Indian Journal of Chemical Technology

Vol. 15, July 2008, pp. 341-348

Sorption of Pb(II) and Cd(II) ions onto chemically unmodified and modified oil
palm fruit fibre adsorbent: Analysis of pseudo second order kinetic models
A A Abia* & E D Asuquo
Department of Pure and Industrial Chemistry, University of Port Harcourt, P. M. B. 5323, Choba, Port Harcourt, Rivers State, Nigeria
Email: abiauniport2005@yahoo.com
Received 7 November 2007; revised 19 February 2008

This study examines the sorption kinetics of Pb (II) and Cd (II) ions from aqueous solutions using unmodified and
chemically modified oil palm fruit fibre. Four different models of the pseudo-second order equation were used to
characterize the metal ion sorption kinetics. The results indicate that different kinetic parameters were obtained from the
four forms of the pseudo-second order equations. The chemical modification of the adsorbent increased the equilibrium
sorption capacity with maximum values of 5.579 mg/g for Pb(II) and 7.980 mg/g for Cd(II) for the 1.0 MOPF adsorbents.
The coefficient of determination (r2) was used to analyse the different pseudo second order equations with the best fit for
each of the different metal ions.
Keywords: Sorption, Kinetics, Pseudo-second order, Oil palm fibre, Cadmium, Lead

