Water Air Soil Pollut (2008) 191:139–148
DOI 10.1007/s11270-007-9613-8
Biosorption of Chromium (III) and Chromium (VI)
by Untreated and Pretreated Cassia fistula Biomass
from Aqueous Solutions
Mazhar Abbas & Raziya Nadeem &
Muhammad Nadeem Zafar & Mamoona Arshad
Received: 1 November 2007 / Accepted: 23 December 2007 / Published online: 14 March 2008
# Springer Science + Business Media B.V. 2007
Abstract The present study explained the effect
of pretreatments on the biosorption of Cr (III) and
Cr (VI) by Cassia fistula biomass from aqueous
solutions. For this purpose Cassia fistula biomass
was pretreated physically by heating, autoclaving,
boiling and chemically with sodium hydroxide,
formaldehyde, gluteraldehyde, acetic acid, hydrogen
peroxide, commercial laundry detergent, orthophos-
phoric, sulphuric acid, nitric acid, and hydrochloric
acid. The adsorption capacity of biomass for Cr (III)
and Cr (VI) was found to be significantly improved
by the treatments of gluteraldehyde (95.41 and
96.21 mg/g) and benzene (85.71 and 90.81 mg/g)
M. Abbas : R. Nadeem : M. N. Zafar
Department of Chemistry, University of Agriculture,
Faisalabad 38040, Pakistan
R. Nadeem
e-mail: raziyaanalyst@yahoo.com
M. N. Zafar
e-mail: znadeempk@yahoo.com
M. Arshad
Bioprocess Technology Division, National Institute for
Biotechnology and Genetic Engineering (NIBGE),
Faisalabad 577, Pakistan
e-mail: mamoonaarshad@yahoo.com
Present address:
M. N. Zafar (*)
Department of Analytical Chemistry, Lund University,
P.O. Box 124, SE-221 00 Lund, Sweden
e-mail: MNadeem.Zafar@analykem.lu.se
respectively. The adsorption capacity was found to
depend on pH, initial metal concentration, dose, size,
kinetics, and temperature. Maximum adsorption of
both the Cr (III) and Cr (VI) was observed at pH 5
and 2. When Freundlich and Langmuir isotherms
were tested, the latter had a better fit with the
experimental data. The kinetic studies showed that
the sorption rates could be described better by a
second order expression than by a more commonly
applied Lagergren equation.
Keywords Cassia fistula . Sorption . Langmuir .
Freundlich . Chromium . Pretreatments
1 Introduction
Release of large quantities of heavy metals into the
natural environment has resulted in a number of
environmental problems (Hanif et al. 2007). Consti-
tuting one of the major causes of environmental
pollution, chromium is one of the most toxic and has
become a serious health concern. Extensive use of
chromium, e.g., in electroplating, tanning, textile
dyeing and as a biocide in power plant cooling water,
results in discharge of chromium-containing effluents
(Barnhart 1997). The effluents from these industries
contain Cr(III) and Cr(VI) at concentrations ranging
from tenths to hundreds of milligrams/liter. While Cr
(VI) is known to be toxic to plants and animals, a
strong oxidizing gent and a potential carcinogen
DO09613; No of Pages
140
(Costa 2003). Cr (III) is generally only toxic to plants
at very high concentrations and is less toxic or non-
toxic to animals.
Chromium exists in nine valence states ranging
from −2 to +6. However only hexavalent chromium
[Cr (VI)] and trivalent chromium [Cr (III)] are
ecologically important because they are the most
stable oxidation forms in the natural environment. Cr
(VI) is known to be highly toxic, mutagenic, and
carcinogenic to living organisms including mammals.
Cr (III), on the other hand, is more stable and is
approximately 100 times less toxic and 1,000 times
less mutagenic than Cr (VI). Various procedures have
been set up to remove heavy metals from water, based
on chemical precipitation, membrane filtration, car-
bon adsorption, ion-exchange, reverse osmosis, and
solvent extraction. These techniques being economi-
cally expensive have disadvantages like incomplete
metal removal, high energy requirements and gener-
ation of toxic sludge or other waste products that
require disposal. Efficient and environmental friendly
methods are thus needed to be developed to reduce
heavy metal content (Han et al. 2003).
Biosorption can be defined as the ability of bio-
logical materials to accumulate heavy metals from
wastewater through metabolically mediated or physico-
chemical pathways of uptake (Fourest et al. 1992). This
investigation studied the use of non-useful parts of
Cassia fistula like bark, leaves, and pods naturally
occurring biosorbent for the batch removal of Cr (III)
and Cr (VI) in a well stirred system under different
experimental conditions. Cassia fistula is very popular
ornamental tree all around the world. Cassia fistula is
commonly known as Amaltas in Pakistan, as Indian
Labrum in India, as Canafistula in Brazil and as
Golden Shower world wide. It belongs to family
Fabaceae, genus Cassia, species Fistula. It is a
medium size deciduous tree, 6–9 m tall with a straight
trunk and spreading branches. Numerous ionizable
chemical groups have been suggested to responsible
for metal biosorption. Cassia fistula presents a high
content of ionizable groups such as carboxyl, carbonyl,
alcoholic and amino groups (Hanif et al. 2007).
The present study is undertaken to examine the
effect of various pretreatments on the capacities of
Cassia fistula biomasses to remove Cr (III) and Cr
(VI) and to study the effect of different conditions
such pH, initial metal concentration, dosage, particle
size and time require for establishment of equilibrium.
Water Air Soil Pollut (2008) 191:139–148
2 Materials and Methods
2.1 Reagents
All reagents used in present study were of analytical
grade. Sodium hydroxide, formaldehyde, gluteralde-
hyde, acetic acid, hydrogen peroxide, commercial
laundry detergent, orthophosphoric, sulphuric acid,
nitric acid, hydrochloric acid were obtained from
Merck while Chromium atomic absorption spectrom-
eter standard solution (1,000 mg/l) was purchased
from Fluka chemicals. All glassware and polypropyl-
ene flasks used were overnight immersed in 10% v/v
HNO 3 and rinsed several times with distilled
deionized water (DDW). For adjusting the pH of
the medium 0.1 N solutions of NaOH and HCl were
used.
2.2 Cassia fistula Biomass
In the present study three different parts (leaves, stem
bark, and pods) of Cassia fistula biomass were used
and the Cassia fistula was harvested from University
of Agriculture, Faisalabad, Pakistan. Sampled exten-
sively washed with distilled water to remove particu-
late material from their surface, and oven dried at 60°C
for 72 h. One kilogram of biomass was sub sampled
for use in the experiments. In order to ensure that
homogeneous samples were collected, standard sam-
pling techniques were applied. Dried biomass was cut,
ground using food processor (Moulinex, France), and
then sieved through Octagon siever (OCT-DIGITAL
4527-01) to obtain adsorbent with homogenous known
particle size. The fraction with <0.255–0.710 mm was
selected for use in the sorption tests. The sieved
sorbents were stored in an air tight plastic container
for further experiments (Hanif et al. 2007).
2.3 Pretreatments of Biomass
Five grams of biomass was physically and chemically
pretreated in different ways as described below.
➢ Boiling (5 g of biosorbent/100 ml of H2O,
boiled for 15 min (Hanif et al. 2007).
➢ Dried at 60 °C for 12 h in an incubator.
➢ Autoclaved for 15 min at 121 °C, 15 psi.
➢ Boiled for 15 min in 500 ml of 0.5 N sodium
hydroxide solution (Selatnia et al 2004).
Water Air Soil Pollut (2008) 191:139–148 141

