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1 Chemical Sciences Journal, Volume 2010: CSJ -9
Biosorption Of Ni (II) And Cd (II) Ions From Aqueous Solutions Onto Rice Straw
1
*G O El-Sayed,
1
H A Dessouki,
2
S S Ibrahim
1
Chemistry Department, Faculty of Science, Benha University, Benha, Egypt
2
National Water Research Center, Central Lab for Environmental Quality Monitoring, Elqanater Elkhayria, Egypt

*Correspondence to: G O El-Sayed, [email protected]
Published online: August 30, 2010
Abstract

The adsorption of Ni(II) and Cd(II) ions onto rice straw was investigated. The effects of pH, initial adsorbent concentration, initial metal ion
concentration, contact time and temperature were studied in batch experiments. The Langmuir and Freundlich models were applied and the
adsorption equilibrium followed the two adsorption isotherms. The maximum adsorption capacities for Ni(II) and Cd(II) were 35.08 and 144.19
mg/g, respectively. Thermodynamic parameters such as free energy change (G), enthalpy change (H) and entropy change (S) have been
calculated on the basis of Langmuir constants. The negative values of G were indicative of the spontaneity of the adsorption process. The
negative values of H revealed the exothermic nature of the adsorption process whereas the positive S reflected an irregular increase of the
randomness at the adsorbent/solution interface during the sorption of metal ions.

Keywords: Nickel; cadmium; adsorption; isotherms; rice straw.


1. Introduction

The presence of heavy metals in the water environment is a major concern due to their toxic effects since they cause severe health
problems to animals and human beings. Many industrial processes produce aqueous effluents containing toxic metal contaminants.
According to the World Health Organization (WHO), the metals of most immediate concern are aluminum, chromium, manganese,
iron, cobalt, nickel, copper, zinc, cadmium, mercury and lead. In particular, cadmium and cadmium compounds are especially
dangerous and highly toxic. Cadmium toxicity contributes to a large number of health conditions, including the major killer diseases
such as heart disease, cancer and diabetes. Cadmium concentrates in the kidney, liver and various other organs and is considered
more toxic than either lead or mercury. It is toxic at levels one tenth that of lead, mercury, aluminum, or nickel [1]. Cadmium is
produced in different industrial activities such as galvanizing, pigments, stabilizers, thermoplastics, batteries and alloys [2]. On the
other hand, nickel is a toxic heavy metal and nickel compounds, are suspected to cause cancer [3]. Waste streams from nickel
electroplating industries and textile industries are the main sources of nickel environmental pollution. The concentrations of these
pollutants must be reduced by means of treatment to meet legislative standards. Several methods have been proposed for the
removal of heavy metals as ion exchange [4], filtration [5], coagulation [6], adsorption [7] and electrochemical deposition [8]. Most
methods to remove metal ions from solution are expensive [9], so the use of cheap agricultural wastes such as rice straw [10],
sawdust [11], carrot residues [12], tobacco dust [13], orange residue [14], apple residue [15], coconut shell powder [16] and
powdered leaves of castor tree [17] as adsorbents have been highlighted for metal removal from wastewater. Rice straw is one of
the abundant lignocellulosic waste materials in the world. In terms of total production, rice is the third most important grain crop in
the world behind wheat and corn [18]. Rice straw has several characteristics that make it a potential adsorbent with binding sites
capable to tack up metals from aqueous solutions. In terms of chemical composition, the straw predominantly contains cellulose
(3247%), hemicellulose (1927%) and lignin (524%) [19]. The aim of this work is to study Ni(II) and Cd(II) ions adsorption from
aqueous solutions onto rice straw as a cheap agricultural waste material. Different factors affecting the adsorption as the initial
solution pH, temperature, contact time, ionic strength and initial metal ion concentration on the adsorption isotherm were
examined to optimize the adsorption process. The biosorption equilibrium and kinetic data are fitted using different models and
process parameters were evaluated. The loading capacity of the rice straw was optimized.