Toxic heavy metal contamination of the ecosystem is
a significant universal problem. They accumulate in
living tissues throughout the food chain, which has
human being at its top. These heavy metals can cause
poisoning, cancer and brain damage when
accumulated in the human body above the tolerance
levels1. These heavy metals are released from a
number of industries such as mining, plating, dyeing,
automobile manufacturing and processing. The
presence of these heavy metals in the environment has
led to a number of environmental problems2. In recent
years, increasing awareness of the environmental
impact of heavy metals has prompted a demand for
the purification of industrial waste waters prior to
discharge into natural waters3.
The main conventional method used to remove
heavy metals from aqueous solution is chemical
precipitation. However, coagulation-precipitation
often involves high operational costs, and in many
cases, it fails to meet strict regulation requirements.
Adsorption has been shown to be a feasible
alternative for removing heavy metals from water.
Synthetic adsorbents such as ion exchange resins or
chelating resins have extremely high potential for
removing metals but the high cost of these materials
limits their application to treatment facilities that
process large volumes of waste water4.
Due to this limitation numerous approaches have
been studied to develop cheap and effective metal
adsorbents. Many workers have shown that
agricultural waste materials can bind substantial
amounts of metals ions5. These include cassava
waste6, banana pith7, peanut skin8, and Medicago
sativa (Alfalfa)9.
Further more, sorption of pollutants from aqueous
solution plays a significant role in water pollution
control. It is, therefore, important to assess the
physicochemical aspects of adsorption in order to
design an appropriate treatment plant. One of the
most fundamental physicochemical aspects for the
evaluation of the sorption as a unit operation is the
kinetics10. Series of kinetic models have been applied
for the modeling of metal ion transport for various
sorption systems. The pseudo-first order rate
equation has been applied to adsorption of soluble
substances11. The second order expression was also
used to describe the kinetics of exchange processes
between the sodium ions from a zeolite A and Cd(II),
Cu(II) and Ni(II) ions from solutions12. Recently the
pseudo-second order equation of Ho has been used for
the description of sorption for various systems13-17.
The purpose of present work is to evaluate the
sorption of Pb(II) and Cd(II) ions from aqueous
solutions using oil palm fruit fibre adsorbent in its
unmodified and chemically modified forms. This is to
provide information in order to assess the
applicability of the sorbent for treatment of
contaminated wastewater. Also kinetic modeling of
342 INDIAN J. CHEM. TECHNOL., JULY 2008
metal ion transport is carried out using the linear
forms of the pseudo-second order equation.
Experimental Procedure
The oil palm fruit fibre (Elaeis guineensis Jacq.)
was obtained from an oil mill in a village near Uyo,
Akwa Ibom State, Nigeria. A 1000 mg/L stock
solution of Pb(II) ion (PbCl2) and Cd(II) ion
(CdCl2.2H2O) [both BDH] were prepared by
dissolving the calculated amount of each salt in
deionized water and diluting the solution to 1000 mL.
From each stock solution, 50 ppm working solutions
of each metal ion was prepared by serial dilution. The
oil palm fruit fibre was de-oiled by washing in hot
deionized water and detergent. It was then rinsed in
hot deionized water to remove all debris and finally
air-dried. The dried fibre was ground using an
electric blender. The fine oil palm fibre particles
were then screened through a set of sieves (250, 150
and 106 µm). The particles that passed through the
106 µm sieve were used for chemical activation and
modification. The 106 µm mesh size oil palm fibre
was soaked in an excess of 0.3 M HNO3 solution for
24 h and then filtered using a Whatman No. 41 filter
paper, rinsed with deionized water and dried.
Chemical modification of adsorbent
The oil palm fibre was weighed and divided into
three parts each weighing 100 g. The first part
labeled “A” was left untreated and called “unmodified
oil palm fruit fibre (UOPF). Parts “B” and “C” were
acid treated by soaking them in an excess of 0.5 and
1.0 M mercaptoacetic acid solutions, respectively.
The two mixtures were stirred for 30 min and left to
stand for 24 h at room temperature. After 24 h the two
mixtures were filtered using a Whatman No. 41 filter
paper. Then, the residue in each filter paper was
soaked in 1.0 M hydroxylamine (NH2OH) for 1 h.
After which the mixture was filtered and rinsed with
deionized water. The two chemically modified
adsorbents were labeled as 0.5 M modified oil palm
fruit fibre (0.5 MOPF) and 1.0 M modified oil palm
fruit fibre (1.0 MOPF).
Determination of thiolation of adsorbents
The degree of incorporation of the thiol (SH) group
onto the surface of the chemically modified
adsorbents (0.5 MOPF and 1.0 MOPF) was
determined by the reported method18, where 0.5 g of
0.5 MOPF and 1.0 MOPF adsorbents were weighed
into two 250 mL Erlenmeyer flasks. To each flask
200 mL of 0.5 M iodine solution was added at pH 7.2.
The flasks were agitated in an EFLI-MK3 model
electric shaker for 10 min and allowed to settle. The
unreacted iodine in each mixture was back titrated
with 0.1 M sodium thiosulphate solution until the
colour of the solution turned yellow, thereafter the
colour of the solution turned blue with the addition of
2 mL of starch solution. The titration with sodium
thiosulphate was continued until the solution
became colourless indicating an end point. The
percentage degree of thiolation of each of the two
adsorbents was computed using the results obtained
from the titration.
Determination of specific surface area of adsorbents
The methylene blue adsorption test (MBT) was
used to determine the specific surface area of the
UOPF, 0.5 MOPF and 1.0 MOPF adsorbents19. Two
grams of each adsorbent were dissolved in 200 mL of
deionized water. A methylene blue solution (10 ppm)
was added to each of the adsorbent mixture and
agitated in a shaker for 2 h and then kept for 24 h to
reach equilibrium. Thereafter, 10 mL aliquot was
withdrawn from each mixture and centrifuged using a
SIGMA 301 – centrifuge. The centrifuged aliquot
was later analyzed in a UNICAM – 8700 UV/visible
Spectrophotometer to determine the amount of
methylene blue absorbed. Furthermore, 20, 30, 40,
50, 60 and 70 ppm solutions of methylene blue were
then added to each adsorbent mixture and the
previous procedure repeated to determine the point of
complete cation replacement. Then, the specific
surface areas of the three adsorbents were calculated.
pH point of zero charge of adsorbent
The plot of zeta potential versus initial adsorbent
pH was used to determine20 the pH point of zero
charge (pHpzc) of each of the three adsorbents.
Aliquotes of NaCl solution (50 mL of 0.01 M) were
measured into different Erlenmeyer flasks. The pH of
each solution in each flask was adjusted to 2, 4, 6, 8,
10 and 12 using 0.1 M HCl or 0.1 M NaOH solutions.
Thereafter, 0.5 g of each adsorbent was added to the
different flasks and agitated in an EFLI model shaker
for 1 h and then allowed to settle for 48 h to reach
equilibrium at 280C. The zeta potential (mV) was
then determined using an electronic instrument 7010 –
pH meter for each of the adsorbent. A plot of zeta
potential (mV) versus initial pH was used to
determine the pH point of zero charge of each
adsorbent.
 ABIA & ASUQUO: OIL PALM FRUIT FIBRE FOR SORPTION OF Pb(II) & Cd(II) 343