➢ Boiled for 15 min in 500 ml of 15% (v/v)
benzene solution.
➢ Boiled for 15 min in 200 ml of 10% (v/v)
acetic acid solution.
➢ Boiled for 15 min in 500 ml of 2% (v/v)
gluteraldehyde solution.
➢ Boiled for 15 min in 300 ml of 10% (v/v)
hydrogen peroxide solution.
➢ Boiled for 15 min in 500 ml of water in which
2.5 g of commercial laundry detergent was
dissolved.
➢ Boiled for 15 min in 200 ml of 10% (v/v)
orthophosphoric acid solution (Cabuk et al.
2005).
➢ 5 g of finally divided biomass was soaked in
100 ml of 0.1 N HCl, 0.1 N HNO3, 0.1 N
H2SO4 (Zafar et al 2007).
After each pretreatment with chemicals the bio-
masses were washed with generous amounts of
deionized water until the pH of the solution was in a
near neutral range (pH 6.8–7.2) and then dried at 60°C
for 12 h.
ments. In all sets of experiments fixed volume of Cr
(III) and Cr (VI) containing (100 ml) was thoroughly
mixed (at 120 rpm on an orbital shaker) with optimized
amount of biosorbent dose (0.1 g/100 ml) of particle
size <0.255 mm for predetermined time interval (15–
1,440 min) at 30°C. To check the influence of pH,
initial metal concentration and contact time, different
conditions of pH (1–5) for Cr (III) and pH (1–10) for
Cr (VI), initial metal concentration (25, 50, 100,
200 mg/l) and contact time (15, 30, 60, 120, 240,
480, 720, 1,440 min) were evaluated during study. The
pH of the medium was adjusted with 0.1 N solutions of
HCl and NaOH. The flasks were placed on a rotating
shaker (PA 250/25. H) with constant shaking. The
selection of these parameters for Cr (III) and Cr (VI)
biosorption by Cassia fistula biomass was based on
earlier experimental studies (Hanif et al. 2007). A
control was also run under similar conditions with the
aqueous solutions. At the end of experiments, the
flasks were removed from the shaker and the solutions
were separated from biomass through filter paper
(Whatman No. 40, ashless).