2. Methods

Rice straw used as the adsorbent in this study was collected from a cultivated area near Benha city. The straw was washed with
distilled water several times and dried at room temperature. The straw was dried in a drying furnace at 90 C for two hrs, ground
and sieved between 400 and 600 m and stored in a plastic bottle prior to use. The rice straw was characterized by applying FTIR
analysis (using Jasco FT/IR-300E spectrometer) to predict the functional groups on the surface of the biomass responsible for the

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2 Research Article
adsorption process. This was done by mixing approximately 1.0 mg dried sample of straw with 100 mg KBr (1%), ground to fine
powder and pressed under vacuum to a pellet. The pellet was analyzed in the range 4000400 cm
1
. The FTIR spectra of the free
unloaded rice straw were compared with those obtained for straw loaded with nickel and cadmium. Also, SEM (Scanning Electron
Microscopy) (Model JEOL JEM-1200EX) was employed for the observation of the surface microporous structure of rice straw before
and after loading with cadmium.

Stock solutions (2000 mg/L) of the nickel and cadmium ions under study were prepared by dissolving an appropriate weight of pure
salt (NiSO
4
or CdCl
2
.2
1
2
H
2
O) in the desired volume of de-ionized water. The stock solution was successively diluted with de-ionized
water to obtain the desired test concentration of metal ion. All the chemicals used in the study were of analytical reagent grade and
all experiments were performed at room temperature (241 C). In order to optimize the design of a sorption system for the
removal of metals from wastewater, it is important to establish the most appropriate correlation for equilibrium curves.
Experimental data acquired at different conditions is fitted to different models of sorption isotherms because equilibrium isotherm
models are used to describe the experimental data. The batch mode was used to study the adsorption of Ni(II) and Cd(II) on rice
straw. Sorption studies were conducted in a number of plugged Pyrex glasses Erlenmeyer containing a definite volume (50 ml in
each case) of solutions of the metal ion of desired concentration, pH and temperature were placed in a thermostatic rotary shaker.
For the studies, 0.2 g of adsorbent was treated with 50 ml of metal ion solution. The flasks were agitated at a 200-rpm constant
shaking rate for 3 hrs to ensure equilibrium was reached. Samples (3 ml) were taken before mixing the sorbent and the metal ion
solution and at pre-determined time intervals. The metal solution was separated from the sorbent by centrifugation at 5000 rpm for
5 min. The metal ion content in the test flask was evaluated by ICP-OES 2010 Serial Optical Emission Spectrometer, Optima
(PerkinElmer). Uptake values were determined as the difference between the initial metal concentration and that in the
supernatant.

All the experiments were carried out in duplicates and the average of the values were used for further calculations. For the
calculation of average value, the percent relative standard deviation for samples was calculated and if the value of standard
deviation for any sample was greater than 5% the data were not used. The pH of the test solution was monitored by using a pH-
meter model HI 8014, Hanna Instruments (Italy). The samples were analyzed three times and the mean values were computed. The
amount of metal ion adsorbed per unit mass of the biosorbent was evaluated by using following equation:
q
mux
=(C
o
C
c
)
v
w

Where, C
o
is the initial metal ion concentration in mg/L, and C
e
is the metal ion concentration at equilibrium in mg/L and V is the
volume of metal ion solution in milliliters, W is the mass of adsorbent in grams. The percent of metal ion removal was evaluated
from the equation:
% Rcmo:ol =
(C
0
-C
c
)
C
0
100
3. Results and Discussion

3.0. Biosorbent characterization

FTIR spectroscopy was applied to identify the functional groups of rice straw responsible for metal adsorption. To reveal the
systematic changes in the spectral features upon reaction with metal ions, FTIR spectra were obtained for the sample after reacting
with Ni(II) and Cd(II) (Figure 1). By comparing the FTIR spectra of rice straw before and after adsorption, there were remarkable
shifts in some bands (Table 1). These bands are the function groups of rice straw participate in Ni(II) and Cd(II) biosorption.

Table 1. FTIR spectral characteristics of rice straw before and after biosorption of Ni(II) and Cd(II).

FTIR
peak
Transmission band (cm
-1
)
Assignment

Reference Before adsorption After adsorption of
Ni(II)
After adsorption of
Cd(II)
1 3340 3326 3427 Stretching vibration
of -OH
20
2 2921 2923 2924 Aliphatic C-H group 21
3 2372 2348 2361 phosphine 22
4 1650 1654 1633 double bands of the
carboxylate
ion
23


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3 Chemical Sciences J ournal, Volume 2010: CSJ -9


Figure 1. FTIR transmission spectra of rice straw (a) unloaded; (b) loaded with Ni(II) and (c) loaded with Cd(II).