Adsorption rate studies qt/t 0, hence

Adsorption rate studies were carried out for the
sorption of Pb(II) and Cd(II) ions from aqueous h = K2 qe2 …(5)
solutions by UOPF, 0.5 MOPF and 1.0 MOPF Eq. (5) can be written as
adsorbents. The Pb(II) and Cd(II) ion solutions
(100 mL of 50 mgL-1) were transferred into different t 1 1
250 mL Erlenmeyer flasks and labeled. To different = + ⋅t …(6)
flasks, 0.5 g of each adsorbent (UOPF, 0.5 MOPF and qt h qe
1.0 MOPF) was added and agitated in a EFL 1 shaker
Eq. (6) may be transformed into the following four
for different time intervals of 10, 15, 20, 30, 45, 60,
forms17:
90 and 120 min at pH 6.2, ionic strength 0.01 M
NaCl and temperature 280C. After each sorption time,
the contents of each flask were filtered using a t 1 1t
Type 1 — = + ...(7)
Whatman No. 41 filter paper. Thereafter, 20 mL of qt Kqe qe
each filtrate was analyzed in a UNICAM 919-Solar
Atomic Absorption spectrophotometer (AAS) for
1  1 1 1
Type 2 — q =  2  t + q
metal ions.
…(8)
t  Kqe  e
Data analysis
The pseudo-second order chemisorption equation13
is expressed as:  1  qt
Type 3 — qt = qe −   …(9)
 Kqe  t
dq t
= K 2 ( qe − qt ) 2 …(1)
dt 2
Type 4 — qt = Kqe − Kqe qt …(10)
where, qe and qt are the sorption capacities at
Equations 7-10 were used to model the sorption
equilibrium and at time t respectively (mg/g) and K2 is
kinetics of Pb(II) and Cd(II) ions removal from
the rate constant of the pseudo-second order
aqueous solutions using unmodified and chemically
sorption (g.mg-1.min-1). For the boundary conditions
modified oil palm fruit fibre adsorbents. The best
t = 0 to t = t and qt = 0 to qt = qt, the integrated form
fitting equation for the experimental data for the
of Eq. (1) is
sorption of the two metals was determined using the
coefficient of determination, r2. For which17 Eq. (11)
1 1 represents;
= + K2 ⋅t …(2)
qe − qt qe
2

This is the integrated rate law for a pseudo-second 2

r =
∑ ( q −q ) m t
order reaction. Equation (2) can be rearranged to 2 ...(11)
∑( q −q ) +∑( q −q )
2
obtain m t m t