2.4 Cr (III) and Cr (VI) Solutions

Stock Cr (III) and Cr (VI) solution (1,000 mg/l) were

a Pods Leaves Bark

100
prepared by dissolving 2.82 g of K2Cr2O7 and
3.769 g of Cr2 (SO4)3 in 100 ml of deionized distilled 80
% removal

water (DDW) and diluting quantitatively to 1,000 ml 60

using DDW. Cr (III) and Cr (VI) solutions of different
40
concentrations were prepared by adequate dilution of
the stock solution with DDW. 20

0
2.5 Determination of the Cr (III) and Cr (VI) Contents 0 1 2 3 4 5 6
in the Solutions pH

The concentration of Cr (III) and Cr (VI) in the b Pods Leaves Bark

solutions before and after the equilibrium was 100

determined by flame atomic absorption spectrometry
80
(FAAS), using a Perkin-Elmer Analyst 300 Atomic
% removal

60
Absorption Spectrometer. The hollow cathode lamp
was operated at 15 mA and the analytical wavelength 40
was set at 218 nm. 20
0
2.6 Batch Biosorption Studies 0 2 4 6 8
pH
The affinity of Cassia fistula biomass to adsorb Cr (III) Fig. 1 a Effect of pH on Cr (III) biosorption. b Effect of pH on
and Cr (VI) was studied in triplicate sets of experi- Cr (VI) biosorption
142 Water Air Soil Pollut (2008) 191:139–148

a Pods Leaves Bark maximum biosorption of Cr (VI) ions on the untreated

120 biomass were observed at pH 2.0. It should be noted
100 that the distribution of Cr (VI) ions species is
q (mg/g)

80
60 dependent on both the total concentration of Cr (VI)
40 and pH of the aqueous solution. The oxy-anions of
20
0
chromium are known to exist in the following
equilibrium (Bajpai et al. 2004).
Su itri ve

ric d
d

ge icA l
Pe id
G eti ide

ld id
Be yde

N e
et H

t
cu ve

Bo g
ng
C

ut en
en
hu ci

ci

tin
O
c

ta Ac
N ati

In Cla

ili
lp cA

A rox

A erg
nz
eh

ba
N

lu c
H2 CrO4 $ HCrO
þ

o
4 þH ; k1 ¼ 1:21
o r

ra

D
h

c
n
sp
ho

ro

op

7 þ H2 O $ 2HCrO4 ;
CrO2
¼ 35:5
yd

k2
rth

H
O

þ
Treatments HCrO4 $ CrO4 þ H ; k3 ¼
2

3  10
7
HCrO
2
þ
7 $ CrO4 þ H ; k4 ¼ 0:85
b Pods Leaves Bark
120
100
Since the distribution of anionic species of Cr (VI)
q (mg/g)

