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December, 2010
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Removal of Zn(II) and Pb (II) ions Using Rice Husk in Food Industrial Wastewater

*ASRARI, ELHAM; TAVALLALI, HOSSEIN; HAGSHENAS, MAHNOOSH

Payame Noor University (PNU), Shiraz, 711955 -1368, Iran
*Corresponding Author
Tel. +98(711) 6222261, Fax: +98 (711) 6222261; elasrari@yahoo.com

ABSTRACT: T he adsorption behavior of Zn2+ and Pb2+ ions on rice husk was investigated using Rice Husk to
remove the metals ions in dairy wastewater. The removal of mentioned heavy metal ions from aqueous solutions was
studied by batch method. The main parameters that influencing Zn2+ and Pb2+ sorption on rice husk were: amount of
adsorbent, contact time and pH value of wastewater. The influences of pH (2–9), contact time (5-70min) and
adsorbent amount (0.5-3 g) have been studied. The percent adsorption of Zn2+ and Pb2+ ions increased with an
increase in contact time and dosage of rice husk. The binding process was strongly affected by pH and the optimum
pH for Zn2+ and Pb2+ ions were 7.0 and 9.0, respectively. The experimental data were analyzed by Langmuir
isotherm. The maximum adsorption capacity of the adsorbent for Zn2+ and Pb2+ ions was calculated from
the Langmuir isotherm and found to be 19.617 and 0.6216 mg/g, respectively. Actually the percent of removing Zn2+
and Pb2+ ions reached maximum to 70% and 96.8%, respectively. @JASEM

Symbols:
q
e- adsorbed metal on the sorbent , (mol/Kg adsorbent)
m- weight of sorbent , (Kg)
V- volume of metal solution , (m3)
Co- initial metal concentration , (mol/ m3)
C metal concentration at any time , (mol/ m3)
e-
q maximum sorption capacity
m-
K
L- adsorption equilibrium constant , (m3/mol)
q- weight adsorbed per unit weight of adsorbent , (mol/Kg adsorbent)
n- Freundlich constant
K adsorption coefficient
f-

Excessive release of heavy metals into the investigated . Biosorption is a promising technique
environment due to industrialization and urbanization for the removal of heavy metals from aqueous
has posed a great problem worldwide. Today, with the environments especially when adsorbents are derived
rapidly increasing urban population, water resources from lingnocellulosic materials (Coelho and et al.,
becoming less and scarcer, there is a strong need to 2007). Rice is the crop all over the world. Every year
reconsider consumption patterns and the way large amount of rice husks is produced. Structurally,
resources used. Unlike organic pollutants, the rice husks consist of cellulose, hemicellulose, and
majority of which are susceptible to biological lignin.
degradation, heavy metal ions do not degrade into
harmless end products (Yu, 2005). The presence of The aim of this study was to find out the effectiveness
heavy metal ions is a major concern due to their of less expensive material that could be used as
toxicity to many life forms. Conventional methods for sorbent for the removal of Zn2+and Pb2+ ions from
removing heavy metals from aqueous solutions dairy wastewater. In this work, the adsorption
include chemical precipitation, ion exchange, behavior was studied by a set of experiments at
adsorption (Gode and Pehlivan, 2006) and membrane various conditions, including pH, contact time and
filtration technologies. Among them, adsorption various biosorbent amounts.
method is simple and relatively cost-effective, thus
has been widely used. Several materials are derived MATERIALS AND METHODS
from natural resources, plant wastes or industrial by- Adsorbent: Rice husks were washed carefully first
products. The removal of heavy metal ions using low- with tap water and then deionized water to remove
cost abundantly available adsorbents: agricultural particulate material from their surface. After that,
wastes such as tea waste and coffee (Orhan and they were dried in an oven at 100 ◦C for 24 hr. The
Buyukgungor, 1993), hazelnut straws, peanut hull, pH measurements were performed with a pH meter
saw dusts, husk (Babarinde, 2002), corncobs, apple (Jenway 3510). An Atomic Absorption Spectrometer
wastes (Maranon and Sastre, 1991), wool fibers, tea (AAS) (GBC –Sens AA) operating with an air–
leaves, banana and orange peels, papaya wood, maize acetylene flame was used to analyze the Zn 2+ and
leaf, leaf powder (Hanafiah and et al., 2007), grape Pb2+ ion concentration in the solution. A deuterium
stalk wastes and different agricultural by-products lamp was used for background correction.
(Pehlivanand and et al., 2006) were used and

*Corresponding Author
Tel. +98(711) 6222261, Fax: +98 (711) 6222261; elasrari@yahoo.com
 160
Removal of Zn(II) and Pb (II) ions

Batch adsorption: the initial pH of the metal

solution was adjusted to values in the pH range of (2– 120
9) by the addition of 0.1M HC1 or 0.1M NaOH prior 100
to experiment. Certain volume of waste water (30 ml)