t where qm is the amount of metal ion on the surface of

qt = ...(3) the oil palm adsorbent at any time, t (mg/g) obtained
1 t
2
+ from the pseudo-second order kinetic model, qt is the
K 2 ⋅ qe qe
amount of metal ion on the surface of the oil palm
fruit fibre adsorbent at time t, (mg/g) obtained from
This has a linear form: the experimental data and qŧ is the average of qt
(mg/g).
t 1 1
= 2
+ ⋅t ...(4) Results and Discussion
qt K 2 ⋅ qe qe
The surface characteristics of the unmodified and
where h (mgg-1.min-1) can be regarded as initial chemically modified oil palm fruit fibre adsorbents
sorption rate as are presented in Table 1. The extent to which the oil
344 INDIAN J. CHEM. TECHNOL., JULY 2008
palm fruit fibre waste were chemically modified using
0.5 M and 1.0 M mercaptoacetic acid solutions was
estimated using the percentage thiol content (%SH).
This estimates the extent to which the mercaptoacetic
acid incorporated the thiol (SH) group onto the
surface of the chemically modified adsorbents. The
functional groups on the oil palm fruit fibre wastes are
phenolic, carboxylic and hydroxyl groups21. Thus, the
incorporation of the thiol functional group is to
increase the concentration of the metal binding sites
on the surface of the adsorbent. Studies have also
indicated that the incorporation of thiol groups on an
adsorbent matrix enhances the binding capacity of the
adsorbent by increasing the number of possible
binding sites for metal ion sorption22. From Table 1, it
can be seen that the percentage thiol content of the
chemically modified adsorbents increased with
concentration of the modifying reagent.
The specific surface area of the three oil palm fruit
fibre wastes is presented in Table 1. It can be seen
that the specific surface area of the adsorbents
increased with chemical modification. It has been
reported that acid modification of a biomass provides
the sorbent with larger surface area and enhanced
porosity which aids metal ion sorption23. Thus, the
increase in the specific surface area of the adsorbents
with chemical modification should enhance the
sorption capacity of the adsorbent. The pH point of
zero charge was also determined for the three
adsorbents and is also presented in Table 1. The pH
point of zero charge (pHpzc) of an adsorbent is the pH
of an adsorbent suspension at which the surface acidic
(or basic) functional groups of an adsorbent no longer
contributes to the pH of the suspension24. It may also
be said to be the pH at which the charge on the solid
surface of the adsorbent is zero. Above pHpzc the
surface charge of the adsorbent is negative25. There
exist a relationship between the value of the pHpzc of
an adsorbent and its adsorption capacity. The
adsorption of cations on any adsorbent is greatly
favourable at a pH above the adsorbent pHpzc24. From
Table 1, it can be seen that the value of the pHpzc is
reduced from 7.1 for UOPF adsorbent to 6.4 for 0.5
Table 1 — Surface characteristics of oil palm fruits
fibre waste adsorbents
Parameter UOPF 0.5 MOPF 1.0 MOPF
2 -1
Specific surface area (m g ) 248.42 289.83
Thiol content (%SH) – 1.35
pHpzc 7.1 6.4
MOPF and 6.0 for 1.0 MOPF adsorbents. This trend
may be due to the increased negative charge
contribution of the thiol group to the adsorbents
surface.
Kinetic modeling of pseudo-second order equations
Kinetic modeling of metal ion sorption for the
removal of an adsorbate from aqueous solution by an
adsorbent is often an attempt to determine the rate of
uptake and residence time of an adsorbate at the solid-
liquid interface. Therefore the sorption capacity and
required contact time are two of the most important
parameters that aid in the understanding of sorption
capability or by the character of sorbent in terms of
kinetics26.
The kinetic modeling for the sorption of Pb(II) and
Cd(II) ions from aqueous solution by the oil palm
fibre waste adsorbents was carried out using the
pseudo-second order equation. The type 1, type 2,
type 3 and type 4 equations of the pseudo-second
order were used17. The choice of the pseudo-second
order model for the analysis of the kinetics of Pb(II)
and Cd(II) ions is based on the fact that the pseudo-
second order equation has been applied to a
wide range of metal-sorbent systems with high
efficiency30-32. The type 1-4 pseudo-second order
linear models for the sorption of Pb(II) ion from
aqueous solutions by the three oil palm fruiting fibre
adsorbents are illustrated in Figs 1-4. An inspection of
the figures shows that the type 1 pseudo-second order
plot was the most linear of the kinetic models. From
the figures, the values of the pseudo-second order
kinetic model constant, K2, the amount of Pb(II) ion
adsorbed by each adsorbent at equilibrium, qe and the
initial sorption rate, h computed from the slope and
intercept values of Figs 1- 4 are presented in Table 2.
Examination of the values of the constants in
Table 2 using the kinetic model fitting parameter, the
coefficient of determination indicates that the value of
the type 1 pseudo-second order equation plot was the
highest. The selection criterion was that the closer the
r2 value of a kinetic equation to unity, the greater the
fitting pattern of that model to the experimental
kinetic data. For the UOPF adsorbent the r2 value of
the type 1 equation was highest. Same pattern was
also observed for the 0.5 MOPF and 1.0 MOPF
adsorbents. The pseudo-second order kinetic plot for
331.23
the four types of linear equations for the sorption of
Cd(II) ion from aqueous solution by the oil palm fruit
2.83
fibre is depicted in Figs 5-8. From these plots the
6 value of the slope and intercept were computed
 ABIA & ASUQUO: OIL PALM FRUIT FIBRE FOR SORPTION OF Pb(II) & Cd(II) 345