80
60 is pH dependent, this could be the main variable for
40
20
removal of Cr (VI) ions by Cassia fistula biomass.
0 The cell wall components have several functional
groups (such as carboxyl, carbonyl, alcoholic and
itr tive

ric d
d

ge icA l
Pe id
G eti ide

ld id
Be yde

N e
et H

t
cu ve

Bo g
ng
C

ut en
en
hu ci

ci

tin
O
c

ta Ac
H

In Cla

ili
lp icA

A rox

A erg
nz
eh

a
a

ba
N

lu c

amino groups). The metal biosorption depends on the

o
o r

ra

D
h
N

c
n
sp

protonation or unprotonation of these functional

ho
Su

ro
op

yd
rth

groups on the cell wall. The ionic forms of the metal

O

Treatments
in solution and the electrical charge of the Cassia
Fig. 2 a Effect of pretreatments on Cr (III) biosorption. b
Effect of pretreatments on Cr (VI) biosorption

a Pods Leaves
Bark Glutaraldehyde Treated Pods
Benzne Treated Pods
2.7 Metal Uptake
150
The Cr (III) and Cr (VI) uptake was calculated by the
q (mg/g)

100
simple concentration difference method. Uptake of Cr
(III) and Cr (VI) were calculated from mass balance 50
equation:
0
q ¼ V ðCi
Ce Þ=M ð1Þ 0 50 100 150 200 250
Concentration (mg/L)

where q is Cr (III) and Cr (VI) uptake capacity (mg/g), b Pods Leaves

V is the volume of the solution (L), Ci is the initial Bark Glutaraldehyde Treated Pods
Benzne Treated Pods
concentration (mg/l), Ce is the final concentration in
solution (mg/l) and M the mass of the sorbent (g). 150
q (mg/g)

100

3 Results and Discussion 50

0
3.1 Effect of pH
0 50 100 150 200 250
Concentration (mg/L)
Figure 1b showed that biosorption of Cr (VI) ions by
Fig. 3 a Effect of initial metal concentration on Cr (III)
untreated Cassia fistula biomass decreased when the biosorption. b Effect of initial metal concentration on Cr (VI)
medium pH increased. As seen from the figure, the biosorption
Water Air Soil Pollut (2008) 191:139–148 143

Table 1 The Langmuir isotherm and Freundlich isotherm parameters

Metal Biosorbents Langmuir parameters Freundlich parameters

Xm (mg/g) KL (dm3/g) R2 q (mg/g) qe (mg/g) K (l/mg) 1/n R2

Cr (III) Pods 107.5 0.2071 0.9921 119.1 125.9 12.28 0.5234 0.9518
Leaves 102.4 0.0897 0.9919 113.3 91.2 13.29 0.4532 0.9554
Bark 101.6 0.0197 0.9917 103 93.32 21.38 0.3241 0.9426
Glutaraldehyde treated pods 114.9 0.4508 0.9854 124.3 141.2 18.15 0.4798 0.9562
Benzene treated pods 112 0.0721 0.9919 121.3 87.09 17.62 0.3698 0.9828
Cr (VI) Pods 121.95 0.1406 0.992 123.7 138 11.94 0.5672 0.9581
Leaves 112.36 0.201 0.9951 115.9 97.72 11.59 0.4829 0.9584
Bark 109.8 0.2615 0.991 107.1 112.2 23.18 0.3349 0.9461
Glutaraldehyde treated pods 131.5 0.3858 0.9928 129.1 144.5 24.19 0.4121 0.9627
Benzene treated pods 126.5 0.07440 0.9917 125.3 134.9 16.63 0.4875 0.9662

fistula biomass depend on the solution pH. At acidic 3.2 Effect of Pretreatment
pH (i.e. 1.0–2.0), protonation of amino groups of the
Cassia fistula cell wall components enhanced the To evaluate the effect of pretreatment on biomass,
biosorption capacities of the biosorbents to Cr (VI) 100 mg/l Cr (III) and Cr (VI) solutions were shaken at
ions. The increased binding of Cr (VI) ions at low pH
can be explained due to the electrostatic binding to
positively charged groups such as amines of the Cassia
a Pods Leaves
Bark Glutaraldehyde Treated Pods
fistula cell wall components (Gupta and Keegan Benzne Treated Pods
1998; Bajpai et al. 2004; Fourest et al. 1992; Sharma
2.5
and Foster 1993).
Carboxyl, carbonyl, alcoholic and amino groups 2
have been identified as the main metal-sequestering
1.5
Ce/qe

sites in biomass and as these groups are acids, its

availability is pH dependent. At pH in the range 3.5– 1
5.5 these groups generate a negatively charged 0.5
surface and electrostatic interactions between cationic
0
species and this surface can be responsible for metal
0 50 100 150 200 250
biosorption. The hypothesis of dissolution of cell Ce
components seems to be viable for the present study,
because of some difficulties of filtration at pH 4.0 and
b Pods Leaves
for solutions which showed an increase of pH. The
Bark Glutaraldehyde Treated Pods
decrease of pH (Fig. 1a) can be attributed to the Benzne Treated Pods
chemical features of the chromium (III) solution
2.5
rather than to the sorption mechanism (Gupta and
Keegan 1998). Chromium (III) in water can undergo 2
hydrolysis and/or complexation reactions. The exten-
Log qe