Scanning electron micrographs realized on raw rice straw and cadmium loaded rice straw are shown on Figure 2. The initial structure
of the rice straw (Figure 2a) shows the presence of a few macropores of various size at the surface, in contrast, mineral matter can
be observed within the macropores of the sample after adsorption of cadmium (Figure 2b).


Figure 2. Scanning electron micrographs of (a) raw rice straw (b) cadmium loaded rice straw.

3.1. Effect of initial pH
The pH of the solution is one of the important factors governing the adsorption of metal ions. Figure 3 shows the effect of pH change
in the range 1 to 8 on the adsorption of Ni(II) and Cd(II) on rice straw. The initial pH of the solution has a significant influence on the
amount of metal ion adsorbed. It was observed from the figure that the removal percent of Ni(II) and Cd(II) ions in the aqueous
solution is low at low pH values and increased with increasing the initial pH of the solution. The removal of Ni(II) was about 28%at a
pH 1.0 and it reached its maximum value (47%) at about pH 5.0. Further increase of pH leads to slight decrease in Ni(II) removal
efficiency. The removal percentage of Cd(II) showed a rapid increase from 25%to 76%when the pH increased from 1.0 to 6.0. This
behavior is expected for many metal ions including nickel and cadmium [24-26]. The influence of pH can be related with the fact
that in an acid environment competition between metals and H
+
ions occurs and the metal retention in such condition is not
significant. With increasing pH, electrostatic repulsion decreases due to reduction of positive charge density on the sorption sites
thus resulting in an enhancement of metal adsorption [27].

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4 Research Article

Figure 3. Effect of pH on removal percent of Ni(II) and Cd(II) ions onto rice straw.

3.2. Effect of contact time
The plot of percent of metal removal against contact time for Ni(II) and Cd(II) ions at optimum pH values is shown in Figure 4. It was
observed that the adsorption of Ni(II) and Cd(II) by rice straw was highly influenced by contact time. The kinetics of metal removal by
rice straw was relatively fast within 5 min and during the first hour was remarkably changed with time. At the equilibrium time the
metal ion uptake of 46%for Ni(II) and 76% for Cd(II) were achieved. The equilibrium time was taken as 90 min for further
experimental measurements. Equilibrium time is a crucial parameter for an optimal removal of metal ions in the waste water. The
increased uptake of both metal ions with contact time can be due to the decreased mass transfer coefficient of the diffusion
controlled reaction between the adsorbent and the metal ion.

Figure 4. Effect of contact time on removal percent of Ni(II) and Cd(II) ions onto rice straw.

3.3. Effect of ionic strength of metal ion solution
Ionic strength of the solution may be an important factor influencing aqueous phase equilibrium between adsorbed species and
adsorbent. Generally, adsorption decreases with increasing ionic strength of the aqueous solution which can be attributed to the
presence of sorption sites of different affinities [28]. The effect of addition of NaCl on the removal capacity of Ni(II) and Cd(II) ions is


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5 Chemical Sciences J ournal, Volume 2010: CSJ -9
shown in Figure 3. The results indicate that there was a little significant decrease in the removal of Ni(II) and Cd(II) ions for the
interval of (1-10 g/L) NaCl ionic concentration.

Figure 5. Effect of NaCl concentration on Ni(II) and Cd(II) removal onto rice straw.

3.4. Effect of temperature
The effect of the solution temperature on the adsorption capacity was investigated for Ni(II) an Cd(II) ions solutions at initial metal
concentration 1000 mg/L and adsorbent dose 20 g/L. Four different temperatures of 25, 30, 35 and 40 C were considered. From
Figure 6, it can be observed the removal percent was slightly decreased for the two metal ions. It decreased from 47% to 44%for
Ni(II) and from 75.5%to 70% for Cd(II) when temperature was increased from 20 to 40 C. These results indicate that the adsorption
of Ni(II) and Cd(II) ions is exothermic in nature [29].

Figure 6. Effect of temperature on Ni(II) and Cd(II) removal by rice straw.

3.5. Effect of initial metal ion concentration
The metal uptake mechanism is particularly dependent on the initial heavy metal concentration: at low concentrations, metals are
adsorbed by specific active sites, while at higher concentrations; lower adsorption yield is due to the saturation of adsorption sites.