%
80
was equilibrated with varying sorbent dosage (0.5 to
3 gr), pH values (2–9), and contact time (5 to 70

Ab s.
min). Experiments were carried out in 100 ml beakers 60
40
to study the effect of parameters (sorbent dosage, pH
values and contact time).The beaker were shaken for Zn
a prescribed length of time by magnetic stirrer. After 20 Pb
filtration thorough the filter paper, Zn2+ and Pb2+ ions 0

remaining in wastewater, determined by AAS. 0 20 40 60 80

The amount of metal ion adsorbed was calculated as: Contact time (min)
C 0− C e
% Adsorption: × 100 (1) Fig. 1- Effect of contact time on the sorption of Zn 2+ and Pb2+ by
rice husks. Adsorption Conditions: 1g sorbent, 30mLof sample, pH
C 0 4. 4, temperature: 25±1 ◦C.
Where C0 and Ce are the initial and equilibrium
concentration of adsorbate,respectively.
The amount of metal adsorbed per Kilogram of the 70
biomass was calculated as follows: 60
(2) 50
(C − C )V
q e= m
.%
0 e 40
Abs

30

Where qe is the adsorbed metal on the sorbent, m is 20 Pb

the weight of sorbent, V is the volume of metal
10 Zn
solution, Co is the initial metal concentration, and Ce
is the metal concentration at any time. The amount of 0
metal ion sorbed at equilibrium, qe, is calculated 0 1 2 3 4
using eq.2.
Adsorbent among (gr)

RESULTS AND DISCUSSION Fig. 2- Effect of sorbent dosage on the sorption of Zn 2+ and Pb2+
on rice husks. Adsorption Conditions; 0.5-3g sorbent, 30mL of
Effect of contact time: The effect of sorption time sample, pH 4.4, temperature: 25±1 ◦C.
on sorption efficiency has been showed in Fig 1.
Adsorption rate is very fast initially; about 60.0% of
Effect of solution pH: Changes in solution pH can
Pb2+ and 10.3% of Zn2+ are removed within 5 min. alter the chemical nature of the functional groups on
The adsorption capacity reaches 96% and 49% of the the rice husks and then the metal adsorption capacity
equilibrium adsorption capacity within 60 min for of the adsorbent. Fig. 3 displayed the Zn2+ and Pb2+
Zn2+ and Pb2+, respectively and the sorption ion adsorption on the rice husks as a function of
tends toward saturation. So the optimum agitating solution pH. It showed that the sorption amount of
time for adsorption of Pb2+ and Zn2+ ion can be Zn2+ and Pb2+ increases with the increase of solution
accepted as 60 min. The initial faster rate of metal pH, the sorption process is pH-dependent. At low
sorption may be explained by the large number of solution pH, the functional groups on the rice husks
sorption sites available for adsorption. For the initial are protonated and positively-charged, their
bare surface, the sticking probability is large, and adsorption capacity is lower; while at higher pH, the
consequently adsorption proceeded with a high rate. deprotonated groups are involved in Zn 2+ and Pb2+
The slower adsorption rate at the end is probably ion adsorption. It can be observed from Fig. 3; the
due to the saturation of active sites and percent sorption of Zn2+ increased with increase in
attainment of equilibrium. pH and reached maximum 70% for at pH 7.0. The
percentage Zn2+ removal increased from 49% to
Effect of amount of sorbent: The effect of variation of 70.0% with an increase of pH from 6.0 to 7.0. The
sorbent amount on the removal of metal ions by rice percentage sorption of Pb2+ increased with increase in
husks is shown in Fig. 2. Amount of sorbent was pH and reached maximum 98.6% at pH 9.0. The
varied from 0.5 to 3 g and equilibrated for 5 min at an
percentage Pb2+ removal increased from 60% to
initial metal ion concentration. It is apparent that the
90.0% with an increase of pH from 3.0 to 6.0.
metal ion concentration in solution decreases with
Although the binding of lead was similar at higher
increasing sorbent amount for a given initial metal
pH, pH 9 was used in the remaining studies. It is also
concentration. This result was anticipated because for a known that heavy metal cations are completely
fixed initial solute concentration, increasing amount of released under circumstances of extreme acidic
adsorbent provides greater surface area. conditions. Metal biosorption is a rather complex

ASRARI, ELHAM; TAVALLALI, HOSSEIN; HAGSHENAS, MAHNOOSH

 161
Removal of Zn(II) and Pb (II) ions

process affected by several factors. Mechanisms practical limiting adsorption capacity when the
involved in the biosorption process include surface is fully covered with metals ion.
adsorption (chemisorption), complexation on surface
and pores, ion exchange, microprecipitation, heavy By plotting Ce/qe versus
metal hydroxide condensation onto the biosurface, C , K and q can be
q = K f Ce n e L m
and surface adsorption (Pehlivan and Arslan, 2007). determined when a
straight line is obtained. The Freundlich model is an
empirical equation based on adsorption on a
100 heterogenous surface. It is given as:
80