1.5
sion of these reactions depends primarily on the total
chromium (III) concentration, pH and the type of 1
anions in the solution. The hydrolysis reaction 0.5
generates divalent cations Cr(OH)2 and protons which
0
contribute to the increase of acidity of the chromium 0 1 2 3 4 5
(III) solutions (Kratochvil and Volesky 1998). Cassia Log Ce
fistula pods have the highest % removal. So pods Fig. 4 a The Langmuir isotherm model for Cr (III). b The
were chosen to evaluate the effect of pretreatments. Freundlich isotherm model for Cr (III)
144 Water Air Soil Pollut (2008) 191:139–148

a Pods Leaves results in increase in biomass metal sorption capacity

Bark Glutaraldehyde Treated Pods due to availability of more biosorption sites. The
Benzne Treated Pods increase was attributed to the exposure of the latent
2 binding sites after pretreatment (Galun et al. 1987). In
case of chemical Pretreatments, pretreatment with
1.5
gluteraldehyde and benzene increased biosorption.
Ce/qe

1
Gluteraldehyde is a cross-linking reagent with multi-
functional groups. According to Jianlong (2002),
0.5 gluteraldehyde pretreated Saccharomyces cerevisiae
biomass retains almost all its original biosorption
0 capacity. In this study, gluteraldehyde pretreatment
0 50 100 150 200 250 significantly increased Cr (III) and Cr (VI) biosorption.
Ce The differences in the results may be due to cell wall
structure. Hydrogen peroxide, commercial laundry
b Pods Leaves detergent, and sodium hydroxide resulted in an
Bark Glutaraldehyde Treated Pods improvement in Cr (III) and Cr (VI) biosorption.
Benzne Treated Pods
Acetic acid and orthophosphoric acid reduced bio-
2.5
sorption of Cr (III) and Cr (VI) to a certain extent while
2 autoclaving and heat significantly reduced biosorption
of Cr (III) and Cr (VI). For further study pods, leaves
1.5
Log qe

and bark without pretreatments and glutaraldehyde

1 and benzene treated pods were chosen.
0.5

0
0 1 2 3 4 5
Log Ce a Pods Leaves
Fig. 5 a The Langmuir isotherm model for Cr (VI). b The Bark Glutaraldehyde Treated Pods
Freundlich isotherm model for Cr (VI) Benzne Treated Pods

120
100
q (mg/g)

120 rpm with 0.1 g of biosorbent having size 80

0.255 mm at pH 5 and 2 for 24 h respectively. 60
Uptake capacity of Cassia fistula pods was signifi- 40
20
cantly increased after pretreatment (Fig. 2a,b) (Galun 0
et al. 1987). Physical and chemical pretreatments of 0 500 1000 1500 2000
biomass were resulted in increased or decreased Time (min)
uptake capacity depending on the pretreatment meth-
od in comparison with biosorption using dead b Pods Leaves
biomass. Physical modifications of biomass such as Bark Glutaraldehyde Treated Pods
Benzne Treated Pods
heat and autoclaving significantly reduced biosorption
of Cr (III) and Cr (VI). This may be attributed to the 150
loss of intracellular uptake. In the previous study Mucor
q (mg/g)

100
rouxii biomass pretreated with autoclave reduced the
biosorption of heavy metals (Yan and Viraraghavan 50
2000). In the same way A. versicolor pretreated with
0
autoclave reduced the biosorption of cadmium, copper, 0 500 1000 1500 2000
and nickel (Kapoor and Viraraghavan 1998). While Time (min)
boiling remove mineral matter from biomass and Fig. 6 a Effect of sorption time on Cr (III) biosorption. b
introduce more sorption sites on biomass surface which Effect of sorption time on Cr (VI) biosorption
Water Air Soil Pollut (2008) 191:139–148 145

