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Center for Rural Development and Technology, Indian Institute of Technology, Delhi 110016, India
b Department of Chemical Engineering, Indian Institute of Technology, Delhi 110016, India
Received 9 December 2003; received in revised form 14 September 2004; accepted 5 January 2005
Abstract
Many investigations have been carried on metal binding capacity of different groups of microorganisms. However, the reports on the
kinetic, thermodynamic and desorption study of biosorption process are quite limited. The present study was carried out in a batch system
using Mucor hiemalis for its sorption and desorption study of Cr(VI). M. hiemalis exhibited the highest Cr(VI) uptake of 53.5 mg/g at an initial
pH of 2.0. Equilibrium data fitted well to Langmuir isotherm model. Biosorption showed pseudo-second order rate kinetics at different initial
concentration of Cr(VI) and different dose of M. hiemalis. The activation energy of the biosorption (Ea ) was estimated as 4.0 kJ/mol using
Arrhenius equation. Using the equilibrium constant value obtained at different temperature, the thermodynamics properties of the biosorption
(G , H and S ) were also determined. The biosorption of Cr(VI) onto M. hiemalis was found to be endothermic. Desorption data
showed that nearly 99% of the Cr(VI) adsorbed on M. hiemalis could be desorbed using 0.1N NaOH. Study with the cyclic use of a batch of
M. hiemalis repeatedly after desorption, showed that it retain its activity up to five sorption and desorption cycles.
2004 Elsevier B.V. All rights reserved.
Keywords: Adsorption; Biosorption; Bioremediation; Mucor hiemalis; Wastewater treatment; Chromium; Desorption
1. Introduction
Rapid industrialization and increase in population has led
many-fold increase in the utilization and release of chemicals including heavy metals. As consequences, these metals are found in toxic concentrations in aqueous systems.
Heavy metals like mercury, cadmium, lead, nickel, and
chromium are toxic, even in extremely minute quantities. Anthropogenic sources of chromium are industries viz., electroplating, leather tanning, metal finishing, chemical industries
and many others. Chromium exists in several oxidation states
out of which Cr(III) and Cr(VI) are most stable form. Because
of its high toxicity and potential carcinogenicity Cr(VI) is of
especial concern. In humans, Cr(VI) causes severe diarrhea,
ulcers, eye and skin irritation, kidney dysfunction and probably lung carcinoma [1]. Various methods used for removal of
Cr ions include chemical reduction and precipitation, reverse
Corresponding author. Tel.: +91 11 26591038 (O)/26591813 (R);
fax: +91 11 26581120.
E-mail address: bkguha iitdelhi@rediffmail.com (B.K. Guha).
1369-703X/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.bej.2005.01.011
186
qeq = Kf Ceq
(1)
Qmax bCeq
1 + bCeq
(2)
where Qmax and b are Langmuir constants denoting maximum adsorption capacity and the affinity of the binding sites,
respectively. These constants can be determined from the
1/Ceq versus 1/qeq . This also represents the physical bondage
between the component and adsorbent.
(5)
where k2 is pseudo-second order rate constant. After integration and applying the same boundary conditions t = 0 and
qt = 0 to t = t and qt = qeq at equilibrium, Eq. (5) becomes
t
1
t
=
+
2
qt
q
k2 (qeq )
eq
(6)
Ea
+ ln A0
RT
(7)
(8)
where R is gas constant (8.314 J/mol K), b is Langmuir constant and T is absolute temperature.
dqt
= k1 (qeq qt )
dt
(3)
(9)
where qt and qeq is sorption capacity at time t and at equilibrium, respectively and k1 is pseudo-first order rate constant.