Fig. 1 — Type 1-pseudo-second order linear model for Pb(II) ion Fig. 3— Type 3 -pseudo-second order linear model for Pb(II) ion
on oil palm adsorbents sorption on oil palm adsorbents

Fig. 2— Type 2-pseudo-second order linear model for Pb(II) ion Fig. 4 — Type 4 pseudo-second order linear model for sorption of
sorption on oil palm adsorbents Pb(II) ion on oil palm adsorbents

Table 2 — Pseudo second order kinetic parameters for Pb(II) on oil palm adsorbents
Adsorbent Type qe (mg/g) K2 (g/mg.min-1) h (mg/g.min-1) r2
2.459 0.9998
UOPF 1 4.873 1.03x10-1 3.663 0.9062
2 4.800 1.58x10-1 3.690 0.8921
3 4.785 1.65x10-1 3.318 0.8921
4 4.811 1.43x10-1
0.5 MOPF 1 5.178 7.10x10-2 1.906 0.9997
2 5.081 1.02x10-1 2.644 0.9087
3 5.070 1.03x10-1 2.655 0.9000
4 5.106 9.23x10-2 2.407 0.9000
1.0 MOPF 1 5.197 6.45x10-2 1.743 0.9989
2 5.037 1.20x10-1 3.058 0.8628
3 5.028 1.20x10-1 3.042 0.8297
4 5.579 6.81x10-1 2.120 0.9045
346 INDIAN J. CHEM. TECHNOL., JULY 2008
Fig. 5 — Type 1- Pseudo-second order model for Cd(II) sorption
on oil palm adsorbents
Fig. 6 — Type 2- Pseudo-second order kinetic equation for Cd(II)
ion sorption on oil palm adsorbents
and used to determine the pseudo-second order kinetic
model constant, K2, the amount of cadmium ion
sorbed at equilibrium, qe and the initial sorption rate,
h. The values of these constants are presented in
Table 3. Also, the analysis of these equations
indicated that for UOPF, 0.5 MOPF and 1.0 MOPF
adsorbents the type 1 pseudo-second order equation
was the best fit with coefficient of determination
value of unity for all three adsorbent systems.
Thus, the type 1 pseudo-second order equation is
the best kinetic model for the description of the
mechanism of Cd(II) on Pb(II) ions from aqueous
solutions. Previous work on the sorption of cadmium
by tree fern17 has also shown that the type 1 pseudo-
second order equation was the best fit kinetic model.
In addition, it can be observed from Tables 2 and 3,
that the values of qe (mg/g) for each metal ion in
respect of the three adsorbents indicates a trend of
which can be given as 1.0 MOPF > 0.5 MOPF >
Fig. 7 — Type 3- Pseudo-second order kinetic model for Cd(II)
ion sorption on oil palm adsorbents
Fig. 8 — Type 4- Pseudo-second order kinetic model for Cd(II)
ion sorption on oil palm adsorbents
UOPF. Indicating that the values of qe for the
1.0 MOPF adsorbent for each metal ion is the highest.
This lends credence to the observation that chemical
modification of an adsorbent increases the adsorbent
capacity for the metal ion. Thus, the 1.0 MOPF
adsorbent had the highest efficiency because the
chemical modification process incorporated more
metal ion binding site onto the adsorbent matrix than
the 0.5 MOPF and the UOPF adsorbents of which the
later was not modified. Another inference that can be
drawn from data in Tables 2 and 3, is that
comparatively, the qe values for Cd(II) are higher than
that for Pb(II). This marked variation in the values of
the amount of each metal ion sorbed at equilibrium,
qe (mg/g) may be attributed to the differences in their
ionic sizes. The ionic radius of Pb(II) is 1.20 A and
that of Cd(II) is 0.97A.
It has been observed that when there is electrical
attraction between adsorbates and adsorbents, ions
 ABIA & ASUQUO: OIL PALM FRUIT FIBRE FOR SORPTION OF Pb(II) & Cd(II) 347