a Pods Leaves 3.4 Equilibrium Modeling

Bark Glutaraldehyde Treated Pods
Benzne Treated Pods
The biomass exhibited adsorption isotherms of
2
Langmuir and Freundlich, which is a characteristic
1.5 of the biomass substrate containing both micropores
Log (qe-q)

and mesopores (Vinod and Anirudhan 2001). The

1
Langmuir equation assumes that adsorption is limited
0.5 to monolayer; its linearized form can be represented
0 as (Langmuir 1916):
0 50 100 150
t (min) Ce =qe ¼ 1=Xm KL þ Ce =Xm ð2Þ
where qe is the metal ion sorbed (mg/g), Ce the
b Pods Leaves equilibrium concentration of metal ion solution, and
Bark Glutaraldehyde Treated Pods
Benzne Treated Pods Xm and KL are the Langmuir constants. The Freund-
20 lich equation is an empirical relationship describing
the adsorption of the solutes from a liquid to solid
15
surface. Linearized form of Freundlich equation is
t/q 10 (Freundlich 1906):
5
log qe ¼ log Ce =n þ log K ð3Þ
0
0 500 1000 1500 2000 where qe is the metal ion sorbed (mg/g), Ce the
t (min) equilibrium concentration of metal ion solution (mg/l),
Fig. 7 a Pseudo first-order kinetic model for Cr (III). b Pseudo
second-order kinetic model for Cr (III)
a Pods Leaves
Bark Glutaraldehyde Treated Pods
Benzne Treated Pods
3.3 Effect of Initial Metal Ion Concentration 2

The metal removals by untreated and pretreated 1.5

Log (qe-q)

biomasses corresponding to different initial metal con- 1

centrations (25, 50, 100 and 200 mg/l) are shown in
Fig. 3a and b. The rate of adsorption is a function of 0.5
the initial concentration of metal ions, which makes it
0
an important factor to be considered for effective 0 50 100 150
biosorption (Ahalya et al. 2005). In general, the data t (min)
revealed that sorption capacity increased with increase
in initial metal ion concentration for Cr (III) and Cr b Pods Leaves
(VI) on sorbents (Fig. 3a,b). This sorption character- Bark Glutaraldehyde Treated Pods
Benzne Treated Pods
istic represented that surface saturation was dependent
on the initial metal ion concentrations. At low 20
concentrations, adsorption sites took up the available 15
metal more quickly. However, at higher concentra-
t/q

10
tions, metal ions need to diffuse to the biomass
5
surface by intraparticle diffusion and greatly hydro-
0
lyzed ions will diffuse at a slower rate (Jnr and Spiff 0 500 1000 1500 2000
2004). On increasing metal concentration, the per- t (min)
centage of metal removed decreased due to diminish- Fig. 8 a Pseudo first-order kinetic model for Cr (VI). b Pseudo
ing loading capacity of biomass. second-order kinetic model for Cr (VI)
146 Water Air Soil Pollut (2008) 191:139–148

Table 2 The pseudo first-order (Lagergren) and pseudo second-order parameters

Metal Biosorbents Pseudo 1st order parameters Pseudo 2nd order parameters

qe (mg/g) K1,ads (min−1) R2 q (mg/g) qe (mg/g) k2,ads (g/mg min) R2

Cr (III) Pods 52.78 5.5×10−4 0.9907 89.2 89.2 3.86×10−4 0.9986

Leaves 52.2 5.2×10−3 0.9942 84.7 86.9 3.37×10−4 0.9984
Bark 53.2 5.8×10−3 0.9942 81.7 84.03 3.82×10−4 0.9985
Glutaraldehyde treated pods 55.08 5.5×10−3 0.9959 95.4 98.03 3.82×10−4 0.9988
Benzene treated pods 49.30 7.4×10−3 0.9878 87.7 87.7 5.14×10−4 0.9993
Cr (VI) Pods 53.03 6.9×10−3 0.9894 89.2 91.7 4.45×10−4 0.9991
Leaves 53.24 5.8×10−3 0.9953 84.7 90.01 6.21×10−4 0.9987
Bark 51.45 6.2×10−3 0.9937 81.7 86.20 4.24×10−4 0.9989
Glutaraldehyde treated pods 55.9 7.4×10−3 0.9964 95.4 98.03 4.46×10−4 0.9993
Benzene treated pods 53.80 8.8×10−3 0.9896 87.7 92.59 5.26×10−4 0.9995