After integration and applying boundary conditions t = 0 and
qt = 0 to t = t and qt = qeq at equilibrium, Eq. (3) becomes
k1 t
log(qeq qt ) = log qeq
2.303
G = H TS
(4)
RT ln b = H TS
(10)
or
ln b =
S
H
+
RT
R
(11)
187
188
a higher extent. This results in a stronger attraction for negatively charged Cr(VI) complex ions in the solution. Hence,
the sorption increases with the increase in the acidity of
the solution. But as the pH rises, the concentration of OH
ions increases and overall charge on the sorbent surface becomes negative which causes hindrance in the sorption of
negatively charged Cr ions like Cr2 O7 2 , CrO4 2 , etc., results in the decreased sorption of Cr(VI) at higher pH. M.
hiemalis biomass contains 3040% chitin and chitosan units
[14], which serves as a matrix of COOH and NH2 groups.
The FTIR spectroscopic analysis of Rhizopus cell wall has
indicated the involvement of amino group in Cr binding [15].
At pH 2.0, the negatively charged chromate ions would interact more strongly with the positively charged functional
groups of M. hiemalis biomass resulting in high Cr(VI) uptake. It is known that the dominant form of Cr(VI) at pH 1.0
is the acid chromate ion species (HCrO4 ) and increasing pH
shifts the concentration of HCrO4 to other forms, CrO4 2
and Cr2 O7 2 . Since there is an increase in sorption of Cr(VI)
as pH increased to 2.0 so it may be suggested that probably
the CrO4 2 and Cr2 O7 2 are the active forms of Cr(VI), which
are being sorbed by the biomass. Reduction in the biosorption
of Cr(VI) at pH value lower than 2.0 is probably due to the
change in the chemical nature of the M. hiemalis due to hydrolytic activity of the acid at high concentration. This might
change the surface characteristics of M. hiemalis including
surface area availability.
Fig. 3. Effect of dose of M. hiemalis on its sorption capacity for Cr(VI). Initial Cr(VI) concentration100 mg/l; pH2.0; contact time4 h; agitator
speed120 rpm.
189
Table 1
Isotherm parameters for Cr(VI) sorption on M. hiemalis
Temperature ( C)
27
40
50
Langmuir constants
Freundlich constants
Qmax (mg/g)
b (l/mg)
r2
Kf
r2
47.4
51.0
53.5
0.0307
0.0448
0.0534
0.9990
0.9928
0.9675
4.56
6.59
7.84
2.53
2.88
3.10
0.8790
0.8585
0.8365
190
Fig. 6. Linearised pseudo-second order kinetic plots at different initial concentration of Cr(VI). pH2.0; dose of M. hiemalis1 g/l;
temperature27 C; agitator speed120 rpm.
to the increase in concentration due to sorption site saturation, which thus shows up the decrease in apparent rate constant (k2 ). As the initial concentration of Cr(VI) increased,
time to achieve equilibrium decreased. At lower concentration (10 mg/l), equilibrium was attained after 90 min of sorption while at higher concentration (500 mg/l) equilibrium was
achieved in 45 min (figure not shown). The linearised plots for
pseudo-second order rate kinetics and the values of various
kinetic parameters obtained for various systems are presented
in Fig. 6 and Table 2. The value of qeq increased from 7.7 to
41.5 mg/g while value of h increased from 0.99 to 6.72 mg/g
min. Value of k2 decreased from 0.0167 to 0.0039 g/mg min.