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6 Research Article
Though an increase in metal uptake was observed, the decrease in percentage adsorption may be attributed to lack of sufficient
surface area to accommodate much more metal available in the solution. This appears to be due to the increase in the number of
ions competing for the available active sites on the surface. In addition, typical mass-transport controlled kinetics of pollutants
removal by the rice straw is another factor which control removal rate of zinc and at higher concentrations, more metal ions are left
in solution [30]. The influence of the initial concentration on the adsorption capacity of Ni(II) and Cd(II) ions is presented in Figure 7.
For Ni(II) removal, a decrease in removal percent from 91%(for C
o
=40 mg/L) to 45%(for C
o
=1000 mg/L) could be observed. The
same behavior was observed with Cd(II), where a decrease in removal percent from 98%(for C
0
=40 mg/L) to 76%(for C
0
=1000
mg/L) occurred.

Figure 7. Effect of initial metal ion concentration on adsorption capacity.

3.6. Adsorption isotherms

The study of adsorption isotherms is fundamental in supplying the essential information required for the design of the sorption
process. The adsorption of a substance from one phase to another leads to a thermodynamically defined distribution of that
substance between the phases as the system reaches equilibrium state [31]. This distribution can be expressed in terms of
adsorption isotherms. In this investigation, Langmuir and Freundlich isotherm models were used to analyze the equilibrium data.

3.6.1. Langmuir adsorption isotherm
Langmuir adsorption isotherm [32] applied to equilibrium adsorption assuming a mono-layer adsorption onto the surface of the
adsorbent with a finite number of identical sites. This isotherm can be represented by the following relationship:
C
c
q
c
=
1
q
mux
b
+
C
c
q
mux

where, q
e
is the metal uptake at equilibrium per unit mass of adsorbent (mg/g), q
max
is the maximum adsorption capacity of metal
per unit mass of adsorbent (mg/g), C
e
is the equilibrium concentration of the metal in solution (mg/L). The plot of C
e
versus C
e
/q
e

should give a straight line its slope equals to 1/q
max
ant the intercept has the value of 1/q
max
b, where b is the adsorption coefficient
(L/mg). From the plot (Figure 8), q
max
and b values of the Ni(II) and Cd(II) were obtained (Table 1). The essential characteristics of
Langmuir isotherm can be expressed by a dimensionless constant called equilibrium parameter R
L
, defined by [33]:
R
L
=
1
1+bC
o

The value of R
L
indicates the type of the isotherm to be either unfavorable (R
L
>1), linear (R
L
=1), favorable (0 <R
L
<1) or irreversible
(R
L
=0). As shown in Table 1, The maximum adsorption capacities of rice straw towards Ni(II) and Cd(II) are 35.08 and 144.19 mg/g,
respectively. The values of R
L
ranged from 0.941 to 0.390 and from 0.982 to 0.694 for Ni(II) and Cd(II) ions, respectively in the initial
metal ion concentrations 40-1000 mg/L. The values of R
L
indicated that the adsorption process is favorable.



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7 Chemical Sciences J ournal, Volume 2010: CSJ -9
Table 2. Langmuir and Freundlich adsorption isotherm parameters for Ni(II) and Cd(II).

Metal Ion Langmuir Isotherm Freundlish Isotherm
q
max
b R
L
R
2
K
F
n R
2

Ni(II) 35.08 0.00156 0.941-0.390 0.9866 0.1388 1.314 0.9930
Cd(II) 144.19 0.00044 0.982-0.694 0.9600 0.0839 1.086 0.9972

Figure 8. Langmuir isotherm for adsorption of Ni(II) and Cd(II) on rice straw.

3.6.2. Freundlich adsorption isotherm

The Freundlich adsorption isotherm is an empirical equation based on the adsorption on a heterogeneous surface [34]. The linear
form of Freundlich adsorption isotherm can be defined by the following equation:
lnq
c =
ln K
P
+
1
n
lnC
c

The constant n is an empirical parameter that varies with the degree of heterogeneity and K
F
is a constant related to adsorption
capacity. The constants n and K
F
were calculated from the previous equation by plotting ln C
e
against ln q
e
(the slope =1/n and the
intercept =ln K
F
) (Figure 9). The values of n (which reflect the intensity of adsorption) are between 1 and 10 represent a favorable
adsorption. From the results are presented in Table 2. It can be seen that the adsorption of Ni(II) on rice straw follows the two
adsorption models, whereas Freundlich model is more fitted in for Cd(II) adsorption (depending of the values of R
2
).