and K and 1/n are constants. A comparison of
Langmuir and Freundlich isotherms is shown in
Table 1. As indicated from Table 1, the coefficients
of determination (R2) of both models were greater
than 0.9 and were close to one, indicating that both
models adequately describe the experimental data of
these metal biosorption experiments (Figs. 4a,b and
5a,b). Data fitted with Langmuir and Freundlich
isotherm models is shown in Table 1. The R2 and
qmax values suggested that the Langmuir isotherm
describes the sorption process well as compared to
Freundlich isotherm.
3.5 Kinetic Study
The experiments were conducted to determine the
time required for pretreated pods (glutaraldehyde,
benzene) and untreated (pods, leaves and stem bark)
to bind the Cr (III) and Cr (VI) ions. The Cr (III) and
Cr (VI) ions uptake was rapid within first 30 min
followed by slow sorption till equilibrium was
reached. From this sorption behavior of Cassia fistula
biomasses it can be concluded that Cr (III) and Cr
(VI) ions uptake by pretreated and untreated bio-
masses followed a two-step mechanism where the
metal ions were physically/chemically taken up onto
the surface of the biosorbents before being taken up
into the inner adsorption sites of dead cells (Volesky
1990). The first step, known as a passive surface
transport, took place quite rapidly i.e. within 30 min
while the second passive diffusion step transport,
could take much longer time to complete (Pavasant
et al. 2006; Sekhar et al. 2003; Sekhar et al. 2004). A
kinetic study with different time intervals with fixed
metals and biosorbents concentrations was performed
and the obtained results are presented Fig. 6a and b.
Maximum biosorption of Cr (III) and Cr (VI)
occurred on glutaraldehyde pods.
3.6 Kinetic Modeling
Kinetics of adsorption by any biological material has
been widely tested by the first order expression given
by Lagergren and pseudo second order approach
(Figs. 7a,b and 8a,b) (Jnr and Spiff 2004; Cheung et
al. 1997; Ho et al. 1996). The first order Lagergren
equation is (Lagergren 1898):


logðqe
qÞ ¼ log qe
k1;ads  t 2:303 ð4Þ
The pseudo second order equation is (Ho 1995; Ho
and McKay 1999):

t=q ¼ 1 k2;ads q2e þ t=qt ð5Þ
where qe is the mass of metal adsorbed at equilibrium
(mg/g), qt the mass of metal at time t (min), K1,ads the
first order reaction rate constant of adsorption (per
min), K2,ads the pseudo second order rate constant of
adsorption (mg/g min) (Loukidou et al. 2004). The
Lagergren first-order rate constant k1 and qe deter-
mined from the model indicated that this model had
failed to estimate qe since the experimental values of
qe differs from estimated ones. The best fit for the
experimental data of this study was achieved by the
application of pseudo second-order kinetic equation.
It is important to notice that it is not necessary to
estimate the experimental value of qe for the applica-
tion of such a model. The coefficients of correlation
Water Air Soil Pollut (2008) 191:139–148
for second-order kinetic model were almost equal
to 1 and the estimated values of qe also agreed with
the experimental ones. Both factors suggest that the
sorption of Cr (III) and Cr (VI) ions followed the
second-order kinetic model, indicating that the rate-
limiting step was a chemical biosorption process
between Cr (III) and Cr (VI) and Cassia fistula
biomasses. Similar conclusions were found by Ho
and McKay as a result of an analysis of data from
literature. They reported that most of the sorption
systems follow a pseudo second-order kinetic model
(Ho and McKay 1999). A comparison between
Lagergren pseudo first order and to pseudo second
order kinetic models was shown in Table 2.
4 Conclusion
Cassia fistula biomass was used for the sorption of Cr
(III) and Cr (VI). Maximum removal of Cr (III) was at
pH 5 and Cr (VI) at pH 2. Different physical and
chemical treatments enhanced the biosorption capacity
of biosorbent but biosorbent treated with gluteralde-
hyde and benzene had the highest capacity. The %
removal was 95.41 and 85.71 for Cr (III) and 96.21 and
90.81 for Cr (VI) with gluteraldehyde and benzene
respectively. The adsorption followed the Langmuir
isotherm and pseudo second-order kinetic model.
Acknowledgement The authors are thankful to Prof. Dr. Munir
Ahmad Sheikh (Chairman, Department of Chemistry, University
of Agriculture, Faisalabad, Pakistan) for the financial support.
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