Table 3 — Pseudo second order kinetic parameters for Cd(II) on oil palm adsorbents
Adsorbent Type qe(mg/g) K2 (g/mg.min-1) h (mg/g.min-1) r2
-1
UOPF 1 7.199 1.27x10 6.618 1.0000
-1
2 7.199 1.51x10 7.836 0.9767
3 7.160 1.57x10-1 8.070 0.9704
-1
4 7.167 1.52x10 7.838 0.9704
0.5 MOPF 1 7.564 1.62x10-2 9.302 1.0000
-1
2 7.674 1.34x10 7.930 0.9430
-2
3 7.553 1.77x10 10.137 0.9535
4 7.563 1.62x10-2 9.679 0.9535
1.0 MOPF 1 7.855 2.08x10-2 12.835 1.0000
2 7.980 1.68x10-1 10.741 0.9578
-1
3 7.846 2.17x10 13.413 0.9912
4 7.848 2.15x10-1 13.298 0.9912

with small ionic radii but higher ionic charge are more
strongly attracted to sites of opposite charge
(adsorbent). However, for ions of similar charge, the
hydrated radius of the hydrated metal ions determines
the order of preference. For sorption, metal ions of
smaller ionic radii move more readily closer to
potential adsorption sites32. Thus, since Cd(II) ion has
a smaller ionic radius than Pb(II) it, therefore, has
greater ease to be sorbed onto the surface of the three
oil palm fruit fibre adsorbents. Hence, Cd(II) shows
higher qe value as compared to that of Pb(II), because
it has the greater affinity to the reactive sites of the
adsorbents. Similar, result was also observed in the
sorption of Cd(II) and Zn(II) ions on the biomass of
Manihot sculenta Crantz wastes6.
Conclusion
This study indicated that mercaptoacetic acid
modified and unmodified oil palm fruit fibre waste
could be used as adsorbents for the removal of Pb(II)
and Cd(II) ions from aqueous solutions. The kinetics
of sorption indicates that the pseudo second order
model can be used to describe the mechanism of
sorption of Pb(II) and Cd(II) ions. Modeling of the
type 1-4 equations of the pseudo-second order model
using the coefficient of determination, as the fitting
parameter indicates that the type 1 pseudo-second
order equation was the best fit for the description
of the mechanism of Cd(II) and Pb(II) ions
from the bulk solution to the adsorbent surfaces.
Chemical modification of the adsorbent also
increased the amount of the metal adsorbed at
equilibrium.
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