(4)
A b s .%

60

40
Where n is the Freundlich constant and Kf is the
20 Zn adsorption coefficient, q is the weight adsorbed per
unit weight of adsorbent and Ce is the equilibrium
Pb
0 metal concentration in fluid. The values of qm , KL
calculated from the experimental data through linear
1 3 5 7 9
regression analysis are presented in Table 1 with the
pH correlation coefficients (R2). Zn2+ sorption capacity
was 19.617mg/g and Pb2+ sorption capacity was
Fig.3- Effect of pH on the adsorption of Zn 2+ and 0.6216 mg/g for rice husks (Table 1).
Pb2+ using rice husks. Adsorption conditions; 1 gr 16
◦
sorbent, 30mL of sample, temperature: 25±1 C.
14

Adsorption isotherm: The effect of pH on the sorption

-4

12
by the rice husks was investigated by keeping the
10

10
solution volume (30 mL) and amount of the rice husks
(mmol/gr) *

8
for 5 min equilibrium time. The percentage of sorption is
highly dependent on the pH. The removal curves are 6
single smooth and continuous suggesting the formation
e

4 Zn
of monolayer of adsorbate on the surface of sorbent. The
q

2
percent metal ion removal of rice husks increased with
increasing pH. (Fig 4, 5) 0
0 2 4 6 8 10
PH

Several isotherm equations have been used for the Fig. 4- Sorption isotherm of Zn2+ ion on rice husks
equilibrium modeling of adsorption systems. Among as a function of pH, 1g sorbent, 30mL of sample,
these, the most widely used are the Langmuir and temperature: 25±1◦C.
Freundlich isotherm equations. The Langmuir
equation assumes that: (1) the solid surface presents a
7
finite number of identical sites which have uniform
6
energy; (2) there are no interactions between
adsorbed species, meaning that the amount adsorbed
-6

5
has no influence on the rate of adsorption; (3) a
q ( me m o l/g r ) 1* 0

monolayer is formed when the solid surface reaches 4

saturation (Huang and et al., 2007). Langmuir 3
equation can be described as:
2 Pb
Ce 1 1 (3)
1
= + C
e 0
qe K L qm qm
0 2 4 6 8 10
Where KL is the adsorption equilibrium constant PH
including the affinity of binding sites, qe is the amount
of bound Zinc and Lead at equilibrium and qm is the Fig. 5 - Sorption isotherm of Pb2+ ion on rice husks as a
maximum sorption capacity, which represents a function of pH/ 1g sorbent, 30mL of sample,
◦
C.1temperature: 25±

ASRARI, ELHAM; TAVALLALI, HOSSEIN; HAGSHENAS, MAHNOOSH

 162
Removal of Zn(II) and Pb (II) ions
Table 1- Parameters of Langmuir isotherm model for Zinc and Lead adsorption by rice husks.

Metals Langmuir isotherm method

qm KL R2
Zn 0.3 0.066 0.9747
Pb 0.003 186.67 0.9951

Conclusions: The rice husks are an agricultural Zakaria, H (2007). Batch study of liquidphase
waste substance. This product exhibits very good adsorption of lead ions using Lalang (Imperata
adsorption for Zinc from wastewater, especially. cylindrica) leaf powder. J Biol Sci 7: 222–230.
Adsorption of Zinc and Lead by rice husks has been
shown to depend significantly on the pH, rice husks Huang, Y H; Chen, C Y; Hsueh, C L; Huang, C.P; Su,
dosage and contact time. The adsorption behavior can L.C (2007). Adsorption thermodynamic and
be well described by Langmuir isotherm model. The kinetic studies of Pb(II) removal from water onto
maximum adsorption capacity was 0.3 and 0.003 m a versatile Al2O3-supported iron oxide. Sep Purif
mol/g for Zinc and Lead, respectively. The initial Technol 55: 23–29.
concentration of Zn2+ and Pb2+ has been 4.3 and 0.05
mg/l in dairy wastewater, respectively. After usage of Maranon, E; Sastre, H (1991). Heavy metal removal
various pH the concentration of heavy metals became in packed beds using applewastes. Bioresour
to 1.3 and 0.007mg/l. Actually the percent of Technol 38 :39–43.
removing zing and lead reached maximum to 70%
and 96.8%, respectively. The rice husks would be Orhan, Y; Buyukgungor, H (1993). The removal of
useful in treatment of wastewater containing Zinc and heavy metals by using agricultural wastes.Wat
Lead. Sci Tech 28 : 247–255.

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Hanafiah, M A K; Ibrahim, S C; Ngah, W S W;

ASRARI, ELHAM; TAVALLALI, HOSSEIN; HAGSHENAS, MAHNOOSH