3.7. Adsorption thermodynamics

The thermodynamic parameters such as Gibbs free energy change G
0
, standard enthalpy change H
0
, and standard entropy change
S
0
were also studied to understand better the effect of temperature on the adsorption. The values of standard Gibbs free energy
change were evaluated by using b values obtained from the Langmuir model presented in Table 2 by applying the following equation
[35].
0
0
=RIlnb =lnK
where R is universal gas constant (8.314 J/mol K) and T is absolute temperature.

The values of G
0
for the biosorption process of Ni(II) and Cd(II) were evaluated at different temperatures and are presented in Table
2.

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8 Research Article

Figure 9. Freundlich isotherm for adsorption of Ni(II) and Cd(II) on rice straw.



Table 3. Thermodynamic parameters of Ni(II) and Cd(II) adsorption on rice straw at different temperatures.

T (K) G (kJ/mol) H (kJ/mol) S (kJ/mol K)
Ni(II) Cd(II) Ni(II) Cd(II) Ni(II) Cd(II)
298 -3.865 -1.090
-5.723


-5.821


0.0199


0.0062

303 -3.930 -1.108
308 -3.994 -1.126
313 -4.060 -1.145

The equilibrium constant K may be related to Hand Sat different temperatures by the following relationship:
lnK =
S
0
R

E
0
RI


The plot of ln K against 1/T (Vants Hoff plot) of the metal ion solution was carried out as indicated in Figure 8, in which the slope
equals to -H/R and the intercept equals to S/R. These thermodynamic parameters are presented in Table 2. The negative values
of G at all temperatures examined indicate the feasibility of the process and the spontaneous nature of the adsorption. The
negative values of H reveal the adsorption is exothermic and physical in nature. Generally, the change in adsorption enthalpy for
physicorption is in the range of 20 to 40 kJ mol
1
, but chemisorption is between 400 and 80 kJ mol
1
[36]. Furthermore, slightly
positive S of Ni(II) and Cd(II) adsorption processes indicate an irregular increase of the randomness at the adsorbent/solution
interface during adsorption.

4. Conclusion
The potential use of rice straw as an adsorbent for nickel and cadmium was studied. It was found that rice straw is an effective
adsorbent for the two metal ions, specially for cadmium, the maximum adsorption capacities for Ni(II) and Cd(II) were 35.08 and
144.19 mg/g, respectively. The sorption capacity was strongly dependent on the adsorbent dosage; initial metal ions concentration
and initial pH. The experimental data well fitted to the Langmuir and Freundlich equations, with good correlation coefficients. The
study of the thermodynamic parameters indicated that the adsorption process was thermodynamically spontaneous under natural
conditions and the adsorption is exothermic in nature.


http://astonjournals.com/csj E-ISSN: 21503494
9 Chemical Sciences J ournal, Volume 2010: CSJ -9

Figure 10. Vants Hoff plot for the determination of H
o
, S
o
and G
o
.


5. Competing Interests

The authors declare that they have no competing interests.

6. Authors Contributions

GOE developed the project and assisted with preparation of the manuscript and data analysis; HAD supervised preparation of the
manuscript; SSI assisted with sample collection and carried out the project.

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List of Abbreviations

b Langmuirs constant related to energy of adsorption (Lmg
1
)
C
o
initial concentration of metal (mg L
1
)
C
e
equilibrium concentration of metal (mg L
1
)
K equilibrium constant at temperature T
K
F
Freundlich constant
n Freundlich constanta
q
e
amount of metal adsorbed (mg g
1
) at equilibrium
q
max
Langmuirs constant related to capacity of adsorption (mg g
1
)
R gas constant (kcal mol
1
K)
R
L
equilibrium parameter, dimensionless
T absolute temperature (K)
V volume of metal solution (L)
W mass of adsorbent (g)
G standard free energy change (kJ mol
1
)
H standard enthalpy change (kJ mol
1
)
S standard entropy change (kJ K
1
mol
1
)

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