involved in Cd(II) removal.
Thermodynamic studies confirmed that process was
8 spontaneous and exothermic. The fitness of the adsorp-
tion data into Langmuir isotherm confirmed the mono-
(C0-Ct)A

6 layer adsorption. The applicability of empirical model

would be useful in designing and fabricating an efficient
10.0 mg l-1
4 12.5 mg l-1 treatment plant for Cd(II) rich effluents.
15.0 mg l-1

2
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