3.6. Effect of dose of sorbent on kinetic parameters of
Cr(VI) sorption
It was observed that Cr(VI) sorption followed pseudosecond order kinetics at all the temperatures studied. The rise
in temperature increased the values of qeq , k2 and h. The
linearised plots for pseudo-second order rate kinetics and the
values of various kinetic parameters obtained are presented in
Fig. 8 and Table 4. The magnitudes of qeq , k2 and h increased
Table 2
Effect of initial concentration of Cr(VI) on kinetic parameters for sorption of Cr(VI) on M. hiemalis
Co (mg/l)
10
100
500
(min1 )
0.0748
0.0845
0.8284
r2
qeq (mg/g)
k2 (g/mg min)
h (mg/g min)
r2
0.9440
0.8372
0.8388
7.7
30.5
41.5
0.0167
0.0055
0.0039
0.99
5.11
6.72
0.9987
0.9926
0.9967
1.0
5.0
10.0
(min1 )
0.0845
0.0562
0.0438
r2
qeq (mg/g)
k2 (g/mg min)
h (mg/g min)
r2
0.8372
0.7885
0.7559
30.5
10.7
8.2
0.0055
0.0522
0.0977
5.11
5.98
6.57
0.9926
0.9995
0.9995
191
Table 5
Gibbs free energy change for the sorption of Cr(VI) on M. hiemalis
Temperature ( C)
Free energy
change (kJ/mol)
27
40
50
18.4
20.2
21.3
from 30.5 to 37.2 mg/g; 0.0055 to 0.0075 g/mg min and 5.12
to 10.6 mg/g min, respectively with the rise in temperature
from 27 to 50 C. The kinetic parameters at different temperatures have been plotted in terms of Arrhenius equation
(Fig. 9). The activation energy for the sorption of Cr(VI) on
M. hiemalis was calculated and its value was found to be
4.0 kJ/mol. From the value of activation energy it appears
that the sorption of Cr(VI) on M. hiemalis is physical adsorption process. This is confirmed from the fact that the activation energy for physical adsorption is usually not more than
46 kJ/mol [22]. This further consolidates the earlier observation of the biosorption data following Langmuir isotherm.
The value of G for the sorption of Cr(VI) on M. hiemalis
at different temperature is given in Table 5. The magnitude
of G increased with the rise in temperature. The negative
value confirms the feasibility of the process and the spontaneous nature of sorption of Cr(VI) on M. hiemalis. The values
of H and S were determined from slope and intercept
of the plot of ln b versus 1/T as shown in Fig. 10. H for the
Table 4
Kinetic parameters for sorption of Cr(VI) on M. hiemalis at different temperature
Temperature ( C)
27
40
50
(min1 )
0.0845
0.0424
0.0450
r2
qeq (mg/g)
k2 (g/mg min)
h (mg/g min)
r2
0.8372
0.8567
0.8795
30.5
34.5
37.2
0.0055
0.0061
0.0075
5.12
7.26
10.38
0.9926
0.9928
0.9675
pH2.0; dose of M. hiemalis1 g/l; initial Cr(VI) concentration100 mg/l; agitator speed120 rpm.
192
Table 6
Desorption of Cr(VI) from M. hiemalis
Cycles
Sorption (mg/g)
Desorption (mg/g)
Desorption (%)
I
II
III
IV
V
27.3
27.0
26.8
26.7
26.4
27.1
26.6
26.6
26.2
26.0
1.1
1.8
2.2
3.3
99.3
99.3
99.2
98.1
98.5
4. Conclusions
The experiments conducted with the biosorption showed
that M. hiemalis can remove Cr(VI) by biosorption. It was
also observed that the extant of biosorption increased with
lowering of pH up to 2.0. It was further observed that specific
sorption capacity decreased with increase in sorbent to sorbate ratio. Biosorption process followed Langmuir isotherm
model. The sorption capacity was found to increase with increase of solute concentration and temperature. The maximum sorption capacity was found to be 53.5 mg/g at 50 C
and pH 2.0. The rate of sorption was found to follow pseudosecond order kinetics. From the value of activation energy of
the process it is suggested that biosorption of Cr(VI) by M.
hiemalis is physical sorption. Further from the value of H
it was revealed that the biosorption process is endothermic.
Experiments were also conducted to regenerate the sorbent
by extracting chromium by NaOH. It was observed that even
after five cycles of sorption and regeneration the sorption efficiency remained quite high. Thus, it may be concluded that
M. hiemalis exhibited the potential for application in treatment of water containing Cr(VI). However, further research is
needed to establish the process with specific attention to the
regeneration of the sorbent and the recovery of the sorbed
metal. Therefore, future research will be oriented towards
column studies.
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